A composite toughened material, articles and methods of making the same
By using a core-shell structure design with composite toughening materials, the problem of urea-formaldehyde material in toilet seat covers cracking easily in dry and cold northern regions has been solved. This achieves crack resistance for the seat cover while maintaining the ceramic texture and high hardness, and also results in low production costs and a uniform appearance.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- XIAMEN JIUMU R & D CO LTD
- Filing Date
- 2023-06-15
- Publication Date
- 2026-05-15
AI Technical Summary
Existing bathroom toilet seat materials such as PP and PVC have problems such as poor hardness, easy scratching, and easy aging and yellowing. Urea-formaldehyde materials are prone to cracking in dry and cold northern regions. Existing toughening methods are either ineffective or costly, affecting the product's appearance and safety.
A composite toughening material, including an outer shell material PVB and a core material inorganic powder, is used to prepare a core-shell granular composite toughening material through a core-shell structure design. This material is then used to modify urea-formaldehyde materials to form crack-resistant products.
Without altering the unique ceramic texture and high hardness of urea-formaldehyde material, the cover plate achieves crack resistance, with a simple production process, low cost, uniform appearance, and ease of large-scale production.
Smart Images
Figure CN116836512B_ABST
Abstract
Description
Technical Field
[0001] This article relates to the field of materials, specifically a composite toughening material, products made from it, and its preparation method. Background Technology
[0002] Currently, most toilet seat materials on the market are urea-formaldehyde, PP, and PVC. Among these, thermoplastic PP and PVC have drawbacks such as poor hardness, susceptibility to scratches, and tendency to yellow and age. Urea-formaldehyde toilet seats are favored by consumers due to their high hardness, scratch resistance, and excellent ceramic-like texture. They also possess advantages such as calcium hardness, scratch resistance, corrosion resistance, and a ceramic-like feel. However, due to the inherent brittleness of urea-formaldehyde, cracking is prone to occur in dry and cold northern regions, seriously affecting user experience and even user safety, becoming an industry-wide problem. Currently, the following measures are often taken to address these issues:
[0003] 1. Using rubber-toughened urea-formaldehyde material: The toughening effect is not good, and the appearance of the cover will be affected due to compatibility issues. It cannot fundamentally solve the problem of cracking of urea-formaldehyde cover, thus affecting the appearance quality of the product.
[0004] 2. Adding reinforcing materials such as stainless steel mesh or fiberglass to the inside of the cover plate is difficult, costly, results in poor appearance quality, and has a high defect rate.
[0005] 3. Increase the thickness of the cover plate: Increasing the product thickness reduces the probability of cracking, but significantly increases production costs and cannot fundamentally solve the cracking problem.
[0006] Meanwhile, in other industries that use urea-formaldehyde materials, there is also the problem of urea-formaldehyde products cracking in dry and cold northern regions.
[0007] There is currently no good solution on the market, which is a bottleneck for the entire industry. Summary of the Invention
[0008] This application provides a composite toughening material, articles made therefrom, and a method for preparing the same. The composite toughening material has a core-shell structure and excellent toughening effect. It has good adhesion and compatibility with existing materials, such as urea-formaldehyde. It achieves crack resistance in cover plate articles without changing the unique ceramic texture and high hardness of urea-formaldehyde material. Furthermore, the production process of the composite toughening material is simple and easy to mass-produce for the market.
[0009] The first aspect of this application provides a composite toughening material, the composite toughening material comprising an outer shell material and a core material encased within the outer shell material.
[0010] In one exemplary embodiment, the outer shell material may be an acetal polymer, optionally selected from one or more of polyvinyl alcohol formaldehyde, polyvinyl alcohol hexal, and polyvinyl alcohol butyral (PVB), preferably polyvinyl alcohol butyral; the core material may be an inorganic powder, optionally selected from one or more of barium sulfate, silicon dioxide, calcium carbonate, talc, titanium dioxide, mica, silicon nitride, silicon carbide, zirconium dioxide, boron carbide, titanium diboride, and aluminum oxide.
