阅读说明：本技术 一种低光雾度、易清洁反绒沙发家具用聚氨酯合成革及其制备方法 (Low-haze and easy-to-clean polyurethane synthetic leather for suede sofa furniture and preparation method thereof ) 是由 王锐林 王燕武 戴俊 汪飞 章振进 邓向琼 黄万里 于 2020-11-04 设计创作，主要内容包括：本发明公开了一种低光雾度、易清洁反绒沙发家具用聚氨酯合成革及其制备方法,所述聚氨酯合成革由外至内依次包括面层、中间层、贴合层和基布层；所述面层由无DMF软质聚碳溶剂型聚氨酯浆料制成,所述无DMF软质聚碳溶剂型聚氨酯浆料由以下组分按重量份组成：无DMF聚碳溶剂型聚氨酯100份,MEK40-60份,色浆10-20份,高密度低温发泡起绒粉剂3-5份,反应型有机硅助剂2-4份。本发明制备的合成革具有低光雾度、易清洁、绒感强、手感柔软丰满以及环保、耐刮、耐磨和耐水解特点。(The invention discloses polyurethane synthetic leather for low haze and easy-to-clean suede sofa furniture and a preparation method thereof, wherein the polyurethane synthetic leather sequentially comprises a surface layer, a middle layer, a laminating layer and a base cloth layer from outside to inside; the surface layer is prepared from DMF-free soft polycarbonate solvent type polyurethane slurry, and the DMF-free soft polycarbonate solvent type polyurethane slurry comprises the following components in parts by weight: 100 parts of DMF-free polycarbonate solvent-based polyurethane, 10-20 parts of MEK40, 3-5 parts of color paste, 3-5 parts of high-density low-temperature foaming raising powder and 2-4 parts of reactive organosilicon assistant. The synthetic leather prepared by the invention has the characteristics of low haze, easy cleaning, strong velvet feeling, soft and plump hand feeling, environmental protection, scratch resistance, wear resistance and hydrolysis resistance.)

1. The utility model provides a low haze, easy clean anti-polyurethane synthetic leather for fine hair sofa furniture which characterized in that: the fabric comprises a surface layer, a middle layer, a binding layer and a base cloth layer from outside to inside in sequence; the surface layer is prepared from DMF-free soft polycarbonate solvent type polyurethane slurry, and the DMF-free soft polycarbonate solvent type polyurethane slurry is prepared from the following components in parts by weight:

2. the polyurethane synthetic leather with low haze and easy cleaning for the suede sofa furniture, according to claim 1, is characterized in that: the intermediate layer is prepared from DMF-free medium modulus polycarbonate solvent type polyurethane slurry, and the DMF-free medium modulus polycarbonate solvent type polyurethane slurry is prepared from the following components in parts by weight:

3. the polyurethane synthetic leather with low haze and easy cleaning for the suede sofa furniture, according to claim 1, is characterized in that: the adhesive layer is prepared from polyether type solvent-free polyurethane bi-component A/B mixed slurry, and the polyether type solvent-free polyurethane bi-component A/B mixed slurry is prepared from the following components in parts by weight:

4. the polyurethane synthetic leather with low haze and easy cleaning for the suede sofa furniture, according to claim 1, is characterized in that: the base cloth layer is made of polyester double-faced napped cloth, and the thickness of the base cloth layer is 1.1-1.3 mm.

5. The preparation method of the polyurethane synthetic leather for the low haze and easy-to-clean suede sofa furniture, which is described in any one of claims 1-4, is characterized in that: the method comprises the following steps:

(1) coating a layer of DMF-free soft polycarbonate solvent type polyurethane slurry on release paper, and drying to obtain a surface layer;

(2) coating a layer of DMF-free medium modulus polycarbonate solvent type polyurethane slurry on the surface layer, and drying to obtain an intermediate layer on the surface layer;

(3) coating a layer of polyether type solvent-free polyurethane bi-component A/B mixed slurry on the middle layer, heating and drying to a semi-crosslinked state, attaching the mixture to the base cloth, continuously drying and curing, and stripping the release paper to obtain a dry semi-finished product;

(4) putting the dry-method semi-finished product into a high-temperature foaming machine for foaming and napping treatment to obtain a napped semi-finished product;

(5) coating a strong polar solvent on the napping surface of the napping semi-finished product for dissolving treatment to obtain the polyurethane synthetic leather for the anti-napping sofa furniture, which has low haze and is easy to clean; the strong polar solvent is prepared from the following components in parts by weight:

100 parts of 30-50 percent DMF (dimethyl formamide),

6-10 parts of wax powder.

