CN111286261A - Waterborne polyurethane paint for non-polar skin layer and skin product prepared from waterborne polyurethane paint - Google Patents

Waterborne polyurethane paint for non-polar skin layer and skin product prepared from waterborne polyurethane paint Download PDF

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CN111286261A
CN111286261A CN201811487181.XA CN201811487181A CN111286261A CN 111286261 A CN111286261 A CN 111286261A CN 201811487181 A CN201811487181 A CN 201811487181A CN 111286261 A CN111286261 A CN 111286261A
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parts
skin
polyurethane paint
aqueous polyurethane
paint
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徐龙城
刘海洋
滕大勇
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Benecke Changshun Auto Trim Zhangjiagang Co Ltd
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Benecke Changshun Auto Trim Zhangjiagang Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2469/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention relates to a waterborne polyurethane paint A for a non-polar skin layer, which comprises the following components in parts by weight: 50-90 parts of resin R2, 0.1-8 parts of cross-linking agent and 5-33 parts of C2‑C4Alcohol, and 5-30 parts of water. The invention also relates to an aqueous polyurethane paint B for non-polar skin layers, which comprises the following components in parts by weight: 5-50 parts of resin R1, 5-40 parts of resin R2, 5-50 parts of flatting agent and 0.1-8 parts of cross-linking agent5-40 parts of C2‑C4Alcohol, and 1-40 parts of water. The invention also relates to a skin product, in particular to a TPO skin, a TPS skin, an SEBS skin, a TPV skin, a TPAE skin, a TPU skin and the like, which are coated with the waterborne polyurethane paint A and/or the waterborne polyurethane paint B. The waterborne polyurethane paint disclosed by the invention can provide good compatibility with a non-polar material when being coated on the non-polar material, particularly a TPO (thermoplastic polyolefin) skin layer, a TPS (thermoplastic polyolefin) skin layer, an SEBS (styrene-ethylene-butadiene-styrene) skin layer, a TPV (thermoplastic polyolefin) skin layer, a TPAE (thermoplastic polyolefin elastomer) skin layer and a TPU (thermoplastic polyurethane) skin layer.

Description

Waterborne polyurethane paint for non-polar skin layer and skin product prepared from waterborne polyurethane paint
Technical Field
The invention relates to aqueous polyurethane paints for non-polar skin layers. More particularly, the present invention relates to an aqueous polyurethane paint for non-polar thermoplastic elastomer skin layers, particularly olefinic thermoplastic elastomer (also referred to as TPO) skin layers, styrenic thermoplastic elastomer (also referred to as TPS) skin layers, styrenic block copolymer thermoplastic elastomer (also referred to as SEBS) skin layers, thermoplastic vulcanizate (also referred to as TPV) skin layers, polyamide-based thermoplastic elastomer (also referred to as TPAE) skin layers, polyurethane-based thermoplastic elastomer (also referred to as TPU) skin layers, and the like. The invention also relates to a skin product prepared from the waterborne polyurethane paint, in particular to a TPO skin, a TPS skin, an SEBS skin, a TPV skin, a TPAE skin, a TPU skin and the like.
Background
The thermoplastic elastomer is a novel high polymer material between rubber and resin, can replace part of rubber, and can modify plastics. Thermoplastic elastomers have the dual properties of rubber and plastic and broad properties that make them widely used in the rubber industry. Thermoplastic elastomers, which are currently developed and industrially produced in various varieties, include polar thermoplastic elastomer materials such as polyvinyl chloride (also referred to as PVC) and the like, and include non-polar thermoplastic elastomer materials such as TPO, TPS, SEBS, TPV, TPAE, TPU and the like.
The thermoplastic elastomer materials listed above can be widely applied to the fields of buildings, automobiles, home furnishing and the like after being made into skin products. The surface of the thermoplastic elastomer material is usually coated with paint for improving the properties of abrasion resistance, scratch resistance, heat resistance, hand feeling and the like. Paints are typically formulated using organic solvents or water. When solvent-based paints containing toluene, N-ethylpyrrolidone, etc. are used for thermoplastic elastomer materials, the requirements of low toxicity and low harm cannot be met. With the increasing environmental awareness of people, the research on the water-based paint is more and more focused. When the polar water-based paint is applied to a polar PVC material, the water-based paint has good compatibility with the PVC material, and the problem of poor adhesion performance does not exist. However, when the water-based paint is applied to a non-polar material such as TPO, TPS, SEBS, TPV, TPAE, and TPU, the compatibility of the water-based paint with the non-polar material is poor, i.e., the adhesion property of the water-based paint with the non-polar material is poor, and some water-based paints are even difficult to apply to the non-polar material.