[0011] In one exemplary embodiment, the viscosity of the outer shell material is 10S to 180S, preferably 10S to 140S; optionally, the particle size of the core material is between 2μm and 50μm.
[0012] In one exemplary embodiment, the ratio of the outer shell material to the core material by weight is (2-43):100, preferably (5-35):100.
[0013] A second aspect of this application provides a method for preparing the composite toughening material, comprising the following steps:
[0014] S100: Preparation of shell material solution;
[0015] S200: Mix the outer shell material solution with the core material to obtain a granular composite toughening material.
[0016] In one exemplary embodiment, step S100 further includes:
[0017] S110: Weighing
[0018] Weigh the shell material and solvent according to the proportions;
[0019] S120: Dissolve
[0020] Pour the solvent into a container equipped with a stirrer, and dissolve the shell material in the solvent in batches to obtain a shell material solution.
[0021] In one exemplary embodiment, the solvent may optionally be an alcohol, ether, ketone, ester, or other organic solvent, wherein the alcohol may be selected from one or more of methanol, ethanol, propylene glycol, and butanol, the ketone may be butanone, and the ester may be ethyl acetate; preferably, the solvent is anhydrous ethanol.
[0022] In one exemplary embodiment, the ratio of shell material to solvent by weight is (3-12):100, preferably (6-10):100.
[0023] In one exemplary embodiment, step S200 further includes:
[0024] S210: Mixed
[0025] The core material is poured into the outer shell material solution in batches and stirred evenly to obtain a clump-like mixed material;
[0026] S220: Drying
[0027] Vacuum drying of the lumpy mixture yields a uniformly mixed block material;
[0028] S230: Crushing
[0029] The block material is crushed to obtain a granular composite toughened material.
[0030] In one exemplary embodiment, in step S210, the ratio of the core material to the shell material solution by weight is 100:(84-400), and the solution is stirred evenly using a water-powder mixer.
[0031] In one exemplary embodiment, in step S220, the clump-like mixed material is placed in a sealed container and vacuum dried; optionally, the container is rotatable in a vacuum chamber, and the entire inner surface of the container may be covered with a hydrophobic, waterproof, and breathable membrane, optionally, the membrane is an expanded polytetrafluoroethylene (i.e., E-PTFE) membrane.
[0032] In one exemplary embodiment, in step S220, the vacuum drying temperature is 50℃~80℃, the vacuum degree is -0.1MPa~-0.2MPa, preferably -0.1MPa, and the drying time is 30~50 minutes.
[0033] In one exemplary embodiment, in step S230, the particle size of the particulate composite toughening material is between 0.05 mm and 0.5 mm.
[0034] A third aspect of this application provides a crack-resistant product, which is a urea-formaldehyde product, and its raw materials include composite toughening materials and urea-formaldehyde particles.
[0035] In one exemplary embodiment, the ratio of the urea-formaldehyde particles to the composite toughening material by weight is 100:(20-30).
[0036] In one exemplary embodiment, optionally, the urea-formaldehyde product is a seat cover, preferably a toilet seat cover.
[0037] In one exemplary embodiment, the crack-resistant article may also be an article that has been toughened and modified with melamine resin, phenolic resin, sheet molding compound (SMC) composite material, or bulk molding compound (BMC) material.
[0038] A fourth aspect of this application provides a method for preparing a crack-resistant article, comprising:
[0039] The granular urea-formaldehyde material is mixed evenly with the granular composite toughening material, and then molded in a molding machine to obtain urea-formaldehyde products.
[0040] Compared with related technologies, the technical effects of this application include:
[0041] 1. The core-shell structure in the composite toughening material gives the composite toughening particles excellent toughening effect and good adhesion and compatibility with urea-formaldehyde materials, achieving crack resistance of the cover plate without changing the unique ceramic texture and high hardness of urea-formaldehyde materials.