6. The method of claim 5, wherein: in the step (1), the release paper is matte release paper.

7. The method of claim 5, wherein: in the step (1), the viscosity of the DMF-free soft polycarbonate solvent type polyurethane slurry is 2500-3500 cps under the test condition of 25 ℃, and the coating thickness is 15-18 threads; the drying temperature is 90-120 ℃.

8. The method of claim 5, wherein: in the step (2), the viscosity of the DMF-free medium modulus polycarbonate solvent-based polyurethane slurry is 3500-4500 cps at 25 ℃, and the coating thickness is 15-18 filaments; the drying temperature is 90-120 ℃.

9. The method of claim 5, wherein: in the step (3), the viscosity of the polyether type solvent-free polyurethane bi-component A/B mixed slurry is 6000-10000cps under the test condition of 25 ℃, and the coating thickness is 30-35 filaments; the temperature for heating and drying is 80-95 ℃; the temperature for drying and curing is 110-130 ℃.

10. The method of claim 5, wherein: in the step (4), the foaming and raising treatment is carried out at the temperature of 140-160 ℃ for 3-8 min.

Technical Field

The invention belongs to the technical field of synthetic leather preparation, and particularly relates to polyurethane synthetic leather with low haze and easy cleaning for suede sofa furniture and a preparation method thereof.

Background

In recent years, suede leather effect products for sofa furniture are very popular in europe and the mainstream market of the world, but due to factors such as the price of leather materials and the yield limit of leather, the demand of consumers for synthetic leather products with the suede leather effect is more urgent. The leather surface of the traditional suede synthetic leather product has weak suede feeling, is easy to generate flowers, and has poor wear resistance, scraping resistance and hydrolysis resistance. Under the background, the synthetic leather for the anti-velvet sofa furniture, which has the characteristics of strong appearance velvet feeling, soft and plump hand feeling, environmental friendliness, scratch resistance, wear resistance, hydrolysis resistance and the like, is prepared by combining material innovation and process innovation.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide the polyurethane synthetic leather for the anti-fluff sofa furniture, which has low haze and is easy to clean

The purpose of the invention is realized by the following technical scheme:

a polyurethane synthetic leather with low haze and easy cleaning for suede sofa furniture comprises a surface layer, a middle layer, a binding layer and a base cloth layer from outside to inside in sequence; the surface layer is prepared from DMF-free soft polycarbonate solvent type polyurethane slurry, and the DMF-free soft polycarbonate solvent type polyurethane slurry is prepared from the following components in parts by weight:

the weak polar organic solvent is preferably one of Methyl Ethyl Ketone (MEK), ethyl acetate (ETAC) and dimethyl carbonate (DMC); the weak-polarity organic solvent can reduce the viscosity of the material, improve the processability and ensure that the material does not contain DMF and other environmentally-friendly solvents.

Compared with the common foaming fluff powder, the high-density low-temperature foaming fluff powder in the slurry has the characteristics of high fluff strength after the fluff is raised, and excellent wear resistance and scratch resistance. The reactive silicone oil assistant is a novel material grafted with-NCO and-Si groups, the reactive silicone oil assistant and-OH in the DMF-free polycarbonate solvent type polyurethane are subjected to a crosslinking reaction at a temperature of more than 100 ℃, and the-Si groups are grafted on the surface layer polyurethane after crosslinking.

In a further scheme, the intermediate layer is made of DMF-free medium-modulus polycarbonate solvent type polyurethane slurry; the DMF-free medium modulus polycarbon solvent-based polyurethane has the characteristics of environmental protection, soft hand feeling and plump hand feeling after leather is formed due to the characteristics of soft medium modulus and resin structure; the added silicone oil assistant improves the scratch resistance and wear resistance of finished leather; the DMF-free medium modulus polycarbonate solvent-based polyurethane slurry is prepared from the following components in parts by weight:

in a further scheme, the laminating layer is made of polyether type solvent-free polyurethane bi-component A/B mixed slurry, the finished leather made of the polyether type solvent-free polyurethane bi-component A/B mixed slurry is soft and full in hand feeling, and meanwhile, the leather surface is free from cracking and powdering after 70 ℃ 95% RH 7W constant temperature and humidity hydrolysis, and is free from cracking after being warped for 1.5 ten thousand times at normal temperature; the polyether type solvent-free polyurethane bi-component A/B mixed slurry is prepared from the following components in parts by weight:

in a further scheme, the base cloth layer is a polyester double-faced napped cloth with the thickness of 1.1-1.3 mm.

