TW201245539A - Synthetic leather for automobile interior decorative material - Google Patents

Abstract

The present invention provides a synthetic leather for automobile interior decorative material whose sticky feeling is as less as a real leather, and having a moist sense of touch. The synthetic leather for automobile interior decorative material is a synthetic leather which forms a resin layer comprising single-layered or multi-layered synthetic resin on a nonwoven fabric or a woven fabric substrate layer with a single-layered or multi-layered structure, which is characterized by: at least one layer of the resin layer contains hygroscopic microparticles, the outermost layer has organic-based microparticles, the increase (Δ H) of the thenar humidity according to the sweating simulation device measurement after starting to sweat for 1 minute is less than or equal to 18%RH, the average surface friction coefficient (MIU)under a load of 1.47N/cm<SP>2</SP> is greater than or equal to 0.20, the surface roughness (SMD) is less than or equal to 2.5, and the compression displacement under a low load (0.098N/cm<SP>2</SP>) is greater than or equal to 0.16mm.

Description

201245539 VI. Description of the Invention: [Technical Field] The present invention relates to a synthetic leather for automotive interior materials that is controlled to be in contact with the dermis. [Prior Art] Leather for general use in automotive interior materials Leather-adjusted appearance, price, and synthetic leather are currently used in a wide range of interior materials, such as Volkswagen's watch panels and car seat skins. Synthetic leather, which has the same humidity as the leather, and which has the same wet leather texture as the leather, is excellent in abrasion resistance and formability. As a vehicle use, especially the automobile flower board skin material, the door decoration material, and the instrumental "ethylene vinyl" are made up of polyvinyl chloride as a constituent component. When it is burned after being discarded, there will be a dioxin, and due to recent environmental problems, Ups' its use is gradually limited. In addition, the synthetic leather curtains other than the gas bake are also discussed. For example, it has been proposed to form a skin layer containing a synthetic resin on a base material layer such as a non-woven fabric, and to provide a layer containing at least a layer of water and a moisture-absorbing heat-absorbing fiber or a layer for absorbing moisture and heat-absorbing powder. Artificial leather (refer to Patent Document 1 (Patent Document Scope)); synthetic leather in which a synthetic resin layer containing sericin is laminated on a fibrous substrate (refer to Patent Document γ Patent Application No. 1); The synthetic leather obtained by sequentially providing a thermoplastic polyurethane foaming layer and a thermoplastic polyamine phthalate elastomeric non-foaming layer on the cloth (refer to Patent Document 3) Item)); a non-woven substrate which is made of a conductive powder-containing polyamino carboxylic acid vine vine vine 曰 又 很 很 -4- -4- -4- 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 Patent Document 4 (part 1 of the scope of the patent application)); dividing the multi-component of the tensile strength of each of the early morning area weights into extremely fine continuous filaments having a fineness &lt;0 • 2dtex and The synthetic leather which has been solidified (refer to Patent Document 5, Japanese Patent Application Laid-Open No. Hei No. Hei No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 2003-511568. 】 [Problems to be solved by the invention] g, the hand, the greasy feeling, and even the sense of the hand have not been controlled to be compatible with the real car interior, and it is to provide a car with a sense of touch, however, including conventional synthesis When the skin of a leather car such as the foot of the leather touches the skin, it feels sticky and sticks to the skin, so it is not yet ideal. That is, although it is synthetic leather, it can equal the rise of the humidity in the palm. And it has the same wet feeling leather as the leather. The purpose of the invention is to solve A synthetic leather which is a synthetic leather, but has the same wet inner material as the leather. -5- 201245539 [Means for Solving the Problem] The present inventors have made efforts to investigate and found that in order to obtain a moist feeling The important ones are (a) less sticky, (b) different from the dry and smooth surface when touched, the surface is thick and has a little resistance, (c) the unevenness is not rough, the texture is fine and smooth. , (d) is extremely soft. We found that the countermeasures for achieving the above-mentioned contents were completed by the four points of "sticky feeling", "sticky feeling, resistance", "smooth and fine texture", and "soft". According to the invention, the synthetic leather for automotive interior materials is applied to a base material layer having a single or multi-layer structure of a nonwoven fabric or a woven fabric, and a synthetic leather comprising a resin layer of a single layer or a plurality of layers of synthetic resin is formed. At least one layer of the resin layer contains hygroscopic fine particles, and the outermost layer of the human touch side contains organic fine particles, and the amount of rise (ΔΗ) of the measured humidity in the palm of the hand after the start of sweating is measured by the sweat simulation device.