TWI691401B - Extruded matt foil with improved mechanical properties and a high weathering resistance - Google Patents

Abstract

The present invention relates to an extruded matt foil comprising at least one layer in which glass beads are uniformly distributed in a polymer matrix comprising at least one fluoropolymer and at least one further layer. The matt foil has a particularly high UV-resistance, a high weathering resistance and excellent mechanical properties. Therefore, the foil of the present invention is highly suitable for surface-protection of materials such as polyvinyl chloride (PVC) and for use in high-pressure laminates (HPLs).

Description

Extruded matte foil with improved mechanical properties and high weather resistance

The present invention relates to an extruded matte foil comprising at least one layer of glass beads uniformly distributed in a polymer matrix containing at least one fluoropolymer, and at least one additional layer. The matte foil has particularly high UV resistance, high weather resistance and excellent mechanical properties. Therefore, the foil of the present invention is very suitable for surface protection of materials such as polyvinyl chloride (PVC) and suitable for use in high-pressure laminates (HPL).

Fluoropolymer foils such as polyvinylidene fluoride (PVDF) have excellent UV resistance and moisture resistance, and provide protection from chemicals, atmospheric reagents, mechanical damage, fungi, dust, and graffiti. Typically, such foils include an additional polymethyl (meth)acrylate (PMMA) layer under the PVDF layer, which contains UV absorbers and UV stabilizers. Such multilayer foils provide excellent protection from solar UV radiation and weathering, and are often used for lamination of UV-sensitive substrates.

WO 2009/000566 A1 describes a PMMA/PVDF foil with excellent weather resistance and high UV protection. This foil contains a mixture of PVDF and PMMA with a ratio of 1:0.01 to 1:1 (w/w) and a UV stabilizer and UV absorber.

Patent application US 2008/0311406 A1 describes a coextruded multilayer foil, which comprises: Surface layer with PVDF and optionally PMMA; intermediate layer containing PVDF and PMMA; and adhesive layer containing functional PMMA.

This application describes the use of foil as a protective layer for (woody) cellulose material boards.

EP 2 756 950 A1 discloses a laminated foil comprising a polymer blend layer of PVDF and acrylic resin and another layer of acrylic resin composition. This application clearly states that the corresponding laminated foil has a glossy appearance.

Object of the present invention

Due to the inherent gloss of the outer PVDF layer, PVDF-based foils usually have a glossy appearance. Although this glossy appearance is considered aesthetic for many purposes, it becomes unfavorable in situations where a matte appearance is required. These applications include coatings for various construction applications such as high-pressure laminates (HPL), window frames, doors, and garage doors.

A common technique used to make PVDF-based foils matte is to mechanically structure their external surfaces, which can be performed during manufacture or lamination, for example by hot embossing. However, when this structured foil is applied to a substrate or later during long-term use of this foil, the structured surface of the foil may easily stretch, compress, or bend. In these cases, the structure on the surface may be damaged at least to some extent, and the affected area appears shiny.

In addition, depending on many factors such as the temperature during processing, the surface material of the roller, etc., the undesirable degree of gloss of these structured foils may be susceptible. This makes the final appearance of the material covered by such foils extremely unreproducible and essentially unpredictable. For example, when such foils are used in laminated substrates, the final appearance of the resulting laminate depends largely on various processing conditions, which is very undesirable.

In order to avoid fluctuations in the appearance of the final product, PVDF-based foils with structured surfaces are typically after use of identical equipment and disposal within a clearly defined narrow temperature range Need to be used immediately. This makes the cost of manufacturing and disposal of materials laminated with corresponding PVDF-based foils particularly high.

The use of uniformly dispersed particles such as glass beads in PMMA sheets has been known for some time. For example, US 7,183,001 B1 describes a thermoplastic composition for shaping light-scattering articles, which comprises: a transparent thermoplastic material made of (meth)acrylic acid copolymer; and particles of hollow glass spheres, or hollow glass spheres Mixture of particles with minerals and/or particles of organic compounds acting as light scattering particles.

In addition, several applications (see, for example, JP H08 H08 183925 A, JP H04-11672, GB 1205268 A, etc.) describe fluoropolymer-based suspensions containing glass beads. Such suspensions can be used to produce anti-stick coatings on metal substrates, and are often used to coat frying pans, for example. These coatings can be distinguished from coextruded foils, especially because there is no orientation of the polymer chains in the coating formed from the suspension. In contrast, extruded foils contain oriented polymer chains.

However, glass beads are never used in fluoropolymer-based polymer matrices for coextruded multilayer foils.

JP H4-173843 describes an extruded monolayer film prepared from a composition containing PVDF, acrylic resin and glass beads. The film can be bonded to the metal substrate by means of an adhesive that can contain acrylic resin, epoxy resin, or fluororesin, preferably a combination thereof.

Despite the foregoing, fluoropolymers are known to have high hydrophobicity and low adhesion to inorganic materials with hydrophilic surfaces such as glass. Due to the expected poor adhesion between the inorganic material particles and the fluoropolymer matrix, the mechanical properties of the entire system have been expected to be quite suitable, especially when the inorganic material particles are substantially spherical.

In addition, it is further generally believed that the surface of the glass beads can serve as a catalyst for decomposing the fluoropolymer material at an increased temperature required for the thermoplastic material treatment of the fluoropolymer material. This thermal decomposition is known to release extremely toxic and corrosive hydrogen fluoride. For example In other words, the material safety data sheets of common commercially available fluoropolymers (such as T850 PVDF from Kurea or Hylar® 9009 PVDF from Solvay) clearly indicate that for this reason, it is necessary to avoid the incorporation of glass into the PVDF matrix.

The incorporation of hydrophobic scattering particles of polymers such as polysiloxane, PMMA or cross-linked polystyrene into the fluoropolymer matrix of coextruded multilayer films has not been implemented. Due to the common view that the chemical resistance of the resulting fluoropolymer foil will be significantly lower than that of the unmodified fluoropolymer foil, PMMA particles have not been used. Polysiloxane particles such as Tospearl® 120 have also been avoided for use in fluoropolymer matrices because of the poor adhesion between these particles and fluoropolymers. In addition, the presence of polysilicon particles in the outer layer of the foil can make the foil unsuitable for printing applications, even if the printed pattern and polysilicon particles are on the opposite side of the foil.

In view of the above, the object solved by the present invention is to provide a fluoropolymer-based foil with a long-term uniform matt appearance. During the subsequent disposal of the foil, especially under increased temperature and/or mechanical pressure, the appearance does not Will be affected or even damaged. In particular, it is important that the foils required can be used in the lamination process to obtain materials with a substantially uniform appearance, regardless of the processing temperature and materials or processing tools such as laminating rollers.

Compared to prior art mechanically textured foils, such foils should also remain uniformly matte after applications where such foils are bent, stretched and subjected to external mechanical pressure or are handled under fluctuating temperatures. In addition, such foils should provide the advantages provided by fluoropolymer foils of the prior art, especially excellent chemical resistance and good mechanical stability to chemicals, humidity and UV radiation.

The present invention is based on the unexpected discovery that the incorporation of glass particles, such as glass beads, into the fluoropolymer layer of a co-extruded multilayer foil substantially uniformly results in excellent mechanical properties and extremely high weather resistance and chemical resistance Characteristic and high temperature resistant foil. Additionally and even more importantly, this Foil-like is used in the lamination process without any considerable gloss appearance to provide a laminate material with a particularly uniform appearance. In detail, the appearance of the final laminate does not depend on factors such as lamination temperature and processing equipment.

In the first aspect of the present invention, the present invention relates to a co-extruded multi-layer foil comprising at least layer A and layer B, wherein the layer A comprises: based on the total weight of the layer A, 40.0 to 97.0 wt% Fluoropolymer; 0.0 to 45.0 wt% polyalkyl (meth)acrylate; and 3.0 to 30.0 wt% glass beads; and the layer B contains: 0.0 to 100.0 wt% based on the total weight of the layer B Poly(meth)acrylate; 0.0 to 95.0wt% of one or several impact modifiers; 0.0 to 40.0wt% of fluoropolymer; 0.0 to 5.0wt% of one or several UV absorbers ; 0.0 to 5.0wt% of one or several UV stabilizers; and 0.0 to 20.0wt% of the adhesion promoting copolymer, which contains (i) 70.0 to 95.0wt% of the methyl group by weight of the adhesion promoting copolymer Methyl acrylate; (ii) 0.5 to 15.0% by weight of maleic anhydride; and (iii) 0.0 to 25.0% by weight of other vinyl copolymerizable monomers having no functional groups other than vinyl functional groups; and Based on the weight of the layer B, the cumulative content of the poly(meth)acrylate and one or several impact modifiers in the layer B is at least 50 wt%, preferably at least 60 wt%, more preferably At least 70% by weight, and even more preferably at least 80% by weight, still more preferably at least 90% by weight, particularly preferably at least 95% by weight.

As those skilled in the art will readily understand, as used herein, the term " foil " as used herein refers to a sheet having a thickness of less than 5 mm, more preferably less than 1 mm. Although the foil of the present invention can be advantageously used as a protective coating, the term " foil " as used in this application should be generally distinguished from the term " coating ". The coating is typically the top layer of a multilayer substrate and cannot be handled separately from the substrate. Compared to a coating, the foil of the present invention is not necessarily a layer of a multilayer article, that is, it does not have to be attached to any substrate, and thus can be handled separately and used for many different purposes.

The non-smooth effect is caused by the glass beads on the surface of the foil. In a preferred embodiment, the glass beads actually protrude (protrudes) from the surface of the foil. Therefore, the glass beads provide diffuse light dispersion, which substantially reduces light reflection, and thereby reduces gloss.

The inventors found that during the lamination process, even at temperatures as high as 120°C or even higher, the foil of the present invention remains uniformly matt, and the mechanical pressure of the lamination roller does not cause the glass beads to " sink " Foil material. The truth is that the glass beads remain visible on the surface of the resulting laminate and ensure that its appearance is uniform and dull. The surface roughness also remains substantially unchanged. This observation is very surprising because, according to common opinion, it is expected that the poor adhesion between the highly hydrophobic fluoropolymer matrix and the hydrophilic glass beads will result in a system with poor mechanical properties.

The term " uniform " as used herein means that the concentration of glass beads within the foil is substantially constant.

Ultimately, the discovery that the material of the present invention has excellent heat resistance is contrary to the common technical bias: the surface of an inorganic material such as glass acts as a catalyst at high temperatures, thereby decomposing the material of the matrix.

The foil of the present invention includes at least layer A and layer B, wherein the layer A includes: based on the total weight of the layer A, 40.0 to 97.0 wt% fluoropolymer; 0.0 to 45.0 wt% poly(meth)acrylic acid Alkyl esters; and 3.0 to 30.0 wt% glass beads; And the layer B contains: based on the total weight of the layer B, 0.0 to 100.0 wt% of poly(meth)acrylate; 0.0 to 95.0 wt% of one or several impact modifiers; 0.0 to 40.0 wt % Of fluoropolymer; 0.0 to 5.0 wt% of one or several UV absorbers; 0.0 to 5.0 wt% of one or several UV stabilizers; and 0.0 to 20.0 wt% of adhesion promoting copolymer, which contains Based on the weight of the adhesion promoting copolymer, (i) 70.0 to 95.0% by weight of methyl methacrylate; (ii) 0.5 to 15.0% by weight of maleic anhydride; and (iii) 0.0 to 25.0% by weight Other vinyl copolymerizable monomers having functional groups other than vinyl functional groups; and wherein by weight of the layer B, the poly(meth)acrylate and one or several impact modifiers in the layer B The cumulative content of the agent is at least 50wt%, preferably at least 60wt%, more preferably at least 70wt%, even more preferably at least 80wt%, still more preferably at least 90wt%, particularly preferably at least 95wt% .

