JPH0316426B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a carpet that has excellent moldability, flame retardancy, and thermal adhesion to felt, and particularly provides a carpet that is useful as a floor covering material for automobiles. Conventionally, carpets are backed with rubber latex such as styrene-butadiene rubber or butadiene-acrylonitrile rubber to prevent the pile threads of the original rug from coming off and to stabilize the shape. When applying to uneven areas, it is difficult to shape the rubber latex backing material due to its high impact resilience, and even when it is shaped, its shape is not sharp and its shape retention is insufficient. . Melt extrusion lamination backing using thermoplastic resins such as polyethylene and ethylene/vinyl acetate copolymers has also been carried out. In this case, it is possible to form an uneven shape by heat processing and to thermally bond it to felt, and this product has a lower ability to retain the shape of the shaped carpet than that using rubber latex as the backing material. Although it has the advantage of being excellent and having a sharp shape, it has the disadvantage of being hard to the touch and having a poor pile locking effect. As a method to compensate for the drawbacks of these backing materials, a rubber latex with polyethylene powder dispersed therein is used as a backing material, and this is applied to the original rug to impregnate it, heated and dried, and then the felt is layered and heated. It has been proposed to press and form felt-backed carpets. However, according to this method, for 100 parts by weight of latex solids, polyethylene powder contains 300 parts by weight.
Since the polyethylene powder is used in an amount of ~700 parts by weight, it is difficult to uniformly disperse the polyethylene powder in the rubber latex, and it is also difficult to uniformly impregnate the raw rug with the powder. Furthermore, a rubber-based latex backing material is applied to the back of the original rug and impregnated, and after drying to remove moisture from the latex, a polyethylene film is melt-laminated on top of this latex backing, and then felt is layered. A method of manufacturing carpet by heating, pressurizing, and molding is generally in practical use, but this method requires two different backing processes: backing with latex coating and extrusion lamination. There are drawbacks. Furthermore, in place of rubber latex, synthetic resin emulsions such as styrene-acrylic resins, vinyl chloride/vinyl acetate copolymers, and ethylene/vinyl acetate copolymers are being used as water-based backing agents that give moldability to carpets. It is increasingly being used as a material. Among the,
Styrene-acrylic resin emulsions are becoming more widely used because they are superior in rigidity, moldability, and heat resistance compared to aqueous emulsions of other resins. On the back side of the backing layer formed from an aqueous emulsion of these thermoplastic resins, cushioning properties,
For the purpose of adding design to the carpet, when felt, foam sheet, etc. are attached and thermally bonded,
From the perspective of thermal adhesion, the lower the glass transition point of the thermoplastic resin in the aqueous emulsion, and the lower the heat resistance for melting, the easier it will be. In this case, it is preferable to use an aqueous emulsion of a thermoplastic resin having a high glass transition point. Currently used styrene-acrylic copolymer resins provide carpets with excellent heat resistance, rigidity, and moldability, but there is room for improvement in terms of thermal adhesion of felts and the like. The present inventor aimed to provide a carpet with well-balanced formability, heat resistance, rigidity, and thermal adhesiveness.
