A barrier material comprising thermoplastic fibers, glass fibers and a coupling agent

Abstract

A solution is proposed which makes it possible to obtain an insulating material comprising thermoplastic fibres which have sufficient adhesion with the glass fibres which constitute the insulating material. [Solution] The present invention relates to an insulating material comprising thermoplastic fibers, glass fibers, and a coupling agent; an acoustic and / or thermal insulating product obtained from the material according to the present invention; and a method for producing the material according to the present invention, comprising a first step of mixing thermoplastic fibers and glass fibers, followed by a heating step.

Description

[Technical field]

[0001] The present invention is in the field of thermal and / or acoustic insulation materials based on glass and organic fibers. More specifically, the present invention relates to a highly durable composite insulation material. [Background technology]

[0002] Composite materials are used in many fields. In the field of insulation, these materials generally comprise a mineral fiber matrix, which serves to give the product the required properties, for example sufficient thermal properties, linked together by a binder, typically based on a thermosetting polymer, which gives the assembly dimensional stability, mechanical strength and / or a homogeneous color. These polymers are easy to implement and have a good affinity for glass fibers.

[0003] However, as part of the ongoing search to improve the durability of materials, in particular to reduce energy consumption and to achieve recyclability of materials, thermosetting polymers are no longer satisfactory. Moreover, these polymers may also contain toxic components and may emit volatile organic compounds during their handling.

[0004] Today, thermoplastic fibers are primarily used as binders in the textile, health and hygiene industries. Solid thermoplastic binders are an advantageous alternative to thermosetting liquid binders to reduce the water and energy consumption associated with the production of insulation materials.

[0005] These binders also have the advantage of allowing less heating, within the bounds of practice in the manufacture of the insulation material, compared to the curing temperatures of thermosetting resin materials, and of allowing complete recycling of the insulation material.

[0006] However, thermoplastic polymers are generally non-polar and therefore do not exhibit sufficient adhesion to mineral materials. In fact, within the barrier material, these polymers only adhere to each other. As a result, they need to be implemented in large quantities in order to obtain satisfactory mechanical properties for the barrier material, such as those disclosed above.

[0007] The production of thermoplastic materials reinforced with glass fibres is known from prior art specific to other technical fields.

[0008] In particular, the following publications describe polymer matrices in which silane-treated glass fibers are used as reinforcing agents: - D. Bikiaris et al., Use of Silane Agents and Poly(propylene-g maleic anhydride) Copolymer as Adhesion Promoters in Glass Fiber / Polypropylene Composites, Journal of Applied Polymer Science,Vol.81,701-709(2001), - D. Bikiaris et al, Use of Silanes and Copolymers as Adhesion Promoters in Glass Fiber / Polyethylene Composites, Journal of Applied Polymer Science,Vol.80,2877-2888(2001) and - SH Pak et al, Acid-Base Interactions on Interfacial Adhesion and Mechanical Responses for Glass-Fiber-Reinforced Low-Density Polyethylene, Journal of Applied Polymer Science, 65, 143-154 (1997).

[0009] CN109023719 proposes a polypropylene-based woven material reinforced with glass fibers. The document mentions the modification of the glass fibers with silane as a coupling agent.

[0010] US 2008 / 0142178 discloses a fiber mat obtained by a wet process containing glass filaments and copolymers of polyvinyl alcohol or polyethylene terephthalate, and mentions the use of a solution for coating the glass containing silane as a coupling agent.

[0011] In the field of acoustic insulation, EP 1,659,382 proposes the use of silane-containing materials as coupling agents on thermoplastic fibres, aramid fibres being used for heat resistance.

[0012] To the inventors' knowledge, it has not been proposed to obtain an insulating material comprising thermoplastic fibers and glass fibers, the adhesion between which makes it possible to achieve the desired mechanical properties according to the desired final insulating product.