[0042] 2. The production process of the toughened urea-formaldehyde material of this application is simple and easy to mass-produce and commercialize.
[0043] 3. When modifying urea-formaldehyde granules by simply adding inorganic rigid particles to PVB powder, there is a problem of uneven appearance, especially after boiling in water, the unevenness becomes more obvious; at the same time, adding other elastomer toughening agents will result in poor appearance due to color difference with the urea-formaldehyde material; however, the urea-formaldehyde products obtained by using the toughened urea-formaldehyde material of this application do not have the phenomenon of uneven appearance because the PVB shell is relatively thin and the inside is wrapped with white inorganic particles.
[0044] 4. Low production cost of this application: Under the condition of having the same anti-cracking effect, the PVB percentage used in this application is lower than that of using PVB powder alone or a mixture of PVB and inorganic rigid particles alone.
[0045] 5. The sealed container used in the drying step of this application has an E-PTFE waterproof and breathable membrane that has certain hydrophobic properties to prevent the mixed materials from adhering to its surface. In addition, the container can rotate continuously, so there is no sedimentation of the inorganic powder material. This ensures the uniform mixing of PVB material and inorganic powder material, and finally obtains a uniformly mixed block material.
[0046] Other features and advantages of this application will be set forth in the following description, and will be apparent in part from the description, or may be learned by practicing the application. Other advantages of this application can be realized and obtained by means of the solutions described in the description and the accompanying drawings. Attached Figure Description
[0047] The accompanying drawings are used to provide an understanding of the technical solutions of this application and constitute a part of the specification. They are used together with the embodiments of this application to explain the technical solutions of this application and do not constitute a limitation on the technical solutions of this application.
[0048] Figure 1The toilet seat prepared according to Example 1 of this application;
[0049] Figure 2 The toilet seat prepared for Comparative Example 1;
[0050] Figure 3 The toilet seat prepared for Comparative Example 2. Detailed Implementation
[0051] This application describes several embodiments, but these descriptions are exemplary and not restrictive, and it will be apparent to those skilled in the art that many more embodiments and implementations are possible within the scope of the embodiments described herein. Although many possible combinations of features are shown in the accompanying drawings and discussed in the detailed description, many other combinations of the disclosed features are also possible. Unless specifically limited, any feature of any embodiment may be used in combination with any other feature in any other embodiment, or may replace any other feature in any other embodiment.
[0052] In the following embodiments and comparative examples:
[0053] Polyvinyl butyral (PVB), viscosity 10S~240S (determined according to GB / T1723-1993 Coating Viscosity Test Method), manufacturer is Qingdao Haocheng Industrial Co., Ltd.
[0054] Barium sulfate, manufactured by Shenzhen Haiyang Powder Technology Co., Ltd., 1250 mesh barium sulfate;
[0055] The silica microspheres are manufactured by Fengyang Lituo New Materials.
[0056] Example 1.
[0057] 1) Weighing:
[0058] PVB and anhydrous ethanol were weighed at a mass ratio of 12:100; the viscosity of PVB was 10S.
[0059] 2) Dissolving:
[0060] Pour anhydrous ethanol into a container equipped with a stirrer, and then dissolve PVB in the anhydrous ethanol in batches to obtain a PVB solution.
[0061] 3) Mixing:
[0062] The inorganic powder material was poured into the PVB solution in step 2) in batches according to the mass ratio of inorganic powder to PVB solution of 50:100, and stirred evenly using a water-powder mixer to obtain a lumpy mixed material; wherein the inorganic powder is barium sulfate powder with a particle size of D50 ≈ 8μm.
[0063] 4) Drying:
[0064] The agglomerated mixed material obtained in step 3) is placed in a sealed container, vacuum dried, and heated to obtain a uniformly mixed block material; wherein, the vacuum drying temperature is 80℃, the vacuum degree is set to -0.2MPa, and the drying time is 30 minutes.
