CN111534111A

CN111534111A - Antibacterial TPE (thermoplastic elastomer) super-soft material as well as preparation method and application thereof

Info

Publication number: CN111534111A
Application number: CN202010434389.6A
Authority: CN
Inventors: 王宇; 楚志华
Original assignee: Dongguan Shanpu Technology Co ltd
Current assignee: Dongguan Shanpu Technology Co ltd
Priority date: 2020-05-20
Filing date: 2020-05-20
Publication date: 2020-08-14

Abstract

The invention relates to the field of modified TPE (thermoplastic elastomer), in particular to an antibacterial TPE super-soft material, a preparation method and application thereof. The antibacterial TPE super-soft material consists of 15-25% of SEPS; 73-84% of 100N base oil; 1-3% of the antibacterial auxiliary agent is prepared by mixing the components, the TPE material obtained by the formula has enough elasticity, and compared with the base material added with other types of mineral oil, the base material can be compounded with a certain amount of antibacterial auxiliary agent for melt extrusion without the condition of mechanical property reduction; the preparation method of the antibacterial TPE super-soft material comprises the steps of raw material stirring, melt extrusion and grain cutting, and the method can ensure that the microstructure of the antibacterial auxiliary agent is not damaged and can play a role for a long time; the antibacterial sex toy is obtained by injection molding of the TPE super-soft material, and has the advantages of high elasticity, high antibacterial performance and high market value.

Description

Antibacterial TPE (thermoplastic elastomer) super-soft material as well as preparation method and application thereof

Technical Field

The invention relates to the field of modified TPE (thermoplastic elastomer), in particular to an antibacterial TPE super-soft material, a preparation method and application thereof.

Background

TPE material, also called Thermoplastic high-elasticity plastic body, or Thermoplastic Elastomer, is a material with high elasticity, high strength, high resilience and injection-moldable processing characteristics, and is generally used for articles such as toys and sports equipment. The TPE material is environment-friendly, nontoxic and safe, has excellent colorability, fatigue resistance and temperature resistance, is soft in touch, excellent in processing performance and free from vulcanization. Since Thermoplastic Polyurethane (TPU) was first prepared by Bayer corporation in 1958, TPE has been rapidly developed, and particularly, after a styrene thermoplastic elastomer is published in 1963, the preparation theory of the thermoplastic elastomer is gradually improved, and the application field is further expanded. TPEs that have been produced industrially in the world are: styrenes (SBS, SIS, SEBS, SEPS), olefins (TP0, TPV), dienes (TPB, TPI), vinyl chlorides (TPVC, TCPE), urethanes (TPU), esters (TPEE), amides (TPAE), organofluorine (TPF), silicones, and vinyls, and the like, and cover almost all fields of synthetic rubbers and synthetic resins at present. The TPE material can be formed independently, and can also be coated and bonded with PP, PE, PC, PS, ABS and other matrix materials. The TPE material can injection moulding for the TPE material can recycle reduce cost.

The modified TPE material is obtained by adding a certain modifier into a common TPE material, so that the performance of the TPE material is enhanced or improved. The antibacterial property of the TPE material is a common modification, and the Chinese patent with the patent publication number of CN107987538A discloses an antibacterial TPE which comprises the main components of SBES, PP, white oil, an antibacterial agent, a flame retardant and an anti-UV agent; the antibacterial agent is composed of one or more of quaternary ammonium salt, chitosan and sorbic acid, and the TPE material can be applied to scenes of light resistance, heat resistance and bacteria resistance. Chinese patent with patent publication No. CN105199291A discloses a highly-antibacterial highly-wear-resistant TPE shock-absorbing knee pad and a preparation method thereof, the main components of the shock-absorbing knee pad comprise SEBS, PP, glyoxal modified chitosan-amino-terminated hyperbranched polyamide-amine compound, chitosan-beta cyclodextrin modified nano titanium oxide and zirconia ceramic microspheres, and when the TPE material is applied to knee pad manufacturing, the knee pad can obtain high antibacterial performance, has good wear resistance and can absorb shock. In addition, CN105367971A in the prior art also discloses an antibacterial, anti-aging and comfortable TPE glove material, a quaternary salt antibacterial agent is added in the formula, the TPE material can be used for manufacturing antibacterial gloves, Chinese patent invention of CN105327404B discloses a TPE composition and a high-performance medical catheter prepared from the TPE composition, a guanidine salt antibacterial agent is added, and the prepared medical catheter has antibacterial performance and better applicability.

