ARTIFICIAL LEATHER AND METHOD FOR PRODUCING SAME

Abstract: A composite sheet comprising a fibre base and an binder, wherein said binder is broken into small fragments and adheres to the fibers. Said composite sheet is produced by a method comprising the step of (a) applying a binder to a fibre base and (b) directing a fluid jet stream to the fibre base during or after coagulation of the binder applied thereto. The composite sheet of this invention is very soft and has considerable strength, because the fluid jet breaks week portions of the binder only to divide the binder into small fragments, without breaking the tougher portions of the binder which mainly contribute to the strength of the leather.

Description: The present invention relates to an artificial leather and a method of producing it. Many attempts have been made to obtain soft and dense artificial leather like that of natural leather. Conventionally, these products comprise a base fibre structure and a binder. Attempts to improve the base fibre structure include the use of non-woven sheet, woven sheet, knitted sheet, and woven or knitted sheet integrated with short fibre web. On the other hand, super-fine fibres have been used as fibres which constitute base fibre sheet. Also the choice of binder for the synthetic leather, such as polyurethane, has been improved. For example, US Patent No 3,544,357 discloses softening methods involving adding a softening agent or a blowing agent to a binder prior to impregnation. Japanese Patent publication No 45502/83 (Tokko-sho 58-45502) discloses softening methods involving adding lubricant or releasing agent to a fibre base prior to impregnation with a binder, Japanese Patent Publication No 9315/66 discloses softening methods involving removing one component of a multi-core type composite fibre which constitute a fibre base after binder impregnation. Further, softening methods involving mechanical crumpling are also known. However, these improvements are not satisfactory because a large amount of binder is necessary to keep strength and dimensional stability and the binder causes the artificial leather to exhibit stiffness and rubber-like elasticity. Furthermore, recent fashion trend necessitate more soft, thinner and lighter fabric (even softer than natural leather). Hitherto applications of the high speed fluid jet treatment to fibrous sheets have been tried. They are: a method for entangling non-woven fabric (US Patent No. 4,476,186), a method for making an integrated sheet in which textile is interlocked with short fibre (US Patent Nos. 4,368,227, 4,145,468, 4,146,663). However, these methods are not methods for treating a sheet to which a binder has been applied. EP 0013589 relates to softening non-woven fabrics using water-jets to break fibre to fibre bonds. In particular, EP 0013589 is concerned with point bonded non-woven fabrics and the water-jet treatment aims to break the tack bonds between fibres inbetween the point bonded sites. This invention provides a new method for producing an artificial leather having improved softness. This method does not bring about a serious decrease of strength and can be applied together with a conventional softening method whilst maintaining both effects independently. According to one aspect of the present invention there is provided an artificial leather comprising a multiplicity of flexible fibres dispersed in and adhered to a binder to form a sheet, said binder including a fragmentary layer comprising a multiplicity of separate independent binder pieces adhered to a multiplicity of said fibres, the pieces not being adhered to each other. According to another aspect of the present invention there is provided a method for producing an artificial leather comprising the step of (a) applying a binder to a fibre base to form a sheet and (b) directing a fluid jet stream onto the fibre base to break up the binder to form a fragmentary layer comprising a multiplicity of separate independent binder pieces not adhered to each other but adhered to said fibres. The present invention provides a soft synthetic leather in which the binder adheres to the fibres in a fragmentary structure. The binder fragments are dispersed substantially discontinuously and independently from other binder fragments in the sheet. On the other hand, in conventional artificial leathers, binder is distributed in a continuous structure. The binder structure can be determined by dissolving out the fibre component only from a composite sheet. With the composite sheet of this invention, the binder remaining after the fibre component has been dissolved out does not keep its sheet (film-like) structure but is in the from of many small fragments, namely, particles or powder. The amount and sizes of the small fragments can be determined by filtering for example with 10 - 60 mesh metallic filter. In this prefered embodiments of invention, the amount of small fragments (filtrate) of less than 10 mesh