WO2022214057A1

WO2022214057A1 - Plastic composition and use thereof, plastic part, preparation method therefor and use thereof

Info

Publication number: WO2022214057A1
Application number: PCT/CN2022/085723
Authority: WO
Inventors: 邹永昆; 张艳鹤
Original assignee: 佛山市顺德区美的饮水机制造有限公司
Priority date: 2021-04-09
Filing date: 2022-04-08
Publication date: 2022-10-13
Also published as: CN113150439A

Abstract

The present invention relates to the field of antibacterial materials for a drinking water equipment, and in particular to a plastic composition and the use thereof, a plastic part, a preparation method therefor and the use thereof. The plastic composition contains a plastic raw material and an antibacterial master batch in the weight ratio of 100 : 1-10. The antibacterial master batch is a polymer grafted with an antibacterial active component, and the grafting rate of the antibacterial active component in the antibacterial master batch is 1-25%. In to the graft polymer antibacterial plastic composition provided in the present invention, since the organic antibacterial active component is bonded to a polymer molecular chain by means of chemical bonds, the antibacterial active component still maintains a good antibacterial effect but does not migrate or precipitate, and the plastic part formed by the plastic composition has a long-acting and stable antibacterial effect, and same does not have the problem of the precipitation of heavy metals, such as silver, not conforming to limits.

Description

A kind of plastic composition and its application, plastic parts and its preparation method and application

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of Chinese patent application 202110387790.3 filed on April 9, 2021, the contents of which are incorporated herein by reference.

technical field

The invention relates to the field of antibacterial materials for drinking water equipment, in particular to a plastic composition and application thereof, a plastic part and a preparation method thereof, and the application of the plastic part in the preparation of antibacterial drinking water equipment.

Background technique

During the use of drinking water equipment such as water dispensers and water purifiers, bacteria will adhere to the surface of plastic parts (water pipes, water storage tanks, pumps, connectors, faucets, etc.) Water with bacteria can cause great threat and damage to human health.

SUMMARY OF THE INVENTION

The purpose of the present invention is to overcome the defects of the prior art that the small molecule organic antibacterial agent is easy to migrate and precipitate, the thermal stability is poor, and the precipitation of heavy metals such as silver in the silver-loaded antibacterial material exceeds the standard.

In order to achieve the above purpose, the first aspect of the present invention provides a plastic composition, the plastic composition contains plastic raw materials and an antibacterial masterbatch in a weight ratio of 100:1-10, and the antibacterial masterbatch is grafted with antibacterial activity. The polymer of the ingredients, the graft ratio of the antibacterial active ingredients in the antibacterial masterbatch is 1-25%;

The antibacterial master batch is selected from at least one of polyhexamethylene monoguanidine grafted polymer and polyhexamethylene biguanide grafted polymer; the polyhexamethylene monoguanidine salt and The salts of the polyhexamethylene biguanide salts are each independently selected from at least one of hydrochloride, sulfate, nitrate, and phosphate.

The structure of the polyhexamethylene mono/biguanide grafted polymer is shown in formula (1):

Wherein, in formula (1), R is a mono/biguanidine salt group grafted onto the polymer molecular chain, and each T is independently selected from hydrogen, methyl, ethyl, and phenyl.

The structure of polyhexamethylene monoguanidine salt oligomer is shown in formula (2):

Wherein, in formula (2), Y is selected from Cl ^- , NO ₃ ^- , SO ₄ ^2- , PO ₄ ^3- , X and Z are hydrogen, n=6, m=2-200.

The structure of polyhexamethylene biguanide oligomer is shown in formula (3):

Wherein, in formula (3), Y is selected from Cl ^- , NO ₃ ^- , SO ₄ ^2- , PO ₄ ^3- , X is hydrogen, n=6, m=2-200.

The second aspect of the present invention provides the application of the plastic composition described in the first aspect above in the preparation of plastic parts.

A third aspect of the present invention provides a plastic component, and the material for forming the plastic component is the plastic composition described in the first aspect.

A fourth aspect of the present invention provides a method for preparing the plastic parts described in the third aspect, the method comprising:

(1) be that the plastic raw material of 100:1-10 and the antibacterial master batch are mixed with the consumption weight ratio to obtain the mixture material I;

(2) Extruding and/or injection molding the mixed material I.

