CN115919810A - Novel black plaster matrix hot-melt pressure-sensitive adhesive and preparation method thereof - Google Patents
Novel black plaster matrix hot-melt pressure-sensitive adhesive and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a novel black plaster matrix hot-melt pressure-sensitive adhesive and a preparation method thereof, wherein the hot-melt pressure-sensitive adhesive comprises 15-40 parts of synthetic rubber, 10-30 parts of naphthenic oil, 0.1-5 parts of antioxidant, 30-50 parts of hydrogenated petroleum resin, 5-20 parts of rosin resin, 0.1-10 parts of pigment and filler and 5-20 parts of grafted epoxidized natural rubber ENR-HMEA; according to the invention, epoxy groups are introduced through the epoxidized natural rubber ENR-25 with the grafting rate of 25%, and the bonding effect of the adhesive in the formula on different skin types is improved by utilizing the characteristic of excellent adhesive force of the epoxy groups. The adhesiveness is improved, the degree of adhesion between the hot-melt pressure-sensitive adhesive and the skin is improved, the sealing performance of the periphery of the hot-melt pressure-sensitive adhesive is guaranteed, and the invasion of external bacteria is prevented; simultaneously, by utilizing the residual part of double bond active groups in ENR-25, hydroxyethyl methacrylate HMEA is introduced in a grafting manner, so that a proper amount of hydrophilic hydroxyl end groups are introduced, and the sweat resistance effect of the adhesive is improved; on the other hand, the introduced HMEA contains an acrylate and is excellent in skin-friendly properties and anti-allergic properties.
Description
Technical Field
The invention relates to the technical field of hot melt adhesives, in particular to a novel black plaster matrix hot melt pressure sensitive adhesive and a preparation method thereof.
Background
The traditional black plaster appears from the period from Wei jin in south to north, the production technology is gradually improved from the period of Tang and Song to recent times, and the black plaster plays an indispensable role all the time. However, the manufacturing process of the black plaster is complex, has no unified standard, and is not easy to control the quality, so that the quality of the black plaster is uneven, and the mass standardized production is difficult to realize.
In recent years, synthetic rubber SBS and SIS pressure-sensitive colloid systems are used to replace traditional black plasters and are put into the market, the problems of batch production and controllable quality of the traditional black plasters can be solved, however, the plaster is poor in adhesive effect and prone to falling off due to the fact that human bodies are prone to sweat and grease and water exist in sweat; meanwhile, the joint parts such as elbows, knees, ankles and the like are easy to stick loosely and fall off.
Therefore, a novel matrix which is stable and can be used for mass production of black plaster is sought, and the defects of the traditional black plaster can be overcome.
Disclosure of Invention
In order to overcome the defects of the prior art, one of the purposes of the invention is to provide a novel black plaster matrix hot-melt pressure-sensitive adhesive, the invention introduces synthetic rubber SIS, petroleum resin and rosin resin, and takes the advantage of good adhesiveness of the traditional hot-melt pressure-sensitive adhesive into consideration, the invention preferably compounds SIS1126 and SIS1220 according to the mass ratio of 3;
furthermore, epoxy groups are introduced through the epoxidized natural rubber ENR-25 with the grafting rate of 25%, and the bonding effect of the adhesive in the formula on different skin types is improved by utilizing the characteristic of excellent adhesive force of the epoxy groups. The adhesiveness is improved, the degree of adhesion between the hot-melt pressure-sensitive adhesive and the skin is improved, the sealing performance of the periphery of the hot-melt pressure-sensitive adhesive is guaranteed, and the invasion of external bacteria is prevented; simultaneously, by utilizing the residual part of double bond active groups in ENR-25, hydroxyethyl methacrylate HMEA is introduced in a grafting manner, so that a proper amount of hydrophilic hydroxyl end groups are introduced, and the sweat resistance effect of the adhesive is improved; on the other hand, the introduced HMEA contains acrylate, and is excellent in skin-fitting property and anti-allergic property;
more importantly, the ENR-HMEA subjected to grafting treatment is matched with the synthetic rubber, the ratio of the ENR-HMEA to the synthetic rubber is preferably 9
The invention also aims to provide a preparation method of the novel black plaster matrix hot-melt pressure-sensitive adhesive, the process is mature and stable, and the problem that the traditional black plaster adhesive cannot be produced in large batch is solved.
