CN113930198B - 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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- 238000011049 filling Methods 0.000 claims abstract description 11
- 230000002745 absorbent Effects 0.000 claims abstract description 7
- 239000002250 absorbent Substances 0.000 claims abstract description 7
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- 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 9
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- 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
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 3
- 239000010690 paraffinic oil Substances 0.000 abstract description 10
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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
- 240000000233 Melia azedarach Species 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
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- 150000001924 cycloalkanes Chemical class 0.000 description 1
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- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
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- 229920002857 polybutadiene Polymers 0.000 description 1
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- 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
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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 raw materials of the oil-filled star-shaped rubber hot melt adhesive comprise, 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 technology, the invention aims to provide the oil-filled star-shaped rubber hot melt adhesive, the oil-filled star-shaped 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-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-filled star-shaped rubber hot melt adhesive, which can fully melt the oil-filled star-shaped rubber, is simple and can realize industrial production.
The oil-filled star-shaped rubber hot melt adhesive comprises 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 absorbent;
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 the styrene in the oil-filled star rubber is 25 to 45 percent.
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 UV326.
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 the 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 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 absorbent;
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.
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 an appropriate amount of oil softener is filled in the later stage of star-shaped rubber production to prepare 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 molecular weight of the oil-filled star-shaped rubber is higher 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, the molecular weight of the oil-filled rubber is generally more than 30 ten thousand, the oil-filled rubber is difficult to process due to the higher molecular weight, the higher temperature and longer time are required for complete melting, the melting temperature of the hot melt adhesive is lower, and the oil-filled rubber is difficult to be melted with other raw materials if the oil-filled rubber is directly added into the hot melt adhesive, so that the oil-filled star-filled rubber is not used for producing the oil-filled rubber at present, and the oil-filled star-shaped rubber is mainly used for shoe processing industry, plastic modification industry 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, the paraffin-based oil is small in molecular weight, compared with the traditional naphthenic oil with large molecular weight, the oil-filled star rubber can be better softened, the oil-filled star rubber is better fused, moreover, the structure of the paraffin-based oil is of a chain structure, compared with a plasticizer with a ring structure, the paraffin-based oil with the chain structure is lower in rigidity and hardness, the oil-filled star rubber can be better softened, 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 industrial development is promoted.
Preferably, the tackifier resin has a molecular weight of 300 to 2000 and the paraffinic oil has a molecular weight of 50 to 400. Because oil charge star type rubber is big in molecular weight, and the molecular weight of plasticizer and tackifying resin is little, and micromolecular plasticizer and tackifying resin encircle to fill between the macromolecule chain, can effectively improve peel strength and cohesive strength of oil charge star type rubber hot melt adhesive, improve the anti precipitation capacity of micromolecule, smell is less simultaneously, and the travelling comfort is better, provides new optional main part material for disposable health supplies 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 disposable sanitary products of baby diapers, baby pull-ups, sanitary towels, medical mattresses, adult diapers, adult pull-ups and the like, and the hot melt adhesive for the disposable sanitary products is required to have certain bonding performance, small smell, soft hand feeling and good low-temperature resistance effect, and can meet the use requirement that the environmental temperature is higher than 5 ℃. The oil-filled star rubber hot melt adhesive has the advantages of low cost, good oil locking performance and excellent high temperature resistance by introducing the oil-filled star rubber into the hot melt adhesive used in the disposable sanitary product industry, and compared with general rubber (the molecular weight is less than 30 ten thousand), the oil-filled star 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 rubber is 30-60 ten thousand, so that the oil-filled star rubber is generally used in the industries of shoe processing, plastic modification and the like, but is difficult to be applied to the hot melt adhesive used in disposable sanitary products.
Further, the melt index of the oil-extended star rubber is 5 to 50 (g/10min, 190 ℃/5 kg);
according to the mass percentage, the content of the styrene in the oil-extended star rubber is 25 to 45 percent.
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, with the composition S-B-S, S is styrene which is a hard segment, B is a butadiene rubber segment which is a soft segment. The more S, the harder the rubber, the harder the hot melt adhesive prepared, the poorer the elasticity and the poorer the low temperature resistance, and vice versa.
When the content of styrene in the oil-extended star rubber is 25-45% and the melt index of the oil-extended star rubber is 5-50 (g/10min, 190 ℃/5 kg), the prepared oil-extended star rubber hot melt adhesive has higher 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 was produced in Taiwan Li Changrong with a 33.3% oil charge; star SBS1485 is produced in Taiwan Li Changrong with oil filling amount of 31%; star SBS1484 is produced in Taiwan Li Changrong with oil filling of 33.3%; star SBS1487 is produced in Taiwan Li Changrong with a 28.5% oil fill.
The rubber structure has two types of linear rubber and star rubber, the linear rubber has lower strength and poor oil locking performance compared with the star rubber, but the linear rubber is easier to process than 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 worth noting that the molecular weight of the P-80 paraffinic oil is 60,C P Paraffin base proportion 67%, C N The proportion of cycloalkyl groups is 33%; KP6010 Paraffin base oil has a molecular weight of 100,C P Paraffin base proportion of 64%, C N The 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. C P The higher the paraffin base content is, the smaller the peeling force constant viscosity data of the obtained hot melt adhesive is; c N The higher the cycloalkane content, the greater the peel force tack data of the resulting hot melt adhesive.
Specifically, KP6010 paraffinic oil is produced by Clarity, and P-80 paraffinic oil is produced by da Lian, dakto.
Stated further, 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, lu Hua HD1100, rayson S5100 or Henghe HM 1000; the hydrogenated C9 petroleum resin is selected from one or more of Ji Long QH4100, tianma AH1000 and Liansuper FM 100; the hydrogenated C5 petroleum resin is one or more of Henghe HS1001 and Chinese information source 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 UV326.