After studying various backing materials, we found that an aqueous thermoplastic resin emulsion with a glass transition point of 80°C or higher, which provides moldability, heat resistance, and rigidity to the carpet, and a resin emulsion, which provides thermal adhesion to phenit, are used as backing materials. i.e., at least two backing layers are applied to the rug material (the backing layer formed from the thermoadhesive resin aqueous emulsion forms the opposite surface to the rug material). ), the amount of backing material used can be reduced, and a carpet with excellent moldability and thermal adhesion can be produced, and the present invention has been achieved. That is, in the present invention, an aqueous thermoplastic resin emulsion with a glass transition point of 80°C or higher is applied to the back side of the original rug at a rate of 60 to 1000 g/m ² (solid content), and dried to form a backing layer. After forming, on top of this backing layer, an aqueous emulsion of a thermal adhesion imparting resin selected from petroleum resins, terpene resins, rosin resins, and ethylene-vinyl acetate copolymers with a softening point of 60 to 120°C is applied. The present invention provides a method for producing a heat-adhesive carpet, which is characterized in that it is coated at a rate of 10 to 200 g/m ² (solid content) and then dried to form a heat-adhesive resin film. In the present invention, any material can be used as the raw material for the carpet, including natural fibers, chemical fibers,
Raw fabrics made from various fibers such as synthetic fibers can be used. In general, raw material for tufted carpet is prepared by erecting piles on a primary base fabric knitted from needle punch carpet or flat yarn obtained from fibers such as wool, nylon, polyacrylonitrile, polyacetate, polypropylene, etc.; A tufted carpet material is used, with a needle punch as the primary base fabric and a pile erected thereon. Among these, inexpensive needle punch carpet is most suitable as a material for laying automobiles. Next, the aqueous thermoplastic resin emulsion used as the backing material that is applied or impregnated onto the back side of the raw rug to impart moldability to the carpet is an aqueous resin emulsion with a glass transition point of 80°C or higher, and is as follows ( Those selected from groups i) to (iv) are preferably used. (i) An aqueous emulsion of a vinylidene chloride copolymer obtained by emulsion polymerization of 50 to 97% by weight of vinylidene chloride and 50 to 3% by weight of a vinyl monomer. Examples of vinyl monomers include vinyl groups such as methyl methacrylate, styrene, acrylonitrile, methacrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, vinyl chloride, maleic anhydride, itaconic acid, acrylamide, and methacrylamide. Monomers with can be used. Among them, vinylidene chloride 83
~97% by weight and 17-3% by weight of acrylic acid lower alkyl ester (alkyl group has 1 to 8 carbon atoms)
The aqueous emulsion of a highly crystalline vinylidene chloride copolymer obtained by emulsion polymerization of the copolymer has a high softening point of 140 to 190°C, and the carpet obtained using this copolymer can be used as an automobile interior material with more severe heat resistance. It satisfies the JIS-D-0204 requirement that carpets maintain their shape at 120°C. Furthermore, since the vinylidene chloride copolymer has a chloro group, it imparts flame retardancy to the resulting carpet. (ii) A copolymer of the monomers of components (a) and (b) below (a) selected from isopropyl methacrylate, styrene, acrylonitrile, methyl methacrylate, methacrylic acid, itaconic acid, acrylamide, and acrylic acid; (b) methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, di-acrylate;
Vinyl monomer selected from ethylhexyl, 2-hydroxyethyl acrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-hydroxyethyl methacrylate, vinyl chloride, ethylene, vinyl acetate or vinylidene chloride 50~ 3% by weight Here, the vinyl monomer as the component (a) is one whose homopolymer has a glass transition point (Tg) of 80°C or higher, and the vinyl monomer or vinyl chloride as the component (b) is , the homopolymer has a glass transition point of less than 80°C. homopolymer of each vinyl monomer
Tg is shown below. Isopropyl methacrylate (81℃), styrene (100℃), acrylonitrile (100℃), methyl methacrylate (105℃), acrylic acid (106℃), methacrylic acid (130℃), itaconic acid (130℃), acrylamide (153℃). 2-ethylhexyl acrylate (-85°C), n-butyl acrylate (-54°C), ethyl acrylate (-22°C), isopropyl acrylate (-5
°C), 2-ethylhexyl methacrylate (-5
°C), 2-hydroxyethyl acrylate (-15
℃), n-propyl acrylate (8℃), n-butyl methacrylate (20℃), vinyl acetate (30℃), t-butyl acrylate (45℃), 2-methacrylate
Hydroxyethyl (55°C), ethyl methacrylate (65°C), isobutyl methacrylate (67°C), vinyl chloride (79°C), vinylidene chloride (-18°C). (iii) An aqueous emulsion of a homopolymer of the vinyl monomer of (a) above (iv) An aqueous emulsion of a resin with a Tg of +80 to 155°C
50 to 97% by weight, preferably 55 to 95% by weight (solids) and 50 to 3% by weight, preferably 45 to 3%, of a resin with a Tg below -85°C to +80°C.