One of the purposes of the invention is realized by adopting the following scheme:
a novel black plaster matrix hot-melt pressure-sensitive adhesive is prepared from the following components in parts by weight:
15-40 parts of synthetic rubber
10-30 parts of naphthenic oil
0.1-5 parts of antioxidant
30-50 parts of hydrogenated petroleum resin
5-20 parts of rosin resin
0.1 to 10 portions of pigment and filler
5-20 parts of grafted epoxidized natural rubber ENR-HMEA.
Further, the novel black plaster matrix hot-melt pressure-sensitive adhesive is prepared from the following components in parts by weight:
15-35 parts of synthetic rubber
Naphthenic oil 20-30 parts
0.1 to 1 portion of antioxidant
30-40 parts of hydrogenated petroleum resin
5-10 parts of rosin resin
0.1 to 2 portions of pigment and filler
10-20 parts of grafted epoxidized natural rubber ENR-HMEA.
Further, the novel black plaster matrix hot-melt pressure-sensitive adhesive is prepared from the following components in parts by weight:
18.1 parts of synthetic rubber
Naphthenic oil 23 parts
0.6 part of antioxidant
39.5 parts of hydrogenated petroleum resin
5-10 parts of rosin resin
0.8 portion of pigment and filler
12 parts of grafted epoxidized natural rubber ENR-HMEA.
Further, the synthesis method of the grafted epoxidized natural rubber ENR-HMEA comprises the following steps:
s1: heating the torque rheometer to 120 ℃, cutting the epoxidized natural rubber into small pieces, and adding the small pieces into the torque rheometer;
s2: weighing monomers of hydroxyethyl methacrylate and dicumyl peroxide, respectively adding the monomers into a rheometer of S1, banburying the monomers for 13-16min, and then discharging and cooling;
s3: and refluxing the discharged mixture in the S2 in a Soxhlet extractor for 24 hours by using acetone, removing a self-polymerization product of monomer hydroxyethyl methacrylate, dicumyl peroxide and hydroxyethyl methacrylate in the product, and drying in a drying oven at the temperature of 60-65 ℃ to constant weight to obtain a grafted product ENR-HMEA, wherein the synthetic grafting rate is 6%.
Further, the epoxidized natural rubber is epoxidized natural rubber ENR-25 having an epoxy value of 25, which is manufactured by Shandong Claine Co.
Further, the mass ratio of the epoxidized natural rubber to the monomer of hydroxyethyl methacrylate to dicumyl peroxide is 100.
Further, the ratio of the grafted epoxidized natural rubber ENR-HMEA to the synthetic rubber is (9-9.5): 4 by mass.
Further, the synthetic rubber is one of SIS and SBS, the SIS is selected from one or a mixture of more than two of SIS1106, SIS1126 and SIS1220 of Yueyang Baling petrochemical company; the SIS1106 has a styrene content of 16% and a diblock content of 17%; the SIS1126 has a styrene content of 16% and a diblock content of 50%; the SIS1220 has a styrene content of 25% and a diblock content of 25%.
Further, the synthetic rubber is compounded by the SIS1126 and the SIS1220 according to the mass ratio of 3.
Further, the naphthenic oil is selected from the naphthenic oil with model number 47135 manufactured by Xinjiang Cramay corporation; the hydrogenated petroleum resin is selected from C5 hydrogenated petroleum resin with the model of 5100 of Exxon company; the rosin resin is a rosin resin with the Ke95F model selected from Kematrin company; the antioxidant is one selected from 1010 type antioxidant and 168 antioxidant produced by BASF corporation; the pigment and filler is selected from carbon black with model number DL-8101 of Delaware chemical company.
The second purpose of the invention is realized by adopting the following technical scheme:
a preparation method of a novel black plaster matrix hot-melt pressure-sensitive adhesive comprises the following steps:
s1: firstly, raising the temperature of kneader oil to 175-180 ℃, pouring proper naphthenic oil into the kneader, simultaneously adding antioxidant, adding synthetic rubber after the temperature in the kneader reaches 130 ℃, and starting stirring;
s2: after the synthetic rubber in the S1 is kneaded to have no obvious particles, adding the grafting treated natural rubber ENR-HMEA according to the formula amount, kneading for 20min, adding the pigment and filler according to the formula amount, and uniformly stirring;
s3: and finally adding petroleum resin, rosin resin and residual naphthenic oil, vacuumizing to remove bubbles, discharging, and cooling to room temperature to obtain the black plaster hot melt adhesive matrix.