丨8% below RH, the average surface friction coefficient (MIU) at 1.47 N/cm2 load is 〇2〇2.5 μπι or less, and the low load is 0 · 16 6 or more. Thus, even when the surface roughness (SMD) is (0.098 N/cm2), the amount of compression displacement is such that a synthetic leather having a wet touch can be obtained. The glass of the organic fine particles preferably has a private point (Tg) of _1 (TC or less), and more preferably, the average particle diameter of the organic micro-teaching is Ιμιη to 3 0 μηι, and the organic fine particles are in the nc The content of the 2, 4 secret lipid layer is preferably 〇5g/m~50g/m2. By this composition, a more moist feeling is obtained instantaneously. The average of the aforementioned hygroscopic particles outside the touch synthetic leather The moisture absorption diameter of the above-mentioned resin layer is preferably 1 μηι to 5 0 μηι 0, and the content is preferably &quot;6 - 201245539 2g/m2~50g/m2 盔 盔 盔 , , , , , , , L And 50% by mass or more of the attribute fine particles are preferably those obtained by using an acrylic crosslinked stellate conjugate. The base layer is a fiber layer of the upper layer and the fiber of the constituent layer. The structure is a non-woven fabric of a two-layer structure with a layered structure. The unit area of the upper layer is 〇u', and the car is 4〇g/m2~150g/m2. The fiber of the upper layer is better than the rabbit. The mass per unit area of the lower layer of O.OOOldtex~0.5dtex' is preferably 4〇/ 2 ug/m~2〇〇g/m2, which constitutes The fiber has a fineness of preferably 1.5 dtex to 1 〇iQdtex. If the substrate layer is a non-woven fabric having an i ^ β early layer or a multilayer structure, the density of the woven non-woven fabric is preferably oxygen. 3 is 12 〇 kg / m ~250kg/m3, the bursting strength is preferably 4 0 0 N ~ 1 〇〇〇N and the technical change,) the smashing soil method, ._ Λ 4 1 is preferably lmm~120mm. [Effects of the Invention] The synthetic leather for automotive interior materials of the present invention contains at least one layer of the resin layer containing hygroscopic particles, and the outermost layer has (four) particles, and the humidity in the palm is measured by the sweating simulation. The rise after the start of 1 minute ( ΔΗ) is 18% RH or less. The average surface friction coefficient (just) at 丨47N/cm2 load is 〇_2G or more, and the surface roughness (smd) is 2.5μπι or less, and low. When the load (〇〇98 N/cm2) is a compression displacement amount of 〇16 mm or more, a wetting contact equivalent to that of the dermis can be obtained. [Embodiment] The details of the present invention will be described below. The synthetic leather for automotive interior materials of the present invention is formed of a synthetic leather comprising a resin layer comprising a layer or a plurality of layers of synthetic resin on a substrate layer having a single or multi-layer structure of a nonwoven fabric or a woven fabric. Further, the feature is as follows: at least one layer of the resin layer contains hygroscopic fine particles, and the outermost layer has 201245539 machine-based particles, and the sweating simulation device measures the measured amount of rise in the palm of the hand after one minute of sweating ( ) is less than 1 8% RH, and the average surface friction coefficient (MIU) at a load of 1,47 N/cm 2 is 0.20 or more, the surface roughness (SMD) is 2.5 μm or less, and the compression is performed at a low load (〇.098 N/cm 2 ). The displacement is 〇. 16mm or more. In the present specification, "multilayer" means two or more layers. In fact, the feeling of stickiness felt by the human body when touching the interior of the automobile can be presumed to be due to the fact that the moisture (sweat) existing between the skin and the inner material is not treated. Therefore, the applicant uses the sweat simulation device test method (muscle skin model test method) to investigate the practical correspondence. As a result, it has been found that the amount of increase (AH) after the resin layer contains hygroscopic fine particles and the humidity in the palm is dried for one minute is controlled to be 1 8% RH or less, whereby the feeling of stickiness can be suppressed. It was found that the wet touch can be obtained by making the outermost