A water-based matte surface treatment agent for PVC calendered leather

Abstract

The present invention relates to a water-based matte treatment agent for PVC calendered leather. It is prepared from raw materials comprising the following components: acrylate-modified water-based polyurethane resin, water-based acrylic (ester) resin, matting powder, water, film-forming aid, wetting agent, defoamer, and thickener. The 100% modulus of the acrylate-modified water-based polyurethane resin after drying and film-forming is 5-18MPa, and the elongation at break is 300%-600%; the glass transition temperature of the water-based acrylic (ester) resin is ‑15°C-10°C, and the elongation at break after drying and film-forming is 500%-1000%. The water-based matte treatment agent for PVC calendered leather is applied to the pre-foaming treatment of PVC calendered leather, and has the performance characteristics of good temperature resistance and good black haze. After the product is coated on the surface of PVC calendered leather through processes such as foaming and absorbing grain, the leather-like surface effect finally obtained is uniform, with good black haze and good comprehensive physical properties.

Description

Technical Field

[0001] The invention relates to a surface treatment agent, in particular to an aqueous matte surface treatment agent used for pre-foaming treatment of PVC calendered leather. Background Art

[0002] PVC calendering is the main production process of PVC artificial leather. The produced PVC calendered leather has the characteristics of low cost, high strength and uniform foaming, and this method has high production efficiency. The foaming agent used in PVC calendered leather is usually an azo foaming agent, which requires a high temperature of more than 180°C to achieve the foaming effect. However, high temperatures above 180°C will cause a large amount of plasticizers in the PVC calendered leather to migrate to the surface, affecting the appearance of the leather. Therefore, PVC calendered leather manufacturers usually apply a layer of surface treatment agent on the PVC calendered leather before high-temperature foaming. This foaming pre-treatment agent usually has a matte effect. On the one hand, it plays a role in covering the plasticizer, and on the other hand, it also brings matte and physical protection effects to the PVC leather.

[0003] At present, some of the pre-foaming treatment agents for PVC calendered leather on the market have adopted water-based solutions. In order to achieve a better matte effect, the formula usually contains self-matting water-based polyurethane resin. This leads to a higher overall cost of the treatment agent, which is not conducive to competing with oily products and affects its promotion. If only ordinary water-based polyurethane resin is used with matting powder to achieve the matte effect, and then foamed at a high temperature above 180°C, the surface gloss after foaming often increases significantly due to the relatively small molecular weight and poor temperature resistance of the water-based polyurethane resin, making it difficult to achieve a good matte / matte effect.

[0004] Patent CN106349914A discloses a matte treatment agent for PVC leather and a preparation method thereof, which improves the feel and scratch resistance of the PVC leather surface by adding wax emulsion and polysiloxane dispersion. However, the patent does not mention the temperature resistance of the matte treatment agent, and whether it can be used for pre-foaming treatment of PVC leather.

[0005] Patent CN103898764A discloses a water-based polyurethane matte treatment agent for PVC leather and a preparation method thereof. Provided is a water-based polyurethane matte treatment agent for calendered PVC leather and a preparation method thereof which is not only safe, environmentally friendly, and low-cost, but also has a good surface treatment effect and can be simultaneously treated with high-temperature embossing of calendered PVC leather. The patent also does not mention the temperature resistance of the matte treatment agent, and whether it can be used for pre-foaming treatment of PVC leather.

[0006] Patent CN102367348A discloses a water-based single-coat matte transfer aluminum coating and its preparation method, wherein it is disclosed that water-based resins include one or more of acrylic resins, polyurethane resins or polyvinyl alcohol resins to prepare matte paint. However, this patent is used for hard substrates and does not involve the temperature resistance of matte treatment agents, and whether it can be used for pre-foaming treatment of PVC leather.

[0007] Patent CN103614027A discloses an outdoor water-based wood matte clear topcoat and its preparation method, which discloses that water-based self-crosslinking acrylic resin can be used as matte paint. However, this patent is used on hard substrates and does not involve the temperature resistance of the matte treatment agent, nor whether it can be used in the pre-foaming treatment of PVC leather.

[0008] Patent CN103703076A discloses an acrylic resin composition, which discloses the composition of acrylic resin, and discloses reducing the Tg of acrylic resin, which can prevent cracking, and is used on the surface of polyvinyl chloride resin, and can be used at high temperatures. However, the limitations and rules of the invention are only based on its acrylic composition plastic parts. For the application scenario of the present invention, PVC calendered leather, when baked at high temperature, the plasticizer in the PVC leather will migrate to the surface in large quantities. The acrylic (ester) resin with a lower Tg will, on the one hand, make the coating itself less cohesive, and on the other hand, it will cause the plasticizer to easily swell the coating. The superposition of these two factors may also cause the coating to crack easily when stretched. At the same time, the patent does not consider the combination of acrylic (ester) resin and matting powder. Therefore, the patent cannot provide a method for using acrylic (ester) resin to effectively solve the problem of maintaining high black haze on the surface of PVC calendered leather matte treatment agent at high temperature without cracking. Summary of the invention

[0009] The purpose of the present invention is to provide a water-based matte treatment agent for PVC calendered leather with high cost performance in view of the above technical gaps. The treatment agent can well match the foaming process of PVC calendered leather. After foaming, absorbing grains and other processes, the leather sample surface effect finally obtained is uniform and has good black fog. At the same time, the present invention adopts a relatively low-priced water-based acrylic (ester) resin as one of the main raw materials, which can reduce the preparation cost of the treatment agent and is conducive to the large-scale promotion of the product.