Therefore, it is required to develop a water-based paint having good compatibility with nonpolar materials such as TPO, TPS, SEBS, TPV, TPAE, and TPU.
Disclosure of Invention
As noted above, there is a need for new waterborne paint formulations to replace traditional solvent-based paints that provide good compatibility with non-polar materials when applied thereto.
In order to solve the above-mentioned technical problems, in one aspect, the present invention provides an aqueous polyurethane paint a comprising the following components in parts by weight:
50 to 90 parts, for example 50 parts, 60 parts, 70 parts, 80 parts, 90 parts or a content ranging between any two of these values of resin R2,
0.1 to 8 parts, for example 0.1 part, 0.5 part, 0.8 part, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts or a content in the range between any two of these values,
5 to 33 parts, for example 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts or C in a content ranging between any two of these values2-C4Alcohol, and
5 to 30 parts, for example 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts or a content in the range between any two of these values.
In a preferred embodiment of the invention, the aqueous polyurethane paint A comprises the following components in parts by weight: 55-80 parts of resin R2, 0.5-5 parts of cross-linking agent and 8-30 parts of C2-C4Alcohol, and 8-25 parts water.
In another preferred embodiment of the present invention, the aqueous polyurethane paint a comprises the following components in parts by weight: 60-70 parts of resin R2, 0.8-2 parts of cross-linking agent and 10-22 parts of C2-C4Alcohol, and 10-20 parts of water.
In addition, the invention provides a water-based polyurethane paint B, which comprises the following components in parts by weight:
5 to 50 parts, for example, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 38 parts, 39 parts, 40 parts, 41 parts, 42 parts, 43 parts, 44 parts, 45 parts, 46 parts, 47 parts, 48 parts, 49 parts, 50 parts or a content ranging between any of these values, of R1,
5 to 40 parts, for example 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 38 parts, 39 parts, 40 parts or a content in a range between any two of these values of R2,
5 to 50 parts, for example 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 38 parts, 39 parts, 40 parts, 41 parts, 42 parts, 43 parts, 44 parts, 45 parts, 46 parts, 47 parts, 48 parts, 49 parts, 50 parts or a content ranging between any two of these values,
0.1 to 8 parts, for example 0.1 part, 0.5 part, 0.8 part, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts or a content in the range between any two of these values,
5 to 40 parts, for example, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 38 parts, 39 parts, 40 parts or C in a content ranging between any two of these numerical values2-C4Alcohol, and
1 to 40 parts, for example, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 38 parts, 39 parts, 40 parts or a content within a range between any two of these values.
In a preferred embodiment of the invention, the aqueous polyurethane paint B comprises the following components in parts by weight: 8-40 parts of resin R1, 6-30 parts of resin R2, 8-40 parts of flatting agent, 0.5-5 parts of cross-linking agent and 8-30 parts of C2-C4Alcohol, and 8-30 parts of water.
In another preferred embodiment of the present invention, the aqueous polyurethane paint B comprises the following components in parts by weight: 10-35 parts of resin R1, 8-25 parts of resin R2, 10-25 parts of flatting agent, 1-2 parts of cross-linking agent and 12-20 parts of C2-C4Alcohol, and 12-20 parts of water.
Preferably, the resin R1 is a mixed aqueous dispersion of 2,2 '-bis (4-hydroxyphenyl) propane polycarbonate and polyurethane 1, wherein the mass ratio of 2,2' -bis (4-hydroxyphenyl) propane polycarbonate to polyurethane 1: water is 10-40:10-50:40-200, preferably 15-35:15-40:50-150, more preferably 18-30:18-35: 60-120. The aqueous dispersions of the propane polycarbonate and polyurethane 1 additionally comprise a pH adjusting agent, for example an alkanolamine, preferably N, N-dimethylethanolamine, N-methylethanolamine, 2-amino-2-methyl-1-propanol and the like, more preferably N, N-dimethylethanolamine. The mass ratio of the pH regulator to water in the aqueous dispersion is 0.5-2:50-60, preferably 1-1.5:52-58, more preferably 1.2-1.4: 55-56. Preferably, the 2,2' -bis (4-hydroxyphenyl) propane polycarbonate has the formula:
Figure BDA0001894816930000041
wherein n is 10 to 35, preferably 12 to 30, more preferably 15 to 25.
