JP2015003445A - Nonwoven fabric for automobile interior material and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for inexpensively and stably manufacturing a skin material preventing bleeding of a foam urethane resin to the skin material and not imparting the texture of nonwoven fabric without using a fluorine-based oil-repelling agent.SOLUTION: The method for manufacturing a nonwoven fabric processed with a non-fluororesin waterproofing agent includes: applying an aqueous coating material comprising at least a non-fluororesin waterproofing agent and a foaming agent and being adjusted to have an expansion ratio of 6-11.5 times and a viscosity of 6,000-14,000 mPa s in an amount of 8.5-22 g/mbased on a nonvolatile content to one surface of a nonwoven fabric composed of a chemical fiber and having a basis weight of 130-200 g/m, a thickness of 1.5-2.5 mm and an apparent density of 0.08-0.12 g/cm; and drying the coating material at a temperature of 95-155°C.

Description

  The present invention relates to a method for producing a nonwoven fabric containing a non-fluorinated waterproofing agent.

  Foam molded urethane sheets are widely used for interior materials for vehicles such as automobiles, particularly ceiling materials, in order to impart heat insulation and sound absorption to the interior materials. Conventionally, an interior material is manufactured by laminating and integrating a skin material such as a nonwoven fabric, a raised knit, a woven fabric, or a vinyl chloride sheet with an adhesive or a heat-adhesive film on a foamed urethane sheet.

  In recent years, in order to simplify the manufacturing process, when foaming a urethane sheet, the skin material is layered before foaming the urethane resin, and the urethane resin foam layer and the skin material are used by utilizing the adhesiveness of the urethane resin. The method of integrally molding the is adopted. However, in this method, depending on the characteristics (kind, thickness, density) of the skin material, it has been pointed out that the urethane resin partially oozes into the skin material due to the foaming pressure when foaming the urethane sheet. However, there have been problems such as impairing the design of the skin material or causing wrinkles in the texture.

  Various studies have been made in various fields as a countermeasure for preventing the urethane resin from seeping out. Patent Document 1 describes a skin material made of a fiber sheet containing a fluorine-based oil repellent. Patent Documents 2 to 4 show examples in which the configuration of the nonwoven fabric used as the base material of the skin material is devised. For example, Patent Document 2 is manufactured by a flash spinning method as a base material of the skin material. The use of non-woven fabric with low air permeability is described. Patent Documents 3 to 4 describe skin materials in which a plurality of nonwoven fabrics having different porosity are laminated and integrated.

Japanese Patent Laid-Open No. 2004-027466 Japanese Patent Laid-Open No. 2003-310551 JP-A-6-171002 JP-A-6-171003

  However, in Patent Document 1, a fluorine-based oil repellent, particularly a perfluoroalkyl acrylate oil repellent is used as the oil repellent. It has been pointed out that water / oil repellents having a perfluoroalkyl group having 8 or more carbon atoms may decompose to produce perfluorooctanoic acid (PFOA) when discharged into the environment. The PFOA has problems of accumulation and harmfulness to the environment and the human body. For this reason, since the use of the water / oil repellent having a perfluoroalkyl group having 8 or more carbon atoms is currently limited, the skin material of Patent Document 1 cannot be used. Moreover, the skin material of patent documents 2-4 has the subject that a manufacturing method is complicated or the leaching prevention effect is not constant.

  Under such circumstances, the present invention is a low-cost skin material that does not impair the texture of the nonwoven fabric by preventing the urethane foam resin from leaching into the skin material without using a fluorine-based oil repellent. The problem was to provide a method for stable production.

  As a result of intensive studies to solve the above problems, the present inventor has previously obtained a foaming ratio and a viscosity before applying a coating containing a non-fluorine-based waterproofing agent and a foaming agent to a nonwoven fabric having a specific configuration. If the temperature is adjusted in the heating and drying process after applying this to the nonwoven fabric and the foam breakage of the paint is controlled, the paint penetrates into the nonwoven fabric. As a result, the present invention was completed.