is at least 30%, preferably at least 50%. Figures 1-3 are microphotographs (magnified at 140 times) of cross-section of composite sheet of the present invention in which a typical fragmentary binder structure is shown, and Fig. 4 is that of a conventional artificial leather in which a continuous binder structure is shown. It is impossible to give the fragmentary structure as shown in Fig. 1 with conventional materials. Figure 5 shows the drape coefficient versus jetting pressure of water stream. Figure 6 shows binders isolated from the composite sheet in which fragments smaller than 30 mesh were removed. Figure 7 shows the weight ratio of fragmentary binder versus jetting pressure of water stream. Figure 8 shows the drape coefficient versus blush abrasion resistance of the artificial leather of the present invention and of the prior art. The composite sheet of the present invention features the structure as stated, and a variety preparation methods may be used. Examples are as follows: The binder is divided into small fragments by physical treatments such as high speed fluid treatment, before, in the course of, or after the binder solution solidifies. Using such methods, a continuous binder structure in sheet is fragmented, making the sheet more flexible. By these methods, the binder is caused, at least in the surface layer of the sheet, to adhere to the fibre in a fragmentary structure; preferably it is adhered fragmentarily to a depth more than 1/4 of the thickness of the sheet from the face and/or back. The depth of the fragmentary structure can be changed according to the degree of flexibility required. As the required flexibility becomes higher, the fragmentary structure is required to reach deeper inside the sheet. The fragmentary structure may be formed throughout the sheet, by which the sheet can be made highly flexible. When strength is important, it is preferable that at least some continuous binder structure is left in the sheet. In this case, it is preferred for the fragmentary structure to be situated in the surface layer rather than in the interior of the sheet, and the continuous adhesion structure is most preferably formed in the interior of the sheet instead of the surface. The sheet becomes more flexible by situating the fragmentary structure in the interior of the sheet than by situating it in the surface. The composite sheet having such a structure may be processed into a suede type synthetic leather, grained surface type synthetic leather and a base sheet of fur-like material, which are extremely flexible and have excellent drapability. Other advantages of the present invention are as follows: since the binder at least in the surface region is divided into small fragments, buffing is easier for suede type synthetic leather, and dense crimps and creases can be given for the grained surface type synthetic leather. In addition, the present invention provides a lower decrease in strength relative to the increase of flexibility. Fibrous sheets suitable for use in the present invention include, but are not limited to the following: needle punched non-woven fabric, water jet punched non-woven fabric, a woven or knitted sheet interlocked with short fibre, pile sheet, spun-bonded non-woven fabric, woven sheets and knitted sheets. A non-woven fabric is particularly prefered for use in the present invention because it is rather hard due to the thickness and interlocking structure of the fibres. Fibre components constituting such sheets include, but are not limited to: synthetic fibres such as polyamide (nylon), polyester, polyacrylonitrile, polyethylene, polypropylene, etc., regenerated fibres such as viscose rayon, cupro, etc., semisynthetic fibres such as acetate, etc., and natural fibres such as wool, cotton and hemp. Synthetic fibre is most preferred because it can easily be made very fine; nylon and polyester are most preferable.. Though the size of fibres may be similar to those in general use, a single yarn of the fibres is preferably less than 1 d from the viewpoint of flexibility, most preferably less than 0.3 d. Microfine fibres may be produced from the following multi-core composite fibres for example: islands-in-sea type fibres having fixed cross-section (Tokko-sho 44-18369) or variable cross-section (a blended spun fibre) (Tokko-sho 41-11632); and separable (by peeling mechanically or chemically, for example by swelling at least one component) type fibre (Tokko-sho 39-28005) comprising plural polymers incompatible with each other. Also included are microfine fibres such as an acrylic fibre obtained by wet spinning through a sintered metal fibre plate as a spinneret and successive drawing, polyester fibre obtained by the super drawing method and polyester fibre obtained by the melt blowing method. When islands-in-sea type or separable (by peeling) type composite fibre is used, the conversion from the composite fibre into microfine fibres may be conducted in any stage of the