[0065] 5) Crushing:
[0066] The block material prepared in step 4) is crushed to obtain a granular composite toughening material with a particle size of 50-100 μm.
[0067] 6) Toughened urea-formaldehyde materials:
[0068] The granular urea-formaldehyde material and the granular composite toughening material prepared in step 5) are mixed evenly at a weight ratio of 100:20 to obtain the toughened urea-formaldehyde material.
[0069] 7) Urea-formaldehyde products
[0070] The toughened urea-formaldehyde material prepared in step 6) is molded in a molding machine to obtain the corresponding crack-resistant urea-formaldehyde product.
[0071] Example 2.
[0072] 1) Weighing:
[0073] PVB and anhydrous ethanol were weighed at a mass ratio of 5:100; the viscosity of PVB was 180S.
[0074] 2) Dissolving:
[0075] Pour anhydrous ethanol into a container equipped with a stirrer, and then dissolve PVB in the anhydrous ethanol in batches to obtain a PVB solution.
[0076] 3) Mixing:
[0077] The inorganic powder material was poured into the PVB solution in step 2) in batches according to the mass ratio of inorganic powder to PVB solution of 70:100, and stirred evenly using a water-powder mixer to obtain a lumpy mixed material; wherein the inorganic powder is silica microspheres with a particle size of 50μm.
[0078] 4) Drying:
[0079] The agglomerated mixed material obtained in step 3) is placed in a sealed container, vacuum dried, and heated to obtain a uniformly mixed block material; wherein, the vacuum drying temperature is 50℃, the vacuum degree is set to -0.1MPa, and the drying time is 50 minutes.
[0080] 5) Crushing:
[0081] The block material prepared in step 4) is crushed to obtain a granular composite toughening material with a particle size of 60-300 μm.
[0082] 6) Toughened urea-formaldehyde materials:
[0083] The granular urea-formaldehyde material and the granular composite toughening material prepared in step 5) are mixed evenly at a weight ratio of 100:30 to obtain the toughened urea-formaldehyde material.
[0084] 7) Urea-formaldehyde products
[0085] The toughened urea-formaldehyde material prepared in step 6) is molded in a molding machine to obtain the corresponding crack-resistant urea-formaldehyde product.
[0086] Comparative Example 1
[0087] 1) Weighing:
[0088] POE (i.e., an elastomer copolymer of ethylene and octene) and anhydrous ethanol were weighed at a mass ratio of 5:100.
[0089] 2) Dissolving:
[0090] Pour anhydrous ethanol into a container equipped with a stirrer, and then add POE in batches to the anhydrous ethanol to obtain a POE / ethanol mixture.
[0091] The other steps are the same as in Example 2.
[0092] Comparative Example 2.
[0093] 1) Weighing:
[0094] POE (i.e., an elastomer copolymer of ethylene and octene) and anhydrous ethanol were weighed at a mass ratio of 12:100.
[0095] 2) Dissolving:
[0096] Pour anhydrous ethanol into a container equipped with a stirrer, and then add POE in batches to the anhydrous ethanol to obtain a POE / ethanol mixture.
[0097] Steps 3)-5) are the same as in Example 2.
[0098] 6) Toughened urea-formaldehyde materials:
[0099] The granular urea-formaldehyde material and the granular composite toughening material prepared in step 5) are mixed evenly at a weight ratio of 100:40 to obtain the toughened urea-formaldehyde material.
[0100] 7) Urea-formaldehyde products
[0101] The toughened urea-formaldehyde material prepared in step 6) is molded in a molding machine to obtain the corresponding crack-resistant urea-formaldehyde product.
[0102] Comparative Example 3.
[0103] 1) Weighing:
[0104] Weigh MBS and anhydrous ethanol at a mass ratio of 5:100.
[0105] 2) Dissolving:
[0106] Anhydrous ethanol was poured into a container equipped with a stirrer, and then MBS was added to the anhydrous ethanol in batches to obtain an MBS / ethanol mixture.
[0107] The other steps are the same as in Example 2.