[0010] The present invention creatively uses water-based acrylic (ester) resin as one of the raw materials, and utilizes its large molecular weight and branching effect to achieve a good temperature resistance effect; through the appropriate glass transition temperature of water-based acrylic (ester), the appropriate type and proportion of cross-linking monomers, and the appropriate resin film elongation, the adverse effects of stickiness and cracking after adding matting powder are avoided. By modifying the water-based polyurethane with acrylate, the compatibility of the water-based polyurethane chain segment and the water-based acrylic (ester) during compounding is improved, and a good surface effect is achieved.

[0011] In order to achieve the above object, the present invention adopts the following technical solutions:

[0012] A water-based matte surface treatment agent for PVC calendered leather, prepared from raw materials comprising the following components:

[0013] (a) acrylate modified waterborne polyurethane resin,

[0014] (b) water-based acrylic resin,

[0015] (c) Matting powder,

[0016] (d) water,

[0017] (e) film-forming aids,

[0018] (f) wetting agents,

[0019] (g) defoaming agents,

[0020] (h) Thickeners.

[0021] As a preferred solution, the water-based matte surface treatment agent for PVC calendered leather of the present invention is prepared from the following raw materials in parts by weight:

[0022] (a) acrylate-modified waterborne polyurethane resin, 15-40 parts by weight, preferably 20-30 parts by weight;

[0023] (b) water-based acrylic (ester) resin, 5-20 parts by weight, preferably 5-10 parts by weight;

[0024] (c) matting powder, 3-6 parts by weight, preferably 3.5-5 parts by weight;

[0025] (d) water, 30-70 parts by weight, preferably 35-60 parts by weight;

[0026] (e) film-forming aid, 1-8 parts by weight, preferably 3-6 parts by weight;

[0027] (f) wetting agent, 1-3 parts by weight, preferably 1.5-2.5 parts by weight;

[0028] (g) defoamer, 0.1-0.5 parts by weight, preferably 0.2-0.4 parts by weight;

[0029] (h) Thickener: 0.5-3 parts by weight, preferably 0.8-1.5 parts by weight.

[0030] In the present invention, the preparation method of the acrylate modified waterborne polyurethane resin comprises the following steps: mixing and dissolving acrylate monomer and isocyanate terminated prepolymer, performing high-speed shear dispersion to obtain a pre-modified latex after neutralization reaction, and then adding an initiator to the pre-modified latex to initiate polymerization to obtain acrylate modified waterborne polyurethane.

[0031] As a preferred solution, in the present invention, the preparation method of the acrylate modified waterborne polyurethane resin comprises the following steps: uniformly mixing polyisocyanate with polyester polyol and chain extender and reacting, wherein the chain extender is a small molecule diol or diamine, the reaction temperature is 70-80°C, the reaction time is 3-5 hours, and a prepolymer P containing an isocyanate group at the end is generated; cooling to 30-40°C, and uniformly mixing the prepolymer P with an acrylate monomer in the presence of a solvent S; then adding triethylamine under shear dispersion conditions (adjusting the speed of the disperser to 1200-1500 rpm), stirring for 5-10 minutes, adding water, and stirring for 15-25 minutes; then adding ethylenediamine for post-chain extension; finally, maintaining the temperature at 30-40°C, adding an initiator to initiate polymerization, and after the polymerization is completed, removing the solvent S from the emulsion by reduced pressure distillation to obtain an acrylate modified waterborne polyurethane resin.

[0032] In the present invention, the polyisocyanate comprises one or more of aromatic polyisocyanate, aliphatic polyisocyanate and alicyclic polyisocyanate.

[0033] In the present invention, the polyester polyol is selected from polycaprolactone diol, polyhexamethylene carbonate diol, polyneopentyl adipate diol, poly1,4-butylene adipate diol, poly1,6-hexanediol adipate diol, poly1,2-propylene adipate diol, polydiethylene adipate diol, polyneopentyl adipate diol, polyethylene adipate diol and diethylene glycol. One or more of the following: random copolyester diols of glycol, random copolyester diols of polyethylene adipate and propylene glycol, random copolyester diols of polyethylene adipate and butylene glycol, random copolyester diols of polyhexane adipate and neopentyl glycol, preferably one or more of polycaprolactone diol, polyhexamethylene carbonate diol, polyneopentyl adipate diol, poly1,6-hexanediol adipate diol.

[0034] In the present invention, the number average molecular weight of the polyester polyol is 1000-3000, preferably 1000-2000.

[0035] In the present invention, the solvent S is selected from one or more of acetone, 2-butanone, N-methylpyrrolidone, and N-ethylpyrrolidone.

[0036] In the present invention, the small molecule alcohol or amine comprises 2,2-dihydroxymethylpropionic acid and / or 2-[(2-aminoethyl)amino]ethanesulfonic acid sodium salt.

[0037] In the present invention, in the acrylate-modified waterborne polyurethane resin, the acrylate monomer includes at least one monomer with a Tg of ≥ 0°C and at least one monomer with a Tg of < 0°C. The monomer with a Tg of ≥ 0°C is selected from methyl acrylate, methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate, butyl methacrylate and isobornyl methacrylate, preferably methyl methacrylate, ethyl methacrylate and butyl methacrylate; the monomer with a Tg of < 0°C is selected from ethyl acrylate, hydroxypropyl acrylate, propyl acrylate, butyl acrylate, tetrahydrofuran acrylate and isooctyl acrylate. Ethyl acrylate and butyl acrylate are preferred.