process. In the present invention, it is most preferable to conduct the conversion before the fragmenting of the binder. The fibrous sheet may have any suiteble texture weight. A suitable value in usual is between 70 and 500 g/m² in terms of the weight in the final product. A fibrous sheet before binder is applied may be shrunk or compressed, in order to give a dense feel to the synthetic leather. Water-soluble polymers such as polyvinyl alcohol, carboxymethyl cellulose, etc. may also be applied temporarily to the sheet in order to facilitate the subsequent process or to improve the hand of the final product. The binders which may be applied to the fibrous sheet include elastomers such as polyurethane, acrylonitrile-butadiene rubber, styrene-butadiene rubber, butyl rubber, neoprene, acryl rubber, silicone rubber, natural rubber, polyamide copolymer, fluorine type elastomers or mixtures thereof. The range of binders which can be selected is wider than before, because the treatment of this invention makes it easy to soften the sheet. Thus, it becomes possible to use harder binders which have strong adhesive force. However, polyurethane is most preferred from standpoints of mechanical strength, hand and practical performance. The binder may be applied in any forms of solution type or dispersion type such as colloid, emulsion and latex, or suspension. A single binder or a mixture of two or more types may be used, and pigments or other additives may be added to the binder. Methods for applying the binder to the fibrous sheet may be any conventional method such as impregnation, coating, or spraying. The amount of the binder applied to the fibrous sheet may be selected according to the type of elastomer and final use of the product. The amount, as solid content, should be 5 to 150%, preferably between 10 to 100%, based on the weight of residual fibre. The use of a fluid jet, such as water jet punching, ensures that only weak adhesion structures in the sheet are broken and that strong adhesion structures remain i.e. the fibres and the strongly adhered parts of the binder remain unbroken and the continuous structure of the binder is converted into fragmentary structure. Consequently, the composite sheet becomes soft whilst maintaining the strength relatively high. The fluid is preferably directed uniformly over the sheet so that the effective depth is at least 1/4 of the binder-adhering layer. The effective depth is the depth in the sheet up to which the directed fluid causes some structural changes in size of the binder. When the depth is too small, the softening effect decreases. The fluid jet is useally a high speed fluid jet. Any fluid may be used, as long as it does not markedly damage or dissolve the fibre or binder. Usually, columna streams of liquid, preferably water are used, since their effects can reach deep into the composite sheet and they are economical and easy to handle. The fluid may, of course, be admixed with additives in order to prevent pressure loss and improve the injection effect. The fluid jet treatment of this invention may be applied in any stage, provided the treatment is conducted after the application of the binder. The treatment can be applied even before completing the solidification of the binder. In such cases, the entanglement of the fibres or the entanglement of the fibres and the binder can be attained simultaneously with the coagulation of the binder and dividing the binder into fragments, together with an optional removal of a temporarily impregnated binder or a component of the composite fibre. Further, the treatment before completion the solidification makes the composite sheet to be adhered and entangled more densely because the structure of the binder is not fixed at the time of treatment. Thus, a dense and soft composite sheet with relatively high strength can be obtained. The shape of the injection orifice is not limited in particular, and any shape may be adaptable, although a round shape is used in general. The round orifice preferably has a hole diameter of 0.05 to 3 mm, most preferably 0.1 to 1.0 mm. The injection pressure of the fluid may be adjusted according to the hole diameter of the orifice, distance between the orifice and the structure of the composite sheet to be treated, processing speed, texture weight, thickness and type, amount and adhesion condition of the binder and type of the fluid. The pressure is between 5 and 500 kg/cm² in general, preferably between 10 and 300 kg/cm² when the fluid is water. When the injection pressure is too low, the present object cannot be fulfilled, while when too high, the sheet strength decreases and serious traces of the fluid injection is brought about. Usually, a row of a plurality of orifices is arranged in widthwise direction of the sheet, and designed to oscillate in a widthwise direction. Preferably, the oscillating is done not only in the widthwise direction but also in the lengthwise direction of the sheet. The