CN116554624A

CN116554624A - Polyvinyl butyral modified material and preparation method and application thereof

Info

Publication number: CN116554624A
Application number: CN202210109473.XA
Authority: CN
Inventors: 张奇洛
Original assignee: Lidexin Materials Co ltd
Current assignee: Lidexin Materials Co ltd
Priority date: 2022-01-28
Filing date: 2022-01-28
Publication date: 2023-08-08

Abstract

The invention provides a polyvinyl butyral modified material, which comprises a polyvinyl butyral composite material, a first filler, an anti-hydrolysis agent, zinc stearate, calcium stearate, a high molecular dispersing agent, a deodorant, tetramethylthiuram monosulfide and trimethylolpropane tri (3-mercaptopropionic acid) ester, wherein the polyvinyl butyral composite material is obtained by plasticizing a composition containing polyvinyl butyral and a first plasticizer. The invention also provides a preparation method of the polyvinyl butyral modified material and a polyvinyl butyral modified product comprising a polyvinyl butyral modified material layer, wherein the polyvinyl butyral modified material layer is prepared from the material comprising the polyvinyl butyral modified material.

Description

Polyvinyl butyral modified material and preparation method and application thereof

Technical Field

The invention relates to a polyvinyl butyral modified material, a preparation method thereof and a polyvinyl butyral modified product comprising a polyvinyl butyral modified material layer, wherein the polyvinyl butyral modified material layer is prepared from a material comprising the polyvinyl butyral modified material.

Background

Polyvinyl butyral (polyvinyl butyral, PVB) is a resin obtained by condensation reaction of polyvinyl alcohol and butyraldehyde, has good optical transparency and adhesion, and can be combined with surfaces of various different materials. Because of its good optical transparency and good adhesion to glass, it is often combined with glass, such as by adding a sandwich film made of polyvinyl butyral material between glass plates, to produce various safety glass, windshields or flat glass. The glass with the polyvinyl butyral interlayer has good transparency, is impact-resistant, and has wide application in aerospace and automobile industries. However, in the actual production of these glass and polyvinyl butyral interlayer films, polyvinyl butyral residue is often produced. In this case, if the polyvinyl butyral residue is directly discarded, not only a certain influence on the environment is caused, but also waste of the polyvinyl butyral material is caused.

Polyvinyl butyrals are also used in the development of other layered composite materials, which are often used as binders in layered materials because of their relatively high water absorption and tackiness. However, the polyvinyl butyral material has strong water absorption and may deteriorate and damage other materials; in addition, the relatively high viscosity characteristics of the polyvinyl butyral material can limit its use. In particular, the viscosity is high under the high-temperature processing condition, and the processing is not easy to carry out, so that the adhesive has no further application in daily necessities.

Therefore, there is still a need to develop a polyvinyl butyral modified material with improved water resistance, adhesion resistance and high temperature resistance to solve the processing difficulties.

Disclosure of Invention

The water absorption and viscosity of the polyvinyl butyral materials are high, so that the polyvinyl butyral materials are not easy to reuse. The invention provides a polyvinyl butyral modified material, which is prepared by mixing a polyvinyl butyral composite material with other materials and modifying the mixture to obtain the polyvinyl butyral modified material with better water resistance, viscosity resistance and high temperature resistance. The polyvinyl butyral modified material layer can be used alone or combined with different basal layers to prepare various polyvinyl butyral modified products. The polyvinyl butyral composite material can be a polyvinyl butyral film obtained by discarding a glass interlayer, and is used as a main raw material for modification.

The invention provides a polyvinyl butyral modified material, which comprises a polyvinyl butyral composite material, a first filler, an anti-hydrolysis agent, zinc stearate, calcium stearate, a high molecular dispersing agent, a deodorant, tetramethylthiuram monosulfide and trimethylolpropane tri (3-mercaptopropionic acid) ester, wherein the polyvinyl butyral composite material is obtained by plasticizing a composition comprising polyvinyl butyral and a first plasticizer.

According to the invention, the polyvinyl butyral modified material exhibits better water resistance. For example, in certain embodiments, the polyvinyl butyral modified material has a moisture content of 8 wt% or less, 5 wt% or less, or 3 wt% or less absorbed after being placed in warm water for 24 hours.

According to the invention, the polyvinyl butyral modified material exhibits a better resistance to tackiness, in particular at high temperatures. For example, in some embodiments, two films of the polyvinyl butyral modified material are pressed with a weight of 3 kilograms (kg) and do not adhere to each other after heating at 150 ℃ for 120 hours.

According to the invention, the polyvinyl butyral modified material can exhibit better high temperature resistance. For example, in certain embodiments, the film made of the polyvinyl butyral modified material is heated at a temperature of 110 ℃ to less than 180 ℃ without changing the film state or changing color. For example, in certain embodiments, the films made of the polyvinyl butyral modified material can withstand high temperatures of 125 ℃ to 175 ℃, or 125 ℃ to 170 ℃.

In certain embodiments, the proportions of the ingredients in the polyvinyl butyral modified material are as follows: the polyvinyl butyral composite material comprises, by weight, 3 to 15 parts of a first filler, 0.3 to 2.5 parts of an anti-hydrolysis agent, 1.5 to 5 parts of zinc stearate, 0.1 to 1.5 parts of calcium stearate, 0.001 to 0.010 part of a high molecular dispersant, 0.8 to 2.5 parts of a deodorant, 0.1 to 0.2 parts of tetramethylthiuram monosulfide, and 0.001 to 0.005 parts of trimethylolpropane tri (3-mercaptopropionic acid) ester, based on 100 parts by weight of the total content of the polyvinyl butyral composite material; and the first plasticizer is contained in the polyvinyl butyral composite in an amount of 3 to 15 parts by weight based on 100 parts by weight of the total content of the polyvinyl butyral composite.

In certain embodiments, the material of the first filler comprises aluminosilicate crystals (crystalline aluminosilicate). In certain embodiments, the aluminosilicate crystals can be kaolin, a commercially available commodity known as anhydrous transparent powder (anhydrous transparent powder), or a combination thereof. The anhydrous transparent powder has a median diameter of 1.92-30.5 microns, an oil absorption value of 12-25 and a pH value of 7.0. In certain embodiments, the first filler is present in an amount of 3 to 15 parts by weight, or 5 to 13 parts by weight, or 7 to 12 parts by weight, or 9 to 11 parts by weight, based on 100 parts by weight of the total polyvinyl butyral composite. In certain embodiments, the first filler is present in an amount that affects the water absorption of the polyvinyl butyral composite, which is about 3% when 12.5 parts by weight of aluminosilicate crystals are added.

In certain embodiments, the hydrolysis inhibitor material comprises a carbodiimide-based hydrolysis inhibitor (carbodiimide type anti-hydrolysis agents). In certain embodiments, the carbodiimide-based hydrolysis inhibitor comprises carbodiimide (carbodiimide), bis (2, 6-diisopropylphenyl) carbodiimide (bis (2, 6-diisopropylphenyl)) or polycarbodiimides (polycarbodiimides) or a combination thereof. In certain embodiments, the anti-hydrolysis agent is present in an amount of 0.3 to 2.5 parts by weight, or 0.5 to 2 parts by weight, or 1 to 1.5 parts by weight, based on 100 parts by weight total of the polyvinyl butyral composite.

In certain embodiments, the material of the first plasticizer is a material comprising a bis2-ethylhexanoate plasticizer type plasticizers, a phthalate plasticizer phthalate type plasticizers, an adipate plasticizer adipate type plasticizers, or a combination thereof. In certain embodiments, the bisisooctanoate-based plasticizer comprises triethylene glycol bisisooctanoate (triethylene glycol bis). In certain embodiments, the phthalate plasticizer comprises di (2-propylheptyl) phthalate (DPHP). In certain embodiments, the adipate plasticizer comprises GLOBINEX W-2370. In certain embodiments, the first plasticizer is present in an amount of 3 to 15 parts by weight, or 5 to 12 parts by weight, or 7 to 10 parts by weight, based on 100 parts by weight of the total polyvinyl butyral composite. In some embodiments, the polyvinyl butyral modified material may further comprise a second plasticizer. The material of the second plasticizer may be selected from the same group as the first plasticizer, and the second plasticizer and the first plasticizer may be the same or different. In certain embodiments, the second plasticizer is present in an amount of 2.5 to 20 parts by weight, or 3 to 18 parts by weight, or 5 to 15 parts by weight, or 7 to 10 parts by weight, based on 100 parts by weight of the total polyvinyl butyral composite. The addition of the second plasticizer may make the polyvinyl butyral modified material softer.

In certain embodiments, zinc stearate and calcium stearate are used as lubricants. In certain embodiments, the zinc stearate is present in an amount of 1.5 to 5 parts by weight, or 2 to 4 parts by weight, or 2.5 to 3.6 parts by weight, or 2.8 to 3.2 parts by weight, based on 100 parts by weight of the total polyvinyl butyral composite. In certain embodiments, the calcium stearate is present in an amount of 0.1 to 1.5 parts by weight, or 0.2 to 1.2 parts by weight, or 0.4 to 1 part by weight, or 0.5 to 0.7 parts by weight, based on 100 parts by weight of the total polyvinyl butyral composite. In some embodiments, the combination of the two lubricants in the amounts described above provides a reduction in viscosity and thus provides better handling and no sticking of the materials to the machine during manufacture.

In certain embodiments, the polymeric dispersant material comprises polysiloxanes (polysiloxanes), high melting point waxes (high melting-point waxes), or combinations thereof. In certain embodiments, the polysiloxanes comprise silicone oils (silicone oils), hydrogen-containing silicone oils (hydrogen silicone oil), high hydrogen-containing silicone oils (methylhydroginsenosides), or combinations thereof. In certain embodiments, the silicone oil comprises polydimethylsiloxane (polydimethyliloxane). In certain embodiments, the high melting wax comprises stearamides, such as stearamide, ethylene bis (stearamide), or combinations thereof. In certain embodiments, the polymeric dispersant is present in an amount of 0.001 to 0.010 parts by weight, or 0.002 to 0.007 parts by weight, or 0.003 to 0.005 parts by weight, based on 100 parts by weight total of the polyvinyl butyral composite. The addition of the polymeric dispersant can make the polyvinyl butyral modified material more wear-resistant.

In certain embodiments, the material of the odor eliminator comprises sodium bicarbonate, a porous inorganic silicate, or a combination thereof. In certain embodiments, the odor eliminator is present in an amount of 0.8 to 3.0 parts by weight, or 2.3 to 2.5 parts by weight, based on 100 parts by weight of the total polyvinyl butyral composite. In certain embodiments, the odor eliminator is a combination of sodium bicarbonate and a porous inorganic silicate in a weight ratio of 2:1 to 1.8:1, or 15:8. the addition of the deodorant can eliminate the pungent smell and bring dry and comfortable hand feeling to the finally prepared polyvinyl butyral modified material film.

In certain embodiments, the tetramethylthiuram monosulfide (tetramethylthiuram monosulfide, TMTM) is present in an amount of 0.1 to 0.2 parts by weight, 0.12 to 0.15 parts by weight, based on 100 parts by weight total of the polyvinyl butyral composite. The addition of tetramethylthiuram monosulfide can make the polyvinyl butyral modified material more resistant to high temperature and adhesion, and has excellent scorch resistance without causing discoloration.

In certain embodiments, trimethylolpropane tris (3-mercaptopropionic acid) ester is used as the polymerization modifier. In certain embodiments, the trimethylolpropane tri (3-mercaptopropionate) is present in an amount of from 0.001 parts by weight to 0.005 parts by weight, or from 0.002 parts by weight to 0.003 parts by weight, based on 100 parts by weight of the total polyvinyl butyral composite. In some embodiments, the addition of trimethylolpropane tri (3-mercaptopropionate) can increase the peel strength of films made from the polyvinyl butyral modified material and provide better fusion of materials in the formulation and less tendency to precipitate.

In certain embodiments, the polyvinyl butyral modified material may further comprise polyvinyl alcohol (polyvinyl alcohol, PVA) to adjust the hardness of the product. The amount of the polyvinyl alcohol added is not particularly limited, and the content of the polyvinyl alcohol is more than 0 to 40 parts by weight, or 5 to 35 parts by weight, or 10 to 30 parts by weight, or 15 to 20 parts by weight, based on 100 parts by weight of the total content of the polyvinyl butyral composite. In certain embodiments, the polyvinyl alcohol is a polyvinyl alcohol powder. The addition of polyvinyl alcohol can increase the hardness of the polyvinyl butyral modified material.