[0038] In the present invention, in the acrylate-modified waterborne polyurethane resin, the ratio of the total amount of acrylate monomers to the prepolymer P is 1:1 to 1:3 in parts by mass;

[0039] In the present invention, the 100% modulus of the acrylate-modified waterborne polyurethane resin after drying and forming a film is 5-18 MPa, and the elongation at break is 300%-600%.

[0040] In the present invention, suitable examples of the acrylate-modified waterborne polyurethane resin include, but are not limited to, industrial products such as Leasys 3970, Leasys 3979, and Leasys 3725 from Wanhua Chemical.

[0041] In the present invention, the preparation method of the water-based acrylic (ester) resin is a seed method, comprising the following steps:

[0042] Adding acrylic acid (ester) monomer, water and emulsifier into a pre-emulsification kettle to prepare a pre-emulsion liquid;

[0043] Dissolving a portion of the initiator in water to obtain a dropwise initiator;

[0044] Dissolve the remaining initiator with water to obtain a bottom initiator;

[0045] Mix the emulsifier and water and add them into the reactor. Stir thoroughly and heat to 80-90°C. Add part of the pre-emulsified liquid, stir evenly and add all the initiator at the bottom of the reactor. React for 10-20 minutes to obtain the seed emulsion.

[0046] Control the temperature in the reactor to 80-90°C, continue to add the remaining pre-emulsion and initiator to the seed emulsion, add for 2-4 hours, and then keep warm for 20-60 minutes;

[0047] The reactor was cooled to 70-80°C, and the post-treatment agent was gradually added to the reactor within 20-60 minutes, and then kept warm for 30-60 minutes; the temperature was cooled to below 45°C, and a pH regulator was added to adjust the pH of the system to 7-9, and the material was filtered out.

[0048] In the present invention, the acrylic acid (ester) monomers used in the preparation of the water-based acrylic acid (ester) resin include conventional monomers and cross-linking monomers.

[0049] In the present invention, the conventional monomers include at least one monomer with a Tg of ≥ 0°C and at least one monomer with a Tg of < 0°C. The monomer with a Tg of ≥ 0°C is selected from acrylic acid, methyl acrylate, methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate, butyl methacrylate and isobornyl methacrylate, preferably acrylic acid, methyl methacrylate, ethyl methacrylate and butyl methacrylate; the monomer with a Tg of < 0°C is selected from ethyl acrylate, hydroxypropyl acrylate, propyl acrylate, butyl acrylate, tetrahydrofuran acrylate and isooctyl acrylate, preferably ethyl acrylate and butyl acrylate.

[0050] In the present invention, in the water-based acrylic (ester) resin, the mass of the monomer with Tg≥0°C accounts for 25-60% of the total amount of acrylic (ester) monomers.

[0051] In the present invention, in the water-based acrylic (ester) resin, the mass of the monomer with Tg < 0°C accounts for 35-70% of the total amount of acrylic (ester) monomers.

[0052] In the present invention, the cross-linking monomer includes one or more of ethyl acetoacetoxy methacrylate, propyl acetoacetoxy methacrylate, butyl acetoacetoxy methacrylate, and allyl acetoacetate.

[0053] In the present invention, in the water-based acrylic (ester) resin, the mass of the cross-linking monomer accounts for 1%-5% of the total amount of acrylic (ester) monomers.

[0054] In the present invention, the emulsifier is preferably one or more of sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, alcohol ether sulfosuccinate, alkyl alcohol ether sulfate, and alkyl alcohol ether phosphate.

[0055] In the present invention, the initiator is preferably one or more of sodium persulfate, potassium persulfate, and ammonium persulfate.

[0056] In the present invention, the post-treatment agent is an oxidant and / or a reducing agent, the oxidant is one or more of tert-butyl hydroperoxide, hydrogen peroxide, sodium persulfate, potassium persulfate, and ammonium persulfate; the reducing agent is one or more of sodium bisulfite, sodium pyrosulfite, and vitamin C.

[0057] In the present invention, the glass transition temperature of the waterborne acrylic (ester) resin is -15°C to 10°C, preferably -10°C to 5°C.

[0058] In the present invention, the elongation at break of the waterborne acrylic (ester) resin after drying and forming a film is 500%-1000%.

[0059] In the present invention, the matting powder is silicon dioxide particles with a particle size of 3-10um.

[0060] In the present invention, the film-forming aid is an organic solvent with a boiling point of 100° C.-200° C., preferably one or more of ethylene glycol butyl ether, diethylene glycol butyl ether, dipropylene glycol methyl ether and dipropylene glycol dimethyl ether.

[0061] In the present invention, the wetting agent is a silicone-modified polyurethane wetting agent.

[0062] In the present invention, the defoamer is a silicone-modified polyurethane defoamer or a mineral oil defoamer.

[0063] In the present invention, the thickener is a polyurethane associative thickener.

[0064] A method for preparing a water-based matte surface treatment agent for PVC calendered leather comprises the following steps: uniformly mixing acrylate-modified water-based polyurethane resin, water-based acrylic (ester) resin, water, film-forming aid, matting powder and defoaming agent according to proportion, filtering, and then adding a wetting agent and a thickener and mixing them uniformly.