[0013] Therefore, there is a need for durable barrier materials that can have satisfactory mechanical properties in their implementation. Summary of the Invention [Problem to be solved by the invention]

[0014] The present invention aims to remedy all or some of the drawbacks of the prior art, in particular those disclosed above, by proposing a solution that makes it possible to obtain an insulating material comprising thermoplastic fibres that have sufficient adhesion with the glass fibres that constitute the insulating material. [Means for solving the problem]

[0015] To this end, according to a first aspect, the present invention relates to an insulating material comprising glass fibres, at least one coupling agent and between 5% and 30% by weight of thermoplastic fibres relative to the total weight of the material. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] Such a material according to the invention is particularly interesting due to the fact that it is completely recyclable, does not require any water consumption and involves a low degree of heating, whilst being satisfactory for use in the field of insulation from the point of view of its mechanical properties, in particular from the point of view of the adhesion of the thermoplastic fibres and the glass fibres to one another.

[0017] The term "glass fibres" is intended to mean fibres contained in glass wool, rock wool and slag wool, such fibres being disclosed for example in EP 1,032,542, EP 1,522,532 and EP 0,399,320.

[0018] The glass fibers according to the invention can have the following composition, expressed by weight relative to the total weight of the glass fibers: - SiO2 50-75%, preferably 60-70%, Na2O 10-25%, preferably 10-25%, CaO 5-15%, preferably 5-10%, - 1-10% MgO, preferably 2-5%, CaO and MgO in total preferably 5-20%, - B2O3 0-10%, preferably 2-8%, Al2O3 0-8%, preferably 1-6%, - 0-5% K2O, preferably 0.5-2%, Na2O and K2O in total preferably 12-20%, - 0-3%, preferably less than 2%, also preferably less than 1% of one or more iron oxides; and - one or more other oxides, in total 0 to 5% by weight, preferably in total less than 3% by weight, The balance consists of unavoidable impurities.

[0019] The glass fibres according to the invention may also have the following compositions, expressed by weight relative to the total weight of the glass fibres, typically found in rock wool: - SiO2 30-50%, preferably 35-45%, Na2O 0-10%, preferably 0.4-7%, CaO 10-35%, preferably 12-25%, - 1-15% MgO, preferably 5-13%, CaO and MgO in total preferably 11-40%, - Al2O3 10-27%, -K2O 0-2%, preferably 0-1% - 0.5% to 15%, preferably 3% to 12%, of one or more iron oxides; and - one or more other oxides, in total from 0 to 5% by weight, preferably in total less than 3% by weight, The balance consists of inevitable impurities.

[0020] Within the meaning of the present invention, "coupling agent" is understood to denote: - organofunctional silanes for treating the glass fibres of the material according to the invention, or a polar coupling agent contained in the thermoplastic fibres of the material according to the invention. Either:

[0021] Thus, an insulating material according to the present invention containing at least one coupling agent comprises an organofunctional silane on the surface of its glass fibers and / or a polar coupling agent in its thermoplastic fibers.

[0022] According to the invention, polar coupling agents are compounds having polar functional groups that may be incorporated into the thermoplastic fibers of the material according to the invention.

[0023] Thus, the polar coupling agent suitable for the present invention can be selected from anhydrides, acids and organofunctional silanes, in particular the polar coupling agent is selected from anhydrides, acids and organofunctional silanes having amine or epoxy functional groups, preferably the polar coupling agent is selected from maleic anhydride, maleic acid and (3-aminopropyl)triethoxysilane (APTES).

[0024] Within the meaning of the present invention, organofunctional silanes are compounds of formula (I): (R'O) 3-n Si(R´´) n -R (I) During the ceremony, - n is an integer selected from 1, 2, and 3; - each R' is independently selected from the group consisting of hydrogen, C1-C8 alkyl, and C1-C8 acyl; - each R´´ is independently selected from C1-C8 alkyl; - R is a carbon chain carrying an organic functional group.

[0025] In particular, R is a carbon chain carrying a functional group selected from an amine functional group, a vinyl functional group, an epoxy functional group, a (meth)acrylic functional group, a sulfide functional group, an alkyl functional group and a phenyl functional group.

[0026] For the purposes of the present invention, "(meth)acrylic functional groups" is understood to mean alternatively methacrylic acid functional groups and acrylic functional groups.

[0027] According to a preferred embodiment of the invention, when the thermoplastic fiber comprises a polar coupling agent, R is a carbon chain having a functional group selected from an amine functional group, an epoxy functional group, a (meth)acrylic functional group, a sulfide functional group.