Preferably, the polyurethane 1 has the formula:
(C10H8N2O2·C6H14O3)x，
wherein x is 3 to 35, preferably 5 to 30, more preferably 6 to 20.
The preparation of a dispersion from the 2,2' -bis (4-hydroxyphenyl) propane polycarbonate, polyurethane 1 and water can be carried out according to conventional methods in the art.
Preferably, the resin R2 is an aqueous polyurethane 2 dispersion, wherein the mass ratio of polyurethane 2 to water is 20-40:40-75, preferably 25-38:52-71, more preferably 29-35: 60-70. The aqueous polyurethane 2 dispersion additionally comprises a pH adjusting agent, for example an alkanolamine, preferably N, N-dimethylethanolamine, N-methylethanolamine, 2-amino-2-methyl-1-propanol, etc., more preferably N, N-dimethylethanolamine. The mass ratio of the pH regulator to water in the aqueous dispersion is 0.5-2:50-65, preferably 1-1.5:55-60, more preferably 1.2-1.4: 56-58. The aqueous polyurethane 2 dispersion may additionally comprise a cosolvent, for example an alkanol, preferably selected from the group consisting of ethanol, n-propanol and n-butanol, more preferably n-butanol. The mass ratio of cosolvent to water in the aqueous dispersion is 2-18:50-70, preferably 3-15:52-68, more preferably 4-10: 55-65.
Preferably, the polyurethane 2 has the formula:
(C10H8N2O2·C6H14O3)y，
wherein y is 15 to 31, preferably 18 to 28, more preferably 20 to 25.
The polyurethane 2 is commercially available, for example as the polyurethane resin permotex EVO series, or is prepared according to conventional methods in the art.
The preparation of a dispersion from the polyurethane 2 and water can be carried out according to conventional methods in the art.
Preferably, the crosslinker is an aliphatic polyisocyanate crosslinker, more preferably selected from Hexamethylene Diisocyanate (HDI) -based octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, tetramethylhexane diisocyanate, isophorone diisocyanate (IPDI) -based 2-isocyanatopropylcyclohexyl isocyanate, dicyclohexylmethane 2,4 '-diisocyanate, dicyclohexylmethane 4,4' -diisocyanate, 1, 4-or 1, 3-bis (isocyanatomethyl) cyclohexane, 1, 4-or 1, 3-or 1, 2-diisocyanatocyclohexane and 2, 4-or 2, 6-diisocyanato-1-methylcyclohexane or mixtures of these polyisocyanates, most preferably aliphatic polyisocyanates based on hexamethylene diisocyanate.
Preferably, the matting agent is an epoxy-bearing polyacrylic resin, which is commercially available, for example from basf as astacin novomat GG or from jaba as Pergopak M, or prepared according to conventional methods in the art.
Preferably, said C2-C4The alcohol is selected from the group consisting of ethanol, 1-propanol, isopropanol, tert-butanol and butanol, preferably from the group consisting of 1-propanol, isopropanol and tert-butanol, more preferably isopropanol.
In addition, the aqueous polyurethane paint a and the aqueous polyurethane paint B may further include other components other than the components already described. These components include, for example, typical paint additives, such as antioxidants, deaerators, wetting agents, dispersants, flow control agents, accelerators, such as silane-based accelerators, rheology auxiliaries, such as thickeners, anti-sagging agents and thixotropic agents, waxes and waxy compounds, biocides, delustrants, radical scavengers, light stabilizers, preferably UV absorbers and/or sterically Hindered Amines (HALS) having an absorption maximum below 370nm, corrosion inhibitors, flame retardants or polymerization inhibitors, as well as soluble dyes, pigments, and other fillers or catalysts. The content of such components is in the usual range for them to be from 0.1 to 20% by weight, based on the total amount of the aqueous polyurethane paint. Such components may be present in the aqueous polyurethane paint in a manner conventional in the art.