angle to the sheet of the high speed fluid may be variable; it is usually 90° ± 45° with respect to the sheet surface. The flued jet treatment of the sheet by the high speed fluid may be directed on one or both sides of the sheet. When the sheet is a non-woven sheet, the treatment may be conducted after the sheet is sliced into a plurality of sheets. The softened sheet of this invention may be subjected to buffing, followed by dyeing, or further to, e.g., an polyurethane coating. The sheet may be made into an artificial leather such as a suede type or a grained surface type which has a more soft touch, improved drapability and is elegant in appearance. The fluid treatment may be applied to a sheet before buffing and/or dyeing. In addition to the effect of giving softness, the treatment can have an effect of napping by properly adjusting the force or angle of the fluid jets. The present invention has the following effects. (1) A synthetic leather excellent in softness, drapability and strength is obtained. (2) It is easy to form naps. (3) A suede type synthetic leather having naps firmly fixed to the base sheet is obtained. (4) Solidification with high efficiency and uniformity is achieved. (5) Dense creases can be given for the grained surface type synthetic leather. (6) The synthetic leather of this invention has deformation recovery properties remarkably similar to those of natural leather. It is easily deformed by stretching in one direction and recovery is only slow and not complete. But subsequent stretching at 90° to the original stretch direction results in dimensional recovery of the deformation preliminary experienced in the original direction. The present method is illustrated by the following examples and comparative examples. Measurements of properties were based on the following methods. Flex rigidity : A method of JIS-L 1079, 5.17 Drape coefficient : F method of JIS-L 1079, 5.17 Strength-elongation test: JIS-L 1079, 5.12.1 Abrasion resistance: Substantially based on ASTM D-1175 Sheafer type abrasion tester Load; 3628.2g Brush; Nylon, 13mm Example 1 - 4 and Comparative Example 1 A web having a weight of 510 g/m² was produced by passing an lslands-in-sea type composite fibre through a card and cross lapper. The composite fibre consists of polyethylene terephthalate (PET) as island component and copolymer of styrene and 2-ethyl-hexylacrylate (weight ratio: 78/22) as sea component in the weight ratio of 60/40 and having a size of 3.0 denier, 36 islands, a length of 51 mm and 15 to 18 crimp/inch. The web was subjected to needle punching at a needle density of 3000 needles/cm² and needle punched sheet having a weight of 525 g/cm² and apparent density of 0.212 g/cm³ was obtained. The needle punched sheet was allowed to shrink by passing it through hot water at 80°C. The area shrinkage was 24.1%. The shrunken sheet was impregnated with a 12% aqueous solution of polyvinyl alcohol so that polyvinyl alcohol (PVA) as solid content be impregnated by 17.2% based on the fibre base. The sheet was repeatedly dipped and squeezed in trichlene (trichloroethylene) so that the sea component of the composite fibre was removed and the composite fibre was converted into ultrafine fibre bundle. Then, the sheet was repeatedly immersed and squeezed in a 12% polyurethane (PU) solution in dimethylformamide (DMF). Just after that, the sheet was immersed in water at 30°C for 5 min to partly coagulate the impregnated PU, and then the both surfaces of the PU impregnated sheet were subjected to high speed fluid treatment. The high speed fluid treatment was conducted under the following conditions: Orifice diameter: 0.25 mm⊘ Orifice pitch : 2.5 mm Oscillating width: 10 mm Oscillating cycle: 3 times/sec Treatment speed : 25 cm/min Water pressure : 25 Kg/cm² (Example 1) 50 Kg/cm² (Example 2) 100 Kg/cm² (Example 3) 150 Kg/cm² (Example 4) After the treatment, the sheet was introduced into water at 30°C to complete coagulation and further washed in hot water for the removal of PVA and DMF. At that time, the amount of PU is 35-40 Wt% based on the weight of the PET fibre. Next the sheet was sliced into halves and both surfaces of the sliced sheet were subjected to a buffing machine to form naps. The buffed sheet was dyed with a disperse dye at 120°C, for 60 minutes using a jet type dying machine and finished. Thus a suede type artificial leather was obtained. As Comparative Example 1, Example 1 was repeated exactly but the water jet process was omitted. These finished sheet had thicknesses of 0.76, 0.75, 0.82, 0.85 and 0.72 mm, weights of 209, 207, 220, 213, 215 g/m² and apparent densities of 0.275, 0.276, 0.268, 0.251, 0.299 g/cm³, respectively. The cross-sections of the composite sheets of Examples 1-3 and Comparative Example 1 are shown in Figures 1-4, respectively. The artificial suede of Examples 1-4 were excellent in drapability. The higher the water pressure the larger the effect. On the other hand, the artificial suede of