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 ultraviolet absorbent, controlling the temperature to be 120-150 ℃, after the tackifying resin is completely melted, vacuumizing until no 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 between 130 ℃ and 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 is prepared from the following raw materials, by mass, 22% of KP6010 (Clarity), 21% of star-shaped SBS1485 (Li Changrong), 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 (Li Changrong) is 35 ten thousand, the oil extension of the star-shaped SBS1485 (Li Changrong) is 31%, the melt index of the star-shaped SBS1485 (Li Changrong) is 8 (g/10min, 190 ℃/5 kg), the styrene content of the oil-extended star-shaped rubber is 32%, the molecular weight of KP6010 (Clarity) 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 (Li Changrong), 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 air bubble exists, stirring and mixing evenly to obtain the oil-filled star-shaped rubber hot melt adhesive.
The hot melt adhesive prepared in this example is suitable for a device for spraying, roll coating or blade coating, and the oil-extended star-shaped rubber of this example is preparedThe hot melt adhesive is placed in a hot melt adhesive cylinder, the temperature is kept at 130 ℃ until the adhesive blocks are completely melted for use, the gluing surface is non-woven fabric or PE film, and the gluing amount is about 1.5g/m 2 And 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
An oil-extended star-shaped rubber hot melt adhesive is prepared from 23% of P-80, 19% of SBS1475 (Li Changrong), 0.5% of antioxidant 1010, 0.5% of antioxidant 168, 56.7% of Ji Long QH4100 and 0.3% of UV326 by mass percent, wherein the molecular weight of SBS1475 (Li Changrong) is 40 ten thousand, the oil-extended amount of SBS1475 (Li Changrong) is 33.3%, the melting index of SBS1475 (Li Changrong) is 5 (g/10min, 190 ℃/5 kg), the content of styrene in SBS1475 (Li Changrong) is 40%, the molecular weight of P-80 is 60, and the molecular weight of Ji Long QH 320 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 (Li Changrong 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; adding 56.7% of Ji Long QH4100 and 0.3% of UV326 in sequence, and heating to melt at 130 ℃; then vacuumizing until no 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/m 2 After pressing and compounding, the basic structure of the disposable hygienic product is obtained, and the viscosity of the oil-filled star-shaped rubber is the main viscosityThe hot melt adhesive product provided by the embodiment of the invention is provided by tackifying resin, and the star SBS1475 oil-filled rubber and a large amount of Ji Long QH4100 are used, so that the peel strength and the cohesive strength of the hot melt adhesive product are greatly improved, the glue is not easy to overflow, 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 was produced in Taiwan Li Changrong with a 33.3% oil charge; star SBS1485 is produced in Taiwan Li Changrong with oil filling amount of 31%; the star SBS1484 is produced in Taiwan Li Changrong, and the oil filling amount is 33.3%; star SBS1487 is produced in Taiwan Li Changrong with a 28.5% oil fill.
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 Ji Long 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 Ji Long 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 Ji Long 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 the 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 used as a test instrument;
and (3) testing the peel strength: testing according to the GB/T2792-2014 standard;
cohesive strength (tensile strength): detecting the cohesive strength of the oil-filled star-shaped rubber hot melt adhesive obtained in the examples 1-5 according to the determination of the tensile stress strain performance of the vulcanized rubber or the thermoplastic rubber in the standard 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 comparative example is a conventional common hot melt adhesive, and 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 UV326.
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 detection results of the table 1, compared with the comparative example 1, the cohesive strength of the oil-filled star-shaped rubber hot melt adhesive prepared in the example 1 is obviously greater than that of the hot melt adhesive in the comparative example 1, the peel strength is also higher than that of the comparative example 1, compared with the comparative example 1, the example 1 also has the advantages of low softening point, low viscosity at high temperature (150 ℃/cps) and low odor, and meanwhile, in the preparation process, the oil-filled star-shaped rubber can be completely melted after being heated for 45 minutes at 130 ℃, so that long-time heating is not needed.
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 (7)
1. The oil-extended 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 absorbent;
the high molecular polymer is oil-extended star rubber, and the molecular weight of the oil-extended star rubber is 30 to 60 ten thousand; according to the mass percentage, the oil filling amount of the oil-filled star rubber is 20 to 40 percent;
the plasticizer is paraffin-based oil, and the tackifying resin is one or more of hydrogenated C9 petroleum resin, hydrogenated C5 petroleum resin and hydrogenated DCPD petroleum resin;
the molecular weight of the paraffinic base oil is 50 to 400; the molecular weight of the tackifying resin is 300 to 2000;
the oil-filled star-shaped rubber hot melt adhesive is applied to the industry of disposable hygienic products.
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 at 190 ℃ under 5kg is 5 to 50g/10min;
the content of styrene in the oil-extended star rubber is 25 to 45 percent by mass.
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 according to claim 1, wherein the paraffinic base oil is KP6010 paraffinic base oil or P-80 paraffinic base oil.
5. 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.
6. The oil-extended star-shaped rubber hot melt adhesive as claimed in claim 1, wherein the ultraviolet absorber is UV326.
7. 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 6, and comprising the following steps:
(1) Adding a plasticizer and an antioxidant into a reaction kettle according to a formula ratio, 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 at 120 to 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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Application publication date: 20220114 Assignee: Zhaoqing Weijia Chengxing New Material Technology Co.,Ltd. Assignor: Foshan Benjia New Material Technology Co.,Ltd. Contract record no.: X2023980052685 Denomination of invention: An oil filled star shaped rubber hot melt adhesive and its preparation method Granted publication date: 20230203 License type: Common License Record date: 20231219 |
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