[0065] The positive effects of the present invention are:

[0066] The acrylate-modified waterborne polyurethane resin is mainly waterborne polyurethane, which retains its excellent elasticity, excellent adhesion to PVC substrates, and excellent plasticizer precipitation prevention performance. At the same time, due to the difference in the structure of waterborne polyurethane and waterborne acrylic acid (ester), the two have different refractive indices, and the compatibility and permeability of compounding together will be slightly poor. By preparing the acrylate-modified waterborne polyurethane resin, its compatibility and permeability when compounded with waterborne acrylic acid (ester) can be improved, and a good PVC leather surface treatment effect can be achieved.

[0067] The water-based acrylic (ester) resin achieves good high temperature resistance through a suitable preparation method and the introduction of a certain amount of cross-linking structure; and avoids the adverse effects of stickiness and cracking of the surface layer after adding matting powder through a suitable glass transition temperature and film elongation limit.

[0068] The matte treatment agent prepared by compounding the acrylate modified waterborne polyurethane resin and the waterborne acrylic (ester) resin in an appropriate ratio has excellent adhesion and excellent performance in preventing plasticizer precipitation on PVC leather, and has excellent bending performance and anti-sticking performance. At the same time, it has a good matching degree with the PVC leather calendering process. After high-temperature foaming, absorbing grain and other processes, the leather sample finally obtained has a uniform surface effect, no defects such as cracks, and has good black fog. DETAILED DESCRIPTION

[0069] The preferred embodiments of the present invention will be described in more detail below. Although the preferred embodiments of the present invention are shown in the examples, it should be understood that the present invention can be implemented in various forms and should not be limited to the embodiments set forth herein.

[0070] 1. Test method for resin modulus and elongation at break:

[0071] The resin was poured onto a glass plate and dried at 50°C to form a film, and then the 100% modulus and elongation at break of the resin film were tested using a universal tensile tester according to the GB / T1701 test method;

[0072] 2. PVC calendered leather surface treatment sample preparation method:

[0073] The prepared matte treatment agent was coated on the unfoamed PVC calendered leather surface with a 100-mesh roller coater, and then foamed at 180-220° C. for about 1 minute; after the foaming was completed, the grain was absorbed with a grain absorbing machine to obtain a PVC calendered leather sample.

[0074] 3. Treatment agent performance test method:

[0075] 1. Appearance test method: observe the blackness and transparency of the leather surface, and whether there are any defects;

[0076] 2. Adhesion test method: fold the leather sample in half, load it with 5kg, press it at 80℃ for 24h, and observe whether there is delamination or white marks at the crease;

[0077] 3. Anti-adhesion test method: fold the leather sample in half, load it with 5kg, press it at 80℃ for 24h, and observe whether there is adhesion at the place where the leather sample is attached;

[0078] 4. Test method for resistance to room temperature bending: Cut the leather sample into 4cm*7cm strips, 3 in each of the warp and weft directions, and test with a room temperature bending instrument;

[0079] 5. Gloss test method: gloss meter test, record the gloss value at an incident angle of 60 degrees;

[0080] 4. Source of raw materials:

[0081] 1. Leasys 3970 (acrylate modified waterborne polyurethane resin, 100% modulus 8 MPa, elongation at break 400%, Wanhua Chemical Group Co., Ltd.);

[0082] 2. Leasys 3979 (acrylate modified waterborne polyurethane resin, 100% modulus 6 MPa, elongation at break 500%, Wanhua Chemical Group Co., Ltd.);

[0083] 3. Leasys 3725 (acrylate modified waterborne polyurethane resin, 100% modulus 16MPa, elongation at break 300%, Wanhua Chemical Group Co., Ltd.)

[0084] 4. Leasys 7377 (waterborne polyurethane resin, 100% modulus 8MPa, elongation at break 370%, Wanhua Chemical Group Co., Ltd.)

[0085] 5. Methyl methacrylate (code name: MMA, Wanhua Chemical Group Co., Ltd.)

[0086] 6. Butyl acrylate (code BA, Wanhua Chemical Group Co., Ltd.)

[0087] 7. Acrylic acid (code AA, Komiou Chemical Reagent Co., Ltd.)

[0088] 8. Ethyl acetoacetate methacrylate (code name AAEM, Eastman)

[0089] 9. Allyl acetoacetate (code name AAAL, Hubei Baidu Chemical)

[0090] 10. Allyl methacrylate (code name BGDMA, Shanghai Ole Chemical)

[0091] 11. PA-1, water-based acrylic (ester) resin, homemade, monomer composition: according to the monomer mass fraction, 33% MMA, 60% BA, 5% AAEM, 2% AA, preparation method: add 100 parts of acrylic (ester) monomer, 30 parts of water, 1 part of sodium dodecyl sulfate into a pre-emulsification kettle to prepare a pre-emulsified liquid; dissolve 0.1 part of ammonium persulfate in 3 parts of water to obtain a drop initiator; dissolve 0.1 part of ammonium persulfate in 1 part of water to obtain a bottom initiator; mix 0.02 part of sodium dodecyl sulfate with 50 parts of water and add it into the reactor, stir well and heat to 8 0-90℃; add 5 parts of pre-emulsion, add all the initiators at the bottom of the kettle after stirring evenly, react for 20 minutes to obtain seed emulsion; control the temperature in the reactor to 80-90℃, continue to add the remaining pre-emulsion and drip the initiator to the seed emulsion, drip for 3 hours, and then keep warm for 30 minutes; cool the reactor to 70-80℃, gradually add 0.2 parts of tert-butyl hydroperoxide and 0.2 parts of sodium bisulfite (dissolved in 4 parts of water) to the reactor within 30 minutes, and then keep warm for 30 minutes; cool to below 45℃, add diethanolamine, adjust the system pH to 8, and filter the material. The final water-based acrylic acid (ester) has a glass transition temperature of -15℃ and an elongation at break of 750%;