layer contain organic fine particles and adjusting the average surface friction coefficient (MIU) and surface roughness (SMD) while controlling the compressive displacement at low load (〇〇98N/cm2). The synthetic leather is felt to complete the present invention. The above test method is a molding evaluation method that takes into consideration the "practical environment in which a certain amount of water vapor and heat are supplied to the surface of the cracked material." This evaluation method uses a sweat simulation measuring device (manufactured by Toyobo Co., Ltd.), water supply amount: 140 g/m2 · h, heating plate temperature: 37 ° C, sample-heating plate distance: 〇. 5 cm, ambient temperature Humidity: 20 ° C &gt;&lt; 65% RH, sweating mode: sweating was performed for 5 minutes from the start of the test, and the temperature and humidity of the space between the heating plate and the sample were measured. The synthetic leather for automotive interior materials of the present invention has a ΔΗ of 18% or less, preferably 16% RH or less, more preferably 15% RH or less. When the above ΔΗ -8 - 201245539 is more than 18% RH, the texture of the synthetic leather used for the interior material of the automobile is so strong that the moist feeling is continuously lost. Further, the lower limit of the aforementioned ΔΗ is not particularly limited and is 〇%rh. In addition, the average surface friction coefficient (MIU) when the synthetic leather for vehicle interior is loaded at 1.47 N/cm 2 is 0.20 or more, more preferably 〇22 or more, and even more preferably 25.25 or more. The average surface friction coefficient is expressed as . The index of leather sensation, the greater the value, the greater the surface resistance and the greater the viscous feeling. As long as the average surface friction coefficient is 0.20 or more, the wet feeling of the synthetic leather for automotive interior materials is more excellent. The upper limit of the above average surface friction coefficient is not (4), and is generally i 〇. In addition, the surface roughness (SMD) of the synthetic leather for interior materials is below UP, preferably 2. 2, and the following, more preferably 2.0 μm or less, surface roughness (SMD) means the texture of the synthetic leather surface (for example, coarse彳, rough, concave A', &gt; μ ^ convex) private display. The smaller the value, the less rough, the more the feeling of no roughness or unevenness, the smoothness and the fine texture, the better the wet/intermediate feeling. The lower limit of the surface roughness (smd) is defined and generally 1 · 0μηι or more. / The low displacement (0.098N/cm2) of synthetic leather for the inner material of the vehicle is 〇.16mm or more, more preferably 〇I or more, and then it is better than 2 bribes. The compression displacement in the low load (0.G98NW) is not the index of the softness of the synthetic leather. The larger the value, the larger the displacement, and the softer the feeling of softness. When the human body touches the object, it is found that the object with a large amount of displacement is relatively soft when it is pressed into the six &amp; ^, so the compression displacement at a low load (〇.〇98N/cm2) As a private label of this softness. The upper limit of the amount of compression displacement at the time of the low load (0.098 N/cm2) is not particularly limited. ' 201245539 The synthetic leather for automotive interior cracking has a unit area of 250g/m2 or more, more preferably 3〇〇g/m2 or more, and even more preferably. The upper limit is preferably 7 〇〇g/m2 or less, more preferably 2::2:...60 (W or less. Unit mass), and yoke can form a synthetic leather excellent in mechanical properties and lightweight material. Substrate layer] As a fiber constituting a non-woven fabric or a material layer having a single-layer or multi-layer structure, it is preferable to include a thermoplastic resin into a constituting fiber, and natural fibers or regenerated fibers, virgin fibers, inorganic fibers, etc. may be used as needed. Blending cotton or blending fiber. Xing ^ 乍 is a thermoplastic resin that forms synthetic fibers, only from:: ability is not particularly limited 'can be used, for example, poly pair stupid: propylene terephthalate, poly-p-phenylene Formic acid is the main body's step-by-step step-by-step use of isophthalic acid as a conjugated polyester such as a blending point; polypropylene, high-density polyethylene, low-density polyethylene, linear low-density polyethylene a poly-smoke such as a di-terpolymer formed by an α-dilute hydrocarbon, a poly-smoke amine such as polystyrene 66; or a mixture of such a thermoplastic resin obtained from such a thermoplastic resin. Core sheath type, eccentric core sheath type, side by side, sea = system There is no particular limitation on the shape of the fiber cross section. It can also be added with various additives