The waterborne polyurethane paint A can be applied to various non-polar thermoplastic elastomer skin layers, such as TPO, TPS, SEBS, TPV, TPAE, TPU and the like, and particularly TPO skin layers. Preferably, the aqueous polyurethane paint a can be used as a primer.
The waterborne polyurethane paint B can be applied to various non-polar thermoplastic elastomer skin layers, in particular to skin layers of TPO, TPS, SEBS, TPV, TPAE, TPU and the like, and especially to a TPO skin layer. Preferably, the aqueous polyurethane paints B can be used as intermediate paints or top paints.
On the other hand, the invention also provides a skin product prepared from the waterborne polyurethane paint, in particular a TPO skin, a TPS skin, an SEBS skin, a TPV skin, a TPAE skin, a TPU skin and the like.
The skin product prepared from the water-based polyurethane paint can be used for or as vehicle interior materials, and can also be used for furniture such as sofas, wardrobes, soft wall packages and the like.
In another preferred embodiment of the present invention, the present invention provides a TPO skin comprising a TPO skin layer and a waterborne polyurethane paint layer, wherein the waterborne polyurethane paint layer is obtained from the waterborne polyurethane paint of the present invention.
In yet another preferred embodiment of the present invention, the present invention provides a TPO skin comprising a bottom-up sponge layer (e.g., PP sponge, PO sponge, PP-PO sponge, etc.), a TPO skin layer, and a waterborne polyurethane paint layer, wherein the waterborne polyurethane paint layer is obtained from the waterborne polyurethane paint of the present invention.
In still another preferred embodiment of the present invention, the present invention provides a TPO skin comprising a bottom-up base fabric layer, a TPO skin layer, and a waterborne polyurethane paint layer, wherein the waterborne polyurethane paint layer is obtained from the waterborne polyurethane paint of the present invention.
Preferably, the TPO skin layer comprises the following components in parts by weight: 20-40 parts of polyethylene, 20-40 parts of polypropylene, 25-40 parts of ethylene butylene rubber or ethylene propylene rubber, 6-15 parts of stearic acid auxiliary agent and 5-9 parts of color master batch.
The sponge layer can be made of foaming sponge. The foaming sponge may, for example, comprise the following components in parts by weight: 35-60 parts of polypropylene, 40-55 parts of toughening material, 15-25 parts of rubber and 20-30 parts of foaming agent.
Preferably, the toughening material includes polyolefin elastomer POE, copolymer SEPS and expanded polystyrene. The polyolefin elastomer POE is rubber formed by butylene and polyolefin resin, and the copolymer SEPS is a block copolymer formed by styrene and conjugated diene.
Preferably, the rubber comprises nitrile rubber, silicone rubber and ethylene propylene diene monomer rubber.
Preferably, the foaming agent comprises the following components in parts by weight: 5-15 parts of azodicarbonamide, 1-5 parts of p-toluenesulfonyl hydrazide, 25-40 parts of polyethylene glycol, 5-15 parts of triethanolamine, 1-5 parts of sodium bicarbonate and 2-3 parts of pentaerythritol.
The skin product of the invention has no special requirements on the base cloth. One skilled in the art can select a suitable base fabric according to the actual application. For example, the base fabric suitable for the present invention may be a chemical fiber fabric, a polyolefin based chemical material, cotton, hemp, polyester, or the like.
In one embodiment of the present invention, preparing the skin article may include the steps of:
1) preparing a non-polar thermoplastic elastomer skin layer;
2) applying the aqueous polyurethane paint of the present invention to the skin layer, wherein the paint may be applied one or more times, such as two or three times; and
3) the skin layer, on which the aqueous polyurethane paint layer is applied, is composited with an optional sponge layer.
In another embodiment of the present invention, preparing the TPO skin may include the steps of:
1) preparing a TPO skin layer;
2) applying an aqueous polyurethane paint a of the present invention and an aqueous polyurethane paint B of the present invention to the TPO skin layer, wherein paint B may be applied one or more times, such as two or three times; and
3) the TPO skin layer, to which the waterborne polyurethane paint layer is applied, is compounded with an optional sponge layer.
Preferably, in step 1), polyethylene, polypropylene, ethylene butylene rubber or ethylene propylene rubber, stearic acid auxiliary agent and color master batch are uniformly mixed, and are put into an extruder to form a TPO film through extrusion; the TPO film was then corona treated to provide a TPO skin layer.