In certain embodiments, the polyvinyl butyral modified material may further comprise a second filler. In certain embodiments, the material of the second filler comprises calcium carbonate. In certain embodiments, the calcium carbonate is present in an amount of 5 to 160 parts by weight, or 20 to 100 parts by weight, or 25 to 50 parts by weight, based on 100 parts by weight of the total content of the polyvinyl butyral composite.

In certain embodiments, the polyvinyl butyral modified material may further comprise a cold-resistant agent. In certain embodiments, the cold-resistant material comprises an adipate-based cold-resistant agent (adipate type cold-resistive agents), polyisobutylene (polyisobutene), or a combination thereof. In certain embodiments, the adipate based cold-resistance agent comprises dioctyl adipate (dioctyl adipates), diisononyl adipate (diisononyl adipate), or a combination thereof. In certain embodiments, the cold-resistant agent is present in an amount of 1.5 to 10 parts by weight, or 2 to 8 parts by weight, or 5 to 6 parts by weight, based on 100 parts by weight of the total content of the polyvinyl butyral composite. In certain embodiments, the cold-resistant agent is a combination of an adipate-based cold-resistant agent and polyisobutylene, wherein the adipate-based cold-resistant agent: the weight ratio of polyisobutene is 1:1. in certain embodiments, the cold-resistant agent is a combination of dioctyl adipate and polyisobutylene, wherein the weight ratio of dioctyl adipate to polyisobutylene is 1:1. in certain embodiments, the cold-resistant agent is a combination of diisononyl adipate and polyisobutylene in a weight ratio of 1:1.

In certain embodiments, the polyvinyl butyral-modified material may further comprise an antioxidant. In certain embodiments, the antioxidant material comprises pentaerythritol esters antioxidants (pentaerythritol ester type anti-oxidans), phosphite antioxidants (phosphite type anti-oxidans), hexamethylenediamine antioxidants (hexamethylenediamine type anti-oxidans), or combinations thereof. In certain embodiments, the pentaerythritol ester antioxidant comprises pentaerythritol tetrakis (3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate) (pentaerythritol tetrakis, i.e., antioxidant 1010). In certain embodiments, the phosphite antioxidant comprises tris (2, 4-di-t-butylphenyl) phosphite (i.e., antioxidant 168). In certain embodiments, the hexamethylenediamine-based antioxidant comprises N, N' -bis (3, 5-di-t-butyl-4-hydroxyphenylpropionyl) hexamethylenediamine (i.e., antioxidant 1098). In certain embodiments, the antioxidant is present in an amount of 0.5 to 2.5 parts by weight, or 1 to 2 parts by weight, or 1.5 to 1.8 parts by weight, based on 100 parts by weight total of the polyvinyl butyral composite. The addition of the antioxidant can delay the aging of the polyvinyl butyral modified material and improve the service life of the product.

In certain embodiments, the polyvinyl butyral modified material may further comprise an ultraviolet light resistant agent. In certain embodiments, the UV resistant material comprises a benzotriazole-based UV resistant agent (benzotriazole type anti-ultraviolet agents), a benzophenone-based UV resistant agent (benzophenonetype anti-ultraviolet agents), or a combination thereof. In certain embodiments, the benzotriazole-based anti-uv agent comprises octreozole (i.e., anti-uv agent 329). In certain embodiments, the benzophenone-based uv-blocking agent comprises 2-hydroxy-4-n-octoxy-benzophenone (2-hydroxy-4-n-octoxy-benzophenone, uv-blocking agent 531). In certain embodiments, the uv resistant agent is present in an amount of 0.1 to 1.5 parts by weight, or 0.3 to 1 parts by weight, or 0.5 to 0.75 parts by weight, based on 100 parts by weight total of the polyvinyl butyral composite. The addition of the ultraviolet resistance agent can strengthen the weather resistance of the polyvinyl butyral modified material.

In certain embodiments, the polyvinyl butyral-modified material may further comprise a colorant. In certain embodiments, the colorant is present in an amount of 0.5 to 35 parts by weight, or 1 to 30 parts by weight, or 5 to 20 parts by weight, or 10 to 16 parts by weight, based on 100 parts by weight of the total polyvinyl butyral composite. In certain embodiments, the colorant comprises inorganic colorants of various colors, which may be formulated as desired.

In certain embodiments, the polyvinyl butyral modified material may further comprise a flame retardant. In certain embodiments, the flame retardant is present in an amount of 1 to 15 parts by weight, or 3 to 8 parts by weight, based on 100 parts by weight total of the polyvinyl butyral composite. In certain embodiments, the material of the flame retardant comprises zinc stannate, zinc hydroxystannate, or a combination thereof. In certain embodiments, the material of the flame retardant is a combination of zinc stannate and zinc hydroxystannate, wherein zinc stannate: the weight ratio of the zinc hydroxystannate is 1:1. zinc stannate and zinc hydroxystannate are mainly used as flame retardants and smoke inhibitors in the plastic industry, are nontoxic, safe and easy-to-use environment-friendly products, and have wide application range, and mainly depend on the operation temperature.

In certain embodiments, the polyvinyl butyral modified material may further comprise a glass frit. In certain embodiments, the glass frit is present in an amount of 3 to 15 parts by weight, or 6 to 12 parts by weight, or 8 to 10 parts by weight, based on 100 parts by weight of the total content of the polyvinyl butyral composite. In certain embodiments, the glass frit material comprises a low melting glass frit. In certain embodiments, the low melting glass frit material comprises borosilicate glass. In some embodiments, when the glass powder is further included in the polyvinyl butyral modified material, the surface structure and the surface energy of the material can be improved, micro-or nano-sized pores are formed on the surface, the inking area is enlarged, a good interface environment is provided for the ink and the adhesive, the curing adhesion force and the color difference of the ink are further improved, and meanwhile, the color migration and the color change caused by environmental impact after the ink is cured are improved, so that printing can be performed on the surface of an article prepared from the polyvinyl butyral modified material. In certain embodiments, the polyvinyl butyral modified material produces an article that is a film of polyvinyl butyral modified material.

In certain embodiments, the polyvinyl butyral-modified material may further comprise a foaming agent. In certain embodiments, the blowing agent is present in an amount of 2 to 10 parts by weight, or 3 to 8 parts by weight, or 5 to 7 parts by weight, based on 100 parts by weight of the total polyvinyl butyral composite. In some embodiments, the blowing agent is azodicarbonamide (AC blowing agent), which is a high temperature blowing agent. In certain embodiments, the blowing agent azodicarbonamide also has the effect of deodorizing by the deodorizing agent and providing dry feel to the finally prepared polyvinyl butyral modified material film; the azodicarbonamide can form a layer of oily surface on the surface of the polyvinyl butyral modified material film, so that the friction coefficient of the material surface is reduced, and good hand feeling is achieved. In some embodiments, the polyvinyl butyral modified material comprises azodicarbonamide, and after the polyvinyl butyral modified material layer is produced, further foaming treatment is performed by using high temperature (such as 190 ℃ to 250 ℃ and 250 ℃ can be completely reacted) to obtain a foamed polyvinyl butyral modified material layer.

In certain embodiments, the polyvinyl butyral modified material may further comprise a thermoplastic polyurethane (thermoplastic polyurethane, TPU) elastomer. In certain embodiments, the thermoplastic polyurethane elastomer is present in an amount of 5 to 15 parts by weight, or 8 to 10 parts by weight, based on 100 parts by weight total of the polyvinyl butyral composite. In some embodiments, the addition of a suitable amount of thermoplastic polyurethane elastomer to the polyvinyl butyral modified material improves the micromechanics (tear strength, snap strength, deformation mechanics, etc.) of the material, while improving the stress relief and shrinkage ratio due to linear exotherm during resin curing, and thus improves dimensional stability.

In certain embodiments, the polyvinyl butyral composite is a polyvinyl butyral remainder. In some embodiments, the polyvinyl butyral remainder is a remainder of glass comprising a polyvinyl butyral interlayer film, but the glass is rejected prior to use. In some embodiments, the polyvinyl butyral remainder is the remainder of a polyvinyl butyral interlayer film. Therefore, the invention can recycle the waste residue to meet the environmental protection requirement of modern people.

In certain embodiments, the polyvinyl butyral-modified material is in the form of particles. In certain embodiments, the particles of the polyvinyl butyral modified material have a diameter of 2 millimeters (mm) to 8mm and a length of 3mm to 8mm. In certain embodiments, the particles of the polyvinyl butyral modified material have a diameter of 5mm and a length of 6mm. The particles of the polyvinyl butyral modified material may be sized to granulate as desired.

In some embodiments, the polyvinyl butyral modified material is produced by mixing the ingredients and modifying the mixture. In some embodiments, the polyvinyl butyral modified material is obtained by mixing the ingredients and then modifying the ingredients multiple times. In some embodiments, the polyvinyl butyral modified material is obtained by mixing the ingredients and then modifying at least twice. In certain embodiments, the temperature of each of the foregoing modifications may be the same or different.

Another object of the present invention is to provide a method for preparing a polyvinyl butyral modified material as described above, comprising the steps of:

(S1) mixing the components comprising the polyvinyl butyral composite material, a first filler, an anti-hydrolysis agent, zinc stearate, calcium stearate, a high molecular dispersing agent, a deodorant, tetramethylthiuram monosulfide and trimethylolpropane tri (3-mercaptopropionic acid) ester, and mixing at 165-175 ℃ for 5-10 minutes to obtain a crude polyvinyl butyral modified material;

(S2) filtering the crude polyvinyl butyral modified material at 150-170 ℃ with a 140-160 mesh screen to obtain the polyvinyl butyral modified material.

In certain embodiments, the foregoing step (S1) is performed in an internal mixer or a ten thousand horsepower machine. In certain embodiments, the aforementioned step (S1) is performed at 170 ℃.

In certain embodiments, step (S2) is performed at least twice. In certain embodiments, step (S2) is filtered at least three times. In certain embodiments, the screen of step (S2) is a 150 mesh screen.

In certain embodiments, the aforementioned step (S2) is performed in a granulator. In certain embodiments, the aforementioned step (S2) is performed in a filter. In certain embodiments, the crude polyvinyl butyral modified material is rolled into a sheet with a roller mill and cut into flexible strips prior to filtration with the filter, facilitating filtration. In certain embodiments, after filtration with the filter, the polyvinyl butyral modified material is rolled into a sheet with a roller mill and cut into flexible strips for subsequent processing. The crude polyvinyl butyral modified material or the polyvinyl butyral modified material is rolled into a sheet with a rolling mill and cut into soft strips for physical processing only without affecting the properties of the polyvinyl butyral modified material. The step (S2) is for filtering out impurities, especially impurities in PVB residue. The PVB remainder is a recycled material and impurities must be removed by the aforementioned step (S2) to obtain a PVB modified material of uniform quality. The arrangement and the filtering times of the production online machine can be adjusted according to the raw material sources and the product demands.

In certain embodiments, the foregoing method further comprises the steps of: (S3) granulating the filtered polyvinyl butyral modified material through a die to obtain granules of the polyvinyl butyral modified material.

In certain embodiments, the particles of the polyvinyl butyral modified material have a diameter of 2mm to 8mm and a length of 3mm to 8mm. The size of the polyvinyl butyral modified material particles can be granulated as desired.

It is another object of the present invention to provide a polyvinyl butyral modified product comprising a layer of polyvinyl butyral modified material made from a material comprising a polyvinyl butyral modified material as described above. In certain embodiments, the layer of polyvinyl butyral modified material is a layer of polyvinyl butyral modified material produced by casting particles of the polyvinyl butyral modified material. In certain embodiments, the layer of polyvinyl butyral modified material may be a cast layer or a calendered layer.

In some embodiments, the polyvinyl butyral modified product further comprises a substrate layer disposed on the polyvinyl butyral modified material layer, wherein the substrate layer is selected from the group consisting of a fabric layer, a metal component-containing plastic layer, a metal component-free plastic layer, and combinations thereof.