That is, the method for producing a non-fluororesin waterproofing nonwoven fabric according to the present invention comprises chemical fibers, has a basis weight of 130 to 200 g / m ² , a thickness of 1.5 to 2.5 mm, and an apparent density of 0.08 to 0.00. A water-based paint containing at least a non-fluorine-based waterproofing agent and a foaming agent on one side of a 12 g / cm ³ non-woven fabric and adjusted to an expansion ratio of 6 to 11.5 times and a viscosity of 6000 to 14000 mPa · s is 8.5 on a non-volatile basis. It is characterized by applying ˜22 g / m ² and drying the paint at a temperature of 95 to 155 ° C. The non-fluorine waterproofing agent is preferably a styrene- (meth) acrylic acid ester waterproofing agent. In a more desirable embodiment, the water-based paint further contains a water repellent containing a monomer unit of (meth) acrylic acid ester having 12 or more carbon atoms in the ester portion, and a paraffinic water repellent. is there. Furthermore, it is desirable that the water-based paint further contains a foam stabilizer. In addition, the nonwoven fabric is preferably a needle punched nonwoven fabric.
Furthermore, the present invention is made of a chemical fiber, impregnated with a non-fluorine waterproofing agent into a nonwoven fabric having a basis weight of 130 to 200 g / m ² , a thickness of 1.5 to 2.5 mm, and an apparent density of 0.08 to 0.12 g / cm ^3. In the position where the non-fluorine waterproofing agent is most impregnated in the nonwoven fabric, the non-fluorine waterproofing agent is impregnated in the range of 1/3 to 1/2 in the thickness direction from one side of the nonwoven fabric. The non-fluorinated resin waterproofing agent processed non-woven fabric characterized by being included.
Further, the present invention is made of a chemical fiber, impregnated with a non-fluorine waterproofing agent in a nonwoven fabric having a basis weight of 130 to 200 g / m ² , a thickness of 1.5 to 2.5 mm, and an apparent density of 0.08 to 0.12 g / cm ^3. A non-fluorinated resin waterproofing agent processed nonwoven fabric and a polyurethane foam laminated body, wherein the non-fluorinated resin waterproofing agent processed nonwoven fabric is at the position where the non-fluorinated waterproofing agent is most impregnated in the nonwoven fabric, The non-fluorinated waterproofing agent is impregnated in a range of 1/3 to 1/2 in the thickness direction from the non-laminated foam polyurethane surface of the nonwoven fabric, and the foamed polyurethane is a non-fluorinated resin waterproofing agent processed nonwoven fabric. A non-woven fabric-urethane foam laminate characterized by being partially impregnated is also included.

  According to the present invention, when applying a foamed water-based paint to a nonwoven fabric having a specific configuration, the expansion ratio is adjusted to 6 to 11.5 times, the viscosity is adjusted to 6000 to 14000 mPa · s, and the subsequent drying step Non-fluororesin-based waterproofing agent processed non-woven fabric that can adjust the foam breaking property of foam in foamed paint by preventing the water and water repellent from penetrating to the back surface of the non-woven fabric. Can be stably produced.

FIG. 1 is an explanatory diagram for explaining an evaluation method in a “foaming paint penetration” test of an example.

  The non-fluororesin waterproofing nonwoven fabric according to the present invention will be described. Non-fluororesin-based waterproofing agent processed non-woven fabric is treated with a waterproofing agent with a waterproofing agent (processing to control the penetration of foamed urethane resin) in order to prevent the urethane resin from seeping out onto the surface of the skin material. On the other hand, in order to improve the adhesiveness with the urethane resin, the side in contact with the urethane resin is not treated with a waterproofing agent for absorbing the urethane resin. Thus, the non-fluororesin waterproofing nonwoven fabric is characterized in that one surface is treated with waterproofing agent, but the opposite surface is not treated with waterproofing agent.

  And this invention has the characteristics in the characteristic of the water-based paint containing a non-fluorine type waterproofing agent used when performing a waterproofing agent process to a base material (nonwoven fabric), and the drying method after coating. What is important in the present invention is that a water-based paint containing a non-fluorine-based waterproofing agent penetrates to a thickness of about ½ of the nonwoven fabric. In the present invention, the water-based paint is foamed, the foamed water-based paint is applied to the nonwoven fabric, and then part or all of the foam in the paint is broken on the nonwoven fabric to adjust the permeability of the water-based paint. doing. Further, the permeability of the water-based paint is finely controlled by adjusting the foam breaking property and the viscosity of the water-based paint after foaming.

<Base material>
First, the nonwoven fabric used as the base material of a non-fluorine resin waterproofing agent processed nonwoven fabric is demonstrated.

  A base material is comprised from a nonwoven fabric. As the nonwoven fabric that can be used in the present invention, various nonwoven fabrics such as wet nonwoven fabric, dry nonwoven fabric, and spunbond nonwoven fabric can be used. The fiber bonding method is not particularly limited, and mechanical entanglement methods such as needle punch method and water entanglement method; thermal bond method such as air-through method, point bond method and flat bond method; chemical bond method; Various bonding methods such as a stitch bond method can be employed. In the present invention, since the base material is bulky and the texture can be softly finished, a mechanical entanglement method such as a needle punch method or a water entanglement method is preferred, and a needle punch nonwoven fabric can be particularly preferably employed.

  In particular, when a nonwoven fabric is produced by the needle punch method, if the needle used for entanglement of the fibers is a large count, that is, a thin needle is used, it is difficult to form a passage when the foamed paint passes through. On the other hand, when a small needle, that is, a thick needle, is used, a passage through which the foamed paint passes is formed, and the broken foam may pass through the nonwoven fabric and penetrate deeply in the thickness direction. For these reasons, when producing a nonwoven fabric by the needle punch method, it is preferable to use a needle having a count of 36 to 42.