Further, the charging amount of the naphthenic oil in the S1 is 60% of the total amount of the synthetic rubber.
Further, the pressure of vacuumizing in the S3 is 0.08-0.1MPa, and the time of vacuumizing and removing bubbles is 25-30min.
Compared with the prior art, the invention has the beneficial effects that at least the following aspects are realized:
(1) According to the invention, synthetic rubber SIS, petroleum resin and rosin resin are introduced, and the advantage of good adhesiveness of the traditional hot melt pressure sensitive adhesive is taken into consideration, the SIS1126 and the SIS1220 are preferably compounded according to the mass ratio of 3;
(2) Furthermore, epoxy groups are introduced through epoxidized natural rubber ENR-25 with the grafting rate of 25%, and the characteristic of excellent adhesion of the epoxy groups is utilized to increase the bonding effect of the adhesive in the formula on different skin types; simultaneously, by utilizing the residual part of double bond active groups in ENR-25, hydroxyethyl methacrylate HMEA is introduced in a grafting manner, so that a proper amount of hydrophilic hydroxyl end groups are introduced, and the sweat resistance effect of the adhesive is improved; on the other hand, the introduced HMEA contains acrylate, and is excellent in skin-fitting property and anti-allergic property;
more importantly, ENR-HMEA after grafting treatment is introduced to be matched with synthetic rubber, the ratio of the ENR-HMEA to the synthetic rubber is preferably 9;
(3) In the synthesis of ENR-HMEA, epoxidized natural rubber ENR-25 with a grafting rate of 25% is adopted, and meanwhile, the mass ratio of the epoxidized natural rubber to monomer hydroxyethyl methacrylate to dicumyl peroxide is 100.75, so that the synthetic grafting rate of the grafted product ENR-HMEA is 6%, and therefore, the prepared epoxy group has good stability, and the natural rubber has the advantage of good skin adhesion, the adhesion advantage of the epoxy group, the skin compliance and proper hydrophilicity of hydroxyethyl methacrylate, and the water and sweat resistance effect of the adhesive film is greatly improved;
(4) The process is mature and stable, and solves the problem that the traditional black plaster adhesive cannot be produced in large batch.
Detailed Description
The present invention is further described below with reference to specific embodiments, and it should be noted that, without conflict, any combination between the embodiments or technical features described below may form a new embodiment.
In the present invention, all parts and percentages are by weight, unless otherwise specified, and the equipment and materials used are commercially available or commonly used in the art. The methods in the following examples are conventional in the art unless otherwise specified.
The invention provides a novel black plaster matrix hot-melt pressure-sensitive adhesive which is prepared from the following components in parts by weight:
15-40 parts of synthetic rubber
10-30 parts of naphthenic oil
0.1 to 5 portions of antioxidant
30-50 parts of hydrogenated petroleum resin
5-20 parts of rosin resin
0.1 to 10 portions of pigment and filler
5-20 parts of grafted epoxidized natural rubber ENR-HMEA.
Further, the novel black plaster matrix hot-melt pressure-sensitive adhesive is prepared from the following components in parts by weight:
15-35 parts of synthetic rubber
Naphthenic oil 20-30 parts
0.1 to 1 portion of antioxidant
30-40 parts of hydrogenated petroleum resin
5-10 parts of rosin resin
0.1 to 2 portions of pigment and filler
10-20 parts of grafted epoxidized natural rubber ENR-HMEA.
Further explaining, the novel black plaster matrix hot-melt pressure-sensitive adhesive is prepared from the following components in parts by weight:
18.1 parts of synthetic rubber
Naphthenic oil 23 parts
0.6 part of antioxidant
39.5 parts of hydrogenated petroleum resin
5-10 parts of rosin resin
0.8 portion of pigment and filler
12 parts of grafted epoxidized natural rubber ENR-HMEA.
Further, the synthesis method of the grafted epoxidized natural rubber ENR-HMEA comprises the following steps:
s1: heating a torque rheometer to 120 ℃, cutting the epoxidized natural rubber into small pieces, and adding the small pieces into the torque rheometer;
s2: weighing monomers of hydroxyethyl methacrylate and dicumyl peroxide, respectively adding the monomers into a rheometer of S1, banburying the monomers for 13-16min, and then discharging and cooling;
s3: and (3) refluxing the discharged mixture in the S2 in a Soxhlet extractor by using acetone for 24 hours to remove the monomer hydroxyethyl methacrylate, dicumyl peroxide and hydroxyethyl methacrylate self-polymerization products in the products, and drying in a drying oven at 60-65 ℃ to constant weight to obtain a grafted product ENR-HMEA, wherein the synthetic grafting rate is 6%.