The matte foil of the present invention is superior to matte foils available in the market in terms of weather resistance and mechanical resistance, and has improved stability over a long period of time (>10 years = long-term stability). The term "stability" as used herein refers not only to the inherent stability of the foil in terms of weathering effects and mechanical damage, but also to the continuity of its protective effect.

In addition, the matte foil of the present invention provides the following advantages:

‧The matte foil of the present invention can be used for laminating various substrates at different temperatures and after using different laminating equipment. The appearance of the resulting laminated product is very uniform and is substantially independent of the processing conditions of materials such as lamination temperature or lamination rolls.

‧It has excellent weather resistance and excellent chemical resistance, for example, compared to commercially available cleaning compositions.

‧It is substantially impermeable to water vapor, that is, its water vapor transmission rate corresponds to the water vapor transmission rate of unmodified PVDF foil.

‧It has dustproof performance to facilitate cleaning.

‧It remains uniformly dull for a long time.

‧It can be manufactured in extrusion equipment at a low cost.

Because the material used in the present invention has excellent thermal stability, it is very suitable for thermoplastic processing (such as extrusion, injection molding) or for foil molding processes (such as cold roll processes).

In another aspect thereof, the present invention relates to a method for manufacturing a foil, wherein in the steps included in the method, in the foil molding process, preferably in the cold roll process, it is composed of the following Object-molded foil: based on the total weight of the composition, 40.0 to 97.0% by weight of fluoropolymer; 0.0 to 45.0% by weight of polyalkyl (meth)acrylate; and 3.0 to 30.0% by weight of glass beads.

In yet another aspect, the invention relates to a multilayer product, preferably a high-pressure laminate, comprising a substrate at least partially covered by the foil, wherein layer A forms the outer surface of the multilayer product; layer B is located on the Between layer A and the substrate; and in the presence of it, layer C is located between the layer B and the substrate.

Another aspect of the present invention relates to a method for manufacturing a foil, wherein in the steps included in the method, in the foil molding process, preferably in the cold roll process, it is molded from a composition including the following Foil: based on the total weight of the composition, 40.0 to 97.0 wt% fluoropolymer; 0.0 to 45.0 wt% polyalkyl (meth)acrylate; and 3.0 to 30.0wt% glass beads.

Yet another aspect of the present invention relates to a multilayer article comprising a substrate at least partially covered by the foil of the present invention. The foil of the present invention has excellent weathering stability and mechanical properties, and when applied as a coating on an article, the foil of the present invention can protect the article from scratches, chemicals, humidity and solar UV radiation . Therefore, the resulting product is very suitable for environments where the resulting product is exposed to these factors, for example, for outdoor use.

Therefore, the main points of the present invention can be summarized as follows:

{1} A coextruded multilayer foil comprising at least layer A and layer B, wherein layer A comprises: based on the total weight of layer A, 40.0 to 97.0 wt% fluoropolymer; 0.0 to 45.0 wt% Polyalkyl (meth)acrylate; and 3.0 to 30.0 wt% of glass beads; and the layer B contains: based on the total weight of the layer B, 0.0 to 100.0 wt% of poly(meth)acrylate; 0.0 One or several impact modifiers to 95.0wt%; fluoropolymers from 0.0 to 40.0wt%; one or several UV absorbers from 0.0 to 5.0wt%; one or several from 0.0 to 5.0wt% UV stabilizer; and 0.0 to 20.0 wt% of the adhesion promoting copolymer, which contains (i) 70.0 to 95.0 wt% of methyl methacrylate based on the weight of the adhesion promoting copolymer; (ii) 0.5 to 15.0wt % Maleic anhydride; and (iii) 0.0 to 25.0 wt% of other vinyl copolymerizable monomers that do not have functional groups other than vinyl functional groups; and wherein the layer B is based on the weight of the layer B The poly(meth)acrylate and one or several impact resistance The cumulative content of the modifying agent is at least 50wt%, preferably at least 60wt%, more preferably at least 70wt%, even more preferably at least 80wt%, still more preferably at least 90wt%, particularly preferably At least 95wt%.

{2} The foil as described in item {1}, wherein the layer A contains: based on the total weight of the layer A, 85.0 to 97.0 wt% of the fluoropolymer; 0.0 wt% of the poly(methyl) Alkyl acrylate; and 3.0 to 15.0wt% glass beads.

{3} The foil as described in item {1} or {2}, wherein the fluoropolymer is selected from polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polytetrafluoroethylene (PTFE), (Ethylene tetrafluoroethylene) copolymer (ETFE), fluorinated ethylene-propylene (FEP) or mixtures thereof.

{4} The foil as described in any one of items {1} to {3}, wherein the fluoropolymer is amorphous-based polyvinylidene fluoride or microcrystalline polyvinylidene fluoride, preferably It has a molecular weight Mw of 50 000 to 300 000 g/mol, which is determined by GPC.

{5} The foil according to any one of items {1} to {4}, wherein the glass beads are substantially spherical and have an average diameter of 2.0 μm to 30.0 μm, preferably 5.0 μm to 20.0 μm.

{6} The foil as described in any one of items {1} to {5}, wherein the polyalkyl (meth)acrylate is a polymethacrylate with an average molar weight Mw of 80 000 g/mol to 180 000 g/mol Methyl acrylate, and can be obtained by the polymerization of the composition, the polymerizable components of the composition include: based on the weight of the polymerizable composition, (a) 50.0 to 99.9% by weight of methyl methacrylate , (B) 0.1 to 50.0 wt% of C ₁ -C ₄ alcohol acrylate, (c) 0.0 to 10.0 wt% of at least one additional monomer copolymerizable with monomers (a) and (b).

{7} The foil as described in any one of items {1} to {6}, wherein based on the weight of the glass beads used, at least 20wt%, more preferably at least 40wt%, even more preferably at least 60wt% , And even More preferably, at least 80 wt% of the diameter of the glass beads is higher than the average thickness of the layer A.

類型化合物；及作為UV穩定劑的0.2至2.0wt%之HALS類型化合物。 {8} The foil as described in any one of items {1} to {7}, wherein the layer B contains: 0.5 to 4.0 wt% of benzene as the first UV absorber based on the total weight of the layer B Pyridazole type compound; 0.5 to 3.0wt% of third as second UV absorber

Type compounds; and 0.2 to 2.0 wt% of HALS type compounds as UV stabilizers.

{9} The foil according to any one of items {1} to {8}, wherein the foil further includes an adhesion promoting layer C, wherein the layer B is located between the layer A and the layer C, and the layer C Contains an adhesion promoting copolymer comprising: (i) 70.0 to 95.0 wt% methyl methacrylate; (ii) 0.5 to 15.0 wt% maleic acid based on the weight of the adhesion promoting copolymer Diacid anhydride; and (iii) 0.0 to 25.0 wt% of other vinyl copolymerizable monomers that do not have functional groups other than the vinyl functional group.

{10} The foil according to any one of items {1} to {9}, wherein the thickness of the layer A is 1.0 μm to 30.0 μm; and the thickness of the layer B is 15.0 μm to 150.0 μm.

{11} A method for manufacturing the foil according to any one of items {1} to {10}, wherein in the steps included in the method, the foil is in a foil molding process, preferably in a cold The roll process is molded from a composition comprising: 40.0 to 97.0 wt% fluoropolymer based on the total weight of the composition; 0.0 to 45.0 wt% polyalkyl (meth)acrylate; and 3.0 to 30.0wt% glass beads.

{12} A multilayer product, preferably a high-pressure laminate, comprising a substrate at least partially covered by the foil according to any one of items {1} to {10}, wherein Layer A forms the outer surface of the multilayer article; layer B is located between the layer A and the substrate; and in the presence of it, layer C is located between the layer B and the substrate.

{13} The multilayer article according to item {12}, wherein the layer B is adjacent to the layer A, and in the presence of the layer C is adjacent to the layer B.

{14}A method for manufacturing a multi-layer article as described in items {12} or {13}, the method comprising using items {1} to {10 by means of co-extrusion, lamination or extrusion lamination } The step of coating the substrate with the foil according to any one of the items.

{15} The method described in item {14}, wherein the multilayer product is a high-pressure laminate, and the step of coating the substrate with the foil described in any one of items {1} to {10} is: It is carried out under the following conditions: the pressure is not lower than 1 MPa, preferably not lower than 4 MPa, more preferably not lower than 6 MPa, and the temperature is not lower than 120°C.

1: Layer A based on fluoropolymer

2: Fluoropolymer matrix

3: glass beads

4: Layer B based on PMMA

5: adhesion promotion layer C

FIG. 1 is a schematic illustration of the matte foil of the present invention, which consists of a layer A based on a fluoropolymer and a layer B based on PMMA:

1. Layer A based on fluoropolymer

2. Fluoropolymer matrix

3. Glass beads

4. Layer B based on PMMA

FIG. 2 schematically illustrates a specific example of a matte foil including a layer A based on a fluoropolymer, a layer B based on PMMA, and an adhesion promoting layer C:

1. Layer A based on fluoropolymer

2. Fluoropolymer matrix

3. Glass beads

4. Layer B based on PMMA

5. Adhesion promoting layer C

Fig. 3 is a photomicrograph of the matte foil of the present invention obtained with a scanning electron microscope. Magnification: 5000x, 10kV, SED detector.

The foil of the present invention comprises a layer A based on a fluoropolymer in which the glass beads are substantially uniformly dispersed in the polymer matrix. In a specific example, the polymer matrix comprises a combination of a fluoropolymer such as PVDF and at least one additional polymer such as polyalkyl (meth)acrylate such as PMMA. In this specific example, based on the total weight of layer A, the content of the fluoropolymer is typically 40.0 to 97.0 wt%, and the content of polyalkyl (meth)acrylate is 0.0 to 45.0 wt%. This corresponds to the following weight ratio of fluoropolymer: polyalkyl (meth)acrylate from about 1:1 to about 1:1. As those skilled in the art will readily understand, the exact composition of the polymer matrix in layer A can be adjusted depending on the intended use of the foil. In the following cases, a special weather-resistant foil can be obtained by using the combination of PMMA/PVDF: the weight ratio of PVDF to PMMA is 1.0: 0.01 to 1:1 (w/w), more preferably 1.0: 0.15 to 1.0 : 0.40 (w/w), a ratio of 1.0:0.15 to 1.0:0.30 (w/w) is particularly preferred.

glass bead

Depending on the desired gloss level of the foil, based on the total weight of layer A, the content of glass beads dispersed in the polymer matrix is usually 3.0 to 30.0 wt%, more preferably 5.0 to 20.0 wt%, and particularly preferably 10.0 to 15.0wt%.

The glass beads may have an aspect ratio of at least about 4:1, more preferably at least about 2:1. Ideally, The glass beads are substantially spherical, that is, the aspect ratio is about 1:1.

Glass beads advantageously have a narrow size distribution. The size distribution can be measured by a conventional device such as a Malvern particle size analyzer (for example, by Mastersizer 2000). Typically, glass beads are solid (ie, non-hollow) glass beads, not limited to any chemical composition and may have a smooth surface or an etched surface. Surface etching can be conveniently performed by contacting glass beads with nitric acid for a sufficient time to obtain the desired degree of surface etching. In order to achieve the best adhesion between the glass beads and the fluoropolymer-based matrix, the glass beads can also have a siloxane layer.

Depending on the desired optical properties of the foil and the desired surface roughness, the size (average diameter, average weight) of the glass beads is typically selected to be 2.0 μm to 30.0 μm, preferably 5.0 μm to 20.0 μm, and even more preferably 8.0 μm to 15.0μm. Typically, if glass beads with an average diameter of less than 2.0 μm are used, the surface of the resulting foil no longer appears dull. On the other hand, the use of glass beads with an average diameter above 30.0 μm produces a relatively high surface roughness, which is undesirable for many applications.