However, the prior art lacks a TPE material which is more suitable for sex toy. The sex toy has high degree of close contact with human bodies and better required antibacterial performance, but the elasticity of the TPE material is easily reduced by adding the antibacterial agent into the TPE material, and the sex toy has high requirement on the elasticity of the material, so that the TPE material in the prior art is difficult to meet the requirement.

Disclosure of Invention

Aiming at the defects in the prior art, the invention aims to provide an antibacterial TPE (thermoplastic elastomer) super-soft material which is enough in elasticity and can meet the antibacterial requirement.

The above object of the present invention is achieved by the following technical solutions: the antibacterial TPE super-soft material is prepared by mixing the following components in percentage by mass:

SEPS 15-25％；

73-84% of 100N base oil;

1-3% of antibacterial auxiliary agent.

By adopting the technical scheme, the SEPS is a material obtained by partially hydrogenating a block copolymer consisting of styrene and conjugated diene, the material is softer than SEBS and SIS materials, and has better mechanical property, weather resistance, electrical insulation, superior heat resistance and excellent chemical corrosion resistance, 100N base oil can be well mixed with the SEPS, after the base oil is absorbed by the SEPS material, the obtained TPE material has enough elasticity, and compared with other types of mineral oil, the base material can be compounded with a larger amount of antibacterial auxiliary agent to be melted and extruded without the elasticity reduction.

Preferably, the 100N base oil viscosity is between 80000-.

By adopting the technical scheme, the TPE material prepared from 100N base oil with the viscosity of 80000-100000cps and SEPS can best meet the requirement on softness.

Preferably, the antibacterial auxiliary agent is nano silver, and the particle size of the nano silver is 15-30 nm.

By adopting the technical scheme, the nano-silver material is wide in antibacterial spectrum and good in antibacterial performance, and can better meet the requirement of the TPE material on the antibacterial performance.

Preferably, the antibacterial auxiliary agent is a chitosan-silver oxide composite antibacterial agent.

By adopting the technical scheme, the chitosan-silver oxide composite antibacterial agent not only has wider antibacterial spectrum and lower cytotoxicity, and can meet the requirement of the TPE material on antibacterial performance, but also has smaller influence on the elasticity of the TPE material, and is more suitable to be used as the antibacterial auxiliary agent of the TPE material.

Preferably, in the chitosan-silver oxide composite antibacterial agent, the deacetylation degree of chitosan is more than or equal to 90%, and the molecular weight is between 50000-100000.

By adopting the technical scheme, the deacetylation degree is more than or equal to 90 percent, and the chitosan with the molecular weight of 50000-100000 can be better compounded with silver oxide to form stable particles.

Preferably, the preparation method of the chitosan-silver oxide composite antibacterial agent comprises the following steps:

step one, adding chitosan powder and n-octane into a reaction kettle, dispersing chitosan by using ultrasonic dispersion stirring to form a chitosan-n-octane dispersion system, filling acetic anhydride serving as a dehydrating agent, heating to 150 ℃, slowly dropwise adding 3- (2, 4-dihydroxy) phenylpropionic acid, after dropwise adding within 10min, performing ultrasonic stirring reaction for 1h, stopping ultrasonic stirring, continuing constant-temperature reaction for 1h, naturally cooling, and performing spray drying to obtain catechol grafted chitosan powder;

and step two, dispersing catechol grafted chitosan powder in deionized water, adjusting the pH value to 5.5, adding 1M silver nitrate solution under magnetic stirring, carrying out ultrasonic stirring reaction for 30min, then slowly adding sodium carbonate, after dropwise addition within 30min, raising the pH value to 10-12, eluting the solid matter obtained by filtering with deionized water for 3-5 times, and carrying out vacuum freeze drying to obtain the chitosan-silver oxide composite antibacterial agent.