[0092] 12. PA-2, water-based acrylic (ester) resin, homemade, monomer composition: according to the monomer mass fraction, 50% MMA, 47% BA, 1% AAEM, 2% AA; except for the monomer composition, the rest of the preparation method is the same as PA-1. The final water-based acrylic (ester) has a glass transition temperature of 8°C and an elongation at break of 820%;

[0093] 13. PA-3, water-based acrylic (ester) resin, homemade, monomer composition: according to the monomer mass fraction, 45% MMA, 51% BA, 3% AAAL, 1% AA; except for the monomer composition, the rest of the preparation method is the same as PA-1. The final water-based acrylic (ester) has a glass transition temperature of 0°C and an elongation at break of 560%;

[0094] 14. PA-4, water-based acrylic (ester) resin, homemade, monomer composition: according to the monomer mass fraction, 50% MMA, 48% BA, 0.5% AAEM, 1.5% AA. Except for the monomer composition, the rest of the preparation method is the same as PA-1. The final water-based acrylic (ester) has a glass transition temperature of 5°C and an elongation at break of 770%.

[0095] 15. PA-5, water-based acrylic (ester) resin, homemade, monomer composition: according to the monomer mass fraction, 65% MMA, 30% BA, 3% AAEM, 2% AA. Except for the monomer composition, the rest of the preparation method is the same as PA-1. The final water-based acrylic (ester) has a glass transition temperature of 30°C and an elongation at break of 350%.

[0096] 16. PA-6, water-based acrylic (ester) resin, self-made, monomer composition: according to the mass fraction of monomers, 30% MMA, 66% BA, 2% AAEM, 2% AA. Except for the monomer composition, the rest of the preparation method is the same as PA-1. The final water-based acrylic (ester) has a glass transition temperature of -22°C and an elongation at break of 1100%.

[0097] 17. PA-7, water-based acrylic (ester) resin, homemade, monomer composition: according to the monomer mass fraction, 50% MMA, 41% BA, 7% AAEM, 2% AA. Except for the monomer composition, the rest of the preparation method is the same as PA-1. The final water-based acrylic (ester) has a glass transition temperature of 10°C and an elongation at break of 390%.

[0098] 18. PA-8, water-based acrylic (ester) resin, homemade, monomer composition: according to the monomer mass fraction, 50% MMA, 47% BA, 1% BGDMA, 2% AA. Except for the monomer composition, the rest of the preparation method is the same as PA-1. The final water-based acrylic (ester) has a glass transition temperature of 9°C and an elongation at break of 550%.

[0099] 19. ACEMATT 3400 (silicon dioxide matting powder, average particle size: 9.5um d50; (laser diffraction method), Evonik Degussa);

[0100] 20. ACEMATT TS100 (silicon dioxide matting powder, average particle size: 9.5um d50; (laser diffraction method), Evonik Degussa);

[0101] 21. 3248 (wetting agent, Chongyao Chemical)

[0102] 22. 8008 (wetting agent, Slok Company)

[0103] 23. Tego 815N (defoaming agent, Evonik Degussa)

[0104] 24. NOPCO-NXZ (defoaming agent, San Nopco);

[0105] 25. Vesmody U605 (associative polyurethane thickener, Wanhua Chemical Group Co., Ltd.);

[0106] 26. Vesmody U505 (associative polyurethane thickener, Wanhua Chemical Group Co., Ltd.);

[0107] 27. Ethylene glycol butyl ether (film-forming aid, Xilong Chemical)

[0108] 28. Dipropylene glycol methyl ether (film-forming aid, Dow Chemical)

[0109] Embodiment 1:

[0110] A water-based matte treatment agent for PVC calendered leather, comprising 20 parts by weight of an acrylate-modified water-based polyurethane resin Leasys 3970, 6 parts by weight of a water-based acrylic (ester) resin PA-1, 3.0 parts by weight of a silica matting powder (ACEMATT 3400), 63.8 parts by weight of water, 3 parts by weight of a film-forming aid ethylene glycol butyl ether, 2 parts by weight of a wetting agent (3248), 0.2 parts by weight of a defoaming agent (Tego 815N) and 2.0 parts by weight of a thickener (Vesmody U605);

[0111] The preparation method of the above-mentioned PVC calendered leather water-based matte surface treatment agent is as follows: according to weight parts, acrylate-modified water-based polyurethane resin, water-based acrylic (ester) resin, silica matting powder, water, film-forming aid, and defoaming agent are mixed and stirred for 1 hour; the obtained mixture is filtered, and then a wetting agent and a thickener are added to the filtered mixture and stirred for about 20 minutes to obtain the PVC calendered leather water-based matte surface treatment agent.

[0112] Embodiment 2:

[0113] A water-based matte treatment agent for PVC calendered leather, comprising 35 parts by weight of acrylate-modified water-based polyurethane resin Leasys 3979, 18 parts by weight of water-based acrylic (ester) resin PA-2, 3.0 parts by weight of silica matting powder (TS-100), 31.4 parts by weight of water, 6 parts by weight of film-forming aid ethylene glycol butyl ether, 2.5 parts by weight of wetting agent (3248), 0.1 parts by weight of defoaming agent (Tego 815N) and 1.0 parts by weight of thickener (Vesmody U605);

[0114] The preparation method of the above-mentioned PVC calendered leather water-based matte surface treatment agent is as follows: according to weight parts, acrylate-modified water-based polyurethane resin, water-based acrylic (ester) resin, silica matting powder, water, film-forming aid, and defoaming agent are mixed and stirred for 1 hour; the obtained mixture is filtered, and then a wetting agent and a thickener are added to the filtered mixture and stirred for about 20 minutes to obtain the PVC calendered leather water-based matte surface treatment agent.