[0028] In a particular embodiment of the invention, depending on the nature of the carbon chain R, the organofunctional silanes used are alkylalkoxysilanes optionally bearing amine, vinyl, epoxy, (meth)acrylic, sulfide or phenyl functional groups.

[0029] Among the organofunctional silanes containing alkyl functions that are suitable for the present invention, mention may in particular be made of ethyltriacetoxysilane and methyltriacetoxysilane.

[0030] Among the organofunctional silanes containing an amine function that are suitable for the present invention, mention may in particular be made of (3-aminopropyl)triethoxysilane (APTES), 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropyl-trimethoxysilane, N-(n-butyl)-3-aminopropyltrimethoxysilane and N-benzyl-N'(3-trimethoxysilyl)-1,2-ethylenediamine.

[0031] Among the organofunctional silanes containing vinyl functions that are suitable for the present invention, mention may in particular be made of vinyltrimethoxysilane and vinyltriethoxysilane.

[0032] Among the organofunctional silanes containing an epoxy function that are suitable for the invention, mention may in particular be made of (3-glycidyloxypropyl)trimethoxysilane (GLYMO) and (3-glycidyloxypropyl)trimethoxysilane (GLYEO).

[0033] Among the organofunctional silanes containing a (meth)acryl function that are suitable for the invention, mention may in particular be made of 3-methacryloxypropyltrimethoxysilane and (3-acryloxypropyl)trimethoxysilane.

[0034] Among the organofunctional silanes containing a sulfide function that are suitable for the present invention, mention may in particular be made of (3-mercaptopropyl)trimethoxysilane.

[0035] Among the organofunctional silanes containing a phenyl function that are suitable for the invention, mention may in particular be made of N-benzyl-N'-(3-trimethoxysilyl)-1,2-ethylenediamine.

[0036] According to one embodiment of the present invention, the organofunctional silane used according to the invention is selected from (3-aminopropyl)triethoxysilane, (3-glycidyloxypropyl)trimethoxysilane and 3-methacryloxypropyltrimethoxysilane. Preferably, the organofunctional silane used according to the invention is (3-aminopropyl)triethoxysilane.

[0037] According to another embodiment of the present invention, R is selected from C1-C8 glycidyloxyalkyl and C1-C8 aminoalkyl.

[0038] In a particular embodiment of the invention, the glass fibre is treated with an organofunctional silane selected from organofunctional silanes having amine functional groups and organofunctional silanes having epoxy functional groups, in particular the glass fibre is treated with an organofunctional silane selected from (3-aminopropyl)triethoxysilane, (3-glycidyloxypropyl)trimethoxysilane and 3-methacryloxypropyltrimethoxysilane, preferably the glass fibre is treated with (3-aminopropyl)triethoxysilane (APTES).

[0039] According to a second aspect, the present invention relates to an acoustic and / or thermal insulation product obtained from the insulation material according to the invention.

[0040] According to a third aspect, the present invention relates to a method for manufacturing an insulating material according to the invention, which comprises a first step of mixing thermoplastic fibres and glass fibres, followed by a heating step.

[0041] The thermoplastic fibres used according to the invention may be selected from fibres of polyolefins, polyethylene terephthalate (PET), poly(vinyl chloride) (PVC), polyvinyl butyral (PVB), polystyrene (PS), polyurethane (PU), polyamide (PA) and copolymers thereof, in particular the thermoplastic fibres are selected from fibres of polyolefins, PET and copolymers thereof, preferably the thermoplastic fibres are selected from fibres of polypropylene (PP), polyethylene (PE) and copolymers thereof.

[0042] In one embodiment, the thermoplastic fibers consist of a thermoplastic phase as defined above.

[0043] In another embodiment of the invention, the thermoplastic fibers are said to be "bicomponent", i.e. they consist of at least two different phases of thermoplastics as defined above. For example, the thermoplastic fibers implemented according to this embodiment may consist of a core and a sheath, or of two continuous phases of thermoplastics juxtaposed. Methods for obtaining such fibers are known to those skilled in the art and are disclosed, for example, in U.S. Pat. No. 4,406,850 and European Patent No. 0,011,954. Such fibers are also commercially available, constituting, for example, the fabric sold under the name FELIBENDY by Kuraray Kuraflex.