A fifth aspect of the present invention provides the application of the plastic parts described in the third aspect in the preparation of antibacterial drinking water equipment.

The features and advantages of the present invention will be described in detail in the detailed description section that follows.

Detailed ways

The endpoints of ranges and any values disclosed herein are not limited to the precise ranges or values, which are to be understood to encompass values proximate to those ranges or values. For ranges of values, the endpoints of each range, the endpoints of each range and the individual point values, and the individual point values can be combined with each other to yield one or more new ranges of values that Ranges should be considered as specifically disclosed herein.

As mentioned above, the first aspect of the present invention provides a plastic composition, the plastic composition contains plastic raw materials and antibacterial masterbatch in a weight ratio of 100:1-10, and the antibacterial masterbatch is grafted with A polymer of antibacterial active ingredients, the graft ratio of the antibacterial active ingredients in the antibacterial master batch is 1-25%;

The inventor found that the graft polymer antibacterial plastic composition provided by the present invention binds the organic antibacterial active ingredients to the polymer molecular chain through chemical bonds, and the antibacterial active ingredients can maintain a good antibacterial effect without long-term use. The phenomenon of migration and precipitation occurs in the antibacterial agent, thus overcoming the shortcomings of easy migration and precipitation of organic antibacterial agents and poor thermal stability.

In some embodiments, the graft ratio of the antibacterial active ingredient in the antibacterial masterbatch is 10-20%.

In some embodiments, the graft ratio of the antibacterial active ingredient in the antibacterial masterbatch is 10-15%.

In some embodiments, the content weight ratio of the plastic raw material and the antibacterial masterbatch in the plastic composition is 100:2-8.

In some embodiments, the content weight ratio of the plastic raw material and the antibacterial masterbatch in the plastic composition is 100:4.5-7.5.

The inventors found that when the plastic composition is prepared by using the antibacterial masterbatch with the grafting ratio of the antibacterial active ingredient 10-20%, and the content weight ratio of the plastic raw material and the antibacterial masterbatch in the plastic composition is 100:2-8 , can obtain better and more stable antibacterial effect.

The inventor found in the research that when the content of antibacterial masterbatch is too high, it will affect the performance of plastic products, including tensile strength, impact strength, etc.; and when the content of antibacterial masterbatch is too low, the antibacterial ability of plastic products will be weak. . When the content weight ratio of the plastic raw material and the antibacterial masterbatch in the plastic composition is 100:4.5-7.5, the plastic parts with better plastic performance and antibacterial ability can be obtained.

In some embodiments, the plastic raw material is selected from at least one of PP and PE.

In some embodiments, the polymer matrix forming the antibacterial masterbatch is selected from at least one of PP and PE.

As mentioned above, the second aspect of the present invention provides the application of the plastic composition described in the first aspect in the preparation of plastic parts.

In the application of the above-mentioned plastic composition in the preparation of plastic parts, the specific application method is a technology well known to those skilled in the art, and the present invention will not repeat them here.

As mentioned above, the third aspect of the present invention provides a plastic component, and the material for forming the plastic component is the plastic composition described in the first aspect.

It should be noted that the corresponding substances involved in the plastic parts of the third aspect of the present invention are the corresponding substances in the plastic composition described in the first aspect of the present invention, and those skilled in the art will not repeat the corresponding substances in this aspect. type and content, which should not be construed as limiting the present invention.

As mentioned above, the fourth aspect of the present invention provides a method for preparing the plastic parts described in the third aspect, the method comprising:

(2) Extruding and/or injection molding the mixed material I.

In some embodiments, in step (1), the mixing conditions include: the rotating speed is 10-200 rpm, and the time is 3-5 min.

In some embodiments, the mixing conditions include: the rotation speed is 30-150rpm, and the time is 4-5min.

In some embodiments, in step (2), the extrusion and/or injection molding conditions include: the temperature is 160-240° C., and the pressure-holding cooling time is 1-15 s.

In some embodiments, the extrusion and/or injection molding conditions include: a temperature of 180-230° C., and a pressure-holding cooling time of 5-10 s.

In the present invention, the purpose of the pressure-holding cooling is to demold the plastic parts. When the plastic parts are cooled, the shrinkage is more sufficient, and there is a gap between the plastic parts and the mold, which is easier to demould.

In some embodiments, the extrusion and/or injection molding conditions include: a temperature of 200-220°C.