[0115] Embodiment 3:

[0116] A water-based matte treatment agent for PVC calendered leather, comprising 25 parts by weight of an acrylate-modified water-based polyurethane resin Leasys 3725, 10 parts by weight of a water-based acrylic (ester) resin PA-3, 4.0 parts by weight of a silica matting powder (TS-100), 51.5 parts by weight of water, 5 parts by weight of a film-forming aid dipropylene glycol methyl ether, 2 parts by weight of a wetting agent (3248), 0.5 parts by weight of a defoaming agent (Tego 815N), and 2.0 parts by weight of a thickener (Vesmody U605);

[0117] The preparation method of the above-mentioned PVC calendered leather water-based matte surface treatment agent is as follows: according to weight parts, acrylate-modified water-based polyurethane resin, water-based acrylic (ester) resin, silica matting powder, water, film-forming aid, and defoaming agent are mixed and stirred for 1 hour; the obtained mixture is filtered, and then a wetting agent and a thickener are added to the filtered mixture and stirred for about 20 minutes to obtain the PVC calendered leather water-based matte surface treatment agent.

[0118] Embodiment 4:

[0119] A water-based matte surface treatment agent for PVC calendered leather, comprising 30 parts by weight of acrylate-modified water-based polyurethane resin Leasys 3970, 12 parts by weight of water-based acrylic (ester) resin PA-2, 5.0 parts by weight of silica matting powder (ACEMATT 3400), 44.4 parts by weight of water, 4 parts by weight of film-forming aid dipropylene glycol methyl ether, 1.5 parts by weight of wetting agent (8008), 0.1 parts by weight of defoaming agent (NOPCO-NXZ) and 3.0 parts by weight of thickener (Vesmody U505);

[0120] The preparation method of the above-mentioned PVC calendered leather water-based matte surface treatment agent is as follows: according to weight parts, acrylate-modified water-based polyurethane resin, water-based acrylic (ester) resin, silica matting powder, water, film-forming aid, and defoaming agent are mixed and stirred for 1 hour; the obtained mixture is filtered, and then a wetting agent and a thickener are added to the filtered mixture and stirred for about 20 minutes to obtain the PVC calendered leather water-based matte surface treatment agent.

[0121] Comparative Example 1:

[0122] A water-based matte treatment agent for PVC calendered leather, comprising 25 parts by weight of an acrylate-modified water-based polyurethane resin Leasys 3970, 4.0 parts by weight of a silica matting powder (ACEMATT 3400), 63.8 parts by weight of water, 3 parts by weight of a film-forming aid ethylene glycol butyl ether, 2 parts by weight of a wetting agent (3248), 0.2 parts by weight of a defoaming agent (Tego 815N), and 2.0 parts by weight of a thickener (Vesmody U605);

[0123] The preparation method of the above-mentioned PVC calendered leather water-based matte surface treatment agent is as follows: according to weight parts, acrylate-modified water-based polyurethane resin, water-based acrylic (ester) resin, silica matting powder, water, film-forming aid, and defoaming agent are mixed and stirred for 1 hour; the obtained mixture is filtered, and then a wetting agent and a thickener are added to the filtered mixture and stirred for about 20 minutes to obtain the PVC calendered leather water-based matte surface treatment agent.

[0124] Comparative Example 2:

[0125] A water-based matte treatment agent for PVC calendered leather, comprising 20 parts by weight of water-based polyurethane resin Leasys 7377, 6 parts by weight of water-based acrylic (ester) resin PA-1, 3.0 parts by weight of silica matting powder (ACEMATT 3400), 63.8 parts by weight of water, 3 parts by weight of film-forming aid ethylene glycol butyl ether, 2 parts by weight of wetting agent (3248), 0.2 parts by weight of defoaming agent (Tego 815N) and 2.0 parts by weight of thickener (Vesmody U605);

[0126] The preparation method of the above-mentioned PVC calendered leather water-based matte surface treatment agent is as follows: according to weight parts, acrylate-modified water-based polyurethane resin, water-based acrylic (ester) resin, silica matting powder, water, film-forming aid, and defoaming agent are mixed and stirred for 1 hour; the obtained mixture is filtered, and then a wetting agent and a thickener are added to the filtered mixture and stirred for about 20 minutes to obtain the PVC calendered leather water-based matte surface treatment agent.

[0127] Comparative Example 3:

[0128] A water-based matte treatment agent for PVC calendered leather, comprising 30 parts by weight of acrylate-modified water-based polyurethane resin Leasys 3970, 12 parts by weight of water-based acrylic (ester) resin PA-4, 5.0 parts by weight of silica matting powder (ACEMATT 3400), 44.3 parts by weight of water, 4 parts by weight of film-forming aid ethylene glycol butyl ether, 2.5 parts by weight of wetting agent (3248), 0.2 parts by weight of defoaming agent (Tego 815N) and 2.0 parts by weight of thickener (Vesmody U605);

[0129] The preparation method of the above-mentioned PVC calendered leather water-based matte surface treatment agent is as follows: according to weight parts, acrylate-modified water-based polyurethane resin, water-based acrylic (ester) resin, silica matting powder, water, film-forming aid, and defoaming agent are mixed and stirred for 1 hour; the obtained mixture is filtered, and then a wetting agent and a thickener are added to the filtered mixture and stirred for about 20 minutes to obtain the PVC calendered leather water-based matte surface treatment agent.