  Needle punching can employ either a method in which one of the upper surface or the lower surface of the web is pierced with a needle; and a method in which both the upper and lower surfaces of the web are pierced with a needle. In the present invention, a method in which both the upper surface and the lower surface of the web are pierced with a needle is more preferable from the viewpoint of preventing permeability of the broken paint and preventing the paint from coming off to the back surface of the nonwoven fabric.

In the needle punching process, the needle depth is preferably about 4 to 7 mm in order to improve the texture of the obtained nonwoven fabric. The total number of needles to be driven is, for example, preferably 600 to 1000 / cm ² , more preferably 700 to 900 / cm ² .

In the present invention, the apparent density of the base material (nonwoven fabric) is an important factor that determines the permeability of the foamed paint and the permeability when foaming the urethane resin. The apparent density of the nonwoven fabric, a 0.08~0.12g / cm ^3, more preferably from 0.085~0.115g / cm ^3, more preferably at 0.087~0.11g / cm ³ is there. When the apparent density of the nonwoven fabric is less than 0.08 g / cm ³ , the fiber gap increases, and the foam coating or urethane resin easily penetrates into the nonwoven fabric, making it difficult to adjust the amount of penetration in these nonwoven fabrics. Therefore, it is not preferable. Moreover, when the apparent density of a nonwoven fabric exceeds 0.12 g / cm < ³ >, since between fibers will become dense and it will become difficult for a foaming coating material and a urethane resin to penetrate | invade inside a nonwoven fabric, it is unpreferable. In addition, the measuring method of the apparent density of a nonwoven fabric is explained in full detail in the Example column.

Moreover, in order to adjust the apparent density within the above range, the balance between the fabric weight and the thickness of the nonwoven fabric is important. The basis weight of the nonwoven fabric is 130 to 200 g / m ² , more preferably 135 to 190 g / m ² , and still more preferably 140 to 175 g / m ² . If the basis weight of the nonwoven fabric is within the above range, it becomes easy to adjust the apparent density of the nonwoven fabric within a predetermined range.

  Moreover, the thickness of a nonwoven fabric is 1.5-2.5 mm, More preferably, it is 1.55-2.4 mm, More preferably, it is 1.6-2.3 mm. If the thickness of the nonwoven fabric is within the above range, it is easy to adjust the apparent density of the nonwoven fabric within a predetermined range.

Chemical fibers can be used as the fibers used in the nonwoven fabric. Specifically, recycled fibers such as rayon, polynosic, cupra, and lyocell; semi-synthetic fibers such as acetate fiber and triacetate fiber; polyamide fibers such as nylon 6 and nylon 66; polyethylene terephthalate fiber, polybutylene terephthalate fiber, and polylactic acid fiber Polyester fiber such as polyarylate; Acrylic fiber such as polyacrylonitrile fiber and polyacrylonitrile-vinyl chloride copolymer fiber; Polyolefin fiber such as polyethylene fiber and polypropylene fiber; Polyvinyl alcohol fiber such as vinylon fiber and polyvinyl alcohol fiber; Poly Polyvinyl chloride fibers such as vinyl chloride fibers, vinylidene fibers, and polyclar fibers; Polyurethane fibers; Polyether fibers such as polyethylene oxide fibers and polypropylene oxide fibers ; And the like are preferable. These fibers may be used alone or in combination.
Among them, recycled fibers and synthetic fibers are preferable, and more preferable are polyester fibers such as polyethylene terephthalate fibers, polybutylene terephthalate fibers and polylactic acid fibers; polyamide fibers such as nylon 6 and nylon 66; polyolefin fibers such as polyethylene fibers and polypropylene fibers. Synthetic fibers such as; Polyester fiber is particularly preferable, and polyethylene terephthalate fiber is optimal. The polyester fiber is desirably contained in an amount of 70% by weight or more (more preferably 90% by weight or more, more preferably 95% by weight or more) in 100% by weight of the nonwoven fabric.

  The fiber used is not particularly limited in both fiber diameter and fiber length. As a fiber diameter of the fiber which comprises a base material, it is preferable that a fineness is 1-30 dtex, for example, More preferably, it is 1.2-20 dtex. Moreover, it is preferable that fiber length is 25-100 mm, for example, More preferably, it is 35-75 mm.

<Water-based paint>
Next, the water-based paint applied to the substrate (nonwoven fabric) will be described.
In the present invention, the water-based paint refers to a liquid containing water as a dispersion medium or solvent and containing at least a non-fluorinated waterproofing agent and a foaming agent.