The inventors found that, in this particularly preferred embodiment, the antibacterial masterbatch can not only melt at a sufficient temperature and be uniformly dispersed, but also will not decompose and fail due to excessive temperature, thereby reducing the performance of the plastic product.

In the present invention, the graft polymer antibacterial plastic composition can select the same plastic raw material and organic matter for graft bonding according to the material of the required plastic parts, and the obtained antibacterial material has good compatibility with the material of the plastic parts, It can endow plastic parts with a long-term and stable antibacterial effect, and there is no problem of excessive precipitation of heavy metals such as silver.

As mentioned above, the fifth aspect of the present invention provides the application of the plastic parts described in the third aspect in the preparation of antibacterial drinking water equipment.

In the application of the above-mentioned plastic parts in the preparation of antibacterial drinking water equipment, the specific application method is a technology well known to those skilled in the art, and the present invention will not repeat them here.

The present invention will be described in detail below by way of examples.

In the following examples, unless otherwise specified, the raw materials involved are all commercially available products.

raw material

Plastic materials:

PP: grade EPC30R-H, Guangdong Maoming Petrochemical Co., Ltd.

PE: grade PE8916, Guangdong Maoming Petrochemical Co., Ltd.

Antibacterial masterbatch:

Polyhexamethylene monoguanidine hydrochloride grafted PP: brand PPNH-1, Shanghai Fuyuan Plastic Technology Co., Ltd., the graft ratio of polyhexamethylene monoguanidine hydrochloride is 20%.

Polyhexamethylene biguanide nitrate grafted PP: brand PPNH-2, Shanghai Fuyuan Plastic Technology Co., Ltd., the graft ratio of polyhexamethylene biguanide nitrate is 12%.

Polyhexamethylene monoguanidine sulfate grafted PE: brand PENH-1, Shanghai Fuyuan Plastic Technology Co., Ltd., the graft ratio of polyhexamethylene monoguanidine sulfate is 15%.

Polyhexamethylene biguanide hydrochloride grafted PE: brand PENH-2, Shanghai Fuyuan Plastic Technology Co., Ltd., the graft ratio of polyhexamethylene biguanide hydrochloride is 8%.

IONPURE silver-glass antibacterial masterbatch: brand IONPURE IPL, Japan Ishizuka Glass Company.

In the following examples, non-bacterial modified PP plastic parts are used as control parts.

The amounts of components in the following examples are all parts by weight, and each part by weight represents 1 g.

In the following examples, the test methods involved are as follows:

1. Antibacterial effect test

The antibacterial effect test is carried out with reference to GB/T 31402-2015 plastic surface antibacterial performance test method.

The calculation method of antibacterial rate is as follows:

Antibacterial rate=(the number of viable bacteria after 24h of the control part - the number of viable bacteria after 24h of the antibacterial part)/the number of viable bacteria after 24h of the control part.

2. Soak Dissolution Test

According to the standard inspection method of Appendix A of "Drinking Water Transmission and Distribution Equipment and Protective Materials Hygiene and Safety Evaluation Specifications (2001)", after soaking the control parts and the plastic parts in the example for 24 hours, test the metal content of the soaking solution. Variety.

Example 1

The plastic parts were prepared according to the following preparation method and the dosage shown in Table 1. Wherein the preparation method is:

(1) PP and polyhexamethylene monoguanidine hydrochloride graft PP are mixed to obtain mixed material I, and the rotating speed is 60rpm, and the time is 4min;

(2) The mixed material I was extruded, the temperature was 220° C., and the pressure-holding cooling time was 10 s to obtain a plastic part sample S1.

The composition of the plastic parts and the specific operation information of Example 1 are listed in Table 1. The remaining examples and comparative examples were carried out by using a process similar to that of Example 1, and the specific conditions are listed in Table 1.

The performance of the plastic parts was tested and evaluated, and the results are shown in Table 2.

Table 1

Table 2

It can be seen from the above results that the comparative example 3 uses IONPURE glass-loaded silver antibacterial masterbatch, and the increase of silver content in water after soaking for 24 hours is much higher than 5ppb, which is not in line with the "Sanitation and Safety Evaluation of Drinking Water Transmission and Distribution Equipment and Protective Materials". Standard (2001), which will cause heavy metal pollution and unsafe factors to drinking water.