In some embodiments, the fabric layer may be a woven, knitted or non-woven fabric (non-woven fabric). In some embodiments, the woven fabric is Oxford fabric. In some embodiments, the fabric layer is made of natural materials (such as cotton, hemp, jute, flax, wool, etc.), synthetic fiber materials (such as polyester, polyamide, etc.), or blends of the foregoing materials. In some embodiments, the fabric layer made of polyester fibers is polyester fabric. In some embodiments, the fabric layer made of polyamide fibers is nylon. In some embodiments, the woven fabric is a mesh fabric. In some embodiments, the nonwoven fabric is a mesh fabric.

In some embodiments, the material of the plastic layer without metal component can be a common plastic type for fabrics, such as polyethylene terephthalate (polyethylene terephthalate, PET) and Polyurethane (PU).

In some embodiments, the metal-containing plastic layer may be an aluminum-containing plastic layer, such as an aluminum-plated PET film. In certain embodiments, the aluminized PET film is 0.02 wt.% aluminum plated on the PET film.

In certain embodiments, the polyvinyl butyral modified articles described above further comprise one or more adhesive layers. In some embodiments, each layer of polyvinyl butyral modified material further comprises an adhesive layer between each layer of polyvinyl butyral modified material and each base layer, which is comprised of an adhesive. In certain embodiments, the adhesive is used in an amount of 20 grams per square meter (g/m ² ) Above (e.g. 20 g/m) ² To 50g/m ² ) When in use, the solvent in the adhesive needs to be baked and removed. In some embodiments, when the amount of the adhesive is less than 20g/m ² (e.g. 4g/m ² To 18g/m ² 、6g/m ² To 16g/m ² 、8g/m ² To 12g/m ² 、10g/m ² To 11g/m ² ) When the adhesive layer on the substrate layer is directly contacted with the high-temperature polyvinyl butyral modified material in the casting step and after the step of casting, the solvent in the adhesive is not required to be bakedThe solvent in the adhesive layer can be removed.

In some embodiments, each adhesive layer is independently composed of a mixture of glue and cross-linking agent. In certain embodiments, the glue material comprises polyurethane glue, acrylic glue, or a combination thereof. In certain embodiments, the crosslinker material comprises a urethane prepolymer-based crosslinker (urethane prepolymer crosslinking agent). In certain embodiments, the crosslinker is present in an amount of 1.5 to 9 parts by weight, or 2 to 8 parts by weight, based on 100 parts by weight total of the glue.

In some embodiments, when the fabric layer is a non-woven fabric made of polypropylene or a knitted fabric made of cotton, polyester or a blend of polyester and cotton, there may be no adhesive layer between the fabric layer and the polyvinyl butyral modified material layer. In some embodiments, when the fabric layer is oxford or dacron, an adhesive layer is provided between the fabric layer and the polyvinyl butyral modified material layer.

In certain embodiments, the layer of polyvinyl butyral modified material is further foamed. In certain embodiments, the foaming agent (azodicarbonamide) is added in step (S1) to produce the polyvinyl butyral modified material layer, and then the polyvinyl butyral modified material layer is foamed at a high temperature to produce the foamed polyvinyl butyral modified material layer. In some embodiments, the polyvinyl butyral modified material (excluding azodicarbonamide) is mixed with azodicarbonamide to form a layer of polyvinyl butyral modified material, which is then foamed to form a foamed layer of polyvinyl butyral modified material. In certain embodiments, the polyvinyl butyral modified material (excluding azodicarbonamide) and azodicarbonamide in the foregoing mixtures are particulates.

It is another object of the present invention to provide a process for preparing a polyvinyl butyral modified article as described hereinbefore comprising the steps of: casting the polyvinyl butyral modified material as described above to form a first layer of polyvinyl butyral modified material. In certain embodiments, the method of making a polyvinyl butyral modified article further comprises the step of cooling the resulting article to form, and separating rolls.

In some embodiments, the first layer of polyvinyl butyral modifying material is cast onto a first substrate layer. In certain embodiments, the step of casting and forming the first layer of polyvinyl butyral modified material is preceded by the step of: and coating an adhesive on the first substrate layer to form a first adhesive layer, wherein the first adhesive layer is positioned between the first polyvinyl butyral modified material layer and the first substrate layer. In certain embodiments, the method of making a polyvinyl butyral modified article further comprises the step of cooling the resulting article to form, and separating rolls.

In certain embodiments, the method of making a polyvinyl butyral modified article further comprises the steps of: and casting the polyvinyl butyral modified material on the other surface of the first substrate layer to form a second polyvinyl butyral modified material layer, so as to obtain a polyvinyl butyral modified product with a substrate layer consisting of the first polyvinyl butyral modified material layer and the second polyvinyl butyral modified material layer Bao Gadi. In certain embodiments, the method further comprises the steps of, prior to casting and forming the second layer of polyvinyl butyral modifying material: and coating an adhesive on the other side of the first substrate layer to form a second adhesive layer, wherein the second adhesive layer is positioned between the second polyvinyl butyral modified material layer and the first substrate layer. In certain embodiments, the method of making a polyvinyl butyral modified article further comprises the step of cooling the resulting article to form, and separating rolls.

In certain embodiments, the method of making a polyvinyl butyral modified article further comprises the steps of: and covering a second substrate layer on the first polyvinyl butyral modified material layer to obtain a polyvinyl butyral modified product with the first polyvinyl butyral modified material layer sandwiched by the first substrate layer and the second substrate layer. In some embodiments, the first layer of polyvinyl butyral modified material is thermally laminated to the second substrate layer. In certain embodiments, the method further comprises the steps of, prior to covering the second substrate layer: and coating an adhesive on the second substrate layer to form a third adhesive layer, wherein the third adhesive layer is positioned between the first polyvinyl butyral modified material layer and the second substrate layer. In certain embodiments, the method of making a polyvinyl butyral modified article further comprises the step of cooling the resulting article to form, and separating rolls.

In some embodiments, the polyvinyl butyral modifying material may be repeatedly cast onto the first layer of polyvinyl butyral modifying material to form a thicker first layer of polyvinyl butyral modifying material. In some embodiments, the polyvinyl butyral modifying material may be repeatedly cast onto the second layer of polyvinyl butyral modifying material to form a thicker second layer of polyvinyl butyral modifying material. In some embodiments, the casting step may be repeated to form a thicker layer of the polyvinyl butyral modified material, followed by subsequent steps (e.g., foaming, embossing, shaping, separating, or a combination thereof). In certain embodiments, the thickness of the layer of polyvinyl butyral modified material formed by each casting is from 0.05mm to 0.5mm, and the number of casting times can be determined according to the thickness of the layer of polyvinyl butyral modified material desired for the final product.

It is another object of the present invention to provide a process for preparing a polyvinyl butyral modified article as described hereinbefore comprising the steps of: calendering the polyvinyl butyral modified material as described above forms a first layer of polyvinyl butyral modified material. In certain embodiments, the method of making a polyvinyl butyral modified article further comprises the step of cooling the resulting first layer of polyvinyl butyral modified material to form and reel.

In some embodiments, the first polyvinyl butyral modified material layer is thermally pressed against a first substrate layer to form a polyvinyl butyral modified product comprising the first polyvinyl butyral modified material layer and the first substrate layer. In certain embodiments, the method further comprises the steps of, prior to hot press fitting the first layer of polyvinyl butyral modified material to the first substrate layer: and coating an adhesive on the first substrate layer to form a first adhesive layer, wherein the first adhesive layer is positioned between the first polyvinyl butyral modified material layer and the first substrate layer. In certain embodiments, the method of making a polyvinyl butyral modified article further comprises the step of cooling the resulting article to form, and separating rolls.

In certain embodiments, the method of making a polyvinyl butyral modified article further comprises the steps of: and (3) performing hot pressing lamination on the polyvinyl butyral modified product comprising the first polyvinyl butyral modified material layer and the first substrate layer and a second polyvinyl butyral modified material layer to obtain a polyvinyl butyral modified product with a substrate layer of the first polyvinyl butyral modified material layer and the second polyvinyl butyral modified material layer Bao Gadi. In certain embodiments, the method further comprises the following steps prior to hot press lamination with the second polyvinyl butyral modified material layer: and coating an adhesive on the other side of the first substrate layer to form a second adhesive layer, wherein the second adhesive layer is positioned between the second polyvinyl butyral modified material layer and the first substrate layer. In certain embodiments, the method of making a polyvinyl butyral modified article further comprises the step of cooling the resulting article to form, and separating rolls.

In certain embodiments, the method of making a polyvinyl butyral modified article further comprises the steps of: and (3) the polyvinyl butyral modified product comprising the first polyvinyl butyral modified material layer and the first substrate layer is further bonded with a second substrate layer through hot pressing, so that a polyvinyl butyral modified product with the first polyvinyl butyral modified material layer sandwiched by the first substrate layer and the second substrate layer is obtained. In some embodiments, the method further comprises the following steps before the second substrate layer is thermally pressed and bonded to the first substrate layer: and coating an adhesive on the first polyvinyl butyral modified material layer to form a third adhesive layer, wherein the third adhesive layer is positioned between the first polyvinyl butyral modified material layer and the second substrate layer. In certain embodiments, the method of making a polyvinyl butyral modified article further comprises the step of cooling the resulting article to form, and separating rolls.

In some embodiments, the hot press may be repeated on the first layer of polyvinyl butyral modified material to bond with other layers of polyvinyl butyral modified material to form a thicker layer of first polyvinyl butyral modified material. In some embodiments, the hot press may be repeated on the second layer of polyvinyl butyral modified material to conform to other layers of first polyvinyl butyral modified material to form a thicker second layer of polyvinyl butyral modified material. In some embodiments, the hot pressing may be repeated to bond other polyvinyl butyral modified material layers to form a thicker polyvinyl butyral modified material layer, and then subsequent steps (such as foaming, embossing, shaping, separating, or a combination thereof) may be performed. In some embodiments, the thickness of the polyvinyl butyral modified material layer formed by each calendering is 0.05mm to 1.2mm, and the number of times of repeated hot press attachment can be determined according to the thickness of the polyvinyl butyral modified material layer required by the final product.

In certain embodiments, the method of making a polyvinyl butyral modified article further comprises the steps of: the first polyvinyl butyral modified material layer and/or the second polyvinyl butyral modified material layer are subjected to embossing treatment and/or foaming treatment.

In some embodiments, the materials of the first and second substrate layers may be the same or different. The materials of each substrate layer are as described above.

In some embodiments, the materials of the first, second and third adhesive layers may be the same or different. The material of each adhesive layer is as described above.

From the above, the PVB residual material modified material provided by the invention has good water resistance, viscosity resistance and high temperature resistance, and can be used for producing PVB modified products containing PVB modified material layers prepared from the PVB modified material by a tape casting or calendaring mode. In addition, the PVB remainder modified material can be prepared by utilizing PVB remainder, and waste materials which are originally discarded are reused, so that the environment-friendly requirement of a new era is met.

Drawings

Fig. 1 is a schematic view of a manufacturing line for PVB modified materials of the present invention.

Fig. 2 is a schematic view of another process line for PVB modified materials of the present invention and process lines used in preparation examples 9-14.

FIG. 3 is a schematic diagram of a production line used in preparation examples 1, 2, 7, 8 of the present invention.

FIG. 4 is a schematic view of a casting machine used in each preparation example of the present invention.

Fig. 5 is a schematic cross-sectional view of one embodiment of a PVB modified article of the present invention.

Fig. 6 is a schematic cross-sectional view of one embodiment of a PVB modified article of the present invention.

FIG. 7 is a schematic view of a production line used in preparation examples 3, 5 and 6 of the present invention.

Fig. 8 is a schematic cross-sectional view of one embodiment of a PVB modified article of the present invention.

FIG. 9 is a schematic diagram of a production line used in preparation example 4 of the present invention.

Fig. 10 is a schematic cross-sectional view of one embodiment of a PVB modified article of the present invention.

Fig. 11 is a schematic cross-sectional view of one embodiment of a PVB modified article of the present invention.

FIG. 12 is a schematic view of a foaming process line used in preparation examples 6 and 7 of the present invention.

Fig. 13 is a schematic cross-sectional view of one embodiment of a PVB modified article of the present invention.