By adopting the technical scheme, the catechol grafted chitosan powder obtained in the step one has better water solubility, and the catechol can bring certain oxidation resistance to the chitosan and enhance the yellowing resistance of the TPE material. In the second step, the PH value is adjusted to 5.5 so that the catechol grafted chitosan can be better dissolved in deionized water, and the hydrogen bonds in the catechol grafted chitosan powder molecules can be broken through ultrasonic stirring, so that the silver oxide can be better combined with the catechol grafted chitosan. The elution function is to remove the residual salt in the solid matter, and the vacuum freeze drying can furthest reserve the microstructure of the chitosan-silver oxide.

Preferably, in the preparation method of the chitosan-silver oxide composite antibacterial agent,

the material used in the first step comprises the following components in parts by weight:

8-12 parts of chitosan powder;

650 portions of n-octane 450-;

30-40 parts of acetic anhydride;

12-15 parts of 3- (2, 4-dihydroxy) phenylpropionic acid;

the materials used in the step two are as follows in parts by weight:

11-13 parts of catechol grafted chitosan powder;

550 portions of deionized water and 650 portions;

3-4 parts of silver nitrate solution;

15-28 parts of sodium carbonate.

By adopting the technical scheme, the formula is reasonable in proportion, and the obtained chitosan-silver oxide composite antibacterial agent has a good effect. The n-octane has a higher boiling point, is less in volatilization amount when heated to 150 ℃, 30-40 parts of acetic anhydride is enough to absorb water generated in amidation reaction of the 3- (2, 4-dihydroxy) phenylpropionic acid and the chitosan, and the addition of the 3- (2, 4-dihydroxy) phenylpropionic acid is excessive, so that the grafting degree of converting the chitosan into catechol grafted chitosan can be improved as much as possible.

The second purpose of the invention is to provide a preparation method of the antibacterial TPE super-soft material, and the prepared TPE material has enough elasticity and good antibacterial performance.

The technical purpose of the invention is realized by the following technical scheme, the preparation method of the antibacterial TPE super-soft material takes the materials in the formula of the TPE super-soft material as raw materials, and comprises the following steps:

step one, adding SEPS and 100N base oil into a mixer, and stirring at the rotating speed of 30r/min for 30min to 100N base oil to be completely absorbed;

adding an antibacterial auxiliary agent into a mixer, and uniformly stirring;

and step three, melt extrusion and granulation.

By adopting the technical scheme, in the first step, the SEPS can fully absorb the 100N base oil under the stirring of the rotating speed of 30r/min, and the antibacterial auxiliary agent is added when the SEPS fully absorbs the white oil, so that the phenomenon that the active ingredients of the antibacterial auxiliary agent are shielded and the antibacterial performance is reduced due to the fact that the 100N base oil is adsorbed by the antibacterial auxiliary agent is avoided.

Preferably, in the third step, the melt extrusion section has seven temperature zones, and the temperature of each temperature zone is as follows:

the first zone is 180 +/-5 ℃;

the second zone 183 + -5 deg.C;

a third zone of 185 +/-5 ℃;

the fourth zone is 187 +/-5 ℃;

the fifth area is 185 +/-5 ℃;

a sixth zone is 185 +/-5 ℃;

the seventh zone is 183. + -. 5 ℃.

By adopting the technical scheme and the melt extrusion temperature, the formed TPE material has the best performance and the lasting antibacterial performance.

The third purpose of the invention is to provide an antibacterial sex toy which has enough elasticity and good antibacterial performance.

The technical purpose of the invention is realized by the following technical scheme that the antibacterial sex toy is obtained by injection molding of the antibacterial TPE super-soft material.