The waterborne polyurethane paint can provide good compatibility with a TPO skin layer when coated on the TPO skin layer.
Meanwhile, except that VOC meets the VOC requirement of 2000L bag method for TPO skin in Shanghai general, other performances of the TPO skin such as abrasion resistance, scratch resistance, heat resistance, hand feeling and the like can be comparable to those of the traditional solvent-based TPO skin.
Examples
The invention is further illustrated below with reference to examples. These examples are given for the purpose of illustration and description only and are not intended to limit the scope of the present invention in any way.
Unless otherwise specified, the same names for the various materials used in the examples and comparative examples indicate that the same brand and batch were used.
In this specification, unless otherwise stated, percentages, parts, etc. given are by weight.
The resin R1 used was an aqueous mixed dispersion of 2,2' -bis (4-hydroxyphenyl) propane polycarbonate and polyurethane 1 having an average particle diameter of 20 to 80nm, a viscosity of <100 mPa.s at 23 ℃, a mass ratio of polycarbonate to polyurethane 1: water of about 2:3:12, a number average molecular weight of the polycarbonate of 5000g/mol and a number average molecular weight of the polyurethane 1 of 4000 g/mol. The resin R1 additionally contained N, N-dimethylethanolamine. The mass ratio of N, N-dimethylethanolamine to water in the resin R1 was 2.2: 100.
The resin R2 used was an aqueous polyurethane 2 dispersion having a density of 1.01g/ml, a viscosity of 200-750 mPas at 23 ℃, an average particle diameter of <150nm, a solids content of 29% to 35% and a pH of 8.5 to 10, the mass ratio of polyurethane 2 to water being about 7: 12. The number average molecular weight of the polyurethane 2 was 7500 g/mol. The resin R2 additionally contained N, N-dimethylethanolamine. The mass ratio of N, N-dimethylethanolamine to water in the resin R2 was 2.3: 100.
The crosslinker used was a hydrophilic aliphatic polyisocyanate based on hexamethylene diisocyanate, having a viscosity of about 2800 mPas at 25 ℃ as measured by DIN EN ISO 319/A.3, an equivalent weight of about 240 and a density of about 1.16g/ml at 20 ℃.
The matting agent used was Astacin Novomatt GG from Pasteur.
Example 1: preparation of TPO skin comprising aqueous polyurethane paint layer
The first step is as follows: preparation of TPO skin layer
The preparation of TPO skin layers was carried out analogously to CN 107163810A: uniformly mixing 30 parts of polyethylene, 30 parts of polypropylene, 35 parts of ethylene butylene rubber or ethylene propylene rubber, 12 parts of stearic acid auxiliary agent and 8 parts of color master batch in parts by weight, putting into an extruder, and extruding to form a TPO film; then carrying out corona treatment on the TPO film to obtain a TPO skin layer;
the second step is that: water paint formulation and coating
Paint A: mixing 65 parts of resin R2, 15 parts of isopropanol and 15 parts of water, uniformly stirring, and adding 1 part of cross-linking agent to prepare the modified polyurethane;
paint B-1: mixing and stirring uniformly 15 parts of resin R1, 20 parts of resin R2, 15 parts of flatting agent, 15 parts of isopropanol and 15 parts of water, and adding 1.5 parts of cross-linking agent to prepare the polyurethane foam;
and (3) paint B-2: mixing and stirring uniformly 30 parts of resin R1, 10 parts of resin R2, 15 parts of flatting agent, 15 parts of isopropanol and 15 parts of water, and adding 1.5 parts of cross-linking agent to prepare the polyurethane foam;
paint A, B-1 and B-2 are sequentially rolled on the TPO skin layer obtained in the first step by a paint coating machine, and the TPO skin layer is fully dried to obtain a TPO skin material with a water-based polyurethane coating;
the third step: the TPO epidermis layer material that will coat with waterborne polyurethane coating carries out the knurling, and the knurling can laminate the polyolefin sponge layer simultaneously also can not laminate the polyolefin sponge layer, makes the TPO skin.
Comparative example 1:
the preparation of a TPO skin comprising a layer of waterborne polyurethane paint not in accordance with the invention was carried out in the same manner as in example 1, except that instead of R2, a polyurethane resin having a lower viscosity and lower molecular weight than R2 was used in the paint A used and in the paints B-1 and B-2.