Further, the epoxidized natural rubber is epoxidized natural rubber ENR-25 having an epoxy value of 25, which is manufactured by Shandong Clein Co.
Further, the mass ratio of the epoxidized natural rubber to the monomer of hydroxyethyl methacrylate to dicumyl peroxide is 100.
Further, the ratio of the grafted epoxidized natural rubber ENR-HMEA to the synthetic rubber is (9-9.5): 4 by mass.
Further, the ratio of the grafted epoxidized natural rubber ENR-HMEA to the synthetic rubber is 9.
Further, the synthetic rubber is one of SIS and SBS, the SIS is selected from one or a mixture of more than two of SIS1106, SIS1126 and SIS1220 of Yueyangba Ling petrochemical company; the SIS1106 has a styrene content of 16% and a diblock content of 17%; the SIS1126 has a styrene content of 16% and a diblock content of 50%; the SIS1220 has a styrene content of 25% and a diblock content of 25%.
Further explaining, the synthetic rubber is SIS1126 or is compounded by the SIS1126 and the SIS1220 according to the mass ratio of 3.
Further, the naphthenic oil is selected from the naphthenic oil with model number 47135 manufactured by Xinjiang Cramay corporation; the hydrogenated petroleum resin is selected from C5 hydrogenated petroleum resin with the model of 5100 of Exxon company; the rosin resin is a rosin resin with the Ke95F model selected from Kematrin company; the antioxidant is one selected from 1010 type antioxidant and 168 antioxidant produced by BASF corporation; the pigment and filler is selected from carbon black with model number DL-8101 of Delaware chemical company.
The formula principle of the invention is as follows:
the synthetic rubber in the formula can be styrene-isoprene-styrene (SIS) and styrene-butadiene-styrene (SBS), the SIS used in the invention is styrene content of 15-25%, the diblock content is 15-50%, the SIS is softer than SBS, the content of the diblock, namely the soft chain segment, of the SIS can influence the annular initial adhesion of the hot melt adhesive, and the performance of the prepared hot melt adhesive can be changed by selecting different diblock contents, the invention is obtained through a large number of tests, preferably, the SIS1126 and the SIS1220 are compounded according to the mass ratio of 3.
According to the invention, one of the key components in the formula, namely the epoxidized natural rubber ENR-HMEA subjected to grafting treatment is synthesized by introducing an epoxy group through the epoxidized natural rubber ENR-25 with the grafting rate of 25%, and the bonding effect of the formula adhesive to different skin types is improved by utilizing the characteristic of excellent adhesive force of the epoxy group; simultaneously, by utilizing the residual part of double bond active groups in ENR-25, hydroxyethyl methacrylate HMEA is introduced in a grafting manner, so that a proper amount of hydrophilic hydroxyl end groups are introduced, and the sweat resistance effect of the adhesive is improved; on the other hand, the introduced HMEA contains an acrylate and is excellent in skin-friendly properties and anti-allergic properties.
The proportion of the grafted epoxidized natural rubber ENR-HMEA and the synthetic rubber is preferably 9, so that the viscosity of the hot melt adhesive can be enhanced to a certain extent, and the stripping force of the hot melt adhesive is not influenced, so that the lasting adhesion performance and the stripping performance of the prepared hot melt type pressure sensitive adhesive are obviously improved; the addition amount of the ENR-HMEA is not suitable to be too large, because the viscosity of the ENR-HMEA is larger, the influence on the viscosity of a formula is larger due to the addition of the ENR-HMEA, the prepared hot melt adhesive is harder, the initial adhesion and stripping force are reduced, the addition amount is not too small, the water resistance and sweat resistance of the prepared hot melt adhesive are influenced, and the ENR-HMEA is easy to fall off due to sweating when being attached to the skin of a human body;
in the synthesis of ENR-HMEA, epoxidized natural rubber ENR-25 with a grafting rate of 25% is adopted, meanwhile, the mass ratio of the epoxidized natural rubber to monomer hydroxyethyl methacrylate to dicumyl peroxide is 100.75, and the synthetic grafting rate of the grafted product ENR-HMEA is 6%, so that the prepared epoxy group has good stability, and the advantages of the natural rubber and the adhesive force advantage of the epoxy group are both considered, and the hydrophilicity, the skin adherence and the proper hydrophilicity of the hydroxyethyl methacrylate greatly improve the water and sweat resistance of the adhesive film. The synthesis process is carried out in a catalyst-free neutral environment at 130 ℃, and is favorable for improving the stability of epoxy groups.