such as matting agent, pigment, antioxidant, ultraviolet absorption, ray nucleating agent, flame retardant, anti-caries agent, etc. / preferably 3 50g/m2 650g /m2 L should be in the fiber of the t-car interior fabric. It must be made of fiber formic acid ethylene glycol, and it can be polymerized with olefins, medium olefins, propylene, polyfluorene, copolymer component system islands, etc. Desirable stabilizer, -10- 201245539 The mass per unit area of the substrate layer is preferably (10) * 2 or more, and more preferably, more than 450 g / m, more preferably 4 〇〇 g / m 2 or less. Further, it is preferable that the mass per unit area of the base material layer is as long as it is possible to obtain a lightweight automotive interior material, and it is preferable to use a nonwoven fabric as the base material layer. Forming the lower layer: There is a composition of miscellaneous and laminated layers. (4) The structure is composed of a mechanically mixed area of 40g/m2 to 150g/m2, and the upper layer of the upper layer is constructed. The coffee is dtex~o.5dtex, and the lower layer is formed. „The fiber of the upper layer has a fineness of 4 (W~200g/m2, which constitutes The layer is a non-woven fabric of a two-layer structure of the product quality. 'The degree of use is ImOdtex. The raw material used for the above-mentioned base material layer is non-woven. The upper and lower layers of the short-fiber non-woven fabric or the long-fiber non-woven fabric can have good mechanical properties. In view of the above, it is preferable to ensure a more potted, "+ good long fiber non-woven fabric. The manufacturing method is not particularly limited, and as for the non-woven fabric, the spinning adhesive method can be exemplified as the long fiber. When the non-woven fabric is woven, the carding method, the air flow method, or the like can be exemplified, and the short fiber can be made into the upper layer of the denseness τ by using the raw material of the base material layer to be less than 5 dtex. The texture and softness are excellent, and the lower limit of the elimination is not determined, but the fineness of the upper substrate is not less than that. It is also preferable to consider the viewpoint of productivity, such as G.Gldtex to G_4dtex, and the range of the upper substrate. For O.ldtex~〇.3dtex 201245539 However, only the upper layer is not included in the right, ^A cloth will 'lack of heavy feeling, A sense of sense' is also lacking as a car inner dream', ^ m η loading material Basic mechanical month t* such as strength. Therefore, by layering the fineness! 5 Α τ麻二文 X~10.0dtex non-woven fabric 曰 骽 Τ Τ Τ 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 汽车 汽车 汽车 汽车 汽车 汽车 汽车 汽车 汽车 汽车 汽车 汽车 汽车 汽车 汽车When the fineness of the underlying substrate is in the range of :dteX to 1 〇.〇dtex, a substrate having a large-volume characteristic disk flexibility can be obtained. In order to obtain a better balance, the fineness of the underlayer of the substrate is preferably UKO.x, more preferably 2 to 6 Å. The mass per unit area of the upper substrate is preferably 4 〇g/m 2 to 15 〇 g/m 2 , more preferably 50 g/m 2 to 140 g/m 2 , still more preferably 6 〇 g/m 2 to 12 〇 g/m 2 . When the mass per unit area is 40 g/m 2 or more, the effect of preventing the unevenness caused by the densification can be extremely effectively exhibited, and if it is 15 μg/m 2 or less, the knitting and weaving with the lower layer can be effectively performed. Mechanical mixing. The mass per unit area of the underlying substrate is preferably 4 〇g/m 2 to 2 〇〇 g/m 2 , more preferably 50 g/m 2 to 180 g/m 2 Å and still more preferably 60 g/m 2 to 160 g/m 2 . When the mass per unit area is 40 g/m 2 or more, a thick feeling and a high-grade feeling of the substrate can be obtained, and if it is 200 g/m 2 or less, the excellent unevenness prevention property of the upper layer densification is not inhibited, and the texture is excellent and heavy. Substrate. Further, the initial stress of the underlying substrate is preferably 经·1 N/5cm to 40N/5cm. As described above, the upper layer having a small fineness does not satisfy the mechanical properties of the interior material for automobiles, and therefore it is necessary to obtain the effect of reinforcing the upper layer in the lower layer. Further, as long as the initial stress of the lower layer is in the above range, it is possible to obtain a strong hybrid between the upper and lower layers in combination with the flexibility of the upper layer, thereby obtaining a laminated substrate having high integrity. In order to obtain a laminated substrate having a softer -12-201245539 wood and having a feeling of gravity and a level of 13⁄4, the preferred stress of the lower layer is 1N/5CII1 to 20N/5cm', more preferably 3N/5cm to 10N/5cm. The density of the substrate having the upper layer and the lower layer is more preferably from 120 kg/m3 to 250 kg/m3, more preferably from 13 〇kg/m3 to 24 〇kg/m3, even more preferably from 140 kg/m3 to 230 kg/m3. When the density of the substrate is 120kg/m3, the density is insufficient, and the main cause of the unevenness is more than 250kg/m3, the thickness is reduced, and the heavy feeling and the high-grade feeling are lost. Moreover, the fracture strength of the substrate having the upper layer and the lower layer is higher than that of the substrate. 