A mixture with 5% by weight. Among these, an aqueous emulsion of a resin having a Tg of 80 to 120°C is more preferred. The aqueous emulsion of the resin (ii) or (iii) is superior to the aqueous vinylidene chloride copolymer emulsion (i) in terms of providing moldability to the carpet, but the emulsion (i) It is superior in terms of imparting flame retardancy to carpet and heat resistance. The resin solid content concentration in the aqueous emulsion of these backing materials is usually 20 to 60% by weight, and the diameter of the dispersed resin particles is 10 microns or less, preferably 0.05 to 1.0 microns. This aqueous emulsion contains SBR latex, as long as it does not impair the moldability of the resulting carpet.
Extender pigments such as polyethylene powder, magnetic iron powder, calcium carbonate, aluminum hydroxide, clay, talc, barium sulfate, pigments such as red iron oxide, malachite green, titanium oxide, dyes, etc. can be blended. In order to provide the carpet with the highest degree of flame retardancy and moldability, a backing layer formed from an aqueous emulsion of the vinylidene chloride copolymer of group (i) and an aqueous emulsion of the copolymer of group (ii) is required. A backing layer is formed by coating separately to form a multilayer structure as shown in FIG. 1 or 2. In the figure, 1 is the original rug, 2 is the backing layer, 2a is the backing layer formed from an aqueous emulsion of vinylidene chloride copolymer, and 2b is the
The backing layer (ii) to (iv) is formed from an aqueous resin emulsion, and the backing layer 3 is formed from an aqueous emulsion of a thermoadhesive resin such as petroleum resin, terpene resin, rosin resin, ethylene, or vinyl acetate copolymer. The thermal adhesion imparting layer 4 is felt, foam sheet or the like. When the backing layer has a multilayer structure, the coating amount of the vinylidene chloride copolymer emulsion (i) should be
15 to 100 g/m ² (in terms of solid content), and the coating amount of the aqueous resin emulsion (ii) to (iv) should be 60 to 1000 g/m ² , which is greater than the coating amount of the vinylidene chloride copolymer emulsion. . How to impart flame retardancy and formability to carpets (i)
A mixture of an emulsion of the vinylidene chloride copolymer (2) and an aqueous emulsion of the resin (ii) or (iii) may be used, but the flame retardance will be lower than when the backing layer has a multilayer structure. do. The aqueous resin emulsion forming the thermal adhesion imparting layer 3 has a softening point (JIS K-5903).
petroleum resin with a temperature of 60-120℃, preferably 70-105℃,
Aqueous emulsions of rosin resins, terpene resins, ethylene, and vinyl acetate copolymers are used. Examples of petroleum resins include alkylstyrene indene resins, resins obtained by heating and polymerizing petroleum-based unsaturated hydrocarbons and/or cyclopentadiene in the presence of catalysts such as sulfuric acid, anhydrous aluminum chloride, and boron fluoride, and resins such as these. Water additives etc. can be used. Examples of the rosin include processed rosins such as abietic acid rosin, water additives thereof, maleic acid adducts thereof, metal salts, and esterified products with alcohols such as glycerin, pentaerythritol, ethylene glycol, and diethylene glycol. In addition, as terpene resins, homopolymers such as α-pinene, β-pinene, and dipentene or copolymers thereof, terpene/phenol copolymers, α-pinene/phenol copolymers, and water-added things are used. Methods for producing emulsions of petroleum resins, rosin resins, terpene resins, and ethylene/vinyl acetate copolymers are described in JP-A-56-78623 and JP-A-56-78623.