[0130] Comparative Example 4:

[0131] A water-based matte treatment agent for PVC calendered leather, comprising 27 parts by weight of an acrylate-modified water-based polyurethane resin Leasys 3979, 15 parts by weight of a water-based acrylic (ester) resin PA-5, 5.0 parts by weight of a silica matting powder (ACEMATT 3400), 44.3 parts by weight of water, 4 parts by weight of a film-forming aid ethylene glycol butyl ether, 2.5 parts by weight of a wetting agent (3248), 0.2 parts by weight of a defoaming agent (Tego 815N), and 2.0 parts by weight of a thickener (Vesmody U605);

[0132] The preparation method of the above-mentioned PVC calendered leather water-based matte surface treatment agent is as follows: according to weight parts, acrylate-modified water-based polyurethane resin, water-based acrylic (ester) resin, silica matting powder, water, film-forming aid, and defoaming agent are mixed and stirred for 1 hour; the obtained mixture is filtered, and then a wetting agent and a thickener are added to the filtered mixture and stirred for about 20 minutes to obtain the PVC calendered leather water-based matte surface treatment agent.

[0133] Comparative Example 5:

[0134] A water-based matte treatment agent for PVC calendered leather, comprising 27 parts by weight of an acrylate-modified water-based polyurethane resin Leasys 3979, 15 parts by weight of a water-based acrylic (ester) resin PA-6, 5.0 parts by weight of a silica matting powder (ACEMATT 3400), 44.3 parts by weight of water, 4 parts by weight of a film-forming aid ethylene glycol butyl ether, 2.5 parts by weight of a wetting agent (3248), 0.2 parts by weight of a defoaming agent (Tego 815N), and 2.0 parts by weight of a thickener (Vesmody U605);

[0135] The preparation method of the above-mentioned PVC calendered leather water-based matte surface treatment agent is as follows: according to weight parts, acrylate-modified water-based polyurethane resin, water-based acrylic (ester) resin, silica matting powder, water, film-forming aid, and defoaming agent are mixed and stirred for 1 hour; the obtained mixture is filtered, and then a wetting agent and a thickener are added to the filtered mixture and stirred for about 20 minutes to obtain the PVC calendered leather water-based matte surface treatment agent.

[0136] Comparative Example 6:

[0137] A water-based matte treatment agent for PVC calendered leather, comprising 27 parts by weight of an acrylate-modified water-based polyurethane resin Leasys 3979, 15 parts by weight of a water-based acrylic (ester) resin PA-7, 5.0 parts by weight of a silica matting powder (ACEMATT 3400), 44.3 parts by weight of water, 4 parts by weight of a film-forming aid ethylene glycol butyl ether, 2.5 parts by weight of a wetting agent (3248), 0.2 parts by weight of a defoaming agent (Tego 815N), and 2.0 parts by weight of a thickener (Vesmody U605);

[0138] The preparation method of the above-mentioned PVC calendered leather water-based matte surface treatment agent is as follows: according to weight parts, acrylate-modified water-based polyurethane resin, water-based acrylic (ester) resin, silica matting powder, water, film-forming aid, and defoaming agent are mixed and stirred for 1 hour; the obtained mixture is filtered, and then a wetting agent and a thickener are added to the filtered mixture and stirred for about 20 minutes to obtain the PVC calendered leather water-based matte surface treatment agent.

[0139] Comparative Example 7:

[0140] A water-based matte treatment agent for PVC calendered leather, comprising 27 parts by weight of an acrylate-modified water-based polyurethane resin Leasys 3979, 15 parts by weight of a water-based acrylic (ester) resin PA-8, 5.0 parts by weight of a silica matting powder (ACEMATT 3400), 44.3 parts by weight of water, 4 parts by weight of a film-forming aid ethylene glycol butyl ether, 2.5 parts by weight of a wetting agent (3248), 0.2 parts by weight of a defoaming agent (Tego 815N), and 2.0 parts by weight of a thickener (Vesmody U605);

[0141] The preparation method of the above-mentioned PVC calendered leather water-based matte surface treatment agent is as follows: according to weight parts, acrylate-modified water-based polyurethane resin, water-based acrylic (ester) resin, silica matting powder, water, film-forming aid, and defoaming agent are mixed and stirred for 1 hour; the obtained mixture is filtered, and then a wetting agent and a thickener are added to the filtered mixture and stirred for about 20 minutes to obtain the PVC calendered leather water-based matte surface treatment agent.

[0142] The performance indicators of the obtained water-based matte treatment agent are shown in Table 1.

[0143] Table 1 Performance comparison between the embodiments and comparative examples

[0144]

[0145]

[0146] As shown in Table 1, the water-based matte surface treatment agent for PVC calendered leather of the present invention has the performance characteristics of good temperature resistance and good black haze. After the product is coated on the surface of PVC calendered leather through foaming, absorbing grain and other processes, the leather sample surface effect is finally obtained, which has a uniform effect, good black haze and good comprehensive physical properties.