The invention also aims to provide a preparation method of the polyurethane synthetic leather for the anti-fluff sofa furniture, which has low haze and is easy to clean, and comprises the following steps:

(1) coating a layer of DMF-free soft polycarbonate solvent type polyurethane slurry on release paper, and drying to obtain a surface layer; preferably, the release paper is matte release paper; the viscosity of the DMF-free soft polycarbonate solvent type polyurethane slurry is 2500-3500 cps under the test condition of 25 ℃, and the coating thickness is 15-18 filaments; the drying temperature is 90-120 ℃.

(2) Coating a layer of DMF-free medium modulus polycarbonate solvent type polyurethane slurry on the surface layer, and drying to obtain an intermediate layer on the surface layer; preferably, the viscosity of the DMF-free medium modulus polycarbonate solvent-based polyurethane slurry is 3500-4500 cps at 25 ℃, and the coating thickness is 15-18 filaments; the drying temperature is 90-120 ℃.

(3) Coating a layer of polyether type solvent-free polyurethane bi-component A/B mixed slurry on the middle layer, heating and drying to a semi-crosslinked state, attaching the mixture to the base cloth, continuously drying and curing, and stripping the release paper to obtain a dry semi-finished product; preferably, the viscosity of the polyether type solvent-free polyurethane two-component A/B mixed slurry under the test condition of 25 ℃ is 6000-10000cps, and the coating thickness is 30-35 filaments; the temperature for heating and drying is 80-95 ℃; the temperature for drying and curing is 110-130 ℃.

(4) Putting the dry-method semi-finished product into a high-temperature foaming machine for foaming and napping treatment to obtain a napped semi-finished product; preferably, the foaming raising treatment temperature is 140-160 ℃, and the time is 3-8 min.

(5) Coating a strong polar solvent on the napping surface of the napping semi-finished product for dissolving treatment to obtain the polyurethane synthetic leather for the anti-napping sofa furniture, which has low haze and is easy to clean; the dissolving treatment temperature is preferably 80-120 ℃, the time is 1-3min, the strong polar solvent enables the raised surface layer microspheres to be damaged and dissolved through a similar compatibility principle to form diffuse reflection, and the raised surface is endowed with low haze and excellent scratch resistance; the strong polar solvent comprises the following components in parts by weight:

100 parts of 30-50 percent DMF (dimethyl formamide),

6-10 parts of wax powder.

Compared with the prior art, the invention has the beneficial effects that:

1. in the preparation process of the surface layer, on one hand, the high-density low-temperature foaming and napping powder is added, so that the napping strength of the surface layer is high after foaming and napping; on the other hand, the reactive organosilicon auxiliary agent and the DMF-free polycarbonate solvent type polyurethane are subjected to a grafting reaction, so that the surface layer is endowed with excellent wear resistance and scratch resistance, and the touch feeling is tender and smooth; in addition, the raised surface is treated by a strong polar solvent, and by utilizing the principle of similar compatibility, the microspheres on the surface layer of the raised surface can be damaged and dissolved to form diffuse reflection, so that the raised surface is endowed with low haze and excellent scratch resistance; the prepared product has the advantages of reverse velvet appearance effect, and strong velvet feeling and vintage feeling; the product prepared by the method has stronger scratch resistance and wear resistance;

2. compared with the common synthetic leather, the invention has better easy-cleaning performance by wax feeling treatment of the raised surface;

3. the invention selects two-component A/B mixed slurry systems of DMF-free polycarbon solvent-based polyurethane, DMF-free medium modulus polycarbon solvent-based polyurethane and polyether-type solvent-free polyurethane as main raw materials for preparing the surface layer, the intermediate layer and the binding layer respectively, so that the prepared product has higher hydrolysis resistance (the hydrolysis resistance of cracking and powdering resistance of leather surface after constant temperature and humidity hydrolysis of 70 ℃ 95% RH 7W and normal temperature deflection for 1.5 ten thousand times is met).