  As the non-fluorine-based waterproofing agent, any non-fluorine-based water repellent that does not contain fluorine can be preferably used. Among them, the wettability with respect to the base material is reduced, and the particle gap is made dense. A non-fluorinated waterproofing agent designed with a water-based dispersion of an acrylic copolymer as a dispersion medium can be preferably used.

  The “aqueous dispersion of acrylic copolymer” means an aqueous dispersion containing a copolymer of an acrylic monomer and another vinyl monomer.

  Examples of the acrylic monomer include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth ) (Meth) acrylic acid esters such as lauryl acrylate and stearyl (meth) acrylate; acrylonitrile, methacrylonitrile; acrylamide, N-methylolacrylamide and the like. Examples of other vinyl monomers include aromatic vinyl monomers such as styrene, α-methylstyrene, and vinyl toluene; vinyl acetate and the like. The aqueous dispersion of the acrylic copolymer is produced by a method in which the above-mentioned monomer is emulsion-polymerized and stably dispersed.

  Examples of such non-fluorine waterproofing agents include Cybinol series manufactured by Seiden Chemical. In particular, in the present invention, a styrene- (meth) acrylic acid ester waterproofing agent, which is a copolymer of styrene and (meth) acrylic acid esters, is preferable.

  The non-fluorine-based waterproofing agent is preferably contained in 5 to 30% by weight in 100% by weight of the aqueous paint, more preferably 7 to 25% by weight, and still more preferably 13 to 20% by weight. By adjusting the amount of the non-fluorinated waterproofing agent within the above range, it is possible to produce a non-fluorinated resin-based waterproofing agent processed nonwoven fabric that suppresses the seepage of the urethane resin during molding and does not impair the texture of the nonwoven fabric. .

  As the foaming agent, various surfactants can be preferably used, and in particular, nonionic surfactants such as polyoxyethylene alkyl ether, fatty acid sorbitan ester, alkyl polyglucoside, fatty acid diethanolamide, alkyl monoglyceryl ether; monoalkyl sulfate Anionic surfactants such as alkyl polyoxyethylene sulfate, alkylbenzene sulfonate, and monoalkyl phosphate; can be preferably used.

  The amount of the foaming agent added is preferably 0.1 to 5% by weight, more preferably 0.2 to 3% by weight, and still more preferably 0.5 to 2% by weight in 100% by weight of the water-based paint. If the addition amount of the foaming agent is less than 0.1% by weight, the aqueous paint may not be foamed to a desired foaming ratio, which is not preferable. Moreover, when the addition amount of a foaming agent exceeds 5 weight%, since the foam breakability of the foamed coating after coating worsens and it becomes difficult for a coating to penetrate in the thickness direction of a nonwoven fabric, it is unpreferable.

  Various additives can be blended in the water-based paint in addition to the non-fluorine waterproofing agent and the foaming agent.

  In addition to the non-fluorine waterproofing agent, for example, a water repellent may be further added to the water-based paint. As the water repellent, a non-fluorine water repellent is used as in the case of the non-fluorine waterproof agent. Examples of the non-fluorine water repellent include (meth) acrylic acid having 12 or more carbon atoms in the ester moiety. A water repellent containing an ester as a monomer unit may be mentioned.

  In the case of adding a water repellent, the water repellent is preferably contained in an amount of 0.1 to 20% by weight, more preferably 1 to 10% by weight, even more preferably 1. 5-7% by weight. The blending ratio with the non-fluorine waterproofing agent described above is a non-fluorine waterproofing agent / water repellent (active ingredient ratio), preferably 55/45 to 100/0% by weight, more preferably 60 / 40-90 / 10% by weight.

  The water-based paint may contain a paraffinic water repellent. Examples of the paraffinic water repellent include water repellents containing a paraffinic resin compound as a main component and a cationic polymer. Examples of such paraffinic water repellent include “TH-44” manufactured by Nikka Chemical Co., Ltd.

  The addition amount of the paraffinic water repellent is preferably 0.1 to 5% by weight, more preferably 0.5 to 3.5% by weight in 100% by weight of the water-based paint. The paraffinic water repellent is preferably added in an amount of 1 to 25% by weight with respect to 100% by weight of the total of the non-fluorine waterproofing agent and the water repellent.

  The water-based paint desirably contains a foam stabilizer. Preferred examples of the foam stabilizer include silicone compounds such as polydimethylsiloxane; ammonium salt compounds of fatty acids such as ammonium stearate; and the like.

  The addition amount of the foam stabilizer is preferably 0.05 to 5% by weight, more preferably 0.1 to 4% by weight, and still more preferably 0.3 to 3.5% by weight in 100% by weight of the aqueous paint. %. When the addition amount of the foam stabilizer is less than 0.05% by weight, the foam may not be formed uniformly. Moreover, even if it exceeds 5 weight%, since the foam cannot be made more uniform with the increase in the addition amount of the foam stabilizer, the foam stabilizer may be wasted, which is not economical.