According to the standard specification of laser diffraction measurement ISO 13320 (2009), the size of glass beads can be measured-indicated as the so-called d ₅₀ value (ie, the particle size of 50% of the particle volume is less than the specified average particle size). Typically, in each case (at a refractive index of 1,462 of the dispersion of particles in the form of butyl acetate), at 2000 rpm and evaluated by Fraunhofer, the Malvern Instruments' Malvern mastersizer 2000 (with microdispersed MS1) determines the size of glass beads by laser light scattering (at a room temperature of 23°C). For this purpose, another equally suitable instrument is the Beckman Coulter LS 13 320 laser diffraction particle size analyzer.

The inventors have found that the foil of the present invention and the substrate laminated with the foil exhibit a particularly uniform matte appearance under the following circumstances: at least 20 wt%, more preferably at least 40 wt%, based on the weight of the glass beads used, Even more preferably at least 60 wt%, and in some cases even at least 80 wt% of the glass beads have a diameter higher than the average thickness of layer A. I don’t want to be bound by theory. In a practical example, the ability of the glass beads to resist external mechanical pressure at increased temperatures during the lamination process is particularly high.

The photomicrograph is used to advantageously determine the average thickness of the foil and the average thickness of the individual layers. The photomicrograph is obtained using a scanning electron microscope such as JEOL JSM-IT300 (available from JEOL GmbH, Freising, Germany). Sample pieces of suitable size for measurement can be obtained by freezing the foil in liquid nitrogen and breaking it mechanically. Use a scanning electron microscope to take pictures of the newly obtained fracture surface.

In order to achieve good mechanical properties of the foil, the glass beads are preferably non-hollow, that is, solid.

Based on 0.01 to 0.2 units, the refractive index of the glass beads (measured against Na-D line (589 nm) at 20° C.) is selected to be different from the refractive index of the polymer material matrix in the layer A of the fluoropolymer.

The chemical composition of the glass beads is not particularly limited, and virtually any commercially available glass can be used. In detail, such glasses include fused silica glass, soda lime silica glass, sodium borosilicate glass, lead oxide glass aluminosilicate glass, and oxidized glass, among which the use of soda lime silica glass is particularly preferred.

The refractive index of soda lime silica glass is usually 1.51 to 1.52. In a particularly preferred embodiment, the glass beads have the following composition: 70.0 to 75.0 wt.% SiO ₂ , 12.0 to 15.0 wt.% Na ₂ O, 0.0 to 1.5 wt.% K ₂ O, 7.0 to 12.0 wt.% of CaO, 0.0 to 5.0 wt.% of MgO, 0.1 to 2.5 wt.% of Al ₂ O ₃ , 0.0 to 0.5 wt.% of Fe ₂ O ₃ .

Examples of suitable glass beads are Spheriglass® products such as Spheriglass® 7025 and Spheriglass® 5000 available from Potters Industries LLC, or Omicron® glass beads Omicron® NP3 and Omicron® NP5 available from Sovitec Mondial S.A.

In some specific examples, the polymer matrix of the fluoropolymer-based layer A consists essentially of one or several fluoropolymers such as PVDF. In these specific examples, based on the total weight of the layer A based on the fluoropolymer, the content of the fluoropolymer is typically 85.0 to 97.0 wt%, more preferably 88.0 to 95.0 wt%, and particularly preferably It is 90.0wt% to 92.0wt%. Therefore, based on the total weight of the fluoropolymer-based layer A, the fluoropolymer-based layer A typically contains 4.0 to 15.0 wt%, preferably 5.0 to 12.0 wt%, particularly preferably 8.0 wt% to 10.0wt% glass beads.

Fluoropolymer

Depending on the intended use of the foil of the present invention, the fluoropolymer may be selected from polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polytetrafluoroethylene (PTFE), (ethylene tetrafluoroethylene) copolymer ( ETFE), fluorinated ethylene-propylene (FEP) or mixtures thereof.

The PVDF polymer used in the foil is a substantially transparent, semi-crystalline, thermoplastic fluoroplastic. Advantageously, PVDF has a high crystalline melting point. When the crystalline melting point of PVDF is at least 150°C and more preferably at least 160°C, the heat resistance of the foil is particularly high. The upper limit of the crystalline melting point is preferably approximately 175°C, which is equal to the crystalline melting point of PVDF. More preferably, the weight-average molecular weight Mw of PVDF is in the range of 50,000 to 300,000 g/mol, more preferably 80,000 to 250 000 g/mol, even more preferably 150,000 to 250 000 g/mol, such as by GPC Determined.

The basic unit of PVDF is vinylidene fluoride, which is polymerized in high-purity water by means of a specific catalyst under controlled pressure and temperature conditions to obtain PVDF. As an example, in the case of using difluorochloroethane as a precursor, vinylidene fluoride can be obtained from hydrogen fluoride and methyl chloride as starting materials. In principle, any commercial grade PVDF (such as Kynar® grade produced by Arkema, Dyneon® grade produced by Dyneon or produced by Solvay) Solef® grade) is suitable for the present invention. For example, the following commercial products can be used: Kynar® 720 (vinylidene fluoride content: 100wt%, crystalline melting point: 169°C) and Kynar® 710 (vinylidene fluoride content: 100wt%, crystalline) manufactured by Arkema Melting point: 169°C); T850 manufactured by KUREHA (vinylidene fluoride content: 100wt%, crystalline melting point: 173°C); Solef® 1006 manufactured by Solvay Solexis (vinylidene fluoride content: 100wt%, crystalline melting point: 174℃) and Solef® 1008 (trade name) (vinylidene fluoride content: 100wt%, crystalline melting point: 174℃).

PVDF has 3 types of bonding modes as a single-body bonding mode: head-to-head bonding; tail-to-tail bonding; and head-to-tail bonding, where head-to-head bonding and tail-to-tail bonding are called " heterogeneity " when bonded "when" heterogeneous linkage of "not more than 10 mole% PVDF in the chemical resistance of the layer A particularly high. From the viewpoint of reducing the heterogeneous bonding rate, PVDF is preferably a resin produced by suspension polymerization.

The heterogeneous bonding rate can be determined based on the peak of the ¹⁹ F-NMR spectrum of PVDF as specified in EP 2 756 950 A1.

Typically, fluoropolymers are not cross-linked and are therefore suitable for thermoplastic processing.

PVDF may include a matting agent to such an extent that the transparency of layer A does not decrease. Organic matting agents and inorganic matting agents can be used as matting agents.

In a specific example, the fluoropolymer is an amorphous or microcrystalline PVDF with a haze value less than 5. For this purpose, the haze value of pure fluoropolymer (PVDF) foil with a thickness of 30 μm was measured at 23° C. according to ASTM D1003. Examples of types of PVDF with appropriate low haze values and particularly good suitability are Solef® 9009 from Solvay, T850 from Kureha and Kynar® 9000HD from Arkema.

Polyalkyl (meth)acrylate

As already mentioned above, the layer A based on the fluoropolymer may further contain up to 45% by weight of polyalkyl (meth)acrylate, such as polymethyl (meth)acrylate (PMMA). PMMA is generally obtained by free radical polymerization of mixtures that include methyl methacrylate. This mix The composition generally comprises at least 40 wt%, preferably at least 60 wt%, particularly preferably at least 80 wt% and even more preferably at least 90 wt% methyl methacrylate, based on the weight of the monomer.

These mixtures used to produce PMMA may also contain other (meth)acrylates copolymerizable with methyl methacrylate. The term " (meth)acrylate " as used herein is intended to cover methyl acrylate, acrylate and mixtures thereof. (Meth) acrylates can be derived from saturated alcohols, such as methyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, third butyl ( Methacrylate, isobutyl (meth)acrylate, pentyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; or derived from unsaturated alcohols, such as oleyl (meth) Group) acrylate, 2-propynyl (meth) acrylate, allyl (meth) acrylate, vinyl (meth) acrylate; and also derived from aryl (meth) acrylate, such as Benzyl (meth) acrylate or phenyl (meth) acrylate, cycloalkyl (meth) acrylate, such as 3-vinylcyclohexyl (meth) acrylate, camphenyl (meth) acrylate Esters; hydroxyalkyl (meth)acrylates, such as 3-hydroxypropyl (meth)acrylate, 3,4-dihydroxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate Ester, 2-hydroxypropyl (meth)acrylate; ethylene glycol di(meth)acrylate, such as 1,4-butanediol (meth)acrylate, (meth)acrylate of ether alcohol, For example, tetrahydrofuranyl (meth)acrylate, vinyloxyethoxyethyl; (meth)acrylic amide and nitrile, such as N-(3-dimethylaminopropyl) (meth)acrylamide , N-(diethylphosphoryl)-(meth)acrylamide, 1-methacrylamide-2-methyl-2-propanol; sulfur-containing methyl acrylate, such as ethyl sulfite Acetylethyl (meth)acrylate, 4-cyanothiobutyl (meth)acrylate, ethylthioacetyl ethyl (meth)acrylate, cyanothiomethyl (meth)acrylate 、Methylsulfinylmethyl(meth)acrylate, bis((meth)acryloyloxyethyl) sulfide; multifunctional (meth)acrylates, such as trimethyl acetyl propane tri( Meth)acrylate.

The polymerization reaction is generally initiated by known free radical initiators. Among the preferred initiators, those skilled in the art are particularly familiar with azo initiators, such as AIBN and 1,1-azobiscyclohexanecarbonitrile, as well as peroxy compounds such as methyl ethyl ketone peroxide, peroxide Acetylacetone, February peroxide Cinnamomide, tert-butyl 2-ethylhexanoate peroxide, ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, dibenzoyl peroxide, third butyl peroxybenzoate, Third butyl peroxyisopropyl carbonate, 2,5-bis(2-ethylhexylperoxy)-2,5-dimethylhexane, third butyl 2-ethylperoxy Hexanoate, tert-butyl 3,5,5-trimethylperoxyhexanoate, dicumyl peroxide, 1,1-bis(tert-butylperoxy)cyclohexane, 1,1 -Bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, cumene hydroperoxide, tert-butyl hydroperoxide, bis(4-tert-butylcyclohexyl) Peroxydicarbonate, mixtures of two or more of the above compounds with each other, and mixtures of the above compounds with compounds that have not been mentioned but can also form free radicals.

唑及氫化乙烯基

唑；乙烯醚及異戊二烯基醚；順丁烯二酸衍生物，諸如順丁烯二酸酐、甲基順丁烯二酸酐、順丁烯二醯亞胺、甲基順丁烯二醯亞胺；以及二烯，諸如二乙烯苯。 The composition to be polymerized may include not only the (meth)acrylate described above, but also other unsaturated monomers copolymerizable with methyl methacrylate and the above (meth)acrylate. Among these substances, in particular: 1-olefins, such as 1-hexene, 1-heptene; branched chain olefins, such as vinylcyclohexane, 3,3-dimethyl-1-propene, 3-methyl 1-diisobutene, 4-methyl-1-pentene; acrylonitrile; vinyl esters, such as vinyl acetate; styrene, substituted styrenes with alkyl substituents in the form of side chains, such as a-methyl Styrene and a-ethylstyrene, substituted styrenes with alkyl substituents in a cyclic form, such as vinyl toluene and p-methylstyrene, halogenated styrenes, such as monochlorostyrene, dichlorostyrene , Trichlorostyrene and tetrachlorostyrene; vinyl heterocyclic compounds, such as 2-vinylpyridine, 3-vinylpyridine, 2-methyl-5-vinylpyridine, 3-ethyl-4-vinylpyridine, 2, 3-dimethyl-5-vinylpyridine, vinylpyrimidine, vinylpiperidine, 9-vinylcarbazole, 3-vinylcarbazole, 4-vinylcarbazole, 1-vinylimidazole, 2-methyl 1-vinylimidazole, N-vinylpyrrolidone, 2-vinylpyrrolidone, N-vinylpyrrolidone, 3-vinylpyrrolidone, N-vinylcaprolactam, N-ethylene Pyrrolidone, vinyl oxirane, vinyl furan, vinyl thiophene, vinyl thiolane, vinyl thiazole and hydrogenated vinyl thiazole, vinyl

Azole and hydrogenated vinyl

Azole; vinyl ethers and isoprenyl ethers; maleic acid derivatives such as maleic anhydride, methyl maleic anhydride, maleic diimide, methyl maleic diimide Imines; and dienes such as divinylbenzene.