Fig. 14 is a schematic cross-sectional view of one embodiment of a PVB modified article of the present invention.

Fig. 15 is a schematic cross-sectional view of one embodiment of a PVB modified article of the present invention.

FIG. 16 is a schematic view of a production line used in preparation examples 10-1, 11-1, 13 to 14 of the present invention.

FIG. 17 is a schematic view of a production line used in preparation examples 10-2, 11-2, 12 of the present invention.

Fig. 18 is a schematic cross-sectional view of one embodiment of a PVB modified article of the present invention.

Detailed Description

The technical means of the present invention will be further described below by way of examples of the present invention.

Materials of all examples and comparative examples were first prepared according to the following table 1.

TABLE 1

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The method for producing a polyvinyl butyral-modified material of the invention (1)

A schematic of the production line of one embodiment of the polyvinyl butyral (PVB) modified materials of the present invention is illustrated in fig. 1. First, according to the formulation described in table 1, a PVB remainder (the PVB remainder comprising PVB and a first plasticizer, wherein the first plasticizer is contained in an amount of 3 to 15 parts by weight based on 100 parts by weight of the total PVB remainder), a first filler (kaolin powder), a second filler (calcium carbonate), a hydrolysis inhibitor (carbodiimide), a cold-resistant agent (polyisobutylene, dioctyl adipate), zinc stearate, calcium stearate, a polymeric dispersant (simethicone), tetramethylthiuram monosulfide, trimethylolpropane tris (3-mercaptopropionate), an elastomer (thermoplastic polyurethane elastomer), a deodorizing agent (porous inorganic silicate and sodium bicarbonate), and a high-temperature foaming agent (azodicarbonamide) were charged into an internal mixer 10, and kneaded at a temperature of 170 ℃ for 8 minutes to obtain a crude modified material.

The crude PVB modified material is then conveyed to a first granulator 20. The crude PVB modified material is held at a temperature of 150℃to 170℃as it passes through screw 201 of first granulator 20 and is extruded under pressure as it passes through zones 201a to 201e of screw 201 (about 1-3 minutes, the temperatures of the zones being the same) and filtered through a 150 mesh screen to provide a once filtered PVB modified material.

The once filtered PVB modified material is then conveyed to a second granulator 21. The PVB modified material after the primary filtration is heated at a temperature of 150 to 170 ℃ while passing through the screw 211 of the second granulator 21, and is extruded under pressure while passing through zones 211a to 211e (about 1 to 3 minutes, each zone having the same temperature) of the screw 211, and is filtered again with a 150 mesh screen (secondary filtration) to obtain the PVB modified material. Finally, the PVB modified material particles are obtained through die granulation, wherein the diameter of the particles is 5mm, and the length of the particles is 6mm. The PVB modified material has uniform particle size, meets the standard of subsequent products, and can be adjusted according to the requirements.

The method (2) for producing a polyvinyl butyral-modified material of the present invention

A schematic of the production line of another embodiment of the polyvinyl butyral (PVB) modified materials of the present invention is shown in the left half of fig. 2. First, according to the formulation described in Table 1, PVB surplus (which contains PVB and a first plasticizer, wherein the total content of PVB surplus is 100 parts by weight, the content of the first plasticizer is 3 to 15 parts by weight), a first filler (kaolin powder), a second filler (calcium carbonate), an anti-hydrolysis agent (carbodiimide), a cold-resistant agent (polyisobutylene, dioctyl adipate), zinc stearate, calcium stearate, a high molecular dispersant (dimethyl silicone oil), tetramethylthiuram monosulfide, trimethylolpropane tris (3-mercaptopropionic acid) ester, an elastomer (thermoplastic polyurethane elastomer), a deodorant (porous inorganic silicate and sodium bicarbonate), and a high temperature foaming agent (azodicarbonamide) are put into a ten-thousand horsepower machine X10 and mixed for 8 minutes at a temperature of 170 ℃ to obtain a crude PVB modified material.

The crude PVB modified material was then fed into a first mill X11, incubated at 160℃and rolled into sheets, and then cut into first flexible strips (which were crude PVB modified material) 10 cm to 20 cm wide and 1 cm to 2 cm thick. The first flexible strand is then fed to a filter X12 set at 160℃and filtered to give a once filtered PVB modified material. Finally, the once filtered PVB modified material is fed to a second calender X13, insulated at 160℃and rolled into a sheet, then cut into a second flexible strip of 10 to 20 cm wide and 1 to 2 cm thick, which is a PVB modified material, and then ready for further processing, such as direct calendaring into a PVB modified material film.

The filtration step of the crude PVB modified material is primarily used to remove impurities from the PVB remainder. The PVB remainder is a recycled material, so that impurities are removed by a filtering step to obtain PVB modified material with uniform quality. The arrangement and the filtering times of the production online machine can be adjusted according to the raw material sources and the product demands.

Alternatively, granulated PVB modified materials can be used to directly prepare calendered films. For example, the particulate PVB modifying material may be first fed into a ten thousand horsepower machine X10 as shown in fig. 2, but heated only to 160 ℃, then directly fed to a first mill X11, repeatedly subjected to step (S2), and then ready for calendaring.

Water resistance test

Using the materials of example 1 and comparative example 1, pellets of PVB-modified materials were prepared by the above-mentioned production method (1), respectively, and then cast into films of 0.2mm thickness, and test pieces were cut out to give test pieces 1A, 1C, each having a total weight of 100 g. Using the material of example 1, a PVB modified material was prepared by the above-mentioned preparation method (2), and then was directly calendered into a film of 0.2mm thickness, and a test piece was cut out to give a test piece 1B having a total weight of 100 g. The test pieces 1A, 1B and 1C were immersed in warm water at 25℃for 24 hours, respectively, and then the surface water was wiped off, weighed, and the amount of water absorbed by the test pieces was calculated. The results are shown in Table 2.

TABLE 2

As shown in Table 2, the water absorption of the test pieces 1A and 1B was greatly reduced compared with that of the test piece 1C, and the test pieces had better water resistance. In addition, the test piece 1C whitens after absorbing water, which is not beneficial to the subsequent preparation of the polyvinyl butyral product; the material of the test pieces 1A, 1B does not have this phenomenon. In addition, the results of test pieces 1A and 1B also show that PVB modified materials obtained by the preparation methods (1) and (2) have similar properties.

High temperature resistance and anti-tackiness test

Using the materials of example 1 and comparative example 2, PVB modified materials were prepared by the above-mentioned preparation method (2), respectively, and then directly rolled into a film having a thickness of 0.2mm, and test pieces having a thickness of 50mm x 100mm were cut to prepare test pieces 2A and 2B.

The test pieces 2A and 2B were placed in an oven at 110℃and heated for 5 minutes, and a high temperature resistance test was performed. The test piece 2A does not become pasty after the high temperature treatment, but the test piece 2B becomes pasty. In addition, when the oven temperature was increased, it was found that when the temperature exceeded 125 ℃, the test piece 2A did not change color after the high temperature treatment, but the test piece 2B began to change color. When heated in an oven at 180℃for 5 minutes, the test piece 2A became pasty, but was not discolored.

The same test piece was used for the anti-tackiness test. Two test pieces 2A and 2B were stacked, and 3kg of gravity was uniformly applied to the test pieces, and the test pieces were placed in an oven at 150℃for heating for 120 hours. As a result, it was found that the test piece 2A was not bonded after the above treatment, but the test piece 2B was bonded. Thus, the PVB modified material of example 1 has better high temperature tack resistance than comparative example 2. If the pellets of PVB modified material were prepared by the above-described preparation method (1) using comparative example 1 (unmodified PVB remainder), and then cast into a film of 0.2mm thickness, test pieces 2C of the same size were prepared for the anti-tackiness test, 3kg of gravity was uniformly applied to the test pieces, and the test pieces were put into a 50℃oven and heated for 12 hours to bond.

Cold resistance test

Using the materials of examples 1 and 2, pellets of PVB-modified materials were prepared by the above-mentioned preparation method (1), respectively, and then cast into films of 0.3mm thickness, and test pieces of 100 mm. Times.100 mm were cut to prepare test pieces 3A and 3B.

Then, the test pieces 3A and 3B were simultaneously placed in a freezing apparatus at 0℃for 60 minutes, the test piece 3A was hardened, and the test piece 3B remained soft. Then, the test pieces 3A and 3B were simultaneously placed in a freezer at-5℃for 60 minutes, the test piece 3A was significantly stiffer, and the test piece 3B was slightly stiffer than the test at 0 ℃. It is therefore recognized that the addition of a mixture of equal amounts of polyisobutylene and dioctyl adipate to the PVB modifying materials of the present invention can maintain the softness of the PVB modifying materials at a temperature of 0 ℃.

Tensile recovery test

Using the materials of examples 1 and 3-1 to 3-3, respectively, pellets of PVB-modified material were prepared by the above-mentioned method (1), and then cast into a 0.2mm thick film of PVB-modified material, and test pieces having a length of 7 inches and a width of 4 inches were cut to prepare test pieces 4A to 4D, which were subjected to a tensile recovery test.

The two ends of the test pieces 4A to 4D were respectively clamped into the clamps of the tensile tester, the two ends were respectively clamped by 0.5 inch, then the test pieces were stretched to a length of 9 inch by 20 kg tensile force, then the test pieces were taken down and laid flat, after the test pieces were naturally restored to a degree that they were not contracted any more, the lengths thereof were measured and the tensile restoring rates were calculated, and the results are shown in Table 3. Calculation formula of tensile recovery: (post-stretching length-pre-stretching length)/pre-stretching length.

TABLE 3 Table 3

As is clear from the results in Table 3, the higher the content of the thermoplastic polyurethane elastomer, the lower the tensile recovery, and the tensile strength was hardly developed by adding 15 parts by weight of the thermoplastic polyurethane elastomer and stretching. However, if the thermoplastic polyurethane elastomer content exceeds 15 parts by weight, the tensile recovery rate starts to rise, and for example, if the thermoplastic polyurethane elastomer content is increased to 18 parts by weight, the tensile recovery rate of a test piece made of the obtained polyvinyl butyral-modified material is 1.3%.

Tensile Strength and tear Strength test

Using the materials of examples 1, 4-2 and comparative example 2, pellets of PVB-modified material were prepared by the above-mentioned method (1), and then cast into a film of 0.365mm thickness, and test pieces of 300 mm. Times.100 mm were cut to prepare test pieces 5A to 5D. The test piece is marked as a longitudinal direction which is the same as the longitudinal direction of the film, and is marked as a transverse direction which is the same as the transverse direction of the film.

The two ends of the test pieces 5A to 5D were respectively clamped into the clamps of the tensile tester, the two ends were respectively clamped by 0.5 inch, and then the tensile force was gradually increased until the test pieces were broken, and the tensile force values at the time of longitudinal and transverse breaking were recorded in kilograms-force (kgf). Each group of test pieces was subjected to three tests and an average value was calculated, and the results are shown in table 4.

Tear testing was also performed using the GB/T16491 test standard. The foregoing materials were used to cast a film of 0.365mm thickness, and V-shaped test pieces having an overall length of 120mm and a bandwidth of 30mm were cut to prepare test pieces 6A to 6D. The V-shaped test piece has a V-shaped included angle of 135 degrees, and square areas (the length of which is contained in the whole length) with the length of 20mm and the width of 30mm are respectively arranged at the left end and the right end of the V-shaped test piece, so that the clamp is convenient to fix and test. The length direction of the V-shaped test piece is marked as the longitudinal direction which is the same as the longitudinal direction of the film, and the length direction of the V-shaped test piece is marked as the transverse direction which is the same as the transverse direction of the film.

The tear test was then performed using an HD-A604S tensile strength tester. The temperature at the time of the test was 23.+ -. 2 ℃ and the relative humidity was 60.+ -. 5% and the distance between the two clamps was 80mm. The test pieces 6A to 6D were fixed on upper and lower jigs with the center line of the test piece aligned with the center line of the jigs, and then the jigs were pulled outward at a speed of 200 millimeters/minute (mm/min), and after the test pieces were broken, the tear strength in kgf was recorded. Each group of test pieces was subjected to three tests and an average value was calculated, and the results are shown in table 4.