[0108] Comparative Example 4.
[0109] 1) Weighing:
[0110] PVB and urea-formaldehyde granules were weighed at a mass ratio of 3:100; the viscosity of PVB was 10S.
[0111] 2) Mixing:
[0112] PVB and granular urea-formaldehyde material are mixed evenly in a ball mill to obtain a urea-formaldehyde + PVB mixture.
[0113] 3) Urea-formaldehyde products
[0114] The toughened urea-formaldehyde material prepared in step 2) is molded in a molding machine to obtain the corresponding crack-resistant urea-formaldehyde product.
[0115] Comparative Example 5.
[0116] 1) Weighing:
[0117] PVB and urea-formaldehyde granular materials were weighed at a mass ratio of 1.5:100; the viscosity of PVB was 180S.
[0118] The other steps are the same as in Comparative Example 4.
[0119] Comparative Example 6.
[0120] PVB, silica inorganic powder, and urea-formaldehyde granules are mechanically mixed in a mass ratio of 1.5:21.5:77, with PVB having a viscosity of 180S; then, the mixture is molded to obtain urea-formaldehyde cover products.
[0121] Comparative Example 7.
[0122] Steps 1)-5) are the same as in Example 1.
[0123] 6) Toughened urea-formaldehyde materials:
[0124] The granular urea-formaldehyde material and the granular composite toughening material prepared in step 5) are mixed evenly at a weight ratio of 100:33 to obtain the toughened urea-formaldehyde material.
[0125] 7) Urea-formaldehyde products
[0126] The toughened urea-formaldehyde material prepared in step 6) is molded in a molding machine to obtain the corresponding crack-resistant urea-formaldehyde product.
[0127] Comparative Example 8.
[0128] Steps 1)-5) are the same as in Example 1.
[0129] 6) Toughened urea-formaldehyde materials:
[0130] The granular urea-formaldehyde material and the granular composite toughening material prepared in step 5) are mixed evenly at a weight ratio of 100:10 to obtain the toughened urea-formaldehyde material.
[0131] 7) Urea-formaldehyde products
[0132] The toughened urea-formaldehyde material prepared in step 6) is molded in a molding machine to obtain the corresponding crack-resistant urea-formaldehyde product.
[0133] Comparative Example 9.
[0134] Urea-formaldehyde granules, commonly available on the market, are directly molded into urea-formaldehyde cover plates.
[0135] Experimental Example 1. (Product Performance Comparison)
[0136] Performance tests were conducted on the urea-formaldehyde cover plates used in the embodiments and comparative examples of this application, and the results are shown in Table 1 and... Figure 1-2 As shown.
[0137] Table 1
[0138]
[0139] As can be seen from the comparison, the cover plate prepared in this application embodiment has a uniform appearance and good crack resistance compared with the comparative example.
[0140] This application includes and contemplates combinations of features known to those skilled in the art. The embodiments and features disclosed in this application can also be combined with any conventional features to form a unique inventive scheme as defined by the claims. Any feature of any embodiment can also be combined with features from other inventive schemes to form another unique inventive scheme as defined by the claims. Therefore, it should be understood that any feature shown and / or discussed in this application can be implemented individually or in any suitable combination. Therefore, the embodiments are not limited except by the limitations imposed by the appended claims and their equivalents. Furthermore, various modifications and changes can be made within the scope of the appended claims.
[0141] Furthermore, in describing representative embodiments, the specification may have presented methods and / or processes as a specific sequence of steps. However, the method or process should not be limited to the specific order of steps described herein, to the extent that it does not depend on such a specific order. As will be understood by those skilled in the art, other sequences of steps are also possible. Therefore, the specific order of steps set forth in the specification should not be construed as a limitation of the claims. Moreover, the claims concerning the method and / or process should not be limited to the steps performed in the written order, and those skilled in the art will readily understand that these orders can be varied and still remain within the spirit and scope of the embodiments of this application.