[0044] This embodiment allows for the selection of two phases with different melting temperatures, such that during the process for producing the insulation material, the thermoplastic fibers are heated to a temperature above the melting point of the first phase but below the melting point of the second phase, such that they retain a certain structural integrity.

[0045] According to this embodiment, the polar coupling agent may be included in a single phase of the thermoplastic fibers, in particular in the case where the thermoplastic fibers consist of a core and a sheath, the polar coupling agent is included in the phase that constitutes the sheath of the thermoplastic fibers.

[0046] The insulating material disclosed in the present invention may contain 1 wt% to 70 wt% thermoplastic fibers, particularly 3 wt% to 50 wt% thermoplastic fibers, and preferably 5 wt% to 30 wt% thermoplastic fibers, based on the total weight of the insulating material.

[0047] The insulation material according to the present invention comprises 5% to 30% by weight of thermoplastic fibers based on the total weight of the insulation material.

[0048] The thermoplastic fibres used in the insulating material according to the invention may have a yarn count of 0.8 dtex to 4 dtex, in particular 0.9 dtex to 3 dtex, preferably 1 dtex to 1.5 dtex.

[0049] Fiber count is traditionally used in the textile industry and refers to the mass in grams of 1000 meters of fiber. Counts are expressed in tex (1 tex = 10 -6 It is expressed in kg / m, and more typically in dtex (1 dtex = 0.1 tex).

[0050] The thermoplastic fibres embodied in the insulating material according to the invention may also have a length of 2 mm to 100 mm, in particular 3 mm to 60 mm, preferably 6 mm to 20 mm.

[0051] As shown in the examples below, the inventors have also observed that the adhesion of the glass fibers and thermoplastic fibers to one another in the insulation material according to the present invention is significantly increased by the presence of polar chemical functional groups on the thermoplastic fibers.

[0052] These functionalities can be introduced by incorporating polar coupling agents into the thermoplastic fibers or by copolymerization of the thermoplastic with polar monomer units.

[0053] Thus, according to one embodiment, the at least one coupling agent present in the insulation material according to the invention is a polar coupling agent contained in the thermoplastic fibers present in the material.

[0054] According to this embodiment, the polar coupling agent may be selected from anhydrides, acids, and organofunctional silanes, in particular, the polar coupling agent is selected from anhydrides, acids, and organofunctional silanes having amine or epoxy functional groups, preferably, the polar coupling agent is selected from maleic anhydride, maleic acid, and (3-aminopropyl)triethoxysilane (APTES).

[0055] Such thermoplastic fibers can be obtained according to methods known to those skilled in the art and are disclosed, for example, in US patent application Ser. No. 09 / 056,875 and WO 2009 / 051283.

[0056] According to another embodiment, the thermoplastic fibers present in the insulation material according to the present invention comprise polar monomer units.

[0057] According to this embodiment, the polar monomeric unit is a monomeric unit of polyvinyl alcohol.

[0058] For example, thermoplastic fibers embodied in the barrier material according to the present invention may include ethylene-vinyl alcohol (EVOH) copolymers.

[0059] Such thermoplastic fibers can be obtained according to methods known to those skilled in the art and are present, for example, in the fabric sold under the name FELIBENDY by Kuraray Kuraflex.

[0060] The insulating material according to the present invention has a coating density of 400 g / m 2 ~12,000g / m 2 , especially 500g / m 2 ~8,000g / m 2 , preferably 600 g / m 2 ~4,000g / m 2 The sheet may have a basis weight of 100 g.

[0061] The insulating material according to the invention may have a thickness of 10 mm to 300 mm, in particular 15 mm to 200 mm, preferably 20 mm to 100 mm.

[0062] The insulating material according to the present invention may have a thermal conductivity of 0.025 W / m·K to 0.050 W / m·K, in particular 0.028 W / m·K to 0.048 W / m·K, preferably 0.030 W / m·K to 0.045 W / m·K.

[0063] These thermal conductivity values ​​are obtained by measurement in accordance with standards NF-EN-12667 and NF-EN-12939.

[0064] The present invention also relates to sound and / or heat insulating products (acoustic and / or thermal insulation products) comprising the insulation material according to the present invention.