Detailed Description

The present invention will be further described with reference to the following examples. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The types and suppliers of reagents used in the following examples were as follows:

release paper was purchased from lotheck release paper, japan;

the DMF-free soft polycarbonate solvent type surface layer polyurethane ST-2131 is a self-produced product of Anli new material company;

the DMF-free medium modulus polycarbonate solvent-based polyurethane ST-2132 is a product of Anli new material company;

solvent free A stock CC 6945/100C-A was purchased from Pasteur, Inc.;

solvent-free B stock CC 6945/100C-B was purchased from Pasteur, Inc.;

high density low temperature foaming napping powder was purchased from Beijing Sengtai and science and technology Limited liability company;

the model of the reactive organosilicon auxiliary agent is CHN-3500-U, and is purchased from Xinyue organosilicon International trade (Shanghai) Co., Ltd;

the additive silicone oil additive has the model of ZHB-201, and is purchased from Qingdao Zhongbao silicon material science and technology limited company;

accelerator 93540 and accelerator 93600 were both purchased from Pasteur, Inc.;

wax powder model 3620, purchased from Nanjing Tianshi New materials science and technology Co.

The reagents are provided only for illustrating the sources and components of the reagents used in the experiments of the present invention, so as to be fully disclosed, and do not indicate that the present invention cannot be realized by using other reagents of the same type or other reagents supplied by other suppliers.

Example 1

(1) Selecting release paper DE-7, coating a layer of DMF-free soft polycarbonate solvent type polyurethane slurry with the thickness of 18 threads on the release paper, wherein the viscosity is 3500cps/25 ℃, and drying for 2min at the gradient temperature of 90 ℃, 100 ℃, 110 ℃ and 120 ℃ to form a surface layer;

the DMF-free soft polycarbonate solvent type polyurethane slurry comprises the following components in parts by weight:

(2) coating a layer of 18-filament-thickness DMF-free medium-modulus polycarbon solvent-based polyurethane slurry with the viscosity of 4500cps/25 deg.C on the surface layer, drying at 90 deg.C, 100 deg.C, 110 deg.C and 120 deg.C for 2min, and making an intermediate layer on the surface layer;

the DMF-free medium modulus polycarbonate solvent-based polyurethane slurry comprises the following components in parts by weight:

(3) coating a layer of polyether type solvent-free polyurethane bi-component A/B mixed slurry with the thickness of 30 threads on the obtained middle layer, drying at the temperature of 80 ℃ to be in a semi-dry cross-linked state, attaching 1.2mm double-sided flannelette base cloth, curing at the high temperature of 120 ℃ for 5min, and peeling to form a dry semi-finished product;

the polyether type solvent-free polyurethane bi-component A/B mixed slurry comprises the following components in parts by weight:

(4) carrying out foaming and napping treatment on the dry-method semi-finished product for 5min by a high-temperature foaming machine under the processes of 150 ℃ and 12m/min of vehicle speed to obtain a napped semi-finished product, wherein the high-temperature foaming machine has a good oven sealing property and stable temperature; the specification of the high-temperature foaming machine oven is 30 sections by 1 meter by 2 layers;

(5) dissolving the raised semi-finished product by a strong polar solvent after surface coating to prepare the polyurethane synthetic leather for the anti-raised sofa furniture, which has low haze and is easy to clean;

the strong polar solvent consists of the following components in parts by weight:

100 parts of 30% DMF;

36206 parts.

The synthetic leather prepared by the embodiment has the characteristics of low haze, easiness in cleaning (W (water-based cleaning agent) meeting the cleaning standard of 1969 furniture industry), strong downy feeling, soft and plump hand feeling, environmental protection, scratch resistance (a five-finger scratch tester: no scratch is constant after one-time reciprocating scratch under the action of 10N), wear resistance (20 thousands of Weishibo is not broken), hydrolysis resistance (the hydrolysis resistance of cracking and powdering of the leather surface after hydrolysis at 70 ℃ by 95% RH by 7W at constant temperature and humidity and no cracking after normal-temperature bending for 1.5 thousands of times).

Example 2

(1) Selecting release paper AR-213, coating a layer of DMF-free soft polycarbonate solvent type polyurethane slurry with a thickness of 15 threads on the release paper, wherein the viscosity of the slurry is 3000cps/25 ℃, and drying for 3min at the gradient temperature of 100 ℃, 120 ℃ and 120 ℃ to form a surface layer;

the DMF-free soft polycarbonate solvent type polyurethane slurry comprises the following components in parts by weight:

(2) coating a layer of 15-filament DMF-free medium modulus polycarbon solvent type polyurethane slurry with a viscosity of 4000cps/25 deg.C on the surface layer, drying at 100 deg.C, 120 deg.C and 120 deg.C for 3min to form an intermediate layer on the surface layer;

the DMF-free medium modulus polycarbonate solvent-based polyurethane slurry is prepared from the following components in parts by weight:

(3) coating a layer of polyether type solvent-free polyurethane bi-component A/B mixed slurry with the thickness of 35 filaments on the obtained middle layer, drying at 85 ℃ to be in a semi-dry cross-linked state, attaching 1.2mm double-sided flannelette base cloth, curing at 130 ℃ for 6min, and peeling to form a dry semi-finished product;

the polyether type solvent-free polyurethane bi-component A/B mixed slurry comprises the following components in parts by weight:

(4) carrying out foaming and napping treatment on the dry-method semi-finished product for 3min by a high-temperature foaming machine under the processes of 160 ℃ and 20m/min of speed to obtain a napped semi-finished product, wherein the high-temperature foaming machine has a good oven sealing property and stable temperature; the specification of the high-temperature foaming machine oven is 30 sections by 1 meter by 2 layers;

(5) after the napping semi-finished product is subjected to surface coating and strong polar solvent dissolving treatment, the polyurethane synthetic leather for the anti-napping sofa furniture, which is low in haze and easy to clean, is prepared;

the strong polar solvent consists of the following components in parts by weight:

100 parts of 40% DMF;

36208 parts.

The synthetic leather prepared by the embodiment has the characteristics of low haze, easiness in cleaning (W (water-based cleaning agent) meeting the cleaning standard of 1969 furniture industry), strong downy feeling, soft and plump hand feeling, environmental protection, scratch resistance (a five-finger scratch tester: no scratch is constant after one-time reciprocating scratch under the action of 10N), wear resistance (20 thousands of Weishibo is not broken), hydrolysis resistance (the hydrolysis resistance of cracking and powdering of the leather surface after hydrolysis at 70 ℃ by 95% RH by 7W at constant temperature and humidity and no cracking after normal-temperature bending for 1.5 thousands of times).

Comparative example 1

(1) Selecting release paper DE-43, coating a layer of DMF-free soft polycarbonate solvent-based polyurethane slurry with a thickness of 16 threads on the release paper, wherein the viscosity of the slurry is 2500cps/25 ℃, and drying for 1min at the gradient temperature of 90 ℃, 100 ℃ and 100 ℃ to form a surface layer;

the DMF-free soft polycarbonate solvent type polyurethane slurry comprises the following components in parts by weight:

(2) coating a layer of 18-filament-thickness DMF-free medium modulus polycarbon solvent type polyurethane slurry with the viscosity of 3500cps/25 ℃ on the prepared surface layer, drying for 1min at the gradient temperature of 90 ℃, 100 ℃, 110 ℃ and 120 ℃, and forming an intermediate layer on the surface layer;

the DMF-free medium modulus polycarbonate solvent-based polyurethane slurry is prepared from the following components in parts by weight:

(3) coating a layer of polyether type solvent-free polyurethane bi-component A/B mixed slurry with the thickness of 33 filaments on the obtained middle layer, attaching 1.2mm double-sided flannelette base cloth under the condition of drying to be in a semi-dry cross-linking state at the temperature of 85 ℃, and stripping to form a dry semi-finished product after curing at the high temperature of 130 ℃ for 8 min;

the polyether type solvent-free polyurethane bi-component A/B mixed slurry comprises the following components in parts by weight:

(4) carrying out foaming and napping treatment on the dry-method semi-finished product for 4min by a high-temperature foaming machine under the processes of 160 ℃ and 15m/min of vehicle speed to obtain a napped semi-finished product, wherein the high-temperature foaming machine has a good oven sealing property and stable temperature; the specification of the high-temperature foaming machine oven is 30 sections by 1 meter by 2 layers;

(5) the raised semi-finished product is subjected to surface coating and weak-polarity solvent dissolution treatment to obtain the pile-feeling synthetic leather;

the weak polar solvent comprises the following components in parts by weight:

100 parts of 50% MEK;

the synthetic leather prepared by the embodiment has strong velvet feeling and hydrolysis resistance (meeting the 7-year ASTM D3690 hydrolysis resistance standard), but has the defects of common haze, poor scratch resistance and poor wear resistance, and the cleaning performance of the synthetic leather cannot meet the W (water-based cleaning agent) of the 1969 furniture industry cleaning standard.

The essence of the present invention is not limited to the above embodiments, and those skilled in the art can and should understand that any changes or modifications based on the spirit of the present invention should fall into the protection scope of the present invention.