The naphthenic oil in the formula is one of petroleum rubber oil, the naphthenic oil mainly comprises naphthenic hydrocarbon, has good affinity and little or no pollution, is preferably the naphthenic oil with the model number of 47135, which is provided by Clarity in Xinjiang, and plays a role in softening in the formula, and in addition, the dosage of the naphthenic oil is preferably between 20 and 30 parts, and the naphthenic oil is matched with the synthetic rubber selected by the invention, so that the colloid can keep proper stripping force and initial adhesion, and the performances required by decoration and adhesion are met; meanwhile, the stability of the epoxy group of the epoxidized natural rubber in the preparation process can be improved, and the problem of ring opening is avoided.
The pigment and filler of the invention is organic pigment such as carbon black, does not contain heavy metal, and can be used for preparing plaster matrixes with different colors according to the requirements of customers.
The preferred hydrogenated DCPD petroleum resin and C5 hydrogenated petroleum resin are used in the formula of the invention, and the formula has good compatibility with the selected SIS of the invention and high peel strength.
The invention also provides a preparation method of the novel black plaster matrix hot-melt pressure-sensitive adhesive, which comprises the following steps:
s1: firstly, raising the temperature of kneader oil to 175-180 ℃, pouring proper naphthenic oil into the kneader, simultaneously adding antioxidant, adding synthetic rubber after the temperature in the kneader reaches 130 ℃, and starting stirring;
s2: after the synthetic rubber in the S1 is kneaded to have no obvious particles, adding the grafting treated natural rubber ENR-HMEA according to the formula amount, kneading for 20min, adding the pigment and filler according to the formula amount, and uniformly stirring;
s3: and finally adding petroleum resin, rosin resin and residual naphthenic oil, vacuumizing to remove bubbles, discharging, and cooling to room temperature to obtain the black plaster hot melt adhesive matrix.
Further, the charging amount of the naphthenic oil in the S1 is 60% of the total amount of the synthetic rubber.
Further, the pressure of vacuumizing in the S3 is 0.08-0.1MPa, and the time of vacuumizing and removing bubbles is 25-30min.
The preparation process of the invention needs to be noted as follows:
according to the application, the proportion of the naphthenic oil and the synthetic rubber which are put into the rubber polymer at the early stage needs to be controlled, the feeding amount of the naphthenic oil is 60 percent of that of the rubber polymer, and the swelling and melting effects of the rubber polymer are best; the reason is that the applicant obtains through a large number of experiments that when the proportion of the rubber oil is too high in the current period, the shearing force in the melting process of the rubber polymer is lower, so that the rubber polymer is difficult to melt; the rubber polymer used in the invention belongs to rubber with strong oil absorption capacity, and when the proportion of rubber oil is too low, the rubber polymer is not convenient to swell and melt, and meanwhile, the shearing force is too high, so that the production equipment is easy to damage; as the main component for preparing the hot melt adhesive, the swelling and melting effects of rubber polymers are poor, so that a large number of independent particles exist in the hot melt adhesive, and more importantly, the particles can not melt after the hot melt adhesive is heated into a liquid state, so that the characteristics of the hot melt adhesive are obviously influenced; furthermore, the particles are gradually deposited, and the glue machine equipment is easily blocked in the spraying process of the hot melt adhesive product, so that the glue spraying is not smooth, and the quality of the hot melt adhesive product is greatly influenced.
The following are specific examples of the present invention, and raw materials, equipments and the like used in the following examples can be obtained by purchasing them unless otherwise specified.
Examples 1 to 4 and comparative examples 1 to 9
The raw materials are weighed according to the mixture ratio in the following table 1, the hot melt adhesive is prepared according to the preparation method shown in the table 1, and the hot melt adhesives of different embodiments are correspondingly obtained, and the details are shown in the table 1:
TABLE 1 raw material proportioning tables for examples 1 to 4 and comparative examples 1 to 9
Wherein the SIS1106 has a styrene content of 16% and a diblock content of 17%; the SIS1126 has a styrene content of 16% and a diblock content of 50%; the SIS1220 has a styrene content of 25% and a diblock content of 25%; the SIS 1209 has a styrene content of 29% and a diblock content of <1%; the styrene content of the SIS 4016 is 18 percent, and the diblock content is 75 percent; the SBS is selected from SBS 791 petrochemical in Yueyang Ba Ling, and the styrene content of the SBS 791 is 30% and the diblock content is less than 1%.