  The viscosity of the water-based paint is also important in the present invention. In order to adjust the viscosity of the aqueous paint, a thickener may be added to the aqueous paint. As the thickener, for example, a thickener derived from natural products such as sodium alginate; an associative thickener such as polyurethane resin; an ammonia thickener such as polyacrylate resin; carboxymethylcellulose (CMC) Cellulosic thickeners; and the like. Of these, associative thickeners such as polyurethane resins are preferred.

  The addition amount of the thickener is preferably 0.05 to 5% by weight, more preferably 0.1 to 3.5% by weight, and still more preferably 0.5% in 100% by weight of the aqueous paint. ~ 2.5 wt%. If the addition amount of the thickener is less than 0.05% by weight, the water-based paint cannot be given an appropriate viscosity, and when the paint is applied, the paint may ooze out to the back of the nonwoven fabric. It is not preferable. On the other hand, if the amount of the thickener exceeds 5% by weight, the viscosity of the water-based paint becomes too high and the water-based paint may not be sufficiently foamed.

  In addition to those exemplified above, dyes, pigments and the like can be added to the water-based paint. By coloring the water-based paint, the design of the non-fluororesin waterproofing nonwoven fabric can be improved. In order to improve the function as an automobile interior material, it is preferable to add a flame retardant, an antistatic agent, a deodorant, an antibacterial agent, or the like to the water-based paint.

  The water-based paint is foamed after the components are mixed and before being applied to the nonwoven fabric. In the present invention, it is necessary to foam the foamed paint after foaming the aqueous paint so that the foaming ratio of the foamed paint (hereinafter sometimes simply referred to as “foamed paint”) is 6 to 11.5 times. Preferably it is 6.1-10.5 times, More preferably, it is 6.1-9.5 times. When the expansion ratio is less than 6 times, the amount of air contained in the water-based paint decreases, and the water-based paint easily passes through the nonwoven fabric. Thereby, since there exists a possibility that an aqueous coating may osmose | permeate to the back side of a nonwoven fabric, it is unpreferable. On the other hand, when the expansion ratio exceeds 11.5 times, it is not preferable because the water-based paint hardly penetrates into the nonwoven fabric.

  The viscosity of the aqueous paint after foaming is also important in the present invention. The viscosity of the foamed paint is 6000 to 14000 mPa · s, more preferably 7000 to 13000 mPa · s, and further preferably 7500 to 10,000 mPa · s. When the viscosity of the foamed paint is less than 6000 mPa · s, the viscosity of the foamed paint is not sufficient, and when the foamed paint is applied to the nonwoven fabric, the paint impregnates more than half of the thickness of the nonwoven fabric, Since there is a possibility of penetration, it is not preferable. Moreover, when a foaming paint impregnates more than half of the thickness direction of a nonwoven fabric, a nonwoven fabric will become hard and it will become difficult to maintain a soft texture. In addition, if the foam paint penetrates deep into the nonwoven fabric, it will be difficult for the nonwoven fabric to absorb the urethane resin when the urethane resin is infiltrated, and the urethane resin and the non-fluorinated resin waterproof agent processing will be difficult. This is not preferable because the bonding strength with the nonwoven fabric is reduced. On the other hand, when the viscosity of the foamed paint exceeds 14000 mPa · s, the viscosity of the foamed paint is too high and the foamed paint hardly penetrates into the nonwoven fabric. Thereby, since a foaming coating adheres only to the surface of a nonwoven fabric, there exists a possibility that the texture of a nonwoven fabric may become a film form. In addition, the measuring method of the viscosity of a foaming coating is explained in full detail in the Example column.

The foamed paint is applied to the nonwoven fabric in an amount of 8.5 to 22 g / m ² on a nonvolatile basis, and the amount of the foamed paint is more preferably 9 to 21.5 g / m ² , and still more preferably 9.3 to 21 g. / M ² . If the amount of the foam coating is less than 8.5 g / m ² , the coating amount is not sufficient, and the amount that can penetrate into the nonwoven fabric is reduced, so that there is a possibility that it cannot penetrate to about half of the thickness of the nonwoven fabric. is there. On the other hand, if the amount of the foamed paint exceeds 22 g / m ² , the amount of the foamed paint is too large, and the texture of the nonwoven fabric may become a film.

  The above-mentioned water-based paint and foamed paint obtained by foaming the same can be used as a semi-permeable waterproof / water-repellent paint applicable to nonwoven fabrics.

<Method for producing non-fluororesin waterproofing nonwoven fabric>
The manufacturing method of non-fluororesin waterproofing nonwoven fabric is
Applying a foamed paint to one side of a substrate (nonwoven fabric);
Heating and drying the nonwoven fabric after applying the foam coating;
including.