In summary, the invention includes at least one of the following beneficial technical effects:

firstly, the TPE material obtained by the formula is high in elasticity, and compared with the base material added with other mineral oil, the base material can be compounded with a certain amount of antibacterial auxiliary agent for melt extrusion without the condition of mechanical property reduction;

secondly, the method can ensure that the microstructure of the antibacterial auxiliary agent is not damaged and can play a role for a long time; thirdly, the antibacterial sex toy has enough elasticity, good antibacterial performance and good market value.

Detailed Description

The present invention will be described in detail with reference to examples.

In various embodiments of the present invention, preferred sources of each feedstock are as follows:

TABLE 1

In table 1, the guanidine salt antibacterial agent was produced according to the method described in "preparation of a novel guanidine salt antibacterial agent and performance study thereof", published by yatiao, dongfeng, etc. 11 th year 2014 in macromolecule bulletin; the chitosan-beta-cyclodextrin modified nano titanium oxide is obtained by grafting beta-cyclodextrin onto a chitosan structural unit to obtain a chitosan-beta-cyclodextrin coupling compound, and then modifying the nano titanium oxide by the coupling compound; the nano silver with the grain diameter of 10-30nm needs to be selected.

Example 1

The antibacterial TPE super-soft material is prepared by mixing the following components in percentage by mass:

material(s)	Percentage content
		SEPS	15％
100N base oil	82％
		Quaternary ammonium salts	3％

TABLE 2

The viscosity of the 100N base oil of the embodiment is 80000 cps;

the preparation method of the antibacterial TPE super-soft material comprises the following steps:

adding an antibacterial auxiliary agent into a mixer, and uniformly stirring;

and step three, melt extrusion and granulation.

In the third step, the melting extrusion section has seven temperature zones, and the temperature of each temperature zone is as follows:

first region

Second region

Third zone

Fourth zone

Fifth zone

The sixth zone

Seventh region

180℃

183℃

185℃

187℃

185℃

183℃

TABLE 3

In the processing engineering, the temperature fluctuation of each temperature zone cannot exceed 5 ℃, otherwise, the machine needs to be stopped for debugging.

The antibacterial TPE ultra-soft material obtained in this example was injection molded to obtain a sex toy as application example 1.

Example 2

The preparation method of the present example is the same as that of example 1, except that the ingredient table of the present example is different from that of example 1, and the specific ingredient table is as follows:

material(s)	Percentage content
		SEPS	19％
100N base oil	79％
		Guanidine salt antibacterial agent	2％

TABLE 4

The 100N base oil of this example had a viscosity of 90000 cps; the antibacterial TPE super-soft material obtained in the embodiment is subjected to injection molding to obtain a sex toy, which is used as application example 2.

Example 3

material(s)	Percentage content
		SEPS	24％
100N base oil	73％
		Chitosan- β -cyclodextrin modified nano titanium oxide	3％

TABLE 5

The viscosity of the 100N base oil of this example was 100000 cps; the antibacterial TPE super-soft material obtained in the embodiment is subjected to injection molding to obtain a sex toy, which is used as application example 3.

Example 4

material(s)	Percentage content
		SEPS	20％
100N base oil	77％
		Nano silver	3％

TABLE 6

The viscosity of the 100N base oil is 80000-100000 cps; the antibacterial TPE super-soft material obtained in the embodiment is subjected to injection molding to obtain a sex toy, which is used as application example 3. (the elasticity was not significantly reduced as compared with example 5, and the elasticity was significantly reduced as compared with comparative example)

Example 5

material(s)	Percentage content
		SEPS	21％
100N base oil	78％
		Nano silver	1％

TABLE 7

The viscosity of the 100N base oil is 80000-100000 cps; the antibacterial TPE ultra-soft material obtained in this example was injection molded to obtain a sex toy as application example 5.