TABLE 4 Table 4

From the results in table 4, it can be seen that the addition of the second filler calcium carbonate reduces the tensile strength and tear strength, and can thereby further tailor the properties of the PVB modifying material.

Preparation of the polyvinyl butyral-modified articles of the invention

Preparation example 1: preparation of a textile comprising a cast layer of a Single-sided polyvinyl butyral modified Material with the polyvinyl butyral modified Material of the invention

As shown in fig. 3, first, a fabric (woven cloth or nonwoven fabric) is sent by a first sender 30. After the fabric is transferred to the first pasting machine 31, an adhesive is coated on one surface of the fabric; the adhesive coated fabric is then fed into oven 32 and heated at a temperature of 100 c to 130 c to evaporate the solvent from the adhesive.

Polyvinyl butyral (PVB) modified material particles as described above, which are melted after passing through zones 402a to 402k of screw 402 and then through zones 403a to 403k of die 403, are fed into hopper 401 of casting machine 40 (the casting machine 40 in fig. 3 and 4 is oriented differently, the structure of casting machine 40 is shown in fig. 4), and the melted PVB modified material is cast onto the adhesive coated surface of the fabric. The temperature of the casting machine 40 is set as follows: the temperature of the screw 402 reaches 135 ℃ to 165 ℃ in the 402k zone, and the temperatures of the zones can be different; the temperature of the mold 403 reaches 155 deg.c to 175 deg.c in the 403k zone, and the temperatures of the zones are the same. The number of zones set by the screw 402 and the die 403 of the casting machine 40 is independently determined, and different widths can be set according to the product requirements, and in this embodiment, 11 zones are set, and generally, but not limited to, 8 to 30 zones can be set.

The fabric having a layer of PVB modified material cast thereon is fed to a first embossing machine 60, embossed, and then cooled and set by a first setting machine 61 to obtain a fabric having a single-sided tape, and the fabric having the single-sided tape is separated by a first separator 70. The schematic cross-sectional view of the fabric comprising a single-sided casting layer is shown in fig. 5, wherein a is a fabric layer and B is a polyvinyl butyral modified material layer.

In addition, when a thicker PVB modified material casting layer is to be formed on the same side of the fabric, the casting step is repeated.

Preparation example 2: preparation of a textile comprising a cast layer of a double sided polyvinyl butyral modified material with the polyvinyl butyral modified material of the invention

A layer of PVB modifying material can also be cast on the other surface of the single-sided tape-cast layer-containing fabric obtained in preparation example 1, without the adhesive, following the procedure described in preparation example 1, to give a double-sided PVB-modified material-containing tape-cast layer-containing fabric. The schematic cross-sectional view of the aforementioned fabric comprising a double-sided tape casting layer is shown in fig. 6, wherein a is the fabric layer, B1 is the first polyvinyl butyral modified material layer, and B2 is the second polyvinyl butyral modified material layer.

Likewise, when a thicker PVB modifying material casting layer is to be formed on the same side of the fabric, the casting step is simply repeated.

Preparation example 3: preparation of double-sided fabrics comprising a cast interlayer with the polyvinyl butyral modified material of the present invention as shown in fig. 7, fabrics (woven or non-woven fabrics) were sent with the first sender 30 and the second sender 50, respectively.

After the first fabric sent out by the first sender 30 is transferred to the first pasting machine 31, an adhesive is coated on one surface of the first fabric; the adhesive coated first fabric is then fed into oven 32 and heated at a temperature of 100 c to 130 c to evaporate the solvent from the adhesive.

The PVB modifying material particles are fed into a feed hopper 401 of a casting machine 40 (the casting machine 40 in fig. 4 and 7 is oriented differently, the structure of the casting machine 40 is shown in fig. 4), and the PVB modifying material particles are melted after passing through regions 402a to 402k of a screw 402, and then the melted PVB modifying material is cast on the adhesive-coated surface of the first fabric through regions 403a to 403k of a die 403. The temperature of the casting machine 40 is set as follows: the temperature of the screw 402 reaches 135 ℃ to 165 ℃ in the 402k zone, and the temperatures of the zones can be different; the temperature of the mold 403 reaches 155 deg.c to 175 deg.c in the 403k zone, and the temperatures of the zones are the same. The number of zones set by the screw 402 and the die 403 of the casting machine 40 is independently determined, and different widths can be set according to the product requirements, and in this embodiment, 11 zones are set, and generally, but not limited to, 8 to 30 zones can be set.

In addition, after the second fabric sent from the second sender 50 is transferred to the second pasting machine 51, an adhesive is coated on one surface of the second fabric, wherein the adhesive is used in an amount of less than 20g/m ² . The PVB-modified material layer cast onto the first fabric was then bonded to the adhesive-coated surface of the second fabric, and fed to the first embosser 60, and then pressed using a flat press roll at a pressure of 12 kg. And after the second fabric is attached to the PVB modified material casting layer on the first fabric, forming a product which is formed by wrapping the PVB modified material casting layer by the first fabric and the second fabric. The product is then fed into a first former 61 for cooling and shaping to obtain a double-sided fabric comprising a casting interlayer, and the double-sided fabric comprising the casting interlayer is separated by a first separator 70. The schematic cross-sectional view of the aforementioned double-sided fabric comprising a cast interlayer is shown in fig. 8, wherein A1 is a first fabric layer, A2 is a second fabric layer, and B is a polyvinyl butyral modified material layer.

Preparation example 4: preparation of aluminized PET film containing one-sided casting layer by using polyvinyl butyral modified material

As shown in fig. 9, first, an aluminized PET film is transmitted by the second transmitter 50. After transferring the aluminized PET film to the second pasting machine 51, an adhesive is coated on one surface of the aluminized PET film, wherein the adhesive is used in an amount of less than 20g/m ² 。

The PVB modifying material particles are fed into a feeding hopper 401 of a casting machine 40 (the casting machine 40 in fig. 9 and 4 is different in direction, the structure of the casting machine 40 is shown in fig. 4), the PVB modifying material particles are melted after passing through regions 402a to 402k of a screw 402, and then the melted PVB modifying material is cast on the surface coated with the adhesive of the aluminized PET film through regions 403a to 403k of a die 403. The temperature of the casting machine 40 is set as follows: the temperature of the screw 402 reaches 135 ℃ to 165 ℃ in the 402k zone, and the temperatures of the zones can be different; the temperature of the mold 403 reaches 155 deg.c to 175 deg.c in the 403k zone, and the temperatures of the zones are the same. The number of zones set by the screw 402 and the die 403 of the casting machine 40 is independently determined, and different widths can be set according to the product requirements, and in this embodiment, 11 zones are set, and generally, but not limited to, 8 to 30 zones can be set.

The aluminized PET film with the one layer of PVB modified material cast is conveyed to a first embossing machine 60 for embossing treatment, then is conveyed to a first molding machine 61 for cooling and molding, and an aluminized PET film containing a single-sided casting layer is obtained, and is rolled by a first rolling machine 70. The schematic cross-section of the aluminized PET film comprising a single-sided casting layer is shown in fig. 10, wherein A3 is an aluminized PET layer and B is a polyvinyl butyral modified material layer.

Similarly, when a thicker PVB modified material casting layer is to be formed on the same surface of the aluminized PET film, the casting step is repeated. Alternatively, as described in preparation example 2, a layer of PVB-modified material was cast on the other side of the aluminized PET film, to obtain an aluminized PET film (not shown) comprising a cast layer of the double-sided PVB-modified material.

Preparation example 5: preparation of the net-sandwiched artificial leather by the polyvinyl butyral modified material

Reverse casting

As shown in fig. 7, first, the mesh cloth is transmitted by the second transmitter 50 located closer to each other. After the web is transferred to the second pasting machine 51, an adhesive is applied to one surface of the web, where the adhesive is used in an amount of less than 20g/m ² . The second transmitter 50 has a short transmission distance, and is advantageous in maintaining the mesh structure of the mesh cloth at the start of preparation.

The PVB modifying material particles are fed into a feed hopper 401 of a casting machine 40 (the casting machine 40 in fig. 4 and 7 is different in direction, the structure of the casting machine 40 is shown in fig. 4), and the PVB modifying material particles are melted after passing through regions 402a to 402k of a screw 402, and then the melted PVB modifying material is cast on the adhesive coated surface of the mesh cloth through regions 403a to 403k of a die 403. The temperature of the casting machine 40 is set as follows: the temperature of the screw 402 reaches 135 ℃ to 165 ℃ in the 402k zone, and the temperatures of the zones can be different; the temperature of the mold 403 reaches 155 deg.c to 175 deg.c in the 403k zone, and the temperatures of the zones are the same. The number of zones set by the screw 402 and the die 403 of the casting machine 40 is independently determined, and different widths can be set according to the product requirements, and in this embodiment, 11 zones are set, and generally, but not limited to, 8 to 30 zones can be set.

The web having a layer of PVB modified material cast thereon is fed to a first embossing machine 60, embossed, and then fed to a first molding machine 61 for cooling and molding to obtain a web having a single-sided casting layer, and the web having the single-sided casting layer is separated by a first separator 70.

Front casting

Next, as shown in fig. 7, the mesh cloth including the one-sided casting layer is transmitted by the first transmitter 30. After the web containing the one-sided casting layer is transferred to the first pasting machine 31, an adhesive is coated on the side of the web on which the polyvinyl butyral modified material is not cast; the web coated on the other side with the adhesive is then fed into an oven 32 and heated at a temperature of 100 to 130 c to evaporate the solvent from the adhesive.

The PVB modifying material particles are fed into a feeding hopper 401 of a casting machine 40 (the casting machine 40 in fig. 4 and 7 is different in direction, the structure of the casting machine 40 is shown in fig. 4), the PVB modifying material particles are melted after passing through regions 402a to 402k of a screw 402, and then the melted PVB modifying material is cast on the other surface of the mesh cloth coated with the adhesive and including a single casting layer through regions 403a to 403k of a die 403. The temperature of the casting machine 40 is set as follows: the temperature of the screw 402 reaches 135 ℃ to 165 ℃ in the 402k zone, and the temperatures of the zones can be different; the temperature of the mold 403 reaches 155 deg.c to 175 deg.c in the 403k zone, and the temperatures of the zones are the same. The number of zones set by the screw 402 and the die 403 of the casting machine 40 is independently determined, and different widths can be set according to the product requirements, and in this embodiment, 11 zones are set, and generally, but not limited to, 8 to 30 zones can be set.

The mesh fabric, on the other side of which a layer of PVB modified material is also cast, is fed to a first embossing machine 60 for embossing, and then fed to a first molding machine 61 for cooling and molding to obtain a net-sandwiched artificial leather, and the net-sandwiched artificial leather is split by a first splitting machine 70. The schematic cross-section of the aforementioned sandwich artificial leather is shown in fig. 11, wherein A4 is a mesh cloth layer, B1 is a first polyvinyl butyral modified material layer, and B2 is a second polyvinyl butyral modified material layer.

In addition, when a thicker PVB-modified material casting layer is to be formed on the front or back side of the mesh cloth, the casting step is repeated on that side.

Preparation example 6: foaming artificial leather prepared from polyvinyl butyral modified material

Single-sided casting

As shown in fig. 7, first, a fabric (woven cloth or nonwoven fabric) is sent by a first sender 30. After the fabric is transferred to the first pasting machine 31, an adhesive is coated on one surface of the fabric; the adhesive coated fabric is then fed into oven 32 and heated at a temperature of 100 c to 130 c to evaporate the solvent from the adhesive.

The PVB modified material particles and the AC foaming agent particles are mixed according to the weight ratio of 100:5-7 are mixed and fed into a hopper 401 of a casting machine 40 (the casting machine 40 in fig. 4 and 7 is oriented differently, the structure of the casting machine 40 is shown in fig. 4), the PVB modified material particles are melted after passing through regions 402a to 402k of a screw 402, and the melted mixed material is cast on the adhesive coated surface of the fabric through regions 403a to 403k of a die 403. The temperature of the casting machine 40 is set as follows: the temperature of the screw 402 reaches 135 ℃ to 165 ℃ in the 402k zone, and the temperatures of the zones can be different; the temperature of the mold 403 reaches 155 deg.c to 175 deg.c in the 403k zone, and the temperatures of the zones are the same. The number of zones set by the screw 402 and the die 403 of the casting machine 40 is independently determined, and different widths can be set according to the product requirements, and in this embodiment, 11 zones are set, and generally, but not limited to, 8 to 30 zones can be set.