Based on the weight of the monomers, the amount of such comonomers generally used is 0.0wt% to 60.0wt%, preferably 0.0 to 40.0wt%, and particularly preferably 0.0 to 20.0wt%, and here The compounds can be used alone or in a mixture.

Also preferred is PMMA, which can be obtained by polymerizing a composition having the following as a polymerizable component: (a) 50.0 to 99.9% by weight of methyl methacrylate, (b) 0.1 to 50.0 wt% of C ₁ -C ₄ alcohol acrylate, (c) 0.0 to 10.0 wt% monomer copolymerizable with monomers (a) and (b).

The use of the component (c) in the range of 8.0 to 10.0 wt% will improve the intrinsic stability of the foil. The component (c) is preferably n-butyl acrylate. As the proportion of component (c) increases, the stability of the foil increases. However, an increase beyond the limit is disadvantageous.

In yet another specific example, the preferred is PMMA, which is composed of 85.0 to 99.5 wt.% methyl methacrylate and 0.5 to 15.0 wt.% methyl acrylate, the amount here is 100 wt.% polymerizable Ingredient meter. Particularly advantageous copolymers are copolymers obtainable by copolymerization of 90.0 to 99.5 wt% of methyl methacrylate and 0.5 to 10.0 wt% of methyl acrylate, where these amounts are 100 wt% of polymerizable ingredients meter. For example, PMMA may include 91.0 wt% methyl methacrylate and 9.0 wt% methyl acrylate, 96.0 wt% methyl methacrylate and 4.0 wt% methyl acrylate, or 99.0 wt% methyl Methyl acrylate and 1.0wt% methyl acrylate. The Vicat softening point VSP (ISO 306-B50) of the PMMA is typically at least 90°C, preferably 95°C to 112°C.

The chain length of the PMMA polymer can be adjusted by the polymerization of the monomer mixture in the presence of a molecular weight modifier. Specific examples are thiols known for this purpose, such as n-butyl mercaptan, n-twelve Alkyl mercaptan, 2-mercaptoethanol or 2-ethylhexyl thioglycolate, or pentaerythritol tetrathioglycolate; based on the weight of the monomer mixture, the molecular weight regulator is generally used in an amount of 0.05 to 5.0 wt%, based on the monomer mixture, preferably 0.1 to 2.0% wt%, and particularly preferably 0.2 to 1.0 wt% (see "Acryl-und Methacrylverbindungen of H. Rauch-Puntigam, Th. Volker" "["Acrylic and Methacrylic Compounds"], Springer Press, Heidelberg, 1967; Houben-Weyl, Methoden der organischen Chemie, [Methods of Organic Chemistry] ], Volume XIV/1, page 66, Georg Thieme, Heidelberg, 1961, or Kirk-Othmer, Encyclopedia of Chemical Technology, Volume 1, page 296 and subsequent pages, J. Wiley , New York, 1978).

The weight-average molar mass Mw of the PMMA used is usually higher than 80 000 g/mol, which is determined by means of gel permeation chromatography (as for all Mw determinations of the matrix PMMA, GPC refers to PMMA as the calibration standard), preferably Ground>120 000g/mol. For the purposes of the present invention, in the case where the weight-average molar mass Mw of PMMA is higher than 140 000 g/mol, it is possible to achieve foils with even greater weather resistance. The weight-average molar mass Mw of PMMA is generally in the range of 80 000 g/mol to 300 000 g/mol. Particularly good weather resistance can be obtained from a foil with PMMA, the average molar mass Mw is in the range of 80 000 g/mol to 180 000 g/mol, preferably in the range of 100 000 g/mol to 180 000 g/mol Within, preferably in the range of 120 000 g/mol to 180 000 g/mol, in each case the determination is made by means of GPC against PMMA calibration standards.

Typically, PMMA is not cross-linked, and it is therefore suitable for thermoplastic processing.

According to the invention, the foil comprises at least layer A and another layer B (see Figure 1). According to the invention, layer A is directly adjacent to layer B. When using the foil of the present invention to protect an article, the fluoropolymer-based layer A forms the outer surface of the article so as to face the environment. Layer B is below layer A, that is, closer to the surface of the article.

Although layer B may also contain at least one fluoropolymer, such as PVDF, the composition of layer B is typically different from the composition of layer A based on fluoropolymer. In detail, layer B is usually substantially Free of glass beads, and even better, substantially free of any scattering particles.

Based on the total weight of layer B, the composition of layer B is as follows: 0.0 to 100.0 wt%, preferably 10.0 to 90.0 wt% poly(meth)acrylate; 0.0 to 95.0 wt%, preferably 10.0 to 90.0wt% of one or several impact modifiers; 0.0 to 40.0wt%, preferably 10.0 to 30.0wt% of fluoropolymer; 0.0 to 5.0wt%, preferably 1.0 to 4.0wt% Or several UV absorbers; 0.0 to 5.0wt%, preferably 0.5 to 3.0wt% of one or several UV stabilizers; and 0.0 to 20.0wt%, preferably 0.0 to 10.0wt% of adhesion promoting copolymer Which includes (i) 70.0 to 95.0 wt% of methyl methacrylate; (ii) 0.5 to 15.0 wt% of maleic anhydride; and (iii) 0.0 to 25.0 wt% based on the weight of the copolymer Other vinyl copolymerizable monomers that do not have functional groups other than vinyl functional groups.

Based on the weight of layer B, the cumulative content of poly(meth)acrylate and one or several impact modifiers in layer B is at least 50 wt%, preferably at least 60 wt%, more preferably at least 70 wt% It is even more preferably at least 80 wt%, still more preferably at least 90 wt%, and particularly preferably at least 95 wt%.

For example, layer B may include 10.0 to 90.0 wt% of poly(meth)acrylate; 10.0 to 90.0 wt% of one or several impact modifiers; 0.0 to 5.0 wt%, preferably 1.0 to 4.0wt% of one or several UV absorbers; 0.0 to 5.0wt%, preferably 0.5 to 3.0wt% of one or several UV stabilizers; and 0.0 to 20.0wt%, preferably 0.0 to 10.0wt% An adhesion promoting copolymer comprising (i) 70.0 to 95.0 wt% methyl methacrylate; (ii) 0.5 to 15.0 wt% maleic anhydride based on the weight of the copolymer; and (iii) 0.0 to 25.0 wt% of other vinyl copolymerizable monomers that do not have functional groups other than vinyl functional groups.

Preferably, the polyalkyl (meth)acrylate in layer B is PMMA as described above, and the fluoropolymer is PVDF as described above.

Impact modifier

The impact modifier used in the present invention is well known to me, and may have different chemical compositions and different polymer architectures. The impact modifier can be cross-linked or thermoplastic. In addition, the impact modifier can be in the form of particles, such as core-shell or core-shell-shell particles. Typically, the average particle size of the particle impact modifier is between 20 and 400 nm, preferably between 50 and 300 nm, more preferably between 100 and 285 nm, and most preferably between 150 Between 270nm. " Particle " in this context means a cross-linked impact modifier that generally has a core-shell or core-shell-shell structure.

In the simplest case, the particle impact modifier is a cross-linked particle obtained by means of emulsion polymerization, and its average particle size is in the range of 10 to 150 nm, preferably 20 to 100 nm, especially 30 to 90 nm. These particles are generally composed of at least 40.0 wt%, preferably 50.0 to 70.0 wt% methyl methacrylate; 20.0 to 40.0 wt%, preferably 25.0 to 35.0 wt% butyl acrylate; And 0.1 to 2.0 wt%, preferably 0.5 to 1.0 wt% of crosslinking monomers, such as multifunctional (meth)acrylates, such as allyl methacrylate; and other monomers, such as 0.0 to 10.0, as appropriate wt%, preferably 0.5 to 5.0% wt% of C ₁ -C ₄ -alkyl methacrylate, such as ethyl acrylate or butyl methacrylate, preferably methyl acrylate, or other vinyl polymerizable monomer Body, such as styrene.

Preferred impact modifiers are polymer particles, which can have a two-layer or three-layer core-shell structure and are obtained by emulsion polymerization (see, for example, EP-A 0 113 924, EP-A 0 522 351, EP- A 0 465 049 and EP-A 0 683 028). The present invention typically requires that the suitable particle size of these emulsion polymers is in the range of 10 to 150 nm, preferably 20 to 120 nm, and particularly preferably 50 to 100 nm.

A three-layer or three-phase structure with one core and two shells can be prepared as follows. Innermost (Hard) shells may consist essentially of, for example, methyl methacrylate; a smaller proportion of comonomers, such as ethyl acrylate; and a certain proportion of crosslinking agents, such as allyl methacrylate. The middle (soft) shell may for example consist of butyl acrylate and, where appropriate, styrene, while the outermost (hard) shell is essentially the same as the matrix polymer and is therefore compatible with the matrix and well bonded. The proportion of polybutyl acrylate in the impact modifier determines the impact modifier, and is preferably in the range of 20.0 to 40.0 wt%, and particularly preferably in the range of 25.0 to 35.0 wt%.

Especially for foil production, it is further preferred, but not limited to, to use a system known in principle from EP 0 528 196 A1, which is a two-phase impact-modified polymer consisting of: a1) 10.0 to 95.0 The wt% coherent hard phase has a glass transition temperature Tg higher than 70°C and is composed of: a11) 80.0 to 100wt% (based on a1) methyl methacrylate, and a12) 0.0wt% to 20.0wt % One or more other ethylenically unsaturated monomers, which are capable of free radical polymerization, and a2) 90.0 to 5.0 wt% of the solid phase, whose glass transition temperature Tg is below -10°C, which is distributed in the hard phase And consist of a21) 50.0 to 99.5 wt% C ₁ -C ₁₀ -alkyl acrylate (based on a2) a22) 0.5 to 5.0 wt% crosslinking monomer, which has two or more than two Ethylenically unsaturated free radicals, which can undergo radical polymerization, and a23) where appropriate, other ethylenically unsaturated monomers can undergo radical polymerization, of which at least 15.0 wt% of the hard phase a1) and the solid phase a2 ) Has a covalent bond.

Two-phase impact modifiers can be produced by conducting a two-stage emulsion polymerization reaction in water, as described in DE-A 38 42 796 as an example. In the first stage, a solid phase a2) is produced, and it is composed of at least 50.0 wt%, preferably greater than 80.0 wt% of low-carbon alkyl acrylate, so a glass transition temperature below -10°C is obtained for this phase . The crosslinking monomer a22) used contains The following are used as graft linking agents: (meth)acrylates of glycols, such as ethylene glycol diacrylate or 1,4-butanediol diacrylate; with two vinyl or allyl Aromatic compounds such as divinylbenzene; or other crosslinking agents with two ethylenically unsaturated free radicals capable of free radical polymerization, such as allyl methacrylate. The crosslinking agent cyanuric acid which can be mentioned as an example and has three or more unsaturated groups capable of radical polymerization (for example, allyl groups or (meth)acrylic groups) Triallyl, trimethylolpropane triacrylate and trimethylolpropane tri(meth)acrylate, as well as isopentaerythritol tetraacrylate and isopentaerythritol tetra(meth)acrylate. US 4,513,118 gives additional examples.

The ethylenically unsaturated monomer capable of free radical polymerization and mentioned under a23) may be (as an example) acrylic acid or methacrylic acid or other alkyl esters thereof (having 1 to 20 carbon atoms but not mentioned above And), and the alkane radical here may be linear, branched or cyclic. In addition, a23) may contain additional aliphatic comonomers, which are capable of free radical polymerization and can be copolymerized with alkyl acrylate a21). However, it is desirable to exclude a considerable proportion of aromatic comonomers, such as styrene, _α -methylstyrene or vinyl toluene, because it leads to undesirable properties of the resulting product—especially in terms of weather resistance.