Since it is described in patent publications such as No. 87421, No. 56-159244, and No. 57-125255, the explanation will be omitted here. As for product names, the petroleum resin emulsions are #75 emulsion and #90 from Toho Oil Resin Co., Ltd.
Emulsion and ND-10 (both prototypes)
Hariestar DS-70L and DS-70E from Harima Kasei Kogyo Co., Ltd., Hariestar DS-70E, Hersize EM-305, and Hersize EM-505 are examples of rosin-based resin emulsions.
Aqueous emulsion of terpene resin is manufactured by Yasuyu Co., Ltd.
An example is Ematux 800 (prototype). These aqueous emulsions of petroleum resins, rosin resins, terpene resins, and ethylene/vinyl acetate copolymers have an average particle diameter of 0.1 to
3 microns, and the solid content concentration is 20 to 65% by weight. The application of these emulsions to the original rug or to the formed backing layer is carried out by a conventional method such as a roll coater or spray coating, preferably by using a roll coater. It is preferable to determine the coating amount of the aqueous emulsion so that the sum of the solid resin content of the backing layer and the thermal adhesive layer is 30 to 100% by weight of the original rug weight. The emulsion can be dried by heating using any method. For example, a heating cylinder, an infrared heating machine, a hot air dryer, a suction dryer, etc. can be used, but it is preferable to use a hot air dryer and a heating cylinder in combination. Also, drying is from 60 to
Although it can be carried out at 200°C, it is preferably carried out at 60 to 150°C from the viewpoint of preventing fiber deterioration. Moisture is removed by heating and drying, and the resin particles in the emulsion are fused to form a continuous film. Since the resin particle size of the aqueous emulsion is small, it is possible to form a thinner backing layer or thermal adhesion imparting layer compared to the melt extrusion lamination method of resin films. In addition, compared to the powder scattering method using polyethylene powder, the resin particle size of the emulsion is smaller, so the emulsion can be spread more uniformly in a smaller amount.
Since it can be applied thinner, the amount of resin used can be reduced. The carpet, which has been given thermal adhesiveness and moldability obtained by heating and drying, is laminated with felt, nonwoven fabric, or foam sheet as necessary on the thermal adhesiveness imparting layer in order to impart a feeling of weight and cushioning properties, and is then used in automobiles, etc. Approx.
Molded under heat and pressure at 100-230℃. The pressure-molded carpet has good shape retention, and the carpet obtained by using a vinylidene chloride copolymer as a backing material also has flame retardancy. Hereinafter, the present invention will be explained in more detail with reference to Examples. Note that parts and percentages in the examples are based on weight unless otherwise specified. Manufacturing example of raw rug fabric A fiber card made by randomly stacking polyethylene terephthalate fibers of 15 denier and a fiber length of 75 to 125 mm is needled at a rate of 100 fibers per square inch using 15-18-32-3RB needles. A needle punch carpet with a thickness of 5 mm and a basis weight of 450 g/cm ² was obtained. Example 1 A crystalline vinylidene chloride copolymer obtained by emulsion polymerization of 80 to 88% by weight of vinylidene chloride and 20 to 12% by weight of methyl acrylate was applied as a backing material to the back side of the needle punch carpet obtained in the above example. The combined aqueous emulsion (resin particle size 0.5-1.3μ, solid content concentration 50% by weight) was mixed with a Ritzker roller at 130g/cm ²
(solid content), and then a needle punch carpet was impregnated with the emulsion using Nipprol. Then, the emulsion-impregnated needle punch carpet was heated to 120℃ for 10 minutes.
The mixture was heated for 1 minute to remove moisture and form a backing layer. Next, petroleum resin aqueous emulsion “ND-10” manufactured by Toho Oil Resins Co., Ltd. (trade name, resin softening point 80°C,
(solid content concentration 57%) was applied to the backing layer by air spray to a concentration of 20 g/cm ² (solid content), and heated at 110°C for 2 minutes to form a thermal adhesive layer.