The foregoing web having cast a layer of PVB modified material mixed with an AC blowing agent is fed to a first setting machine 61 for cooling setting to obtain a web containing a single-sided casting layer, and the web containing the single-sided casting layer is slit by a first slit roll 70.

Foaming

And (3) foaming the fabric comprising the single-sided casting layer to obtain the fabric comprising the single-sided foaming casting layer. The foaming treatment is carried out at a temperature of 160 ℃ to 250 ℃ for a treatment time of 1.5 to 2 minutes.

As shown in fig. 12, the fabric including the single-sided foam casting layer is sent with a third sender 80. The fabric comprising the single-sided foam casting layer is fed into a foaming furnace 81, and heated by passing through zones 81a to 81e of the foaming furnace 81, wherein the temperature of zone 81e is 160 ℃ to 250 ℃, and the temperatures of the zones can be different. The fabric including the single-sided foaming casting layer after the heat treatment is transferred to the second embossing machine 90, and the embossing treatment is performed under the condition that the second embossing machine 90 is introduced with cold water with the temperature of 10 ℃ for backflow, and then the fabric is transferred to the second setting machine 91 for cooling setting, so as to obtain a foaming artificial leather, and the foaming artificial leather is rolled by the second roll separator 100. A schematic cross-sectional view of the foamed artificial leather is shown in FIG. 13, wherein A is a fabric layer and B3 is a foamed polyvinyl butyral modified material layer.

Preparation example 7: preparation of foaming single glue film by the polyvinyl butyral modified material

Single layer casting

As shown in fig. 3, first, the PVB modifying material particles and the AC blowing agent particles were mixed in a weight ratio of 100:5-7 are mixed and fed into a hopper 401 of a casting machine 40 (the casting machine 40 in fig. 3 and 4 is oriented differently, the structure of the casting machine 40 is shown in fig. 4), the PVB modified material particles are melted after passing through regions 402a to 402k of a screw 402, and the melted mixed material is cast and fed between a first embossing wheel 601 and a rubber wheel 602 of a first embosser 60 after passing through regions 403a to 403k of a die 403. The temperature of the casting machine 40 is set as follows: the temperature of the screw 402 reaches 135 ℃ to 165 ℃ in the 402k zone, and the temperatures of the zones can be different; the temperature of the mold 403 reaches 155 deg.c to 175 deg.c in the 403k zone, and the temperatures of the zones are the same. The number of zones set by the screw 402 and the die 403 of the casting machine 40 is independently determined, and different widths can be set according to the product requirements, and in this embodiment, 11 zones are set, and generally, but not limited to, 8 to 30 zones can be set.

And conveying the cast film of the PVB modified material to a first setting machine 61 for cooling setting to obtain a single-layer cast film of the PVB modified material, and separating the single-layer cast film of the PVB modified material by a first separator 70.

Foaming

And foaming the single-layer casting film of the PVB modified material to obtain the single-layer foaming casting film of the PVB modified material. The foaming treatment is carried out at a temperature of 160 ℃ to 250 ℃ for a treatment time of 1.5 to 2 minutes.

As shown in fig. 12, a single layer cast film of the PVB modified material is sent with a third sender 80. The single layer cast film of PVB modified material is fed into a foaming furnace 81 and heated through zones 81a to 81e of the foaming furnace 81, wherein the temperature in zone 81e is 160 ℃ to 250 ℃, and the temperatures in the zones can be different. The single-layer foaming casting film of the PVB modified material after the heat treatment is conveyed to a second embossing machine 90, embossing treatment is carried out under the condition that the second embossing machine 90 is filled with cold water with the temperature of 10 ℃ for backflow, then the single-layer foaming casting film is conveyed to a second shaping machine 91 for cooling shaping, a foaming single-glue film is obtained, and the foaming single-glue film is split by a second splitting machine 100. The schematic cross-section of the foamed single-layer film is shown in fig. 14, wherein B3 is a foamed polyvinyl butyral modified material layer.

Preparation example 8: cast film of polyvinyl butyral modified material prepared by polyvinyl butyral modified material of the invention

As shown in fig. 3, first, the PVB-modified material particles are fed into a feed hopper 401 of a casting machine 40 (the casting machine 40 in fig. 3 and 4 is different in direction, the structure of the casting machine 40 is shown in fig. 4), and the PVB-modified material particles are melted after passing through regions 402a to 402k of a screw 402, and then the melted mixed material is cast and fed between a first embossing wheel 601 and a rubber wheel 602 of a first embosser 60 through regions 403a to 403k of a die 403. The temperature of the casting machine 40 is set as follows: the temperature of the screw 402 reaches 135 ℃ to 165 ℃ in the 402k zone, and the temperatures of the zones can be different; the temperature of the mold 403 reaches 155 deg.c to 175 deg.c in the 403k zone, and the temperatures of the zones are the same. The number of zones set by the screw 402 and the die 403 of the casting machine 40 is independently determined, and different widths can be set according to the product requirements, and in this embodiment, 11 zones are set, and generally, but not limited to, 8 to 30 zones can be set.

The cast film of the PVB modified material is conveyed to a first embossing machine 60 for embossing treatment, then is conveyed to a first shaping machine 61 for cooling shaping to obtain a PVB modified material film, and is split by a first splitting machine 70. A schematic cross-sectional view of the PVB-modified material film described above is shown in fig. 15, wherein B is a layer of polyvinyl butyral-modified material.

Preparation example 9: preparation of calendered films of polyvinyl butyral modified materials from the polyvinyl butyral modified materials of the invention

As shown in FIG. 2, the polyvinyl butyral modified material having a uniformity of 99% or more is first fed directly from the second rolling mill X13 to the multi-roll mill X20 and extruded at 170 to 185 ℃. In fig. 2, the multi-roll machine X20 includes a first roll X201, a second roll X202, a third roll X203, and a fourth roll X204, which have temperatures of 170 ℃,175 ℃,180 ℃,185 ℃, respectively. The number of rollers of the multi-roller machine X20 can be set according to the product requirement, and the higher the number of rollers is, the higher the product flatness is. And conveying the rolled film of the PVB modified material to a third embossing machine X30 for embossing, conveying the rolled film of the PVB modified material to a third shaping machine X32 for cooling shaping to obtain a PVB modified material film, and using a third roll-dividing machine X33 to divide and roll the PVB modified material film. A schematic cross-sectional view of the PVB-modified material film described above is shown in fig. 15, wherein B is a layer of polyvinyl butyral-modified material.

Preparation example 10-1: preparation of fabrics comprising monolayer polyvinyl butyral modified material films from the polyvinyl butyral modified materials of the invention

Preparation example 9 as shown in fig. 16, first, a fabric (oxford or dacron) was sent by a fourth sender X40. Transferring the fabric to a thirdAfter the pasting machine X41, an adhesive is coated on one surface of the fabric, wherein the adhesive dosage is lower than 20g/m ² . The adhesive coated fabric was then fed into a heated oven set X42, where the solvent in the adhesive was evaporated. In fig. 16, the heating oven set X42 includes a first heating oven X421, a second heating oven X422, a third heating oven X423, a fourth heating oven X424, and a fifth heating oven X425, which have temperatures of 150 ℃,160 ℃,170 ℃,180 ℃, and 165 ℃, respectively. The number of the heating ovens of the heating oven set X42 may be set according to the product requirement, and in this embodiment, 5 heating ovens are set, and generally, 5 to 10 heating ovens may be set, but not limited thereto. The adhesive coated fabric is then sent to a fourth embosser X51.

The PVB sheet was sent by a fifth sender X50 to a fourth embosser X51, and the PVB sheet was bonded to the adhesive-coated surface of the fabric, and then pressed by a flat press roll at a pressure of 12 kg. And then feeding the single-sided PVB modified material film into a fourth setting machine X52 for cooling setting to obtain a fabric containing the single-sided PVB modified material film, and using a fourth roll-dividing machine X54 to divide and roll the fabric containing the single-sided PVB modified material film. A schematic cross-sectional view of the foregoing fabric comprising a single-sided PVB-modified material film is shown in fig. 5, wherein a is a fabric layer and B is a polyvinyl butyral-modified material layer.

If the fabric is a cloth (e.g., nonwoven, knitted) that does not require sizing, the fabric may also be conveyed to the third embosser X30 in the line of fig. 2 by a conveying frame X31 for lamination with the PVB modifying material film.

Preparation example 10-2: preparation of fabrics comprising monolayer polyvinyl butyral modified material films from the polyvinyl butyral modified materials of the invention

As shown in fig. 17, a fabric is first sent by a seventh sender X70, and is sent through a pair of two first heating wheels X62 to the middle of a pair of two second embossing wheels X63. The temperature of the first heating wheel X62 was 130 ℃.

Following preparation example 9, the PVB modified material film was sent with a sixth sender X60. After the PVB-modified material film is conveyed to fourth paste machine X61,applying an adhesive to a surface of the PVB modified material film, wherein the adhesive is present in an amount of less than 20g/m ² . The PVB modified material film coated with the adhesive is sent into a second heating wheel X64, then is sent between a pair of first heating wheels X62, so that the solvent in the adhesive is evaporated, and then is sent to the middle of two second embossing wheels X63 in a pair, wherein the contact part of the PVB modified material film and the PVB modified material film is a pattern roller, and the contact part of the PVB modified material film and the fabric is a rubber roller. The temperature of the second heating wheel X64 is also 130 ℃. A heating cover X65 is arranged above the second heating wheel X64 and is used for heating the first heating wheel X62 and the second heating wheel X64, and the temperature is higher and can reach as high as 200 ℃.

The fabric was bonded to the adhesive-coated surface of the PVB-modified material film, and the resultant was pressed by a flat press roll at a pressure of 12 kg. And then feeding the fabric into a cold cutting wheel X66 for cooling and shaping to obtain a fabric containing the single PVB modified material film, and separating the fabric containing the single PVB modified material film by a fifth separator X67. A schematic cross-sectional view of the foregoing fabric comprising a single ply PVB-modified material film is shown in fig. 5, wherein a is a fabric ply and B is a polyvinyl butyral-modified material ply.

Preparation example 11-1: preparation of fabrics comprising double-layer polyvinyl butyral modified material films from the polyvinyl butyral modified materials of the invention

Preparation example 10-1 as shown in fig. 16, first, the aforementioned web comprising a single-sided PVB-modified material film was sent by a fourth sender X40. After transferring the web comprising the single-sided PVB-modified material film to the third pasting machine X41, an adhesive is applied to the other surface of the web (i.e., the surface not in contact with the PVB-modified material film), wherein the adhesive is used in an amount of less than 20g/m ² . The adhesive coated fabric comprising the single-sided PVB-modified material film is then fed into a heated oven set X42 where the solvent in the adhesive is evaporated. In fig. 16, the heating oven set X42 includes a first heating oven X421, a second heating oven X422, a third heating oven X423, a fourth heating oven X424, and a fifth heating oven X425, which have temperatures of 150 ℃,160 ℃,170 ℃,180 ℃, and 165 ℃, respectively. Number of heating ovens of heating oven group X42 The purpose can be set according to the product requirement, and in this embodiment, 5 is set, and generally, 5 to 10 can be set, but not limited to this. The adhesive coated web comprising the single sided PVB modifying material film is then sent to a fourth embosser X51.

Further, another PVB sheet was sent by a fifth sender X50 to a fourth embosser X51, and the other PVB sheet was attached to the adhesive-coated surface of the fabric comprising the single-sided PVB sheet, and then pressed by a flat press roll at a pressure of 12 kg. And then feeding the two-sided PVB modified material film into a fourth setting machine X52 for cooling setting to obtain a fabric containing the two-sided PVB modified material film, and using a fourth roll-dividing machine X54 to divide and roll the fabric containing the two-sided PVB modified material film. A schematic cross-sectional view of the foregoing web comprising a double sided PVB-modified material film is shown in fig. 6, wherein a is the web layer, B1 is the first polyvinyl butyral-modified material layer, and B2 is the second polyvinyl butyral-modified material layer.