When a solid phase is produced in the first stage, care must be taken to set the particle size and its polydispersity. Here, the particle size of the solid phase essentially depends on the concentration of the emulsifier, and the particle size can be advantageously controlled by using seed latex. Based on the aqueous phase, an emulsifier with a concentration of 0.15 to 1.0 wt% is used to achieve the following particles: its average (weight average) particle size is less than 130 nm, preferably less than 70 nm, and its particle size polydispersity P _{80 is} less than 0.5 (P ₈₀ is determined based on the cumulative evaluation of the particle size distribution determined by the ultracentrifuge; the relationship is: P ₈₀ =[(r ₉₀ -r ₁₀ )/r ₅₀ )-1, where r ₁₀ , r ₅₀ , r ₉₀ = average cumulative particle radius, which is greater than 10%, 50%, 90% of the particle radius, and less than 90%, 50%, 10% of the particle radius), preferably less than 0.2. This applies in particular to anionic emulsifiers, examples of which are particularly preferably alkoxylated and sulfated paraffins. Based on the aqueous phase, examples of the polymerization initiator used are 0.01 to 0.5 wt% of alkali metal peroxybisulfate or ammonium peroxybisulfate, and the polymerization reaction is initiated at a temperature of 20 to 100°C. It is preferred to use a redox system. An example is a combination of 0.01 to 0.05 wt% organic hydrogen peroxide and 0.05 to 0.15 wt% sodium hydroxymethylsulfinate at a temperature of 20 to 80°C.

The glass transition temperature of the hard phase a1) (which has at least 15 wt% with covalent bonding with the solid phase a2)) is at least 70°C, and this phase may be composed of methyl methacrylate only. One or more other ethylenically unsaturated monomers capable of free radical polymerization of up to 20% by weight can be present as comonomer a12) in the hard phase, and the alkyl (meth)acrylate used here (preferably Ground, the amount of alkyl acrylate having 1 to 4 carbon atoms is such that the glass transition temperature is not lower than the glass transition temperature mentioned above.

In the second stage, the polymerization of the hard phase a1) is also carried out in the emulsion using conventional auxiliary agents (for example, auxiliary agents also used for the polymerization of the hard phase a2).

Thermoplastic impact modifiers have a different mechanism of action than particulate impact modifiers. It is usually mixed with a matrix material. Under conditions such as the formation of domains, such as the use of block copolymers, the preferred size of these domains (the size of which can be determined, for example, by electron microscopy) corresponds to the preferred size of core-shell particles.

There are various types of thermoplastic impact modifiers. An example of this is aliphatic thermoplastic polyurethane (TPU), such as the Desmopan® product available from Covestro AG. For example, TPUs Desmopan® WDP 85784A, WDP 85092A, WDP 89085A and WDP 89051D (all of which have a refractive index between 1.490 and 1.500) are particularly suitable as impact modifiers.

Therefore, another type of thermoplastic polymer used in the foil of the present invention as an impact modifier is methyl acrylate-acrylate block copolymer, especially acrylic TPE, which contains PMMA-poly-n-acrylic butyl Ester-PMMA triblock copolymer, and it is commercially available under the Kurarity® product name from Kuraray. The poly-n-butyl acrylate blocks form nanodomains in the polymer matrix, with a size between 10 and 20 nm.

In the case of impact-modified cross-linked particles, especially core-shell or core-shell-shell particles, based on the weight of layer B, layer B based on PMMA may contain between 0.0 and 95.0 wt% The impact modifier is preferably between 10 and 90 wt%, particularly preferably between 15 and 85 wt% (for example, 25 to 35 wt% or 80 to 90 wt%). Foils containing 25 to 35% by weight of impact modifier in PMMA-based layer B are relatively hard and are particularly advantageous for use in high-pressure laminates. Foils with 80 to 90 wt% impact modifier in PMMA-based layer B are very suitable for applications requiring high mechanical flexibility.

In the case where the impact modifier used is a thermoplastic material (for example, the listed aliphatic TPU or acrylic TPE), based on the weight of layer B, these substances are usually present in a concentration between 3.0 and 90 wt% Between, preferably between 6.0 and 25 wt%, and particularly preferably between 9.0 and 15 wt% of the matrix material.

Based on the weight of layer B, the cumulative content of PMMA and impact modifier (hereinafter referred to as " impact modified PMMA ") in layer B is at least 50 wt%, preferably at least 60 wt%, and more preferably At least 70% by weight, and even more preferably at least 80% by weight, still more preferably at least 90% by weight, particularly preferably at least 95% by weight.

UV absorber and UV stabilizer

Light stabilizers are well known to me and are described in detail in Hans Zweifel, Plastics Additives Handbook, Hanze Press, 5th edition, 2001, page 141 and subsequent pages as examples. Light stabilizers should be understood to include UV absorbers, UV stabilizers and free radical scavengers.

酮、羥基苯基苯并三唑、三

或丙二酸亞苄酯之群組。UV穩定劑/自由基清除劑之最佳已知代表係由位阻胺(受阻胺光穩定劑，HALS)之群組提供。 UV absorbers can be derived from substituted benzophenone, salicylate, cinnamate, oxanilide, benzo, as examples

Ketone, hydroxyphenyl benzotriazole, tri

Or a group of benzylidene malonate. The best known representatives of UV stabilizers/radical scavengers are provided by the group of hindered amines (hindered amine light stabilizers, HALS).

類型之UV吸收劑，‧組分C：UV穩定劑(HALS化合物)。 Preferably, for example, the combination of the UV absorber and the UV stabilizer used in layer B is composed of the following components: ‧Component A: UV absorber of the benzotriazole type, ‧Component B: belonging to the three

Type UV absorber, component C: UV stabilizer (HALS compound).

The individual components can be used in the form of individual substances or mixtures.

Examples of UV absorbers (component A) belonging to the benzotriazole type that can be used are: 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-[2-hydroxy-3, 5-bis( _α , _α -dimethylbenzyl)phenyl]-benzotriazole, 2-(2-hydroxy-3,5-di-third-butylphenyl)benzotriazole, 2-(2-hydroxy-3,5-butyl-5-methyl-phenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl )-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-third-pentylphenyl) benzotriazole, 2-(2-hydroxy-5-third-butyl Phenyl)benzotriazole, 2-(2-hydroxy-3-secondbutyl-5-third-butylphenyl)benzotriazole and 2-(2-hydroxy-5-third-octyl Phenyl)benzotriazole, phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethyl Butyl)].

Based on the weight of the PMMA-based layer B, the amount of UV absorber belonging to the benzotriazole type used is 0.1 to 10.0 wt%, preferably 0.2 to 6.0 wt%, and very preferably 0.5 to 4.0 wt% . It is also possible to use mixtures of different UV absorbers of the benzotriazole type.

類型之UV吸收劑(組分B)(諸如2-(4,6-二苯基-1,3,5-三

-2-基)-5-己氧基苯酚)較佳地與組分A組合使用。 three

Types of UV absorbers (component B) (such as 2-(4,6-diphenyl-1,3,5-tri

-2-yl)-5-hexyloxyphenol) is preferably used in combination with component A.

類型之UV吸收劑的所使用量為0.0至5.0wt%，較佳為0.2至3.0wt%，且極其較佳為0.5至2.0wt%。亦有可能使用不同三

之混合物。 Based on the weight of layer B, three

The amount of UV absorber of the type used is 0.0 to 5.0 wt%, preferably 0.2 to 3.0 wt%, and very preferably 0.5 to 2.0 wt%. It is also possible to use different three

Of mixture.

Hindered amines, hindered amine light stabilizers (HALS, H indered A mine L ight S tabilizer) UV stabilizer known per se. These UV stabilizers can be used to inhibit aging in paints and plastics, especially polyolefin plastics (Kunststoffe, 74 (1984) 10, pages 620 to 623; Farbe+Lack, Volume 96, 9/1990, Pages 689 to 693). The tetramethylpiperidine group present in the HALS compound is responsible for the stabilizing effect. The compounds of this class have no substitution on the piperidine nitrogen or no alkyl or acetyl substitution on the piperidine nitrogen. Hindered amines will not be absorbed in the UV region. Hindered amines scavenge free radicals that have been formed, and UV absorbers cannot do this. Examples of HALS compounds (which have a stabilizing effect and can also be used in the form of a mixture) are: bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, 8-acetyl- 3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro(4,5)-decane-2,5-dione, bis(2,2, 6,6-tetramethyl-4-piperidinyl) succinate, poly( N -β-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxy piperidine succinate ) Or bis( N -methyl-2,2,6,6-tetramethyl-4-piperidinyl) sebacate.

Based on the weight of layer B, the amount of the HALS compound used in layer B is typically 0.0 to 5.0 wt%, preferably 0.1 to 3.0 wt%, and very preferably 0.2 to 2.0 wt%. It is also possible to use mixtures of different HALS compounds.

Other co-stabilizers that can be used are the HALS compounds described above, disulphites (such as sodium disulphite), and hindered phenols and phosphites. Based on the weight of layer B, such co-stabilizers may be present in a concentration of 0.1 to 5.0 wt.%.

The hindered phenol is particularly suitable for the foil of the present invention. Preferred sterically hindered phenols include 6-tert-butyl-3-methylphenyl derivatives, 2,6-di-tert-butyl-p-cresol, 2,6-tert-butyl-4-ethyl Phenol, 2,2'-methylenebis-(4-ethyl-6-tert-butylphenol), 4,4'-butylenebis(6-tert-butyl-m-cresol), 4 ,4'-thiobis(6-tert-butyl-m-cresol), 4,4'-dihydroxydiphenylcyclohexane, alkylated bisphenol, styrenated phenol, 2,6- Di-tert-butyl-4-methylphenol, n-octadecyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl) propionate, 2,2'- Methylbis(4-methyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenyl), 4,4'-butylenebis (3-methyl-6-tert-butylphenol), octadecanoyl-p-(3,5-di-4-butyl-4-hydroxyphenyl) propionate, 1,1,3-tri (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3-5-di-t-butyl- 4 hydroxybenzyl)benzene, tetrakis[methylene-3(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane. Commercially available hindered phenols include SUMILIZER BHT BP-76, WXR, GA-80 and BP-101 (SUMITOMO), IRGANOX 1076, 565, 1035, 1425WL, 3114, 1330 and 1010 (BASF SE), MARK AO-50, -80, -30, -20, -330 and- 60 (ADEKA ARGUS), as well as TOMINOX SS, TT (YOSHITOMI), IONOX WSP (ICI), SANTONOX (MONSANTO), ANTAGECRYSTAL (KAWAGUCHI), NOCLIZER NS-6 (OUCHI SHINKO), TOPANOL CA (ICI), CYANOX 1790 (ACC ).

類型化合物；及作為UV穩定劑的0.2至2.0wt%之HALS類型化合物。 In a preferred embodiment, the layer B contains: based on the total weight of the layer B, 0.5 to 4.0 wt% of the benzotriazole type compound as the first UV absorber; 0.5 to 4.0% as the second UV absorber 3.0wt% of three

Type compounds; and 0.2 to 2.0 wt% of HALS type compounds as UV stabilizers.

Adhesion promoting copolymer

Typically, the adhesion promoting copolymer in layer B and/or layer C (if this layer is present) comprises: (i) 50.0 to 95% by weight of C ₁ -C ₆ alcohol methyl acrylate, (ii) 0.5 to 15.0% % Adhesion promoting monomer, (iii) 5.0 to 25.0 wt% of at least one vinyl aromatic substance, and optionally (iv) 0.0 to 5.0 wt% of alkane having 1 to 6 carbon atoms in the ester group Acrylate.

For example, the adhesion promoting copolymer in layer B and/or layer C (if this layer is present) may include (i) 70.0 to 95.0% by weight of methyl methacrylate based on the weight of the adhesion promoting copolymer; ( ii) 0.5 to 15.0% by weight of maleic anhydride; and (iii) 0.0 to 25.0% by weight of other vinyl copolymerizable monomers that do not have functional groups other than vinyl functional groups.