After cooling to room temperature, a carpet having moldability and heat adhesive properties was obtained. The surface temperature of this carpet increases from the thermal adhesive layer side.
After heating with a far infrared heater at 180℃ for 60 seconds to soften the vinylidene chloride copolymer and petroleum resin, and then applying a 15mm thick felt to the thermal adhesive layer,
Compression molding was performed using a water-cooled press mold under a pressure of 5 kg/cm ² for 5 minutes to produce a carpet for installation in an automobile interior. Regarding this carpet for installation, the mold fidelity (formability) of the uneven shape obtained by compression molding, the adhesive strength between the felt and the needle punch carpet, and
Flame retardancy was evaluated according to JIS D-1201-1977. The results are shown in Table 1. Example 2 On the back side of the needle punch carpet used in Example 1, n-butyl acrylate (22.5% by weight) was applied.
Styrene (75% by weight) - Acrylic acid (2.5% by weight)
Aqueous emulsion of copolymer (softening point of copolymer
118℃, resin particle size 0.1 to 0.2 microns, solid content 50% by weight) with a Ritzker roller to 100 g/cm ² (solid content)
The emulsion was then impregnated into the needle punch carpet using Nipprol. After impregnating the emulsion and heating the needle-punch carpet at 130°C to remove moisture and form a first backing layer, the aqueous emulsion of vinylidene chloride copolymer used in Example 1 was air-sprayed. 50 g/cm ² (solid content) on the first backing layer using
A second backing layer was formed by drying at 120°C. On this second backing layer, the aqueous petroleum resin emulsion used in Example 1 was applied using a Ricker roller at a concentration of 20 g/m ² (solid content), and dried at 110°C for 2 minutes. to form a thermal adhesive layer,
Then, it was cooled to room temperature to obtain a carpet having moldability and heat adhesive properties. Thereafter, it was lined with felt and compression molded in the same manner as in Example 1 to obtain a carpet for use in an automobile interior having the physical properties shown in Table 1. Example 3 A carpet for an automobile interior was obtained in the same manner as in Example 2, except that the order of application of the aqueous emulsion of the acrylic copolymer and the aqueous emulsion of the vinylidene chloride copolymer was reversed. Example 4 In Example 1, instead of the aqueous emulsion of the vinylidene chloride copolymer, a 1:2 mixture of the aqueous emulsion of the vinylidene chloride copolymer and the aqueous emulsion of the acrylic copolymer used in Example 2 ( A carpet for the interior of a car was obtained in the same manner except that the weight ratio was used. Example 5 In Example 1, instead of the aqueous emulsion of vinylidene chloride copolymer, 200 parts (solid content 100 parts) of the aqueous emulsion of the acrylic copolymer used in Example 2 was added with A carpet for the interior of a car was obtained in the same manner except that 40 parts of chlorine-based flame retardant "Nonne BC-24Em" (trade name) manufactured by Co., Ltd. was used. Comparative Example 1 In Example 2, a carpet for interior of an automobile was obtained by heating and compression molding the felt directly in contact with the backing layer without applying the aqueous emulsion of petroleum resin. Comparative Example 2 In Example 2, ethylene/vinyl acetate copolymer latex “Sumikaflex” manufactured by Sumitomo Chemical Co., Ltd. was used instead of the petroleum resin aqueous emulsion.
400" (trade name, glass transition temperature 0° C.) was used. Example 6 In Example 2, instead of the petroleum resin emulsion, a carpet made by Harima Kasei Kogyo Co., Ltd. was used. A carpet for interior of a car was obtained in the same manner except that a modified rosin aqueous emulsion "Harrierstar DS-70E" (trade name, modified rosin softening point 70°C, solid content 47%) was used. Example 7 Example 7 In 2, instead of the aqueous petroleum resin emulsion, an aqueous emulsion of a terpene/phenol copolymer [EMAX 80 (trade name) manufactured by Yasu Oil Co., Ltd., softening point of the copolymer 80°C, resin particle size 1 to 3μ,
A carpet for the interior of a car was obtained in the same manner except that a solid content of 40% was used. Table 1 shows the performance of the carpets for laying obtained in Examples 1 to 7 and Comparative Examples 1 and 2.