If the web is a non-rubberized fabric (e.g., nonwoven, knitted fabric), the web containing the single-sided PVB-modifying material film can also be conveyed to a third embosser X30 in the production line of fig. 2 with a conveying frame X31 and laminated with another PVB-modifying material film.

Preparation example 11-2: preparation of fabrics comprising double-layer polyvinyl butyral modified material films from the polyvinyl butyral modified materials of the invention

Following preparation example 9, the PVB modified material film was sent with a sixth sender X60. After the PVB modified material film is transferred to a fourth pasting machine X61, an adhesive is coated on one surface of the PVB modified material film, wherein the adhesive dosage is lower than 20g/m ² . The PVB modified material film coated with the adhesive is then sent to a second heating wheel X64, then is sent between a pair of first heating wheels X62, so that the solvent in the adhesive is evaporated, and then is sent to a pair of PVB modified material filmsIntermediate the two second embossing wheels X63. In addition, another PVB modifying material film is sent with an eighth sender X80. After the further PVB-modified material film is transferred to the fifth pasting machine X81, an adhesive is coated on one surface of the further PVB-modified material film, wherein the adhesive is used in an amount of less than 20g/m ² . The film of another PVB modifying material coated with adhesive is then fed into another second heated wheel X64', between the pair of first heated wheels X62, to evaporate the solvent in the adhesive, and then between the pair of second embossing wheels X63. According to the product requirement, a pattern roller is used on one side, and a rubber roller is used on the other side. The temperature of the second heating wheel X64 is also 130 ℃. A heating cover X65 is arranged above the second heating wheel X64 and is used for heating the first heating wheel X62 and the second heating wheel X64, and the temperature is higher and can reach as high as 200 ℃.

The two surfaces of the fabric were bonded to the adhesive-coated surfaces of the two PVB-modified material films, respectively, and the two surfaces were pressed by a flat press roll at a pressure of 12 kg. And then feeding the fabric into a cold cutting wheel X66 for cooling and shaping to obtain a fabric containing the double-sided PVB modified material film, and separating the fabric containing the double-sided PVB modified material film by a fifth separator X67. A schematic cross-sectional view of the foregoing web comprising a double sided PVB-modified material film is shown in fig. 6, wherein a is the web layer, B1 is the first polyvinyl butyral-modified material layer, and B2 is the second polyvinyl butyral-modified material layer.

Preparation example 12: preparation of double-layer fabrics comprising single-layer polyvinyl butyral modified material films from the polyvinyl butyral modified materials of the invention

Preparation example 10-1 as shown in fig. 17, first, the web containing a single-sided PVB-modified material film was sent with a sixth sender X60. After the web comprising the single-sided PVB-modified material film is transferred to fourth laminator X61, an adhesive is applied to the other surface of the single-sided PVB-modified material film (i.e., the surface not adhered to the web), where the adhesive is used in an amount of less than 20g/m ² . The fabric coated with the adhesive and containing the single-sided PVB modified material film is then fed into a second heated wheel X64 and then between a pair of first heated wheels X62 The solvent in the adhesive is evaporated and then transferred to the middle of the pair of two second embossing rollers X63. Wherein the temperature of the first heating wheel X62 is 130 ℃.

Thereafter, as shown in fig. 17, the second web sent from the seventh sender X70 is transferred through the pair of two first heated wheels X62 to the middle of the pair of two embossing wheels X63, wherein the web in contact with the PVB modifying material film is a patterned roll and the web in contact with the web is a rubber roll. The temperature of the second heating wheel X64 is also 130 ℃. A heating cover X65 is arranged above the second heating wheel X64 and is used for heating the first heating wheel X62 and the second heating wheel X64, and the temperature is higher and can reach as high as 200 ℃.

The second fabric was attached to the adhesive coated surface of the PVB modifying material film and then pressed using a flat press roll at a pressure of 12 kg. And then feeding the double-layer fabric containing the single-layer PVB modified material film into a cold cutting wheel X66 for cooling and shaping, and separating the double-layer fabric containing the single-layer PVB modified material film by a fifth separating machine X67. The schematic cross-sectional view of the foregoing two-layer fabric comprising a single layer PVB-modified material film is shown in fig. 8, wherein A1 is a first fabric layer, A2 is a second fabric layer, and B is a layer of polyvinyl butyral-modified material.

Preparation example 13: preparation of Single layer fabrics comprising Single layer polyvinyl butyral modified Material foamed films Using the polyvinyl butyral modified Material of the invention

This preparation example was carried out using a material to which an additional blowing agent azodicarbonamide was added, as in example 6 (containing 5 parts by weight of blowing agent azodicarbonamide), and a PVB modified material film (containing blowing agent azodicarbonamide) as described above was produced in the same manner as in preparation example 9.

As shown in fig. 16, first, a fabric (oxford or dacron) is sent by a fourth sender X40. After the fabric is transferred to the third pasting machine X41, an adhesive is coated on one surface of the fabric, wherein the adhesive is used in an amount of less than 20g/m ² . The adhesive coated fabric was then fed into a heated oven set X42, where the solvent in the adhesive was evaporated. In fig. 16, the heating oven group X42 includes a first heating oven X421, a second heating ovenX422, third heating oven X423, fourth heating oven X424, and fifth heating oven X425, the temperatures of which are 150 ℃,160 ℃,170 ℃,180 ℃,165 ℃ respectively. The number of the heating ovens of the heating oven set X42 may be set according to the product requirement, and in this embodiment, 5 heating ovens are set, and generally, 5 to 10 heating ovens may be set, but not limited thereto. The adhesive coated fabric is then sent to a fourth embosser X51.

The PVB sheet (including azodicarbonamide as a foaming agent) was fed to a fourth embosser X51 by a fifth feeding machine X50, and the PVB sheet was bonded to the adhesive-coated surface of the fabric, and then pressed by a flat press roll at a pressure of 12 kg. And then feeding the single-sided PVB modified material film into a fourth setting machine X52 for cooling setting to obtain a fabric containing the single-sided PVB modified material film, and using a fourth roll-dividing machine X54 to divide and roll the fabric containing the single-sided PVB modified material film.

Thereafter, as shown in fig. 16, first, the web containing the single-sided PVB-modified material film is fed directly into a heated oven set X42 with a fourth conveyor X40. At this time, the heating oven set X42 includes a first heating oven X421, a second heating oven X422, a third heating oven X423, a fourth heating oven X424, and a fifth heating oven X425, the temperatures of which are 160 ℃,170 ℃,180 ℃,190 ℃,165 ℃, respectively, and since the formulation including the foaming agent azodicarbonamide is used in the present preparation example, the temperature of the heating oven set X42 can foam the polyvinyl butyral modified material layer in the fabric including the single-sided PVB modified material film, so as to form a foamed polyvinyl butyral modified material layer. And (3) conveying the fabric containing the foamed polyvinyl butyral modified material layer to a fourth embossing machine X51 for embossing treatment, conveying the fabric into a fourth shaping machine X52 for cooling shaping to obtain a fabric containing the single-sided PVB modified material foamed film, and using a fourth roll-dividing machine X54 to divide and roll the fabric containing the single-sided PVB modified material foamed film. The embossing treatment step can be skipped in advance, and the embossing can be performed after the subsequent processing. The schematic cross-sectional view of the aforementioned fabric comprising a foamed film of a single-sided PVB-modified material is shown in fig. 13, wherein a is a fabric layer and B3 is a foamed polyvinyl butyral-modified material layer.

Preparation example 14: foaming artificial leather prepared from polyvinyl butyral modified material

As shown in fig. 16, first, the web containing the single-sided PVB-modified material film is sent by a fourth sender X40. After the web comprising the single-sided PVB-modified material film is transferred to the third pasting machine X41, an adhesive is coated on the other surface (i.e., the surface which is not adhered to the web) of the single-sided PVB-modified material film, wherein the adhesive is used in an amount of less than 20g/m ² . The adhesive coated fabric comprising the single-sided PVB-modified material film is then fed into a heated oven set X42 where the solvent in the adhesive is evaporated. In fig. 16, the heating oven set X42 includes a first heating oven X421, a second heating oven X422, a third heating oven X423, a fourth heating oven X424, and a fifth heating oven X425, which have temperatures of 110 ℃,120 ℃,130 ℃,140 ℃, and 135 ℃, respectively. The temperature should not exceed 140℃in order to avoid excessive losses of the blowing agent azodicarbonamide. The number of the heating ovens of the heating oven set X42 may be set according to the product requirement, and in this embodiment, 5 heating ovens are set, and generally, 5 to 10 heating ovens may be set, but not limited thereto. The adhesive coated fabric is then sent to a fourth embosser X51.

Further, a polyurethane film (on a release paper) was sent by a fifth sender X50 and transferred to a fourth embosser X51, and the polyurethane film (surface not bonded to the release paper) was bonded to the adhesive-coated surface of the fabric comprising a single-sided PVB-modified material film, and then the fabric was pressed by a flat press roll at a pressure of 12 kg. And then feeding the fabric into a fourth setting machine X52 for cooling setting to obtain a fabric containing the polyurethane film and the PVB modified material film, separating the release paper from the fabric containing the polyurethane film and the PVB modified material film, separating the release paper by a sixth separator X53, and separating the fabric containing the polyurethane film and the PVB modified material film by a fourth separator X54.

Finally, the web comprising the polyurethane film and the PVB-modified material film is sent with a fourth sender X40. The fabric comprising the polyurethane film and the PVB-modified material film was directly transferred to a heated oven set X42, where the solvent in the adhesive was evaporated. At this time, the temperatures of the first heating oven X421, the second heating oven X422, the third heating oven X423, the fourth heating oven X424, and the fifth heating oven X425 of the heating oven set X42 were 160 ℃,170 ℃,180 ℃,190 ℃,165 ℃, respectively. After the heating treatment, the PVB modified material film can be foamed to obtain a fabric containing the polyurethane film and the PVB modified material foamed film, the fabric is transmitted to a fourth embossing machine X51 for embossing treatment, and a fourth roll-dividing machine X54 is used for dividing the fabric containing the polyurethane film and the PVB modified material foamed film. The schematic cross-section of the fabric comprising the polyurethane film and the PVB modified material foamed film is shown in FIG. 18, wherein A is a fabric layer, B3 is a foamed polyvinyl butyral modified material layer, and C is a polyurethane layer.

Peel strength test of polyvinyl butyral articles

First, pellets of PVB modified materials were prepared by the above-mentioned method (1) using the materials of example 4-1 and comparative example 2, and PVB products were prepared according to preparation example 1, and test pieces of 130 mm. Times.30 mm were cut out from the PVB products in the transverse and longitudinal directions to prepare test pieces 7A and 7B. Further, using the materials of example 4-1 and comparative example 2, PVB modified materials were prepared by the above-mentioned method (2), PVB products were prepared according to preparation example 10-1, and test pieces 130 mm. Times.30 mm were cut out from the PVB products in the transverse and longitudinal directions to prepare test pieces 7C and 7D. The PVB articles of preparation examples 1, 10-1 comprise a single layer PVB modifying material film and a layer of fabric; the substrate layer (fabric) used is chemical fiber cloth (specification 600D x 300D, 64T); the adhesive is polyurethane glue.

At the optional end of the long side of each test piece, the PVB modifying material layer and the basal layer are peeled off by 25mm. The test strip is labeled as longitudinal, the same as the longitudinal direction of the PVB article, and the test strip is labeled as transverse, the same as the transverse direction of the PVB article.

The peel test was then performed using an HD-A604S tensile strength tester (conforming to GB/T16491 test standard). The temperature at the time of the test was 23.+ -. 2 ℃ and the relative humidity was 60.+ -. 5% and the distance between the two clamps was 25mm. The peeled portion of the sample was separated, the PVB casting layer was brought into contact with the upper jig, the base layer was brought into contact with the lower jig, and the portion of the sample other end which was not peeled was aligned with the center line between the jigs, and the direction of the applied force was balanced. The jig was then pulled outward at a test speed of 100mm/min, and after the PVB casting layer and the base layer of the test specimen were completely separated, the test was ended. The transverse and longitudinal peel strength are the average of the results obtained for the three samples. The results are shown in Table 5.