The monomer (i) is selected from the group of alkyl (meth)acrylates having 1 to 6 carbon atoms in the ester groups such as: ethyl methacrylate, propyl methacrylate, methyl alcohol Isopropyl acrylate, butyl methacrylate, isobutyl methacrylate, third butyl methacrylate, amyl methacrylate, isoamyl methacrylate, hexyl methacrylate, 2,2- Dibutyl methacrylate, cyclopentyl methacrylate, and cyclohexyl methacrylate and particularly preferred methyl methacrylate.

The monomer (iii) may be selected from the group of vinyl aromatic substances such as: _α -halogen styrene, p-methyl styrene, p-third butyl styrene, vinyl naphthalene, and preferably , _Α -methylstyrene and styrene, of which styrene is particularly preferred.

The adhesion promoting monomers (ii) are those monomers capable of free radical polymerization, and these monomers have functional groups that can interact with the material to be coated. This interaction is intended to be achieved at least via chemical (covalent) bonds. In addition, as an example, the interaction may be promoted by hydrogen bonding, coupling, dipole force or thermodynamic compatibility (entanglement of polymer chains), or the like. These interactions generally involve heteroatoms such as nitrogen or oxygen. The functional groups that may be mentioned are amine groups, especially dialkylamine groups, (cyclo) amide groups, amide imine groups, hydroxyl groups, (cyclo)oxy groups, carboxyl groups, (iso)cyano groups group. These monomers are known to me (see H. Rauch Puntigam, Th. Volker, Acryl und Methacrylverbindungen, Springer Press 1967; Kirk-Othmer, Encyclopedia of Chemical Technology), third Edition, Volume 1, pages 394 to 400, J. Wiley 1978; DE-A 25 56 080; DE-A 26 34 003).

Adhesion-improving monomers therefore preferably belong to the following monomer categories: nitrogen-containing vinyl heterocycles, preferably having a 5-membered ring along the side of the 6-membered ring; and/or copolymerizable polyethylene carboxylic acid; and/ Or hydroxyalkyl-, alkoxyalkyl-, epoxy- or aminoalkyl substituted esters, or amides of fumaric acid, maleic acid, itaconic acid, acrylic acid or methacrylic acid . Nitrogen heterocyclic mono-systems that may be specifically mentioned are from the class of monomers of vinylimidazole, vinyllactam, vinylcarbazole and vinylpyridine. These monomers Examples of imidazole compounds (which are not intended to represent any limited form) are: N-vinylimidazole (also known as vinyl-1-imidazole), N-vinylmethyl-2-imidazole, N-vinylethyl 2-imidazole, N-vinylphenyl-2-imidazole, N-vinyldimethyl-2,4-imidazole, N-vinylbenzimidazole, N-vinylimidazole (also known as ethylene Yl-1-imidazoline), N-vinylmethyl-2-imidazoline, N-vinylphenyl-2-imidazoline and vinyl-2-imidazole.

Specific examples of monomers which may be mentioned as derived from lactam are compounds such as: N-vinylpyrrolidone, N-vinylmethyl-5-pyrrolidone, N-vinylmethyl -3-pyrrolidone, N-vinylethyl-5-pyrrolidone, N-vinyldimethyl-5,5-pyrrolidone, N-vinylphenyl-5-pyrrolidone, N -Allylpyrrolidone, N-vinylthiopyrrolidone, N-vinylpiperidone, N-vinyldiethyl-6,6-piperidone, N-vinylcaprolactam, N-vinylmethyl-7-caprolactam, N-vinylethyl-7-caprolactam, N-vinyldimethyl-7,7-caprolactam, N-allyl Caprolactam, N-vinyl octylamide.

Among the monomers derived from carbazole, the following may be specifically mentioned: N-vinylcarbazole, N-propenylcarbazole, N-butenylcarbazole, N-hexenylcarbazole, and N- (Methyl-1-ethylene)carbazole. Among the copolymerizable polyethylene carboxylic acids, particular mention may be made of maleic acid, fumaric acid, itaconic acid and their suitable salts, esters or amides. The following epoxy-, oxy- or alkoxy-substituted alkyl esters of (meth)acrylic acid may also be mentioned: glycidyl methacrylate, 2-hydroxyethyl (meth)acrylate, hydroxy Propyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate , 2-(2-Butoxyethoxy) ethyl methacrylate, 2-(ethoxyethyloxy) ethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate , 2-[2-(2-ethoxyethoxy)ethoxy]ethyl (meth)acrylate, 3-methoxybutyl-1-(meth)acrylate, 2-alkoxy Methyl ethyl (meth)acrylate, 2-hexyloxyethyl (meth)acrylate.

The following amine-substituted alkyl esters of (meth)acrylic acid may also be mentioned: 2-dimethylaminoethyl (meth)acrylate, 2-diethylaminoethyl, (meth)acrylate, 3 -Dimethylamino-2,2-dimethylpropane 1-(meth)acrylate, 3-dimethylamino-2,2-dimethylpropyl 1-(meth)acrylate, 2-morpholinoethyl (meth)acrylate, 2 -Third butylaminoethyl (meth)acrylate, 3-(dimethylamino)propyl (meth)acrylate, 2-(dimethylaminoethoxyethyl) (methyl Radical) acrylate.

Mention may be made of examples of the following monomers that are representative of (meth)acrylamide: N-methyl(meth)acrylamide, N-dimethylaminoethyl(meth)-acrylamide, N -Dimethylaminopropyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-third butyl(methyl)-acrylamide, N-isobutyl(meth) Group) acrylamide, N-decyl(methyl)-acrylamide, N-cyclohexyl(meth)acrylamide, N-[3-(dimethylamino)-2,2-dimethyl Propylpropyl]methacrylamide, N-[2-hydroxyethyl](meth)acrylamide.

It is particularly advantageous to use " adhesion promoting monomers " (ii) selected from the group consisting of: glycidyl methacrylate (GMA); maleic acid derivatives, such as maleic acid, Maleic anhydride (MA), methyl maleic anhydride, maleic diimide, methyl maleic diimide, maleic diamide (MA), phenyl maleic acid Diimide and cyclohexyl maleic diimide; fumaric acid derivatives; methacrylic anhydride; acrylic acid anhydride.

Preferably, the adhesion promoting monomer (ii) is maleic anhydride.

The alkyl acrylate (iv) may be incorporated in an amount of up to 5.0 wt% as the case may be to improve adhesion and promote the rheology of the copolymer. The alkyl acrylate having 1 to 6 carbon atoms in the ester group may be, for example: ethyl acrylate, isopropyl acrylate, propyl acrylate, isobutyl acrylate, third butyl acrylate , amyl acrylate, hexyl acrylate Esters, and preferably, butyl acrylate and especially preferred methyl acrylate.

In a preferred embodiment, the adhesion promoting copolymer includes: (i) 50.0 to 95.0 wt%, preferably 60.0 to 90.0 wt%, more preferably 70.0 to 85.0 wt%, or even more based on the weight of the copolymer 70 to 80 wt% of methyl methacrylate; (ii) 0.2 to 25.0 wt%, preferably 0.5 to 20.0 wt%, more preferably 1.0 to 15.0 wt%, and even more preferably 5.0 to 12.0 wt% Of maleic anhydride; and (iii) 0.0 to 25.0 wt%, preferably 2.0 to 15.0 wt% of other vinyl copolymerizable monomers that do not have functional groups other than vinyl functional groups.

In a particularly preferred embodiment, the adhesion promoting copolymer is a copolymer of MMA, styrene and maleic anhydride.

Depending on the substrate to be protected, the adhesion promoting copolymer may be located in a separate layer C instead of the PMMA-based layer B (see FIG. 2). In this specific example, the layer C with the adhesion promoting copolymer contains, based on the weight of the copolymer, (i) 50.0 to 95.0 wt%, preferably 60.0 to 90.0 wt%, more preferably 70.0 to 85.0 wt%, or even More preferably 70 to 80wt% of methyl methacrylate; (ii) 0.2 to 25.0wt%, preferably 0.5 to 20.0wt%, more preferably 1.0 to 15.0wt%, and even more preferably 5.0 to 12.0wt % Maleic anhydride; and (iii) 0.0 to 25.0 wt%, preferably 2.0 to 15.0 wt% of other vinyl copolymerizable monomers that do not have functional groups other than vinyl functional groups.

Typically, if layer C is present, the order of the layers in the foil of the present invention is as follows: A-B-C. In a preferred embodiment, the foil of the present invention is composed of layers A, B, and C positioned relative to each other in this order.

Depending on the substrate on which the foil is applied, layer B may be substantially free of adhesion promoting copolymer. In this case, the PMMA-based layer B may include: based on the total weight of the layer B, 10.0 to 90.0 wt% of poly(meth)acrylate; 10.0 to 90.0 wt% of one or several impact modifiers Agent; 0.0 to 5.0wt%, preferably 1.0 to 4.0wt% of one or several UV absorbers; 0.0 to 5.0wt%, preferably 0.5 to 3.0wt% of one or several UV stabilizers.

The adhesion promoting copolymer can be obtained via free radical polymerization in a manner known per se. As an example, EP 264 590 A1 describes a method for preparing copolymers from: A monomer mixture consisting of methyl acrylate, vinylidene compound, maleic anhydride; and, where appropriate, a low-carbon alkyl acrylate, the preparation is performed by the following operations: in the presence or absence of a non-polymerizable organic solvent Under the conditions of 50% conversion for polymerization; and in the presence of an organic solvent, within the temperature range of 75 to 150 ℃, continue the polymerization at a conversion rate exceeding at least 50% to at least 80% conversion; and Next, the low molecular weight volatile components are vaporized.

JP-A 60-147 417 describes a method for preparing a copolymer by the following operation: at a temperature of 100 to 180 ℃, will be composed of methyl methacrylate, maleic anhydride and at least one vinylidene compound The monomer mixture is fed into a polymerization reactor, which is suitable for solution polymerization or bulk polymerization; and for polymerizing materials. DE-A 44 40 219 describes another method of preparation.

The adhesion promoting copolymers described in EP 264 590 A1 and JP-A 60-147 417 can be advantageously used in the foil of the present invention.

Foil performance

Depending on the intended purpose, the total thickness of the foil of the invention can be between 1.0 μm and 300.0 μm, more preferably between 1.0 μm and 200.0 μm, and even more preferably between 5.0 μm and 100.0 μm between.

The thickness of the foil and its layers of the present invention can be determined by mechanical scanning according to the specification ISO 4593-1993. In addition, a scanning electron microscope can be used to determine the thickness of the inventive foil and its individual layers, as described above. For this purpose, foil samples can be frozen in liquid nitrogen, mechanically broken, and the newly obtained surface analyzed.

The thickness of the layer A based on the fluoropolymer is typically 1.0 μm to 30.0 μm, preferably 5.0 μm to 20.0 μm.

The thickness of layer B is generally between 10.0 μm and 200.0 μm, preferably between 15.0 μm and 150.0 μm.

In the presence of it, the thickness of the adhesion promoting layer C is usually 1.0 μm to 30.0 μm, preferably 5.0 μm to 20.0 μm.

The roughness value Rz of the outer surface of the layer A of the foil of the invention is typically at least 0.7 μm according to the DIN 4768 standard, preferably 1.0 to 2.0 μm. A commercially available instrument such as Form Talysurf 50 produced by Rank Taylor Hobson GmbH can be used for the roughness measurement.

The gloss (R 60°) of the outer surface of layer A is generally at most 40 according to DIN 67530 (01/1982) standard, preferably at most 30, especially 15 to 30. The gloss measurement can be performed using an RL laboratory reflectometer (such as a Fa. Dr. Hach-Lange reflectometer).