Comparative Example 1 was not soft and had rather rubber-like elasticity. The fact was shown in Figure 5. Each suede was cut into 1cm x 1cm piece and immersed into sufficient amount of o-chlorophenol (OCP) for 24 hrs at room temperature to dissolve out the PET fibre component selectively leaving the PU undissolved. After the dissolution, by slight shaking, all of the PU of the suedes of Example 2-4 were dispersed as small fragments and no sheet-like structure remained. The PU of the suede of Example 1 was remained mostly as relatively large fragments and partly as small fragments, though they were slightly swelled. The PU of the suede of Comparative Example 1 remained keeping substantially the original sheet structure. Next, each PU/OCP mixture was filtered with 30 mesh metallic wire-mesh. PU residues were washed with OCP sufficiently and dried. They are shown in Figure 6. The relation of the amount of PU residue versus water pressure is shown in Figure 7. From Figure 7, by the fluid jet treatment, the continuous binder structure of PU can be broken into a fragmentary structure and the fragmentary structure brings about an artificial leather excellent drapability. Examples 5-8, Comparative Examples 2-5 The sea component removed sheets of Example 1 were impregnated with PU solutions in DMF. The concentrations of PU were 10% (Example 5), 12% (Example 6), 14% (Example 7) and 16% (Example 8). Just after the impregnation, the sheets were immersed in 30°C water for 5 minutes to partly coagulate the impregnated PU, taken out and subjected to water jet treatment on both surfaces. The water pressure was 50 kg/cm², and other conditions were the same as Example 1-4. Comparative Examples 2-5 were also conducted according to Example 5-8 respectively, but omitting the water jet treatment. After that, the coagulation of PU was completed in 30°C water, and the PVA and the DMF were removed in hot water. The resulting sheets were sliced into halves and both surfaces of the sliced sheets were subjected to a buffing machine to form naps. The buffed sheets were dyed with disperse dye at 120°C, for 60 minutes using a jet dying machine. Next the dyed sheets were finished and artificial suede were obtained. The relation between drape coefficient and abrasion resistance of the resultany artificial suede are shown in Figure 8. From the results, it is apparent that, by the water jet treatment, a soft and strong composite sheet can be made and that the softening effects are larger than can be attained only by controlling the amount of binder. Example 9, Comparative Example 6: A web was produced through a card and a crosslapper using an islands-in-sea type composite fibre consisting of copolymerized polystyrene with 2-ethyl-hexylacrylate as sea component and polyethyleneterephthalate as island component under the conditions: islands-in-sea ratio: 50/50; number of island: 36; denier of the composite fibre: 3 d; fibre length: 51 mm; number of crimp: 15 crimps/inch. A needle-punched sheet of 550 g/m² was obtained after being subjected to needle punching at 3000 needles/cm². The needle-punched sheet had a weight of 716 g/m² after being shrunk in hot water at 85°C. The shrunken sheet was impregnated with 10% aqueous PVA solution in an amount of 17.5 wt% as solid content based on the composite fibre, and after drying, the sea component was removed with trichloroethylene, to convert the composite fibre into microfine fibre bundle. The sheet with the sea component removed was impregnated with 12.5% PU and 1.0% black pigment paste solution in DMF and the PU was solidified in water bath. The PVA and DMF were removed while the sheet was immersed in hot water and squeezed repeatedly. The amount of polyurethane adhered to the fibre was 40 wt% based on the weight of PET fibre. The sheet has a weight of 500 g/m² and thickness of 1.76 mm. The sheet was subjected to a high speed water jet treatment by passing it once each for both surfaces through a high speed water jet apparatus in which orifices of 0.25 mm diameter were arranged straight in an interval of 2.5 mm in the widthwise direction of the process line, under the following conditions. Besides, in Comparative Example 6, the same treatment as Example 9 was conducted but omitted the high speed water stream treatment. Water pressure: Condition A: 100 kg/cm²; Condition B: 50 kg/cm² oscillating width of orifice: 10 mm Oscilating cycle of orifice: 3 times/sec Distance between orifice and sheet: 50 mm Jet angle with respect to sheet surface: 90° Moving speed of sheet: 25 cm/min The sheet obtained in Example 9, followed by drying, was found to shrink slightly in the lengthwise direction but was of excellent flexibility. In contrast, the sheet obtained in Comparative Example 6 was found to be hard and had a conspicuous rubber-like elasticity. Next, the sheets were sliced into halves and both surface of the sliced sheets were subjected to buffing by a buffing machine provided with a sandpaper of 