  In the step of applying the foam paint to one side of the substrate, the coating method is not particularly limited as long as the foam paint can be applied to the nonwoven fabric. In the present invention, it is preferable to apply the foamed paint to the nonwoven fabric by the doctor coating method so that the foamed foam does not break up in large quantities.

  In addition, temperature is important in the process of heating and drying the nonwoven fabric after application of the foam coating. This is because if the temperature at the time of heating / drying is too high, the foam of the foamed paint expands due to the heating, and a large amount of foam may break. On the other hand, if the temperature at the time of heating and drying is too low, the foam of the foamed paint does not sufficiently break down, and the paint may not easily penetrate into the nonwoven fabric. For this reason, the temperature in the heating / drying step needs to be adjusted to 95 to 155 ° C, more preferably 100 to 150 ° C, and still more preferably 110 to 145 ° C. When the temperature is lower than 95 ° C., the foam of the foamed paint does not sufficiently break, and the paint may not easily penetrate into the nonwoven fabric. Moreover, when it exceeds 155 degreeC, the foam of a foamed coating material expand | swells by heating, there is a possibility that a large amount may be broken and a coating material may osmose | permeate to the back surface of a nonwoven fabric.

  Although the drying time of the nonwoven fabric after foaming paint application is not specifically limited, For example, 0.5-5 minutes are preferable, More preferably, it is 1-3 minutes. By adjusting the drying time within the above range, the foam of the foamed paint can be appropriately broken to sufficiently dry the nonwoven fabric after the foam paint is applied.

  Furthermore, after the heating / drying step, various embossing processes can be applied to the non-fluororesin waterproofing nonwoven fabric for the purpose of improving the design.

<Non-fluorine resin waterproofing agent nonwoven fabric>
In the present invention, as described above, since the permeability in the thickness direction of the nonwoven fabric is adjusted, the non-fluorinated waterproofing agent is processed at the position where the non-fluorinated waterproofing agent is most impregnated in the nonwoven fabric. The non-woven fabric has a structure in which the non-fluorinated waterproofing agent is impregnated in the range of 1/3 to 1/2 in the thickness direction from one side (coating surface) of the non-woven fabric. In this way, the non-fluorinated waterproofing agent is attached only to the one side (paint coating surface) side of the nonwoven fabric, so that the portion of the non-fluorinated waterproofing agent oozes out to the surface of the urethane foam resin. Can be prevented. On the other hand, the portion to which the non-fluorine waterproofing agent is not attached is impregnated with the urethane foam resin and firmly fixed to the urethane foam resin, so that it is difficult to peel off when used as a skin material.

<Usage method of non-fluororesin waterproofing nonwoven fabric>
When performing foam molding of urethane resin using this non-fluorine resin waterproofing agent nonwoven fabric, layer the opposite side of the water-based paint coating surface in contact with the urethane resin, and foam the urethane resin. It is good to do. By performing urethane resin foam molding in this way, a portion of the urethane resin impregnates the non-fluorinated resin waterproofing agent nonwoven fabric, so the peel strength between the urethane resin and the non-fluorine resin waterproofing agent nonwoven fabric is high. Increase. In addition, since the seepage of the urethane resin can be suppressed, the non-fluororesin waterproofing agent processed nonwoven fabric can be preferably used as a skin material that can provide an interior material with a beautiful appearance.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, but may be appropriately modified within a range that can meet the purpose described above and below. Of course, it is possible to implement them, and they are all included in the technical scope of the present invention.

The characteristic evaluation method of the non-fluororesin waterproofing agent processed nonwoven fabric obtained from the following Examples and Comparative Examples is as follows.
(1) Basis weight; basis weight of base material was measured according to JIS L1913 method 6.2 (2) thickness; thickness of base material was measured according to JIS L1913 method 6.1

(3) Foaming ratio: a value obtained by measuring the weight of 300 ml of water-based paint before and after mechanical foaming with an electronic balance and dividing the weight of the water-based paint before foaming by the weight of the foamed paint (that is, the weight of the water-based paint before foaming) / Weight of foamed paint) was defined as the expansion ratio.

(4) Viscosity: The viscosity of the foam coating was measured using a No. 3 rotor using a B-type viscometer (BM-II type manufactured by Toki Sangyo Co., Ltd.) under the conditions of a rotation speed of 6 rpm and a temperature of 21 ° C. .

(5) Apparent density: The apparent density of the substrate was determined by dividing the basis weight measured by the above-described method by the thickness and converting the unit to g / cm ³ .