Claims

1. A water-based matte surface treatment agent for PVC calendered leather, prepared from raw materials comprising the following components: (a) 15-40 parts by weight of an acrylate-modified waterborne polyurethane resin, wherein an acrylate monomer is used in the preparation of the acrylate-modified waterborne polyurethane resin, and the acrylate monomer comprises at least one monomer having a Tg of ≥ 0°C and at least one monomer having a Tg of < 0°C; (b) water-based acrylic (ester) resin, 5-20 parts by weight, (c) Matting powder, (d) water, (e) film-forming aids, (f) wetting agents, (g) defoaming agents, (h) thickeners; The acrylic acid (ester) monomers used in the preparation of the water-based acrylic (ester) resin include conventional monomers and crosslinking monomers; the conventional monomers include at least one monomer with a Tg of ≥ 0°C and at least one monomer with a Tg of < 0°C; the crosslinking monomers include one or more of ethyl acetoacetoxy methacrylate, propyl acetoacetoxy methacrylate, butyl acetoacetoxy methacrylate, and allyl acetoacetate; In the water-based acrylic resin, the mass of the cross-linking monomer accounts for 1%-5% of the total amount of acrylic monomers; the mass of the monomers with Tg≥0°C accounts for 25-60% of the total amount of acrylic monomers; the mass of the monomers with Tg<0°C accounts for 35-70% of the total amount of acrylic monomers.

2. The water-based matte surface treatment agent for PVC calendered leather according to claim 1, characterized in that: It is prepared from the following raw materials in parts by weight: (a) acrylate modified waterborne polyurethane resin, 15-40 parts by weight; (b) water-based acrylic resin, 5-20 parts by weight; (c) matting powder, 3-6 parts by weight; (d) water, 30-70 parts by weight; (e) film-forming aid, 1-8 parts by weight; (f) wetting agent, 1-3 parts by weight; (g) defoamer, 0.1-0.5 weight part; (h) thickener, 0.5-3 parts by weight.

3. The water-based matte surface treatment agent for PVC calendered leather according to claim 1, characterized in that: It is prepared from the following raw materials in parts by weight: (a) acrylate modified waterborne polyurethane resin, 20-30 parts by weight; (b) water-based acrylic resin, 5-10 parts by weight; (c) matting powder, 3.5-5 parts by weight; (d) water, 35-60 parts by weight; (e) film-forming aid, 3-6 parts by weight; (f) wetting agent, 1.5-2.5 parts by weight; (g) defoamer, 0.2-0.4 weight part; (h) thickener, 0.8-1.5 parts by weight.

4. The water-based matte surface treatment agent for PVC calendered leather according to claim 1, characterized in that: The preparation method of the acrylate modified waterborne polyurethane resin comprises the following steps: mixing and dissolving acrylate monomers and isocyanate terminated prepolymers, performing high-speed shear dispersion to obtain a pre-modified emulsion after neutralization reaction, and then adding an initiator to the pre-modified emulsion to initiate polymerization to obtain acrylate modified waterborne polyurethane.

5. The water-based matte surface treatment agent for PVC calendered leather according to claim 1, characterized in that: In the acrylate-modified waterborne polyurethane resin, the monomer with Tg≥0°C is selected from one or more of methyl acrylate, methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate, butyl methacrylate and isobornyl methacrylate; the monomer with Tg<0°C is selected from one or more of ethyl acrylate, hydroxypropyl acrylate, propyl acrylate, butyl acrylate, tetrahydrofuran acrylate and isooctyl acrylate.

6. The water-based matte surface treatment agent for PVC calendered leather according to claim 1, characterized in that: The 100% modulus of the acrylate modified waterborne polyurethane resin after drying and forming a film is 5-18MPa, and the elongation at break is 300%-600%.

7. The water-based matte surface treatment agent for PVC calendered leather according to claim 1, characterized in that: The preparation method of the water-based acrylic (ester) resin comprises the following steps: Adding acrylic acid (ester) monomer, water and emulsifier into a pre-emulsification kettle to prepare a pre-emulsion liquid; Dissolving part of the initiator in water to obtain a dropwise initiator; dissolving the remaining initiator in water to obtain a bottom initiator; Mix the emulsifier and water and add them into the reactor. Stir thoroughly and heat to 80-90°C. Add part of the pre-emulsified liquid, stir evenly and add all the initiator at the bottom of the reactor. React for 10-20 minutes to obtain the seed emulsion. Control the temperature in the reactor to 80-90°C, continue to add the remaining pre-emulsion and initiator to the seed emulsion, add for 2-4 hours, and then keep warm for 20-60 minutes; The reactor was cooled to 70-80°C, and the post-treatment agent was gradually added to the reactor within 20-60 minutes, and then kept warm for 30-60 minutes; the temperature was cooled to below 45°C, and a pH regulator was added to adjust the pH of the system to 7-9, and the material was filtered out.

8. The water-based matte surface treatment agent for PVC calendered leather according to claim 1, characterized in that: In the water-based acrylic (ester) resin, the monomer with Tg≥0°C is selected from one or more of acrylic acid, methyl acrylate, methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate, butyl methacrylate and isobornyl methacrylate; the monomer with Tg<0°C is selected from one or more of ethyl acrylate, hydroxypropyl acrylate, propyl acrylate, butyl acrylate, tetrahydrofuran acrylate and isooctyl acrylate.

9. The water-based matte surface treatment agent for PVC calendered leather according to claim 1, characterized in that: The glass transition temperature of the water-based acrylic (ester) resin is -15°C to 10°C.

10. The water-based matte surface treatment agent for PVC calendered leather according to claim 1, characterized in that: The glass transition temperature of the water-based acrylic (ester) resin is -10°C to 5°C.

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