Example 6

The preparation method of the embodiment is the same as that of the embodiment 1, except that the ingredient table of the embodiment is different from that of the embodiment 1, and the specific ingredient table is as follows:

material(s)	Percentage content
		SEPS	19％
100N base oil	78％
		Chitosan-silver oxide composite antibacterial agent	3％

TABLE 8

The viscosity of the 100N base oil is 80000-100000 cps; in the chitosan-silver oxide composite antibacterial agent of the embodiment, the deacetylation degree of chitosan is 90%, and the molecular weight is 50000-100000.

The preparation method of the chitosan-silver oxide composite antibacterial agent comprises the following steps:

The formulation of the chitosan-silver oxide composite antibacterial agent prepared in this example is as follows:

material(s)	Number of parts
		Chitosan powder	8
N-octane	500
		Acetic anhydride	33
3- (2, 4-dihydroxy) phenylpropionic acid	15
		Catechol grafted chitosan powder	11
Deionized water	580
		Silver nitrate solution	4
Sodium carbonate	28

TABLE 9

The antibacterial TPE ultra-soft material obtained in this example was injection molded to obtain a sex toy as application example 6.

Example 7

watch 10

The antibacterial TPE ultra-soft material obtained in this example was injection molded to obtain a sex toy as application example 7.

Example 8

The formulation and preparation method of the antibacterial TPE super-soft material in this example are the same as those in example 6, except that the dosage of the ingredients for preparing the chitosan-silver oxide composite antibacterial agent in this example is different, specifically as follows:

material(s)	Number of parts
		Chitosan powder	12
N-octane	450
		Acetic anhydride	40
3- (2, 4-dihydroxy) phenylpropionic acid	12
		Catechol grafted chitosan powder	13
Deionized water	650
		Silver nitrate solution	4
Sodium carbonate	28

TABLE 11

The antibacterial TPE super-soft material obtained in the embodiment is subjected to injection molding to obtain a sex toy, which is used as application example 8.

Example 9

material(s)	Number of parts
		Chitosan powder	10
N-octane	630
		Acetic anhydride	38
3- (2, 4-dihydroxy) phenylpropionic acid	12
		Catechol grafted chitosan powder	11
Deionized water	550
		Silver nitrate solution	3
Sodium carbonate	15

TABLE 12

The antibacterial TPE ultra-soft material obtained in this example was injection molded to obtain a sex toy as application example 9.

Example 10

watch 13

The antibacterial TPE ultra-soft material obtained in this example was injection molded to obtain a sex toy as application example 10.

Comparative example 1

Using the TPE material prepared from example 4 of patent publication CN105199291A, an article of interest was injection molded as comparative application example 1.

Comparative example 2

The preparation method of the embodiment is the same as that of the embodiment 5, except that the ingredient table of the embodiment is different from that of the embodiment 5, and the specific ingredient table is as follows:

material(s)	Percentage content
		SEPS	19％
60N base oil	78％
		Chitosan-silver oxide composite antibacterial agent	3％

TABLE 14

The antibacterial TPE material obtained by the comparative example is used for injection molding of sex toy as comparative application example 2.

Comparative example 3

material(s)	Percentage content
		SEPS	20％
60N base oil	79％
		Chitosan-silver oxide composite antibacterial agent	1％

Watch 15

The antibacterial TPE material obtained by the comparative example was used as comparative application example 3.

Comparative example 4

TABLE 16

The antibacterial TPE material obtained by the comparative example is used for injection molding of sex toy as comparative application example 4.

Comparative example 5

material(s)	Percentage content
		SEPS	20％
150N base oil	79％
		Chitosan-silver oxide composite antibacterial agent	1％

TABLE 17

The antibacterial TPE material obtained by the comparative example was used as comparative application example 5.

The hardness test, the elasticity test and the antibacterial performance test are carried out on the above examples 1 to 10 and examples 1 to 5, and the selected standards are as follows:

(1) the hardness test adopts Shore hardness, the lower the hardness, the softer the touch, and the better the effect;

(2) the elasticity test is characterized by using tensile strength, and the higher the tensile strength is, the better the elasticity of the material is, the softer the touch feeling is, and the better the effect is, by adopting the ASTM D412 standard test;

(3) the antibacterial property was measured according to JIS Z2801, and the higher the antibacterial value was, the better the antibacterial effect was.