TABLE 5

Test piece	7A	7B	7C	7D
					Material	Example 4-1	Comparative example 2	Example 4-1	Comparative example 2
Film formation method	Particle casting	Particle casting	Direct calendaring	Direct calendaring
					Process for producing a solid-state image sensor	Preparation example 1	Preparation example 1	PREPARATION EXAMPLE 10-1	PREPARATION EXAMPLE 10-1
PVB layer thickness (mm)	0.2	0.2	0.2	0.2
					Adhesive amount (g/m) ² )	20	20	20	20
Transverse peel Strength (kgf)	1.3 to 2.1	0.2 to 0.8	1.3 to 2.1	0.2 to 0.8
					Machine direction peel strength (kgf)	1.8 to 2.5	0.5 to 1.0	1.8 to 2.5	0.5 to 1.0

As can be seen from Table 5, the PVB product obtained with the material of example 4-1 had higher peel strength in both the transverse and longitudinal directions between the PVB-modified material layer and the substrate layer than the PVB product obtained with the material of comparative example 2. In the PVB product made from the material of comparative example 2, the PVB modified material layer was easily peeled, but the material of example 4-1 greatly enhanced the peel strength, was not easily peeled, and had better application in the preparation of the polyvinyl butyral product. In addition, if a foaming step is added in the process, in which the temperature of the foaming furnace 81 is sequentially increased from 81a to 81e (e.g., 180℃at 195℃at 210℃at 225℃at 180℃depending on the amount of the foaming agent), the peel strength of the PVB casting layer obtained is increased by 0.2kgf to 0.4kgf.

Tear strength test of polyvinyl butyral articles

First, using the material of example 4-1, pellets of PVB-modified material were prepared separately in accordance with the aforementioned method (1), and then PVB articles were prepared in accordance with preparation example 2. In addition, using the materials of examples 4-1 to 4-3, PVB modified materials were prepared separately in the aforementioned method (2), and PVB articles were prepared according to preparation example 11-1. The above PVB articles each comprise a double layer PVB modifying material film and a layer of fabric. The used substrate layer (fabric) homogenized fiber textile (specification 250D x 250D,21T*19T) and the adhesive is polyurethane glue.

Tear testing was performed as described previously under GB/T16491 test standard. V-shaped test pieces having an overall length of 120mm and a bandwidth of 30mm were cut from the PVB product described above to prepare test pieces 8A to 8D. The V-shaped test piece has a V-shaped included angle of 135 degrees, and square areas (the length of which is contained in the whole length) with the length of 20mm and the width of 30mm are respectively arranged at the left end and the right end of the V-shaped test piece, so that the clamp is convenient to fix and test. The length direction of the V-shaped test strip is labeled as the machine direction and the same as the transverse direction of the PVB article is labeled as the transverse direction.

The tear test was then performed using an HD-A604S tensile strength tester. The temperature at the time of the test was 23.+ -. 2 ℃ and the relative humidity was 60.+ -. 5% and the distance between the two clamps was 80mm. The test pieces 8A to 8D were fixed to the upper and lower clamps, respectively, with the center line of the test piece aligned with the center line of the clamps, and then the clamps were pulled outward at a speed of 200mm/min, and after the test pieces were broken, the tearing strength was recorded. Each group of test pieces was subjected to three tests and an average value was calculated, and the results are shown in table 6.

TABLE 6

As can be seen from the above table, PVB products prepared using the materials of example 4-1 either by casting (preparation 2) or by calendaring (preparation 11-1) exhibited comparable transverse and machine direction tear strengths, indicating that similar PVB products were obtained using either casting or calendaring of the same material. In addition, the resulting PVB product had lower transverse and longitudinal tear strengths when using the materials of example 4-1 than the PVB products of examples 4-2 and 4-3. Thus, when a PVB article having a higher tear strength is desired, thermoplastic polyurethane elastomer can be added in amounts that provide for a wider range of applications in the preparation of polyvinyl butyral articles. In addition, when the thermoplastic polyurethane elastomer is added in excess of 18 parts by weight, the tear strength decreases (data not shown).

Flame retardant testing of polyvinyl butyral articles

Using the materials of examples 4-1, 5-1 and 5-2, PVB modified materials were prepared by the respective methods of preparation (2) described above, followed by the preparation of PVB articles according to preparation 11-1. The above PVB articles each comprise a double layer PVB modifying material film and a layer of fabric. The used substrate layers (fabrics) are all chemical fiber woven fabrics (standard 250D x 250D,21T*19T), and the adhesives are all polyurethane glue.

From the PVB product, 140mm x 80mm test pieces were cut to prepare test pieces 9A to 9C. The test strip is labeled as longitudinal, the same as the longitudinal direction of the PVB article, and the test strip is labeled as transverse, the same as the transverse direction of the PVB article. And folding each test piece in half along the length direction, then carrying out flame retardant test by using an FAA VC-2 type automatic flame vertical combustion test box, taking three test pieces from each group, and calculating the average value.

TABLE 7

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As is clear from Table 7, the polyvinyl butyral modified material was excellent in flame retardant effect by adding 8 parts by weight of the total amount of flame retardants (1:1 zinc stannate and zinc hydroxystannate). Therefore, when the flame retardancy of the product needs to be improved, zinc stannate and/or zinc hydroxystannate can be added in an appropriate amount, and the product can be widely applied to the preparation of polyvinyl butyral products.

From the above, the polyvinyl butyral modified material of the present invention has better water resistance and anti-tackiness. In addition, various polyvinyl butyral modified products prepared from the polyvinyl butyral modified material can be used for preparing outdoor products and other daily necessities, such as dust covers, tents, raincoats, bags, handbags, household necessities, sports goods, lamp box cloth, advertisement cloth, ground mats and the like. In addition, materials such as polyvinyl butyral and plasticizer may be additionally added to the glass laminate film for reuse.

The above examples are only illustrative of the present invention and are not intended to limit the scope of the present invention. The scope of the invention is indicated by the claims rather than by the foregoing description of the embodiments.

Claims

1. A polyvinyl butyral modified material comprises a polyvinyl butyral composite material, a first filler, an anti-hydrolysis agent, zinc stearate, calcium stearate, a high molecular dispersing agent, a deodorant, tetramethylthiuram monosulfide and trimethylolpropane tri (3-mercaptopropionic acid) ester, wherein the polyvinyl butyral composite material is obtained by plasticizing a composition comprising polyvinyl butyral and a first plasticizer.

2. The polyvinyl butyral modified material of claim 1, wherein the first filler is present in an amount of 3 to 15 parts by weight, the hydrolysis inhibitor is present in an amount of 0.3 to 2.5 parts by weight, the zinc stearate is present in an amount of 1.5 to 5 parts by weight, the calcium stearate is present in an amount of 0.1 to 1.5 parts by weight, the polymeric dispersant is present in an amount of 0.001 to 0.010 parts by weight, the odor eliminator is present in an amount of 0.8 to 1.0 parts by weight, the tetramethylthiuram monosulfide is present in an amount of 0.1 to 0.2 parts by weight, and the trimethylolpropane tris (3-mercaptopropionate) is present in an amount of 0.001 to 0.003 parts by weight, based on 100 parts by weight of the total polyvinyl butyral composite material; and the first plasticizer is contained in the polyvinyl butyral composite in an amount of 3 to 15 parts by weight based on 100 parts by weight of the total content of the polyvinyl butyral composite.

3. The polyvinyl butyral modified material of claim 1, wherein the material of the first filler comprises aluminosilicate crystals.

4. The polyvinyl butyral modified material as claimed in claim 1, wherein the hydrolysis inhibitor material comprises carbodiimide-based hydrolysis inhibitors.

5. The polyvinyl butyral modified material of claim 1, wherein the polymeric dispersant material comprises polysiloxanes, high melting point waxes, or combinations thereof.

6. The polyvinyl butyral modified material of claim 1, wherein the odor eliminator comprises sodium bicarbonate, a porous inorganic silicate, or a combination thereof.

7. The polyvinyl butyral modified material of any one of claims 1-6, wherein the polyvinyl butyral composite is a polyvinyl butyral residue.

8. The polyvinyl butyral modified material of claim 1, further comprising a second plasticizer in an amount of 2.5 to 20 parts by weight based on 100 parts by weight of the total content of the polyvinyl butyral composite, and the second plasticizer comprises a diisooctanoate plasticizer, a phthalate plasticizer, an adipate plasticizer, or a combination thereof.

9. The polyvinyl butyral modified material of claim 1, further comprising polyvinyl alcohol in an amount of greater than 0 to 40 parts by weight based on 100 parts by weight of the total content of the polyvinyl butyral composite.

10. The polyvinyl butyral modified material of claim 1, further comprising a second filler in an amount of 5 to 160 parts by weight based on 100 parts by weight of the total content of the polyvinyl butyral composite, and the material of the second filler comprises calcium carbonate.

11. The polyvinyl butyral modified material of claim 1, further comprising a cold-resistant agent in an amount of 1.5 to 10 parts by weight based on 100 parts by weight of the total content of the polyvinyl butyral composite, and the cold-resistant agent comprises an adipate type cold-resistant agent, polyisobutylene, or a combination thereof.

12. The polyvinyl butyral modified material of claim 1, further comprising an antioxidant in an amount of 0.5 to 2.5 parts by weight based on 100 parts by weight of the total content of the polyvinyl butyral composite, and the antioxidant material comprises pentaerythritol esters antioxidants, phosphite esters antioxidants, hexamethylenediamine antioxidants, or a combination thereof.

13. The polyvinyl butyral modified material of claim 1, further comprising an anti-uv agent in an amount of 0.1 to 1.5 parts by weight based on 100 parts by weight of the total content of the polyvinyl butyral composite, and the anti-uv agent comprises a benzotriazole-based anti-uv agent, a benzophenone-based anti-uv agent, or a combination thereof.

14. The polyvinyl butyral modified material of claim 1, further comprising a colorant in an amount of 0.5 to 35 parts by weight based on 100 parts by weight of the total content of the polyvinyl butyral composite, and the material of the colorant comprises an inorganic colorant.

15. The polyvinyl butyral modified material of claim 1, further comprising a flame retardant in an amount of 1 to 15 parts by weight based on 100 parts by weight of the total content of the polyvinyl butyral composite, and the flame retardant material comprises zinc stannate, zinc hydroxystannate, or a combination thereof.

16. The polyvinyl butyral modified material of claim 1, further comprising glass frit in an amount of 3 to 15 parts by weight based on 100 parts by weight of the total content of the polyvinyl butyral composite.

17. The polyvinyl butyral modified material as claimed in claim 1, further comprising a foaming agent in an amount of 2 to 10 parts by weight based on 100 parts by weight of the total content of the polyvinyl butyral composite material, and the foaming agent is azodicarbonamide.

18. The polyvinyl butyral modified material of claim 1, further comprising a thermoplastic polyurethane elastomer in an amount of 5 to 15 parts by weight based on 100 parts by weight of the total content of the polyvinyl butyral composite.

19. A process for preparing the polyvinyl butyral modified material as claimed in any one of claims 1 to 18, comprising the steps of:

20. The method of claim 19, wherein step (S2) is performed by at least two filtration.

21. The method of manufacturing of claim 19, further comprising the steps of:

(S3) granulating the filtered polyvinyl butyral modified material through a die to obtain granules of the polyvinyl butyral modified material.

22. A polyvinyl butyral modified article comprising a layer of polyvinyl butyral modified material, and the layer of polyvinyl butyral modified material made from a material comprising the polyvinyl butyral modified material of any one of claims 1 to 18.

23. The polyvinyl butyral modified article of claim 22, wherein the polyvinyl butyral modified article further comprises a substrate layer disposed on the polyvinyl butyral modified material layer, wherein the substrate layer is selected from the group consisting of a fabric layer, a metal-containing plastic layer, a metal-free plastic layer, and combinations thereof.

24. The polyvinyl butyral-modified article of claim 23, wherein the layer of polyvinyl butyral-modified material further comprises an adhesive layer independently from the base layer.

25. The polyvinyl butyral modified product of claim 24, wherein the adhesive layer is independently composed of a mixture of a glue and a cross-linking agent, and the glue is selected from the group consisting of polyurethane glue, acrylic glue, and combinations thereof.

26. The polyvinyl butyral-modified article of any of claims 22-25, wherein the layer of polyvinyl butyral-modified material is foamed.