(6) Permeation of foamed paint: A test liquid in which 0.5% by weight of pigment was added to an aqueous paint was prepared, and the test liquid was foamed with a general-purpose mechanical foaming machine. After coating the foam test solution on the nonwoven fabric, the center of the test piece was cut with a cutter, and a micrograph of the cut surface was taken and visually observed. The evaluation is as follows, and the evaluation contents are shown in FIG.
○: At the position where the paint is most impregnated, the boundary line between the paint and the non-woven fabric was in the range of 1/3 to 1/2 in the thickness direction from the foamed paint coated surface 2. Δ: The paint was most impregnated. The boundary line between the coating material and the nonwoven fabric was in the range of 1/5 to 1/3 in the thickness direction from the foam coating material coating surface 2 ×: the aqueous coating material penetrated to the back surface 3 (partial) Can not be penetrated)

(7) Exudation: A test solution in which 0.5% by weight of pigment was added to an acrylic resin (corresponding to a viscosity of 200 mPa · s) was prepared, and 5 drops of the test solution were dropped on a thick nonwoven fabric with a dropper. A cotton cloth was layered on top. A test piece was stacked thereon and pressed with a heated flat plate press (145 ° C., 4 kg / cm ² ) for 5 seconds, and then the seepage of the resin on the surface of the test piece was visually observed. The evaluation is as follows.
○: No adhesion to the test piece ×: Adhesion to the test piece (including a small amount of adhesion)

(8) Appearance / fluff evaluation; Appearance / fluff evaluation was determined visually. The evaluation is as follows.
○: No fluff on 10 cm square of test piece Δ: 1 to 5 fluff on 10 cm square of test piece ×: 6 or more fluff on 10 cm square of test piece

<Production of foam paint>
A foamed paint was prepared by the following method.
First, a water-based paint was prepared. Each component is as follows.
(A) Non-fluorinated waterproofing agent: Styrene- (meth) acrylic acid ester waterproofing agent (“Sybinol X510-365E” manufactured by Saiden Chemical Co., Ltd.)
(B) Water repellent: A water repellent containing a (meth) acrylic acid ester having 12 or more carbon atoms in the ester moiety as a monomer unit (“Neo Seed NR-90” manufactured by Nikka Chemical Co., Ltd.)
(C) Paraffinic water repellent: “TH-44” manufactured by Nikka Chemical Co., Ltd.
(D) Foaming agent: Mayformer F210
(E) Foam stabilizer: foam stabilizer containing 33% ammonium stearate ("DC-100A" manufactured by San Nopco)
(F) Thickener: Polyurethane resin associative thickener (“Neo Sticker N” manufactured by Nikka Chemical Co., Ltd.)

  Next, the prepared water-based paint was foamed with a general-purpose mechanical foaming machine to obtain a foamed paint. The foamed paint was creamy.

<Production of non-fluororesin waterproofing nonwoven fabric>
Examples 1-3
100% by weight of a polyester fiber having a fineness of 2.2 dtex and a fiber length of 51 mm was weighed in a usual manner, and the fiber was sent out in a certain direction with a card machine to form an intermediate web, which was then lapped to produce a web having a basis weight of 160 g / m ² . . This web is subjected to needle punching with a needle of needle number 40 alternately from the vertical direction of the web so that the needle depth is 5 to 6.5 mm and the total number of driven needles is 800 pieces / cm ^2. A needle punched nonwoven fabric of 157 g / m ² was obtained.
Next, the foamed paint produced by the above method was applied to one side of the obtained nonwoven fabric by the doctor coating method, and a part of the foamed paint was impregnated into the nonwoven fabric. Then, the nonwoven fabric after foaming paint coating was introduce | transduced into the hot air dryer heated to 130 degreeC, and the drying process for 1.5 minutes was performed.
Various evaluations described above were performed using the obtained non-fluorinated resin waterproofing nonwoven fabric. The results are shown in Table 2.
In Table 2, “non-fluororesin waterproofing nonwoven fabric” is simply referred to as “product”.

Examples 4-8
A non-fluororesin waterproofing nonwoven fabric was obtained by the same method as in Example 1 except that the type of foam paint was changed. In Example 7, since the air mixing amount was adjusted at the time of creating the foam paint, the foam ratio was high. Details of the evaluation results are also shown in Table 2.

Examples 9-10
A non-fluorinated resin waterproofing nonwoven fabric was obtained by the same method as in Example 1 except that the heat treatment temperature was changed in the nonwoven fabric drying step after the foam coating was applied. The results are shown in Table 3.

Examples 11-12
A non-fluorinated resin waterproofing nonwoven fabric was obtained by the same method as in Example 1 except that the basis weight of the needle punch nonwoven fabric used as the base material was changed. The results are shown in Table 3.

Comparative Examples 1-4
In Comparative Examples 1 and 2, a non-fluorinated resin waterproofing agent processed nonwoven fabric was obtained by the same method as in Example 1 except that the heat treatment temperature was changed in the nonwoven fabric drying step after foam coating coating.
Moreover, in Comparative Examples 3-4, the non-fluororesin type waterproofing agent nonwoven fabric was obtained by the method similar to Example 1 except having changed the kind of foaming coating material, and having changed the viscosity and the expansion ratio. The results are shown in Table 3.