The synthesis method of ENR (25) -HMEA comprises the following steps:
heating a torque rheometer to 120 ℃, cutting 100 parts of epoxidized natural rubber ENR-25 (commercially available epoxidized natural rubber with an epoxidized grafting rate of 25%) into small pieces, adding the small pieces into the torque rheometer, weighing 5 parts of monomer Hydroxyethyl Methacrylate (HMEA) and 0.75 part of initiator dicumyl peroxide (DCP) into the rheometer respectively, banburying the two parts together for 15min, and then discharging and cooling the mixture;
and refluxing the discharged mixture in a Soxhlet extractor by using acetone for 24 hours to remove the monomer, the initiator and the HMEA self-polymerization product in the product, and drying in a drying oven at 60 ℃ to constant weight to obtain a grafted product ENR-HMEA, wherein the synthetic grafting rate in the step is 6%.
The ENR (25) -HMEA (ENR: HMEA = 100) synthesis method is as follows, except that the proportions of epoxidized natural rubber ENR-25, hydroxyethyl Methacrylate (HMEA), dicumyl peroxide (DCP) are 100: 0.75.
the ENR (25) -HMEA (ENR: HMEA = 100) synthesis method is as follows, except that the proportions of epoxidized natural rubber ENR-25, hydroxyethyl Methacrylate (HMEA), dicumyl peroxide (DCP) are 100: 0.75.
the natural rubber ENR-25 only grafted with the epoxy group is epoxidized natural rubber with an epoxy value of 25 percent produced by Shandong Krein company.
The physical blending method of ENR-25 and HMEA comprises the following steps: 100 parts of epoxidized natural rubber ENR-25 and 5 parts of HMEA are stirred and mixed.
The method for synthesizing ENR (10) -HMEA and ENR (50) -HMEA may be performed by referring to the method for synthesizing ENR (25) -HMEA. Further, the ENR (10) is an epoxidized natural rubber having an epoxy value of 10% manufactured by Shandong Claine Corp; ENR (50) epoxidized natural rubber having an epoxy value of 50% manufactured by Shandong Claine Co.
The preparation method of the hot melt adhesive refers to the following steps:
s1: heating kneading machine oil to 175 ℃, pouring proper naphthenic oil into the kneading machine, simultaneously adding antioxidant, adding synthetic rubber after the temperature in the kneading machine reaches 130 ℃, and starting stirring; wherein the dosage of the naphthenic oil is 60 percent of the total amount of the synthetic rubber;
s2: after the synthetic rubber in the S1 is kneaded to have no obvious particles, adding the grafted natural rubber ENR-HMEA with the formula amount, kneading for 20min, adding the pigment and filler with the formula amount, and uniformly stirring;
s3: and finally adding petroleum resin, rosin resin and residual naphthenic oil, vacuumizing to remove bubbles, discharging, and cooling to room temperature to obtain the black plaster hot melt adhesive matrix.
Among them, examples 2 to 4 and comparative examples 1 to 2 are different from example 1 in the preparation process in that natural rubber is added in S2.
Effect evaluation and Performance detection
The hot melt adhesive performance of each example and comparative example is detected, and the detection method comprises the following steps:
the black plaster hot melt adhesives obtained according to the examples and the comparative examples are uniformly glued on a PET substrate by transfer coating, and the thickness of the glue is 30 +/-2 g/m 2 . The ring initial adhesion and peel strength performance of the sample was tested at room temperature of 23 + -2 deg.C and relative humidity of 45 + -10%. The peel strength of the hot melt adhesive is tested according to the specific regulations of the national standard GB/T2792-2014, and the annular initial adhesion is tested according to the specific regulations of the national standard GB/T31125-2014.
Simultaneously, a blade coating direct coating method is applied, and the coating thickness is110 +/-5 g/m 2 On the white cotton cloth base material, the back permeation of the white cotton cloth is observed, and meanwhile, the white cotton cloth is respectively cut into the size with the length multiplied by the width =6 multiplied by 4cm, and is attached to the elbow joint and the position easy to sweat on the back, and the attaching effect is observed.