The test results were as follows:

watch 18

Comparing application examples 1-3 with application examples 4-10, it can be known that the antibacterial effect of the silver oxide or chitosan-silver oxide composite antibacterial agent is better;

comparing application examples 1-5 with application examples 6-10, it can be known that the elasticity of the SEPS material is less likely to be reduced by selecting the chitosan-silver oxide composite antibacterial agent;

comparing the application examples 6-10 with the comparative application examples 1-5, it can be known that the TPE material prepared by matching 100N base oil with SEPS has the most elasticity;

comparing the application examples 6 and 7 with the comparative application examples 2 and 3 and the comparative application examples 4 and 5, it can be known that the elasticity of the TPE material is reduced and the antibacterial performance is improved by adding more antibacterial additives; however, the combination of 100N base oil with SEPS did not result in a significant reduction in elasticity.

The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiment, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.

Claims

1. The antibacterial TPE super-soft material is characterized by being prepared by mixing the following components in percentage by mass:

SEPS 15-25%；

73-84% of 100N base oil;

1-3% of antibacterial auxiliary agent.

2. The antibacterial TPE ultra-soft material as claimed in claim 1, wherein: the viscosity of the 100N base oil is between 80000 and 100000 cps.

3. The antibacterial TPE ultra-soft material as claimed in claim 1, wherein: the antibacterial auxiliary agent is nano silver, and the particle size of the nano silver is 15-30 nm.

4. The antibacterial TPE ultra-soft material as claimed in claim 1, wherein: the antibacterial auxiliary agent is a chitosan-silver oxide composite antibacterial agent.

5. The antibacterial TPE (thermoplastic elastomer) super-soft material as claimed in claim 4, wherein: in the chitosan-silver oxide composite antibacterial agent, the deacetylation degree of chitosan is more than or equal to 90%, and the molecular weight is between 50000-100000.

6. The antibacterial TPE (thermoplastic elastomer) super-soft material as claimed in claim 4, wherein the preparation method of the chitosan-silver oxide composite antibacterial agent is as follows:

7. The antibacterial TPE (thermoplastic elastomer) super-soft material as claimed in claim 6, wherein: in the preparation method of the chitosan-silver oxide composite antibacterial agent,

8-12 parts of chitosan powder;

650 portions of n-octane 450-;

30-40 parts of acetic anhydride;

12-15 parts of 3- (2, 4-dihydroxy) phenylpropionic acid;

the materials used in the step two are as follows in parts by weight:

11-13 parts of tea phenol grafted chitosan powder;

550 portions of deionized water and 650 portions;

3-4 parts of silver nitrate solution;

15-28 parts of sodium carbonate.

8. A method for preparing an antibacterial TPE ultra-soft material, which is characterized in that materials in a TPE ultra-soft material formulation provided in any one of claims 1 to 7 are used as raw materials, and the method comprises the following steps:

adding an antibacterial auxiliary agent into a mixer, and uniformly stirring;

and step three, melt extrusion and granulation.

9. The antibacterial TPE (thermoplastic elastomer) ultra-soft material as claimed in claim 1, wherein in the third step, the melt extrusion section comprises seven temperature zones, and the temperature of each temperature zone is as follows:

the first zone is 180 +/-5 ℃;

the second zone 183 + -5 deg.C;

a third zone of 185 +/-5 ℃;

the fourth zone is 187 +/-5 ℃;

the fifth area is 185 +/-5 ℃;

a sixth zone is 185 +/-5 ℃;

the seventh zone is 183. + -. 5 ℃.

10. An antibacterial sex toy is characterized in that: the antibacterial TPE super-soft material is obtained by injection molding of the antibacterial TPE super-soft material of any one of claims 1 to 7.