150 mesh. The resulting sheet was dyed using disperse dye at 120°C for 50 min and finished through reduction clearing and addition of anti-static agent. As a result, the sheet obtained in the Example was a leather-like sheet having a high flexibility, good drapability and good hand closely resembling natural suede. In contrast, the sheet obtained in the Comparative Example was a leather-like sheet having a hard hand. The physical properties of the leather-like sheets are shown Table 1. Example 9 Comparative Example 6 Water pressure 100 kg/cm² Water pressure 50 kg/cm² Weight (g/m²) 215 212 210 Thickness (mm) 0.67 0.64 0.62 Flex Rigidity (mm) Length 27 31 46 Width 25 27 35 Drape coefficient 0.25 0.29 0.40 Tensile strength (kg/cm²) length 8.1 7.4 7.5 width 6.0 5.9 6.1 Tensile elongation (%) length 101 95 86 width 120 122 117 Example 10 and Comparative Example 7 The needle-punched sheet of Example 1 was shrunk in 80°C hot water. The area shrinkage was 23.8%. The shrunken sheet was impregnated 20% aqueous emulsion of PU as a binder and dryed at 100°C, for 20 minutes in hot flue dryer. The amount of the binder was 25.4 wt% as solid based on the fibre base. The dryed sheet was repeatedly immersed in trichloroethylene and squeezed to remove the sea component and heat treated at 150°C, for 5 minutes. Then both surfaces of the heat treated sheet were treated once each with high pressure water jets of 100 kg/cm². Other conditions of water jet treatment was substantially the same as Example 1-4. Comparative Example 7 was conducted under the same conditions as Example 10, but the Water jet treatment was omitted. The sheets of Example 10 and Comparative Example 7 had weights of 588 and 593 g/m², thickness of 2.35 and 2.28 mm, apparent densities of 0.250 and 0.260 g/cm², respectively. Next, the two sheets were sliced into halves and both surfaces of the each sliced sheet was buffed with buffing machine. And the buffed sheets were dyed with disperse dye using a jet dying machine and finished. The artificial suede of Example 10 was very soft and covered with dense naps. In contrast, the artificial suede of Comparative Example 7 was hard.

Claims: An artificial leather comprising a multiplicity of flexible fibres dispersed in and adhered to a binder to form a sheet, said binder including a fragmentary layer comprising a multiplicity of separate independent binder pieces adhered to a multiplicity of said fibres, the pieces not being adhered to each other. An artificial leather according to claim 1, wherein at least one surface of said composite sheet is covered with naps. An artificial leather according to claim 1 or 2, wherein said fibres have average fineness less than 0.5 denier. An artificial leather according to any of claims 1 to 3, wherein said binder is a polyurethane-type elastomer. An artificial leather according to any of claims 1 to 4, wherein more that 30 wt% of said binder pieces have a particle size of less than 10 mesh, preferably less than 30 mesh and more preferably less than 50 mesh. An artificial leather according to any of claims 1 to 5, wherein said sheet is a non-woven type sheet, preferably a needle punched sheet. An artificial leather according to any of claims 1 to 6, wherein at least one surface of said composite sheet is covered with a grained surface. An artificial leather according to any preceding claim wherein the fragmentary layer has an effective depth of at least ¼ of the sheet. An artificial leather according to claim 8, wherein the fragmentary layer extends throughout the sheet. An artificial leather according to any preceding claim wherein the binder is a binder coagulated in water. A method for producing an artificial leather comprising the step of (a) applying a binder to a fibre base to form a sheet and (b) directing a fluid jet stream onto the fibre base to break up the binder to form a fragmentary layer comprising a multiplicity of separate independent binder pieces not adhered to each other but adhered to said fibres. A method according to claim 11, wherein at least one surface of said sheet is treated to form naps. A method according to claim 11 or 12, wherein the fibre base is formed from fibres having an average fineness less than 0.5 denier. A method according to any of claims 11 to 13, wherein a polyurethane-type binder is applied to the fibre base. A method according to any of claims 11 to 14 wherein said fluid is water. A method according to any of claims 11 to 15, wherein said fluid jet stream is applied before completion of the solidification of said binder. A method according to any of claims 11 to 15 wherein said binder is solidified before said fluid jet stream is applied to the fibre base. A method according to any of claims 11 to 16 wherein coagulation of the binder is performed by immersion in water.

Inventors: FUKUNAGA, HIROKI, FUSHIDA, MINETO, TAGUCHI, SETSUO
Applicants: TORAY INDUSTRIES, INC.
Application year: 1985
Main classification: D04H1
IPC codes: D04H1