Method for manufacturing foil

Depending on the intended application, the foil of the invention can be produced in any desired thickness. Even under mechanical pressure at increased temperature (for example, during the lamination process), under special weather resistance and mechanical stability, and under the extremely high weather resistance and mechanical protection provided to the substrate, this is unexpected The factor can also maintain a uniform level of mattness. However, for the purposes of the present invention, relatively thin plastic moldings, ie, films or foils, which are characterized by a thickness in the range of 10.0 to 200.0 μm, preferably 40.0 to 120.0 μm Within a range, particularly preferably within a range of 50.0 to 90.0 μm.

The mixture of these components can be prepared by dry blending of the individual components of layers A, B and C, the components being in powder, granular or preferably granular form. Such mixtures can also be processed by melting and mixing the individual components in the molten state or by melting the dry premix of the individual components to obtain a ready-to-use molding composition. As an example, this treatment can be carried out in a single or twin screw extruder. The resulting extrudate can then be granulated. End users can blend directly or add conventional additives, adjuvants and/or fillers as needed.

It can then be by a method known per se (example is co-extrusion or lamination) or by extrusion Lamination to produce the multilayer foil of the present invention.

A particular production variation relates to a method comprising the following steps, in which the foil of the present invention is molded in a foil molding process, preferably in a cold roll process, consisting of a composition comprising: Based on the total weight of the composition, 40.0 to 97.0 wt% of fluoropolymer; 0.0 to 45.0 wt% of polyalkyl (meth)acrylate; and 3.0 to 25.0 wt% of glass beads.

This composition forms layer A of the resulting foil.

The composition of layer B (if C is present) is as described above.

Apply the foil to the substrate

The inventive foil has a wide range of applications. A preferred use of foil is to coat plastic molded parts. Here, it is particularly advantageous to coat plastic moldings containing or consisting of PVC. Advantageously, as an example, the protected substrate is a window frame composed of aluminum, wood, plastic, or a composite material, and the protected substrate can carry a decorative foil, preferably composed of PVC. The product was then protected from weathering by using inventive foils. Another preferred use of the inventive foil is the design of substrate materials with high specifications and long-lasting surface finish.

As those skilled in the art will readily understand, applying the foil of the invention to the substrate causes layer A to form the outer surface of the coated substrate. In other words, if the foil of the present invention consists essentially of layers A and B, layer B is located between layer A and the substrate. In a specific example in which the foil of the present invention further includes layer C, layer C is located between layer B and the surface of the coated substrate.

Therefore, another aspect of the invention is a method for manufacturing a coated article, comprising the step of applying a foil to the surface of the substrate.

In all cases, applying the inventive foil to the substrate is relatively simple. The foil is preferably applied to the material to be protected by means of coextrusion. Apply foil to the material to be protected by means of foil lamination It is also possible. Also preferred is the use which is characterized in that the foil is applied to the material to be protected by means of extrusion lamination. Preferably, the extrusion lamination is performed at a temperature greater than or equal to 120° C. and after applying the following mechanical pressure: greater than or equal to 1 MPa, preferably greater than or equal to 2 MPa, more preferably greater than or equal to 4 MPa, more It is preferably greater than or equal to 6 MPa, and more preferably greater than or equal to 7 MPa.

In a specific example of the present invention, the article itself may be a foil or a sheet, which can be conveniently stored and/or disposed in the form of a roller.

In a particularly preferred embodiment, the multilayer material obtainable using the foil of the present invention is a decorative high-pressure laminate (HPL) according to the EN 438-6 standard, which is made of a fibrous material impregnated with a curable resin (for example, paper) The mesh layer is constructed, and these layers are bonded to each other by the high-pressure process described below. The surface layer of the material is impregnated with an amine-based plastic-based resin (for example, melamine resin), which has decorative colors or patterns on one or both sides. During the high-pressure process, the amine groups or methylolamine groups present in the decorative layer then act as a reaction partner for covalent bonding to the polymethyl acrylate layer (in this case, a foil) to perform the surface deal with. In particular, US 2017/019 7391 A1 describes corresponding high-voltage laminates.

Therefore, one aspect of the present invention relates to a method for manufacturing a high-pressure laminate using the foil as described above.

The high-pressure process produces a permanent bond between the decorative layer applied according to the invention and the polymethyl acrylate layer. The temperature set during the manufacturing process and associated insertion of melamine resin saturated decorative paper into the foil ensures that it is sufficient to form a covalent bond, and therefore permanently bond to the material.

The high-pressure process is defined as the simultaneous use of heat (temperature greater than or equal to 120°C) and high pressure (greater than or equal to 5 MPa), with the result that the curable resin flows and then hardens to produce a relatively high density (at least 1.35) with the desired surface structure g/cm ³ ) homogeneous non-porous material.

Notably, during the preparation of high-pressure laminates, despite the use of high temperature and pressure, the surface roughness and matteness of the foil of the present invention remained substantially unchanged. In the resulting laminate, glass beads The surface of layer A protrudes and remains visible, even at temperatures up to 170°C during the manufacture of the laminate.

SEM image

SEM images were obtained using a scanning electron microscope JEOL JSM-IT300 (available from JEOL Ltd.).

The measurement parameters are as follows: the electron flow from the tungsten wire (cathode)

Vacuum system: rotary pump/oil diffusion pump

X-Y-Z-rotation-tilt: fully maneuverable

Working distance (WD): 5 to 70mm (usually 10mm)

Sample rotation: 360°

Sample tilt: -5 to maximum 90° (depending on WD)

Magnification: 10x to 300 000x

Maximum resolution: ~3nm

Detector: Secondary Electronics (SE)

Backscattered electrons (BSE, 5 segments)

Energy dispersive X-ray analysis (EDS)

Sample preparation

To measure the foil thickness, the sample was frozen and mechanically fractured using liquid nitrogen. For this purpose, brittle fracture is performed. Analyze the fracture surface obtained.

Conductive layer

Sputter all standard specimens with gold to obtain a conductive surface.

Image measurement

Measure the average thickness of the foil and the average thickness of the individual layers in the SEM image. In order to realize the subsequent measurement of the existing images, all images and related measurement parameters are stored in the SEM image data According to the database.

Examples

Example 1 (Comparative foil)

By using a single-screw extruder with a diameter of 35 mm and a single-screw extruder with a diameter of 25 mm at 240 to 250° C. (melting temperature) at an extrusion speed of 7.3 m/min, the preparation does not have glass beads and PMMA/PVDF foil with a total thickness of 50 μm.

The thickness of the co-extruded PVDF layer A is 5 μm. Layer A consists of 100 wt% of PVDF T850, which is commercially available from Kureha.

The thickness of the co-extruded PMMA-based layer B is 45 μm. Layer B is prepared from a compounded mixture consisting of: a) 85.6wt% polymer acrylic core-shell impact modifier, which has a composition of the following: 61.3wt% methyl methacrylate, 38.0wt% butyl acrylate, 0.7wt% allyl methacrylate, b) 12.3wt% PLEXIGLAS® 7H, which can be purchased from Evonik Performance Materials GmbH, c) 1.0wt % Tinuvin® 360, which can be purchased from BASF SE (BASF SE), d) 0.4wt% Sabostab® UV 119, which can be purchased from Sabo SpA, d) 0.7wt% Tinuvin® 1600, which is available from BASF AG.

Example 2 (Foil according to the invention)

A PMMA/PVDF matte foil with a thickness of 50 μm was prepared by coextrusion under the same conditions as in Example 1.

The co-extruded PVDF-based layer A has a thickness of 5 μm and has the following composition: a) 90wt% PVDF T850, available from Kureha, b) 10wt% Omicron® NP3 P0 glass beads, available from Sovitec Mondial SA.

The thickness of PMMA-based layer B is 45 μm, and is prepared from a compounded mixture consisting of: a) 85.6 wt% polymer acrylic core-shell impact modifier, which has a composition of: 61.3 wt% methyl methacrylate, 38.0wt% butyl acrylate, 0.7wt% allyl methacrylate, b) 12.3wt% PLEXIGLAS® 7H, which can be purchased from Evonik Performance Materials Co., Ltd., c ) 1.0wt% Tinuvin® 360, available from BASF AG, d) 0.4wt% Sabostab® UV 119, available from Sabo SpA, d) 0.7wt% Tinuvin® 1600, available from BASF Stock company.

Example 3 (Foil according to the invention)

A PMMA/PVDF matte foil with a thickness of 50 μm was prepared by coextrusion under the same conditions as in Example 1.

The co-extruded PVDF-based layer A has a thickness of 5 μm and has the following composition: a) 90 wt% of PVDF T850, which can be purchased from Kureha, b) 10 wt% of Spheriglass® 5000 CP-26 glass beads, which Available from Potters Ind. LLC.

The thickness of PMMA-based layer B is 45 μm, and is prepared from a compound mixture consisting of: a) 85.6 wt% polymer acrylic core-shell impact modifier, which has the following composition: 61.3wt% methyl methacrylate, 38.0wt% butyl acrylate, 0.7wt% allyl methacrylate, b) 12.3wt% PLEXIGLAS® 7H, which can be purchased from Evonik Performance Materials Co., Ltd., c) 1.0wt% Tinuvin® 360, which can be purchased from BASF AG, d) 0.4wt% Sabostab® UV 119, which can be purchased from Sabo SpA, d) 0.7wt% Tinuvin® 1600, which is available from BASF AG.

Example 4 (Foil according to the invention)

A PMMA/PVDF matte foil with a thickness of 50 μm was prepared by coextrusion under the same conditions as in Example 1.

The co-extruded PVDF-based layer A has a thickness of 5 μm and has the following composition: a) 93.0 wt% of PVDF T850, which can be purchased from Kureha, b) 7.0 wt% of Omicron® NP3 P0 glass beads, which Can be purchased from Sofitel Mondial Ltd.

The thickness of PMMA-based layer B is 45 μm, and is prepared from a compounded mixture consisting of: a) 85.6 wt% polymer acrylic core-shell impact modifier, which has a composition of: 61.3 wt% methyl methacrylate, 38.0wt% butyl acrylate, 0.7wt% allyl methacrylate, b) 12.3wt% PLEXIGLAS® 7H, which can be purchased from Evonik Performance Materials Co., Ltd., c ) 1.0wt% Tinuvin® 360, which is available from BASF AG, d) 0.4wt% Sabostab® UV 119, which is available from Sabo SpA, d) 0.7wt% Tinuvin® 1600, which can be purchased from BASF AG.

Next, the foils of Examples 1 to 4 were laminated to a black PVC decorative film. Subsequently, the gloss of the coated PVC decorative film was measured using the REFO 60 portable reflectometer from Dr Hach-Lange at an angle of 60° according to the specification DIN 67530.

The UPM Z005 from Zwick was used to measure the yield stress and nominal tensile strain of the co-extruded PMMA/PVDF foil at break according to ISO 527-3/2/100.

Example 5 (Comparative foil)

PMMA/PVDF foil without glass beads was prepared by coextrusion under the same conditions as in Example 1.

The thickness of the co-extruded PVDF layer A is between 5 μm and 8 μm. Layer A consists of 100 wt% of PVDF T850, which can be purchased from Kureha.

The thickness of the co-extruded PMMA-based layer B is 45 μm. Layer B is prepared from a compounded mixture consisting of: a) 85.6wt% polymer acrylic core-shell impact modifier, which has a composition of the following: 61.3wt% methyl methacrylate, 38.0wt% butyl acrylate, 0.7wt% allyl methacrylate, b) 12.3wt% PLEXIGLAS® 7H, which can be purchased from Evonik Performance Materials Co., Ltd., c) 1.0wt% Tinuvin® 360, It can be purchased from BASF AG, d) 0.4 wt% Sabostab® UV 119, which can be purchased from Sabo SpA, d) 0.7 wt% Tinuvin® 1600, which can be purchased from BASF AG.

Example 6 (Foil according to the invention)

Under the same conditions as in Example 1, a thickness of 53 μm was prepared by coextrusion PMMA/PVDF matte foil.

Subsequently, the foil was analyzed using a scanning electron microscope as described above. The micrograph obtained is shown in FIG. 3.