[0065] Such products are particularly provided in the form of rolls or panels.

[0066] It can be used, for example, in buildings, in industry or in transport means, in particular in trains or means of transport. The product according to the invention can be used to insulate any type of building, tertiary sector building or residential area (multi-unit house or private house). It can be used, for example, in systems for insulating through the exterior, systems for insulating wooden frame houses, sandwich panels, ventilation ducts, etc.

[0067] The invention also relates to a method for producing an insulating material according to the invention, comprising a first step of mixing thermoplastic fibres and glass fibres, followed by a heating step.

[0068] The heating step of the method according to the invention may involve heating at a temperature of from 90°C to 260°C, in particular from 100°C to 250°C, preferably from 110°C to 240°C.

[0069] In embodiments in which the thermoplastic fibers are said to be "bicomponent," the temperature of the heating step is selected based, inter alia, on the melting temperatures of the components. Thus, the temperature of the heating step is preferably higher than the melting temperature of a first phase of the thermoplastic fibers and lower than the melting temperature of a second phase of the thermoplastic fibers.

[0070] The following examples illustrate the invention in a non-limiting manner.

[0071] example To measure the adhesion between thermoplastic and glass fibers, samples of these materials are prepared. For each measurement, three glass plates, traditionally used for the microscopic observation of samples, and a polymer mat consisting of fibers with a polypropylene core and a polyethylene sheath are used.

[0072] The polymer mat can be obtained from the FELIBENDY commercial compound sold by Kuraray Kuraflex. The mat used in the following examples has a thickness of 0.1 mm to 1 mm and a weight of about 140 g / m 2 The sheet has a basis weight of 1.0 g.

[0073] The glass plate is washed with water, then with ethanol, and organic residues are removed using a burner flame.

[0074] For each measurement, the samples are obtained by arranging them vertically according to three layers: - a first layer consisting of two glass panes, an upper pane and a lower pane, the two panes being adjacent across their width; - a second layer consisting of a polymer web, which overlaps the two glass panes of the first layer and partially covers them, - A third layer consisting of a glass plate, covering the polymer mat of the second layer.

[0075] The samples thus obtained are subjected to a baking step in an oven at 140° C. for 10 minutes.

[0076] The adhesion between the materials is then measured using a universal testing instrument; Instron 5965L9952, referenced to a 2580 / 2kN cell, with the upper plate engaged in the moving jaw of the instrument moving at a speed of 2 mm / min. The maximum force measured is considered to be the breaking load of the system.

[0077] Table 1 below shows the various systems evaluated and the average breaking load measured for each of them during the four tests.

[0078] [Table 1]

[0079] For Examples 1 and 3 according to the invention, the surface treatment of the glass with the organofunctional silane is carried out after the above mentioned cleaning step using paper soaked with (3-aminopropyl)triethoxysilane (APTES), passed over the surface of the glass plate and then contacted with the polymer mat.

[0080] For examples 2 and 3 according to the invention, a polymer mat is used which further comprises maleic anhydride dispersed in the thermoplastic fibers.

[0081] By comparing the breaking loads of Example 1 according to the invention and Comparative Example 4, or by comparing the breaking loads of Example 3 according to the invention and Example 2 according to the invention, it is clearly shown that the surface treatment of glass with an organofunctional silane, here APTES, makes it possible to significantly improve the adhesion of the glass substrate and the thermoplastic fibers to one another.

[0082] In addition, by comparing the breaking load measured for Example 2 according to the invention with that of Comparative Example 4, it is also clear that the presence of a polar coupling agent in the thermoplastic fibers, here the presence of maleic anhydride, makes it possible to significantly improve the mutual adhesion between the glass substrate and the thermoplastic fibers.

[0083] It is further noted that for example 3 according to the invention, it is not possible to disassemble the glass plate and the polymer mat without breaking the glass. In fact, the break occurs in the thermoplastic mat and not at the interface with the glass plate. In this case, the measured breaking load only represents the cohesion of the polymer mat and not its adhesion to the glass plate. The breaking load representing the adhesion between the polymer mat and the glass plate is therefore in fact higher than the breaking load measured. It is therefore also demonstrated that the combined presence of a coupling agent in the form of an organofunctional silane used for the surface treatment of the glass substrate and a polar coupling agent present in the thermoplastic fibers makes it possible to significantly improve this adhesion.