Claims
1. A crack-resistant product, wherein the crack-resistant product is a urea-formaldehyde product, and its raw materials are composed of composite toughening materials and urea-formaldehyde particles, wherein, By weight, the ratio of urea-formaldehyde particles to composite toughening material is 100:(20~30); The composite toughening material consists of an outer shell material and a core material encased within the outer shell material; by weight, the ratio of the outer shell material to the core material is (2~43):100; The outer shell material is an acetal polymer; The core material is inorganic powder; The inorganic powder is selected from one or more of barium sulfate, silicon dioxide, calcium carbonate, talc, titanium dioxide, mica, silicon nitride, silicon carbide, zirconium dioxide, boron carbide, titanium diboride, and aluminum oxide. The particle size of the core material is between 2μm and 50μm; The outer shell material is selected from one or more of polyvinyl alcohol formaldehyde, polyvinyl alcohol hexal, and polyvinyl alcohol butyral. The particle size of the granular composite toughening material is between 0.05 mm and 0.5 mm.
2. The crack-resistant product according to claim 1, wherein, By weight, the ratio of the outer shell material to the core material is (5~35):
100.
3. The crack-resistant product according to claim 1 or 2, wherein, The outer shell material is polyvinyl butyral.
4. The crack-resistant product according to claim 1 or 2, wherein, The viscosity of the outer shell material is 10S~180S.
5. The crack-resistant product according to claim 4, wherein, The viscosity of the outer shell material is 10S~140S.
6. The crack-resistant product according to claim 1 or 2, wherein, The crack-resistant product is a toilet seat.
7. A method for preparing a crack-resistant article according to any one of claims 1 to 6, comprising: The granular urea-formaldehyde material is mixed evenly with the granular composite toughening material, and then molded in a molding machine to obtain urea-formaldehyde products.
8. The method according to claim 7, wherein, The preparation method of the composite toughening material includes the following steps: S100: Preparation of shell material solution; S200: Mix the outer shell material solution with the core material to obtain a granular composite toughening material.
9. The method according to claim 8, wherein, Step S100 also includes: S110: Weighing Weigh the shell material and solvent according to the proportions; S120: Dissolve Pour the solvent into a container equipped with a stirrer, and then dissolve the shell material in the solvent in batches to obtain a shell material solution; The ratio of shell material to solvent by weight is (3~12):
100.
10. The method according to claim 9, wherein, By weight, the ratio of shell material to solvent is (6~10):
100.
11. The method according to claim 10, wherein, The solvent is an alcohol, ether, ketone, ester or other organic solvent, wherein the alcohol is selected from one or more of methanol, ethanol, propylene glycol and butanol, the ketone is butanone, and the ester is ethyl acetate.
12. The method according to claim 11, wherein, The solvent is anhydrous ethanol.
13. The method according to any one of claims 7 to 12, wherein, Step S200 also includes: S210: Mixed The core material is poured into the outer shell material solution in batches and stirred evenly to obtain a clump-like mixed material; S220: Drying Vacuum drying of the lumpy mixture yields a uniformly mixed block material; S230: Crushing The block material is crushed to obtain a granular composite toughened material.
14. The method according to claim 13, wherein, In step S210, the core material to shell material solution is calculated at a ratio of 100:(84~400) by weight, and the solution is stirred evenly using a water-powder mixer; and / or In step S220, the lumpy mixture is placed in a sealed container and vacuum dried; the container is rotatable within the vacuum chamber, and its entire inner surface is covered with a hydrophobic, waterproof, and breathable membrane; the vacuum drying temperature is 50℃~80℃, the vacuum degree is -0.1MPa~-0.2MPa; the drying time is 30~50 minutes; and / or In step S230, the particle size of the granular composite toughening material is between 0.05 mm and 0.5 mm.
15. The method according to claim 14, wherein, The entire inner surface of the container is covered with a hydrophobic expanded polytetrafluoroethylene film; and / or The vacuum level is -0.1 MPa.