See table 2 for test items and results:
table 2 shows the hot melt adhesive performance test data of each example and comparative example
As can be seen from table 2, the most preferred embodiment of the present invention is embodiment 1, which combines the advantages of natural rubber, such as good adhesion to skin, adhesion of epoxy group, and skin conformability and appropriate hydrophilicity of hydroxyethyl methacrylate, and improves the water-resistant and sweat-resistant effects of the adhesive film, and the adhesive film is not easy to fall off after a large amount of sweating and during bathing with the adhesive plaster.
Example 2 an experiment using ENR-10 with a lower epoxy value resulted in a lower probability of collision of the reactive molecules with HMEA due to too few epoxy groups and a grafting ratio of HMEA of less than 2%, and therefore the hydrophilic performance advantage of HMEA was insufficient and the effect of attachment to the skin after sweating was not good.
Example 3 with ENR50 having an epoxy value of 50 available on the market, there are too many epoxy groups, compared with other components in the formulation, the stability of the epoxy groups is relatively poor, slow internal self-polymerization and intermolecular reaction occur during long-term storage and transportation, the adhesive becomes hard and yellow slowly after a long time, the viscosity is reduced slowly, and the storage period of the adhesive is further reduced.
Example 4 simple physical blending of ENR with HMEA, the inherent cohesive strength of the colloid is insufficient due to the absence of the formation of functional macromolecules, resulting in low overall adhesion.
Comparative example 1 an unmodified natural rubber was added, and since the natural rubber has a superior effect of bonding to human skin to synthetic rubber and a certain perspiration resistance effect, the initial tack after peeling was almost not increased but the effect of bonding to human skin was significantly increased after the addition of the natural rubber.
The comparison example 2 is added with epoxy modified natural rubber ENR-25, the epoxy group is added, the adhesive effect of the adhesive film to the tested base material is obviously improved, the adhesive force is obviously increased, but the sweat resistance is still poor, and the adhesive film is easy to fall off when sweating on human skin.
The synthetic rubber of the comparative example 3 does not adopt the compounding of the SIS1126 and the SIS1220, only the SIS1126 is selected, the styrene content of the SIS1126 is 16 percent, and the diblock content is 50 percent; the initial adhesion is slightly increased, the cohesive strength is reduced, and the stripping and permanent adhesion effects are reduced.
The synthetic rubber of comparative example 4 was selected only for SIS1220, since its diblock content was 25%; the initial adhesion is reduced.
In the ENR (25) -HMEA synthesis of comparative example 5, the proportions of epoxidized natural rubber ENR-25, hydroxyethyl Methacrylate (HMEA), dicumyl peroxide (DCP) were 100: 0.75, too many hydrophilic hydroxyl end groups are introduced, the hydrophilicity is too good, the water solubility of the adhesive is easily deteriorated after water soaking, and the adhesive falls off.
In the ENR (25) -HMEA synthesis of comparative example 6, the proportions of epoxidized natural rubber ENR-25, hydroxyethyl Methacrylate (HMEA), dicumyl peroxide (DCP) were 100: 0.75, too little hydrophilic hydroxyl end groups are introduced, resulting in oleophilic and hydrophobic gums, poor sweat resistance, and reduced skin fit.
The synthetic rubber of comparative example 7 was SBS 791, which greatly reduced the peel force and initial tack of the hot melt adhesive because SBS was harder than SIS.
In comparative example 8, the amount of the synthetic rubber was 30 parts or more and ENR (25) -HMEA was not added, and the water-resistant and sweat-resistant effects were almost absent, and the rubber dropped quickly upon sweating during exercise.
In comparative example 9, the addition amount of ENR (25) -HMEA is 2 times that of example 1, the influence of excessive ENR (25) -HMEA on the viscosity of the hot melt adhesive is large, the adhesive is hard, and the initial adhesion and the peeling force are reduced.
The above embodiments are only preferred embodiments of the present invention, and the scope of the present invention should not be limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are intended to be covered by the claims.
Claims (10)
1. A novel black plaster matrix hot-melt pressure-sensitive adhesive is characterized by being prepared from the following components in parts by weight:
15-40 parts of synthetic rubber
10-30 parts of naphthenic oil
0.1 to 5 portions of antioxidant
30-50 parts of hydrogenated petroleum resin
5-20 parts of rosin resin
0.1 to 10 portions of pigment and filler
5-20 parts of grafted epoxidized natural rubber ENR-HMEA.