[0084] In conclusion, the results shown in Table 1 above therefore demonstrate that coupling agents allow a significant increase in the adhesion of the glass substrate with the thermoplastic fibres. This coupling agent can take the form of an organofunctional silane introduced by surface treatment of the glass substrate, or a polar coupling agent present in the thermoplastic fibres. In particular, adhesion is greatest when the coupling agents are an organofunctional silane introduced by surface treatment of the glass and a polar coupling agent in the thermoplastic fibres.

Claims

1. 1. An insulating material comprising glass fibers, at least one coupling agent, and 5% to 30% by weight of thermoplastic fibers based on the total weight of said material.

2. 10. The insulating material of claim 1, wherein the at least one coupling agent is an organofunctional silane and the glass fiber is treated with the organofunctional silane.

3. 3. The insulating material of claim 1 or 2, wherein at least one coupling agent is a polar coupling agent included in the thermoplastic fibers.

4. 4. The blocking material of claim 3, wherein the polar coupling agent is selected from anhydrides, acids and organofunctional silanes, particularly, the polar coupling agent is selected from anhydrides, acids and organofunctional silanes having amine or epoxy functional groups, preferably, the polar coupling agent is selected from maleic anhydride, maleic acid and (3-aminopropyl)triethoxysilane (APTES).

5. The insulating material of claim 1 or 2, wherein the thermoplastic fibers include polar monomer units.

6. 6. The insulating material of claim 5, wherein the polar monomeric unit is a monomeric unit of polyvinyl alcohol.

7. 3. The insulating material according to claim 1 or 2, wherein the thermoplastic fibers are selected from fibers of polyolefin, polyethylene terephthalate (PET), poly(vinyl chloride) (PVC), polyvinyl butyral (PVB), polystyrene (PS), polyurethane (PU), polyamide (PA) and copolymers thereof, in particular, the thermoplastic fibers are selected from fibers of polyolefin, PET and copolymers thereof, preferably, the thermoplastic fibers are selected from fibers of polypropylene (PP), polyethylene (PE) and copolymers thereof.

8. 3. The insulating material of claim 1 or 2, Shielding material having a thermal conductivity of 0.025 W / m·K to 0.050 W / m·K, in particular 0.028 W / m·K to 0.048 W / m·K, preferably 0.030 W / m·K to 0.045 W / m·K.

9. 3. The insulating material according to claim 1 or 2, wherein the thermoplastic fibres have a yarn count of 0.8 dtex to 4 dtex, in particular 0.9 dtex to 3 dtex, preferably 1 dtex to 1.5 dtex.

10. 3. The insulating material according to claim 1 or 2, wherein the thermoplastic fibres have a length of from 2 mm to 100 mm, in particular from 3 mm to 60 mm, preferably from 6 mm to 20 mm.

11. 3. The insulating material of claim 2, wherein the glass fiber is treated with an organofunctional silane selected from organofunctional silanes having amine functional groups and organofunctional silanes having epoxy functional groups, in particular, the glass fiber is treated with an organofunctional silane selected from (3-aminopropyl)triethoxysilane, (3-glycidyloxypropyl)trimethoxysilane, and 3-methacryloxypropyltrimethoxysilane, and preferably, the glass fiber is treated with (3-aminopropyl)triethoxysilane (APTES).

12. 3. The insulating material of claim 1 or 2, having a thickness of 400 g / m ２ ~12,000g / m ２ , especially 500 g / m ２ Up to 8,000 g / m ２ , preferably 600 g / m ２ Up to 4,000 g / m ２ The insulating material has a basis weight of

13. 3. The insulating material according to claim 1 or 2, having a thickness of 10 mm to 300 mm, in particular 15 mm to 200 mm, preferably 20 mm to 100 mm.

14. 3. An acoustic and / or thermal insulation product comprising the insulation material of claim 1 or 2.

15. 3. A method for producing the insulation material of claim 1 or 2, comprising a first step of mixing the thermoplastic fibers and the glass fibers, followed by a heating step.