Comparative example 2: preparation of TPO skin comprising traditional solvent type polyurethane paint layer
The preparation of a TPO skin including a solvent-borne polyurethane paint layer was performed in the same manner as in example 1, except that toluene and isopropyl alcohol were used as solvents instead of water and isopropyl alcohol.
And (3) performance testing:
1. paint adhesion
The TPO skin prepared according to the examples and comparative examples of the present invention having a width of 2.5cm was adhered to a PP sheet having a width of 2.5cm on the side coated with paint using 502 glue, and the adhesion between the TPO skin and the PP sheet was tested using a tensile machine after 10 minutes. The results are shown in table 1 below:
table 1: paint adhesion
Figure BDA0001894816930000101
As can be seen from Table 1, the paint adhesion of the TPO skin prepared according to the example 1 of the present invention is more than 30N, which can meet the paint adhesion requirement after the part is molded.
2. The VOC test results according to the 2000L bag method of PATAC-001-003 are shown in Table 2 below:
TABLE 2
Figure BDA0001894816930000102
ND: not detected
As can be seen from Table 2, the TPO skin of the present invention including the waterborne polyurethane paint layer has a significantly reduced hazardous material content, as compared to the VOC test using the 2000L bagging method, which meets the VOC requirements of the PATAC2000L TPO skin.
3. The results of the tests for abrasion resistance, scratch resistance, thermal aging resistance, hand, light aging resistance and chemical resistance are shown in table 3 below:
TABLE 3
Figure BDA0001894816930000111
As can be seen from Table 3, the TPO skin comprising the waterborne polyurethane paint layer of the present invention has wear resistance, scratch resistance, light aging resistance comparable to that of the conventional solvent-based TPO skin; the thermal aging resistance is slightly inferior to that of the traditional solvent TPO skin, but the requirement of stricter thermal discoloration resistance can be met; the hand feeling is slightly dry to the traditional solvent TPO skin; the chemical resistance is reduced to a certain extent compared with the traditional solvent-type TPO skin, but the requirement of GMW GS 97034-5 on chemical resistance can still be met.

Claims (10)

1. An aqueous polyurethane paint A for non-polar skin layers, comprising the following components in parts by weight:
50 to 90 parts, preferably 55 to 80 parts, more preferably 60 to 70 parts of resin R2,
0.1 to 8 parts, preferably 0.5 to 5 parts, more preferably 0.8 to 2 parts of a crosslinking agent,
5-33 parts, preferably 8-30 parts, more preferably 10-22 parts of C2-C4Alcohol, and
5-30 parts, preferably 8-25 parts, more preferably 10-20 parts of water.
2. An aqueous polyurethane paint B for non-polar skin layers, comprising the following components in parts by weight:
5 to 50 parts, preferably 8 to 40 parts, more preferably 10 to 35 parts of resin R1,
5 to 40 parts, preferably 6 to 30 parts, more preferably 8 to 25 parts of resin R2,
5 to 50 parts, preferably 8 to 40 parts, more preferably 10 to 25 parts of a matting agent,
0.1 to 8 parts, preferably 0.5 to 5 parts, more preferably 1 to 2 parts of a crosslinking agent,
5-40 parts, preferably 8-30 parts, more preferably 12-20 parts of C2-C4Alcohol, and
1 to 40 parts, preferably 8 to 30 parts, more preferably 12 to 20 parts of water.
3. The aqueous polyurethane paint a according to claim 1 or the aqueous polyurethane paint B according to claim 2, wherein the resin R2 is an aqueous polyurethane 2 dispersion, wherein the mass ratio of polyurethane 2: water is 20-40:40-75, preferably 25-38:52-71, more preferably 29-35:60-70,
wherein the polyurethane 2 has the formula:
(C10H8N2O2·C6H14O3)y，
wherein y is 15 to 31, preferably 18 to 28, more preferably 20 to 25.
4. The aqueous polyurethane paint a or the aqueous polyurethane paint B according to claim 3, wherein the aqueous polyurethane 2 dispersion additionally contains a pH adjuster, such as an alkanolamine, preferably N, N-dimethylethanolamine, N-methylethanolamine, 2-amino-2-methyl-1-propanol, etc., more preferably N, N-dimethylethanolamine, in a mass ratio of pH adjuster to water of 0.5 to 2:50 to 65, preferably 1 to 1.5:55 to 60, more preferably 1.2 to 1.4:56 to 58.