The co-extruded PVDF-based layer A has a thickness of 5 μm to 10 μm and has the following composition: a) 75 wt% of PVDF T850, which can be purchased from Kureha, b) 25 wt% of Spheriglass® 7010 CP-26 glass beads (Diameter less than 10 μm), which can be purchased from Potters Ind. LLC.

The thickness of PMMA-based layer B is 45 μm, and is prepared from a compounded mixture consisting of: a) 85.6 wt% polymer acrylic core-shell impact modifier, which has a composition of: 61.3 wt% methyl methacrylate, 38.0wt% butyl acrylate, 0.7wt% allyl methacrylate, b) 12.3wt% PLEXIGLAS® 7H, which can be purchased from Evonik Performance Materials Co., Ltd., c ) 1.0wt% Tinuvin® 360, available from BASF AG, d) 0.4wt% Sabostab® UV 119, available from Sabo SpA, d) 0.7wt% Tinuvin® 1600, available from BASF Stock company.

Example 7 (Foil according to the invention)

A PMMA/PVDF matte foil with a thickness of 53 μm was prepared by co-extrusion under the same conditions as in Example 1.

The co-extruded PVDF-based layer A has a thickness of 5 μm to 10 μm and has the following composition: a) 83.33 wt% of PVDF T850, which can be purchased from Kureha Corporation, b) 16.67 wt% of Spheriglass® 7010 CP-26 glass beads (diameter less than 10 μm), which can be purchased from Potters Ind. LLC.

The thickness of PMMA-based layer B is 45 μm, and is prepared from a compounded mixture consisting of: a) 85.6 wt% polymer acrylic core-shell impact modifier, which has a composition of: 61.3 wt% methyl methacrylate, 38.0wt% butyl acrylate, 0.7wt% allyl methacrylate, b) 12.3wt% PLEXIGLAS® 7H, which can be purchased from Evonik Performance Materials Co., Ltd., c ) 1.0wt% Tinuvin® 360, available from BASF AG, d) 0.4wt% Sabostab® UV 119, available from Sabo SpA, d) 0.7wt% Tinuvin® 1600, available from BASF Stock company.

The measurement results are summarized in Table 1:

Due to the inherent glossiness of the unmodified PVDF layer, the matte foils of Examples 2 to 4 have a uniform matte appearance, while the foil of Example 1 is glossy.

Importantly, the matte foils of Examples 2 to 4 have excellent mechanical properties and do not show any stress whitening or deterioration of the elongation at break test results. The measured yield stress value is only slightly smaller than the value of the unmodified foil of Example 1. This demonstrates the unexpectedly high adhesion between the PVDF matrix of the PVDF layer and the glass beads embedded in it.

Examples 8 to 10 Study on thermal stability

In the following test, the thermal stability of the molding compound composed of PVDF and glass beads was studied.

Example 8: For reference, unmodified PVDF Kureha T850 was used.

Example 9: Composition consisting of PVDF Kureha T850 with 20wt% glass beads Omicron® NP3 P0.

Example 10: A composition consisting of PVDF Kureha T850 with 20% by weight of Spheriglass® Potters 5000 CP-26.

Thermogravimetric analysis (TGA) was performed on the samples of Examples 8 to 10. The samples are not adjusted. The measurement was performed using Q5000 from TA Instruments under a nitrogen atmosphere at 240°C for 60 minutes. After 40 minutes, at 240°C, all samples showed a residual aging rate of about 0.1%.

Under these conditions, all three samples exhibit substantially the same behavior.

Then, the molecular weight distribution of the soluble portion of the sample is analyzed. These samples were dissolved in a standard eluent available from System AC (based on DMA as a solvent) at 50°C. The same eluent system is also used for measurement. Before analysis by centrifugation, the undissolved residue of the sample (glass beads) is separated.

GPC measurement conditions:

Column: 1 front column 8 x 50mm + 3 GRAM columns 8 x 300mm (in Mainz's company PSS)

Front column GRAM 10μ 8 x 50mm

1 GRAM 30A 10μ 8 x 300mm

2 GRAM 10000A 10μ 8 x 300mm

3 GRAM 10000A 10μ 8 x 300mm

Instrument: Agilent 1100 series pump G1310A

PSS SECcurity inline degasser

Agilent 1100 Series Autosampler G1313A

Agilent 1100 series column oven G1316A 60℃

Agilent 1100 series RI detector G1362A 40℃

Agilent 1100 series control module G1323B

Eluent: N,N-dimethylacetamide (HPLC grade) + 0.3% (3g/l) LiBr + 0.1mol (6g/l) CH ₃ COOH + 1% H ₂ O

Flow rate: 1ml/min

Injection volume: 100μl

Detection: RI: 40℃ temperature

Sample solution concentration: 2g/l

Standard: PMMA (for example, PSS (Mainz))

Standard solution concentration: 1g/l (for Mw>106: 0.5g/l) (narrow distribution)

Internal standard: 1,2-dichlorobenzene, 0.5μl/100μl (injector program for autosampler)

The industry standard is based on ISO 16014-1 using size exclusion chromatography DIN 55672-2 Gelpermeationschromatographie (GPC) to determine the average molecular weight and molecular weight distribution of the polymer plastic-Teil 2: N,N-dimethylacetamide ( DMAC) als Elutionsmittel Gel Permeation Chromatography (GPC)-Part 2: N,N-Dimethylacetamide (DMAC) as a dissolving solvent deviation: Temperature (60°C instead of 80°C), eluent composition (add acid and water).

The measured molecular weight distribution of the samples is summarized in Table 2:

The data in Table 2 shows that a significant difference between samples cannot be detected. All three samples exhibit substantially the same behavior.

These results indicate that contrary to common technical prejudices, the detectable catalytic decomposition of PVDF on the surface of glass beads does not proceed at 240°C. Therefore, the thermal stability of the foil of the present invention substantially corresponds to the thermal stability of the corresponding unmodified foil.

Example 11

In order to simulate the conditions during the lamination process, at 150°C and 180°C, the foils of Examples 5 to 7 were pressed onto black PMMA boards using polished steel plates or matte rubber plates. Subsequently, the gloss value at 60° was measured.

The results obtained are summarized in Table 3 below:

The foils of Examples 6 and 7 substantially retained their gloss level below and above the melting temperature range of PVDF (170°C) during lamination. Both materials have a homogeneous matte appearance (which is essentially independent) and temperature during the manufacturing process, as well as the surface texture of the tools used. In detail, no undesirably high gloss areas or edges were observed.

This is not the case with the foil of Comparative Example 5. Here, the degree of gloss strongly depends on Process parameters such as temperature, and the surface of the tool used. This dependency makes the lamination process more difficult and more costly because of the need to use a relatively narrow temperature range and specific tools.

1: Layer A based on fluoropolymer

2: Fluoropolymer matrix

3: glass beads

4: Layer B based on PMMA

Claims (14)

A co-extruded multilayer foil comprising at least layer A and layer B, wherein layer A comprises: based on the total weight of layer A, 40.0 to 97.0 wt% fluoropolymer selected from polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polytetrafluoroethylene (PTFE), (ethylene tetrafluoroethylene) copolymer (ETFE), fluorinated ethylene-propylene (FEP) or mixtures or copolymers thereof; 0.0 to 45.0wt % Polyalkyl (meth)acrylate; and 3.0 to 30.0 wt% glass beads; and the layer B contains: based on the total weight of the layer B, 0.0 to 100.0 wt% poly(meth)acrylate ; 0.0 to 95.0wt% of one or several impact modifiers, which are selected from particulate impact modifiers and thermoplastic impact modifiers; 0.0 to 40.0wt% of fluoropolymers, which are selected from Polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polytetrafluoroethylene (PTFE), (ethylene tetrafluoroethylene) copolymer (ETFE), fluorinated ethylene-propylene (FEP) or mixtures or copolymers thereof ; 0.0 to 5.0wt% of one or several UV absorbers; 0.0 to 5.0wt% of one or several UV stabilizers; and 0.0 to 20.0wt% of the adhesion promoting copolymer, which includes the adhesion promoting copolymer By weight, (i) 70.0 to 95.0% by weight of methyl methacrylate; (ii) 0.5 to 15.0% by weight of maleic anhydride; and (iii) 0.0 to 25.0% by weight having no functional groups other than vinyl Other vinyl copolymerizable monomers with functional groups other than functional groups; and wherein, based on the weight of the layer B, the poly(meth)acrylate and one or several impacts in the layer B The cumulative content of the modifier is at least 50 wt%. The foil according to claim 1, wherein the layer A comprises: based on the total weight of the layer A, 85.0 to 97.0 wt% of the fluoropolymer; 0.0 wt% of the polyalkyl (meth)acrylate; And 3.0 to 15.0wt% glass beads. The foil according to claim 1 or 2, wherein the fluoropolymer is amorphous-based polyvinylidene fluoride or microcrystalline polyvinylidene fluoride. The foil according to claim 1 or 2, wherein the glass beads are substantially spherical and have an average diameter of 2.0 μm to 30.0 μm. The foil according to claim 1 or 2, wherein the polyalkyl (meth)acrylate is a polymethyl methacrylate having an average molar weight Mw of 80 000 g/mol to 180 000 g/mol, and can be composed of Obtained by the polymerization of the material, the polymerizable component of the composition includes: (a) 50.0 to 99.9% by weight of methyl methacrylate, (b) 0.1 to 50.0% by weight, based on the weight of the polymerizable composition C ₁ -C ₄ alcohol acrylate, (c) 0.0 to 10.0 wt% of at least one additional monomer copolymerizable with the monomers (a) and (b). The foil according to claim 1 or 2, wherein the diameter of at least 20 wt% of the glass beads is higher than the average thickness of the layer A based on the weight of the glass beads used. The foil according to claim 1 or 2, wherein the layer B comprises: based on the total weight of the layer B, as a first UV absorber, 0.5 to 4.0 wt% of a benzotriazole type compound; as a second UV The third of 0.5 to 3.0wt% of the absorbent

Type compounds: and 0.2 to 2.0 wt% of HALS type compounds as UV stabilizers. The foil according to claim 1 or 2, wherein the foil further comprises an adhesion promoting layer C, which The layer B is located between the layer A and the layer C, and the layer C contains an adhesion promoting copolymer. The adhesion promoting copolymer includes: (i) 70.0 to 95.0 wt% based on the weight of the adhesion promoting copolymer Methyl methacrylate; (ii) 0.5 to 15.0 wt% maleic anhydride; and (iii) 0.0 to 25.0 wt% of other vinyl copolymerizable monomers that do not have functional groups other than the vinyl functional group body. The foil according to claim 1 or 2, wherein the thickness of the layer A is 1.0 μm to 30.0 μm; and the thickness of the layer B is 15.0 μm to 150.0 μm. A method for manufacturing the foil according to any one of claims 1 to 9, wherein the method includes wherein the foil is in a foil molding process in which the layer A is formed from a composition including the following Molding steps: based on the total weight of the composition, 40.0 to 97.0 wt% of fluoropolymer; 0.0 to 45.0 wt% of polyalkyl (meth)acrylate; and 3.0 to 30.0 wt% of glass beads. A multilayer article comprising a substrate at least partially covered by the foil of any one of claims 1 to 9, wherein the layer A forms the outer surface of the multilayer article; the layer B is located between the layer A and the substrate And; in the case of existence, the layer C is located between the layer B and the substrate. The multilayer article of claim 11, wherein the layer B is adjacent to the layer A, and in the presence of the layer C is adjacent to the layer B. A method for manufacturing a multilayer article as described in claim 11 or 12, which method comprises using the foil as described in any one of claims 1 to 9 by means of co-extrusion, lamination or extrusion lamination To coat the substrate. The method according to claim 13, wherein the multilayer product is a high-pressure laminate, and the step of coating the substrate with the foil according to any one of claims 1 to 9 is performed under the following conditions: the pressure is not It is lower than 1MPa and the temperature is not lower than 120℃.

Images