In contrast, the antibacterial parts provided by the present invention not only have strong antibacterial effects on Escherichia coli and Staphylococcus aureus, but also the increase of silver content in water after soaking for 24 hours is 0, indicating that there is no silver precipitation and release. This is because the graft polymer antibacterial plastic parts provided by the present invention bond the organic antibacterial active ingredients to the polymer molecular chain through chemical bonds. It does not contain silver ions and will not precipitate heavy metals such as silver into the water, and there is no problem of excessive precipitation of heavy metals such as silver.

To sum up,

(1) In the graft polymer antibacterial plastic composition provided in some embodiments, since the organic antibacterial active ingredient is bonded to the polymer macromolecular chain through chemical bonds, the antibacterial active ingredient still maintains a good antibacterial effect but does not migrate and precipitate, so Overcome the shortcomings of small molecular organic antibacterial agents, such as easy migration and precipitation, poor thermal stability, etc.;

(2) In order to obtain better compatibility, the graft polymer antibacterial plastic composition provided in some embodiments can select the same plastic raw material and organic matter for graft bonding according to the material of the required plastic parts to obtain antibacterial Masterbatch, the antibacterial masterbatch obtained in this way has better compatibility with the material of plastic parts and longer-lasting and stable antibacterial effect, and there is no problem of excessive precipitation of heavy metals such as silver.

The preferred embodiments of the present invention have been described above in detail, however, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, a variety of simple modifications can be made to the technical solutions of the present invention, including the combination of various technical features in any other suitable manner. These simple modifications and combinations should also be regarded as the content disclosed in the present invention. All belong to the protection scope of the present invention.

Claims

A plastic composition, characterized in that the plastic composition contains plastic raw materials and an antibacterial masterbatch in a weight ratio of 100:1-10, the antibacterial masterbatch is a polymer grafted with antibacterial active ingredients, and the The grafting rate of the antibacterial active ingredients in the antibacterial masterbatch is 1-25%;

The antibacterial masterbatch is selected from at least one of polyhexamethylene monoguanidine grafted polymer and polyhexamethylene biguanide grafted polymer; the polyhexamethylene monoguanidine salt and The salts of the polyhexamethylene biguanide salts are each independently selected from at least one of hydrochloride, sulfate, nitrate, and phosphate.
The plastic composition according to claim 1, wherein the graft ratio of the antibacterial active ingredient in the antibacterial master batch is 10-20%.
The plastic composition according to claim 1, wherein the graft ratio of the antibacterial active ingredient in the antibacterial master batch is 10-15%.
The plastic composition according to any one of the foregoing, wherein the content weight ratio of the plastic raw material and the antibacterial masterbatch in the plastic composition is 100:2-8.
The plastic composition according to any one of the foregoing, wherein the content weight ratio of the plastic raw material and the antibacterial masterbatch in the plastic composition is 100:4.5-7.5.
The plastic composition according to any one of the foregoing, wherein the plastic raw material is selected from at least one of PP and PE.
The plastic composition according to any one of the foregoing, wherein the polymer matrix forming the antibacterial masterbatch is selected from at least one of PP and PE.
Application of the plastic composition according to any one of claims 1 to 7 in the preparation of plastic parts.
A plastic component, characterized in that the material for forming the plastic component is the plastic composition according to any one of claims 1-7.
A method for preparing the plastic parts of claim 9, wherein the method comprises:

(1) be that the plastic raw material of 100:1-10 and the antibacterial master batch are mixed with the consumption weight ratio to obtain the mixture material I;

(2) Extruding and/or injection molding the mixed material I.
The method according to claim 10, characterized in that, in step (1), the mixing conditions include: the rotating speed is 10-200 rpm, and the time is 3-5 min.
The method according to claim 10, characterized in that, in step (1), the mixing conditions include: the rotating speed is 30-150 rpm, and the time is 4-5 min.
The method according to any one of claims 10-12, characterized in that, in step (2), the extrusion and/or injection molding conditions include: a temperature of 160-240° C., pressure-holding Cooldown time is 1-15s.
The method according to any one of claims 10-12, characterized in that, in step (2), the extrusion and/or injection molding conditions include: a temperature of 180-230° C., pressure-holding Cooldown time is 5-10s.
The method according to any one of claims 10-12, characterized in that, in step (2), the extrusion and/or injection molding conditions include: a temperature of 200-220°C.
Application of the plastic parts of claim 9 in the preparation of antibacterial drinking water equipment.