5. The aqueous polyurethane paint B according to any one of claims 2 to 4, wherein the resin R1 is a 2,2' -bis (4-hydroxyphenyl) propane polycarbonate and polyurethane 1 mixed aqueous dispersion, wherein the mass ratio of 2,2' -bis (4-hydroxyphenyl) propane polycarbonate to polyurethane 1: water is 10-40:10-50:40-200, preferably 15-35:15-40:50-150, more preferably 18-30:18-35:60-120, wherein the 2,2' -bis (4-hydroxyphenyl) propane polycarbonate has the following formula:
Figure FDA0001894816920000021
wherein n is 10 to 35, preferably 12 to 30, more preferably 15 to 25,
wherein the polyurethane 1 has the formula:
(C10H8N2O2·C6H14O3)x，
wherein x is 3 to 35, preferably 5 to 30, more preferably 6 to 20.
6. The aqueous polyurethane paint B according to any one of claims 2 to 5, wherein the aqueous dispersions of the propane polycarbonate and polyurethane 1 additionally comprise pH regulators, such as alkanolamines, preferably N, N-dimethylethanolamine, N-methylethanolamine, 2-amino-2-methyl-1-propanol, etc., more preferably N, N-dimethylethanolamine, in a mass ratio of pH regulator to water of 0.5 to 2:50 to 60, preferably 1 to 1.5:52 to 58, more preferably 1.2 to 1.4:55 to 56.
7. The aqueous polyurethane paint a according to any one of claims 1 or 3 to 6 or the aqueous polyurethane paint B according to any one of claims 2 to 6, wherein the crosslinker is an aliphatic polyisocyanate crosslinker, preferably selected from Hexamethylene Diisocyanate (HDI) -based octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, tetramethylhexane diisocyanate, isophorone diisocyanate (IPDI), 2-isocyanatopropylcyclohexyl isocyanate, dicyclohexylmethane 2,4 '-diisocyanate, dicyclohexylmethane 4,4' -diisocyanate, 1, 4-or 1, 3-bis (isocyanatomethyl) cyclohexane, aliphatic polyisocyanates based on 1, 4-or 1, 3-or 1, 2-diisocyanatocyclohexane and 2, 4-or 2, 6-diisocyanato-1-methylcyclohexane or mixtures of these polyisocyanates, more preferably on the basis of hexamethylene diisocyanate.
8. The aqueous polyurethane paint a according to any one of claims 1 or 3-7 or the aqueous polyurethane paint B according to any one of claims 2-7, wherein the matting agent is an epoxy-bearing polyacrylic resin, for example commercially available as Astacin Novomatt GG from basf or as Pergopak M from yabao.
9. The aqueous polyurethane paint A of any one of claims 1 or 3-8 or the aqueous polyurethane paint B of any one of claims 2-8, wherein C2-C4The alcohol is selected from the group consisting of ethanol, 1-propanol, isopropanol, tert-butanol and butanol, preferably from the group consisting of 1-propanol, isopropanol and tert-butanol, more preferably isopropanol.
10. Skin article, in particular a TPO skin, a TPS skin, a SEBS skin, a TPV skin, a TPAE skin, a TPU skin or the like, coated with a water-borne polyurethane paint a according to any one of claims 1 or 3 to 9 and/or a water-borne polyurethane paint B according to any one of claims 2 to 9.
CN201811487181.XA 2018-12-06 2018-12-06 Waterborne polyurethane paint for non-polar skin layer and skin product prepared from waterborne polyurethane paint Pending CN111286261A (en)

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CN107351495A (en) * 2017-05-24 2017-11-17 贝内克-长顺汽车内饰材料（张家港）有限公司 A kind of polychrome TPO automotive interior materials and preparation method thereof
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CN102741307A (en) * 2009-10-15 2012-10-17 拜尔材料科学股份公司 Use of nmp-free coatings for automotive interiors
CN104260517A (en) * 2014-09-18 2015-01-07 东莞市雄林新材料科技股份有限公司 Waterproof moisture-permeable TPU film having drying function and preparation method thereof
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