[Manufacturing method]

30 parts of ethylene/vinyl acetate copolymer [Ebu Afflex 220 (trade name) manufactured by Mitsui Petrochemical Industries, Ltd.: Vinyl acetate content 28%, MFR = 150 g/10 minutes] and chlorinated polypropylene [Hardren 15LP manufactured by Toyo Kasei Co., Ltd.
(trade name); chlorine content 30%], 20 parts of a terpene-phenol copolymer resin [YS Polyster 2130 (trade name) manufactured by Yaskawa Oil Co., Ltd.], and 20 parts of paraffin wax having a melting point of 70°C were mixed. This mixture was extruded at a rate of 100 parts/hour using a co-rotating intermeshing twin-screw extruder (trade name of Ikegu Iron Works Co., Ltd.).
It was continuously supplied from a hopper of PCM45, triple thread shallow groove type, L/D = 30). In addition, an aqueous solution of a saponified copolymer of acrylic acid (30 mol%), butyl methacrylate (60 mol%), and rariul methacrylate (10 mol%) was added through the supply port provided in the first vent part of the same extruder. Ten
gear pump (discharge pressure 3Kg/hour)
cm ² G) and continuously supplied water at 90°C from the supply port provided in the second vent part using a plunger pump at a rate of 90 parts/hour. Continuous pressing was performed at a temperature (cylinder temperature, same hereinafter) of 110°C to obtain a milky white aqueous dispersion with a film forming temperature of 72°C.

[Brief explanation of the drawing]

1 and 2 are cross-sectional views of a carpet having moldability and heat adhesive properties, respectively, obtained according to an embodiment of the present invention, and FIG. 3 shows a carpet in which a backing material is further brought into contact with the carpet. This is a carpet for use in automobile interiors obtained by compression molding. In the figure, 1 is the original rug, 2 is the backing layer, 3 is the thermal adhesion imparting resin layer, and 4 is felt.

Claims (1)

[Claims] 1. On the back side of the original rug, an aqueous emulsion of a thermoplastic resin with a glass transition point of 80°C or higher is applied at 60 to 1000°C.
g/m ² (solid content) and dried to form a backing layer. On top of this backing layer, petroleum resin, terpene resin, or rosin resin with a softening point of 60 to 120°C is applied. , an aqueous emulsion of a thermoadhesive resin selected from ethylene/vinyl acetate copolymers is applied at a rate of 10 to 200 g/m ² (solid content), and then dried to form a thermoadhesive resin film. A method for producing a thermoadhesive carpet, characterized in that: 2. The aqueous resin emulsion with a glass transition point of 80°C or higher is composed of (a) a vinyl monomer 50 to 97 selected from isopropyl methacrylate, styrene, acrylonitrile, methyl methacrylate, methacrylic acid, itaconic acid, acrylamide, and acrylic acid; (b) Methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate,
t-butyl acrylate, n.butyl methacrylate, isobutyl methacrylate, 2-acrylate
Ethylhexyl, 2-hydroxyethyl acrylate, ethyl methacrylate, 2-methacrylate
Claim 1, which is an aqueous emulsion of a copolymer with a vinyl monomer selected from hydroxyethyl, vinyl chloride, ethylene, and vinyl acetate, or 50 to 3% by weight of vinylidene chloride. Production method. 3. The manufacturing method according to claim 1, wherein the glass transition point of the thermoplastic resin in the emulsion is 10° C. or more higher than the softening point of the thermoadhesive resin.