The non-fluorinated resin waterproofing agent processed nonwoven fabrics obtained in Examples 1 to 12 satisfy the conditions at the time of production, and therefore, all of the three items of paint penetration, seepage, appearance and fluff are good. I'm getting results.
On the other hand, the non-fluorine resin waterproofing agent processed nonwoven fabric obtained in Comparative Example 1 has a small amount of paint applied, and therefore cannot sufficiently penetrate the paint into the nonwoven fabric. Moreover, since there is little adhesion amount, the fuzz on the surface of a nonwoven fabric cannot be suppressed.
Moreover, since the non-fluorine resin waterproofing agent processed non-woven fabric obtained in Comparative Example 2 has an excessive amount of paint, the non-fluororesin waterproofing agent processed non-woven fabric looks like a film and the resin oozes out. It became.
In addition, since the non-fluororesin waterproofing nonwoven fabric obtained in Comparative Example 3 has a low viscosity of the foamed paint, the paint penetrates to the back surface of the nonwoven fabric. For this reason, the non-woven fabric cannot absorb the resin sufficiently, and the resin oozes out.
Furthermore, since the non-fluororesin waterproofing nonwoven fabric obtained in Comparative Example 4 has a high viscosity of the foamed paint, the paint cannot penetrate into the nonwoven fabric.

  The non-fluorinated resin waterproofing nonwoven fabric obtained in the present invention is treated with waterproofing agent on one side, but not treated with waterproofing agent on the opposite side. Can be preferably used as a skin material in various materials. Moreover, since the non-fluororesin waterproofing nonwoven fabric obtained by the present invention has less fuzz, it is also beautiful to the eye and can be suitably used for applications requiring high decorative properties such as interior materials for vehicles. In addition, since it is relatively easy to add a pigment to the pattern and texture of the nonwoven fabric used as the base material and the water-based paint, it is possible to simply improve the design of the non-fluorinated resin waterproofing nonwoven fabric.

1 Non-fluorinated resin waterproofing agent processed nonwoven fabric 2 Foam paint coated surface 3 Back surface (contact surface with urethane resin)

Claims (7)

Made of chemical fiber, on one side of a nonwoven fabric with a basis weight of 130 to 200 g / m ² , a thickness of 1.5 to 2.5 mm, and an apparent density of 0.08 to 0.12 g / cm ³ ,
Apply at least 8.5 to 22 g / m ^{2 of} an aqueous paint containing a non-fluorine-based waterproofing agent and a foaming agent, adjusted to a foaming ratio of 6 to 11.5 times, and a viscosity of 6000 to 14000 mPa · s, based on nonvolatile content,
A method for producing a non-fluorinated resin waterproofing nonwoven fabric, wherein the paint is dried at a temperature of 95 to 155 ° C.   The production method according to claim 1, wherein the non-fluorine waterproofing agent is a styrene- (meth) acrylic acid ester waterproofing agent.   The water-based paint according to claim 1 or 2, further comprising a water repellent containing a (meth) acrylic acid ester having 12 or more carbon atoms in the ester moiety as a monomer unit, and a paraffinic water repellent. Production method.   The manufacturing method according to claim 1, wherein the water-based paint further contains a foam stabilizer.   The said nonwoven fabric is a needle punch nonwoven fabric, The manufacturing method of any one of Claims 1-4. A non-fluorinated waterproofing agent is impregnated into a non-woven fabric having a basis weight of 130 to 200 g / m ² , a thickness of 1.5 to 2.5 mm, and an apparent density of 0.08 to 0.12 g / cm ³ .
In the position where the non-fluorine waterproofing agent is most impregnated in the nonwoven fabric, the non-fluorine waterproofing agent is impregnated in the range of 1/3 to 1/2 in the thickness direction from one side of the nonwoven fabric. Non-fluororesin waterproofing agent processed non-woven fabric. A non-fluorine resin-based non-fluorine-based resin impregnated with a non-fluorine waterproofing agent in a non-woven fabric made of a chemical fiber and having a basis weight of 130 to 200 g / m ² , a thickness of 1.5 to 2.5 mm, and an apparent density of 0.08 to 0.12 g / cm ³ A laminate of a waterproofing agent processed nonwoven fabric and polyurethane foam,
In the non-fluorinated resin waterproofing agent processed nonwoven fabric, the non-fluorinated waterproofing agent is formed in the thickness direction from the non-laminated foamed polyurethane surface of the nonwoven fabric at a position where the non-fluorinated waterproofing agent is most impregnated in the nonwoven fabric. Impregnated in the range of 1/3 to 1/2,
A nonwoven fabric-foamed urethane laminate, wherein the polyurethane foam is impregnated into a part of the non-fluororesin waterproofing nonwoven fabric.