2. A novel black plaster matrix hot melt pressure sensitive adhesive as claimed in claim 1, wherein the synthesis method of the graft-treated epoxidized natural rubber ENR-HMEA comprises the steps of:
s1: heating the torque rheometer to 120 ℃, cutting the epoxidized natural rubber into small pieces, and adding the small pieces into the torque rheometer;
s2: weighing monomers of hydroxyethyl methacrylate and dicumyl peroxide, respectively adding the monomers into a rheometer of S1, banburying for 13-16min, and then discharging and cooling;
s3: and (3) refluxing the discharged mixture in the S2 in a Soxhlet extractor by using acetone for 24 hours to remove the monomer hydroxyethyl methacrylate, dicumyl peroxide and hydroxyethyl methacrylate self-polymerization products in the products, and drying in a drying oven at 60-65 ℃ to constant weight to obtain a grafted product ENR-HMEA, wherein the synthetic grafting rate is 6%.
3. A novel black plaster matrix hot melt pressure sensitive adhesive as claimed in claim 2, wherein said epoxidized natural rubber is epoxidized natural rubber ENR-25 having an epoxy value of 25 manufactured by Shandong Claine corporation.
4. A novel black plaster matrix hot melt pressure sensitive adhesive as claimed in claim 2, wherein the mass ratio of the epoxidized natural rubber, the monomer hydroxyethyl methacrylate and the dicumyl peroxide is 100.
5. A novel black plaster matrix hot-melt pressure-sensitive adhesive as claimed in claim 1, wherein the ratio of the graft-treated epoxidized natural rubber ENR-HMEA to the synthetic rubber is (9-9.5): 4 by mass.
6. A novel black plaster matrix hot melt pressure sensitive adhesive as claimed in claim 1, wherein the synthetic rubber is one of SIS and SBS, the SIS is selected from one or a mixture of more than two of SIS1106, SIS1126 and SIS1220 of yueyang barling petrochemical company; the SIS has a styrene content of 15-25% and a diblock content of 15-60%.
7. A novel black plaster matrix hot melt pressure sensitive adhesive as claimed in claim 1, wherein said naphthenic oil is selected from the group consisting of model 47135 naphthenic oil manufactured by cramaryi, n.k.a.; the hydrogenated petroleum resin is selected from C5 hydrogenated petroleum resin with the model of 5100 of Exxon company; the rosin resin is a rosin resin with the Ke95F model selected from Kematrin company; the antioxidant is one selected from 1010 type antioxidant and 168 antioxidant produced by BASF corporation; the pigment and filler is selected from carbon black with model number DL-8101 of Delaware chemical company.
8. A preparation method of a novel black plaster matrix hot-melt pressure-sensitive adhesive is characterized by comprising the following steps:
s1: heating kneading machine oil to 175-180 ℃, pouring proper amount of naphthenic oil into the kneading machine, simultaneously adding antioxidant, adding synthetic rubber after the temperature in the kneading machine reaches 130 ℃, and starting stirring;
s2: after the synthetic rubber in the S1 is kneaded to have no obvious particles, adding the grafting treated natural rubber ENR-HMEA according to the formula amount, kneading for 20min, adding the pigment and filler according to the formula amount, and uniformly stirring;
s3: and finally adding petroleum resin, rosin resin and residual naphthenic oil, vacuumizing to remove bubbles, discharging, and cooling to room temperature to obtain the black plaster hot melt adhesive matrix.
9. The method of claim 8, wherein the amount of naphthenic oil added in S1 is 60% of the total amount of the synthetic rubber.
10. A method for preparing a novel black plaster matrix hot-melt pressure-sensitive adhesive as claimed in claim 8, wherein the pressure of evacuation in S3 is 0.08-0.1MPa, and the time for evacuation and bubble removal is 25-30min.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202211709441.XA CN115919810A (en) | 2022-12-29 | 2022-12-29 | Novel black plaster matrix hot-melt pressure-sensitive adhesive and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202211709441.XA CN115919810A (en) | 2022-12-29 | 2022-12-29 | Novel black plaster matrix hot-melt pressure-sensitive adhesive and preparation method thereof |
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| CN202211709441.XA Pending CN115919810A (en) | 2022-12-29 | 2022-12-29 | Novel black plaster matrix hot-melt pressure-sensitive adhesive and preparation method thereof |
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| CN (1) | CN115919810A (en) |
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