400N~1000N, more preferably in the range of 500N~900N. If it is used above, for example, when the synthetic leather is processed and used as a car interior material, it is less likely to cause breakage during expansion, and the use is expanded. Further, the bending resistance of the substrate having the upper layer and the lower layer is more preferably from 50 mm to 120 mm, and further from 70 mm to 100 mm. The reason is that as long as it has a vehicle-like property of 1 mm to 120 mm, when it is processed as synthetic leather for automotive interior materials, the final product which is flexible in the use of the substrate is completed. [Resin layer] The resin layer is formed of a synthetic resin, and may be a single layer or a synthetic resin which forms each resin layer, and may, for example, be a polyaminomethyl laurel, a polyamine resin or a polyacrylate resin. , polyvinyl acetate ruthenium, polyacrylonitrile resin, and the like. These synthetic resins may be used singly or in combination of two or more. Among these, it is preferred that the polyamino phthalate tree is initially less than A. Also R is good. Jia is the 400N seat. The best way is for the softness of the layer. The ester ester tree can also be fat. -13- 201245539 As a specific component of a polyamino phthalate resin, it is generally called "polyurethane resin, polyamine phthalate urea resin", and is a polyolefin ether having a molecular weight of 400 to 4,000. a single or a mixture of a diol, a polyester polyol having a hydroxyl group at the terminal, a poly-ε-caprolactone polyol, or a polycarbonate polyol, and an organic diisocyanate, and having two activities as needed A compound of hydrogen is obtained by chain extension. The polyolefin ether diol may, for example, be polytetramethylene ether glycol, polypropylene glycol, polyethylene glycol, glycerin propylene oxide adduct or polyether polyol having terminal ethylene oxide added thereto. , ethylene monomer grafted polyether polyol. The polyester polyol may, for example, be an alkyl diol such as ethylene glycol, butylene glycol, hexanediol, diethylene glycol, dipropylene glycol or neopentyl glycol, and succinic acid or glutaric acid. A carboxylic acid such as adipic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid or trimellitic acid is reacted to form an acid at the end. The polycarbonate polyol may, for example, be a polyethylene carbonate diol, a polytetradecyl carbonate diol or a polyhexamethylene carbonate diol. The organic diisocyanate may, for example, be aroma such as 2,4- and 2,6-nonylbenzene diisocyanate, 4,4'-diphenyldecane diisocyanate, 1,5-naphthalene diisocyanate or xylene diisocyanate. Isocyanate; 1,6-hexamethylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 3-isocyanate decyl-3,5,5'-trimethylcyclohexyl isocyanate, 2,6 An aliphatic isocyanate such as a diisocyanate decyl hexanoate, which may be used singly or in combination of two or more. As the chain extender, hydrazine, ethylenediamine, tetramethylenediamine, water, piperidine'isophoronediamine, ethylene glycol, dibutyl-14-201245539, hexanediol may be used singly or in combination. , diethylene glycol, oxyethylene bromide and dimethylolpropionic acid, highly hydrophilic glycols, dipropylene dipropylene glycol, neopentyl glycol, etc., or an adduct of cyclic aminohexane sulfonic acid, etc. Class. The bean is a urethane resin, and the hydrolysis resistance is excellent, and the composition of the octagonal component is preferably a polycarbonate system using a polycarbonate polyol or a ureido formic acid resin. Further, in particular, the abrasion resistance of the synthetic leather is improved. The resin layer present on the outermost surface of the synthetic leather is preferably a polycarbonate-based polyurethane resin which is a siloxane.刖 石 氧 氧 氧 氧 氧 改性 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨Isocyanide

Acid-based and non-reactive bureaucratic A tablets, such as trialkyl fluorenyl, triaryl bauxite, etc., polycarbonate polyamine decanoic acid Particles] means particles that are hygroscopic. The amount %, preferably 20 mass. /. The upper limit of the hygroscopic fine particles is, as the name suggests, more specifically, the moisture absorption rate is more than 5 masses, more preferably 35 mass% or more. The moisture absorption rate is about 65 mass%. As a preferred of such particles, there is a propylene "'-q, 1 which is obtained by using propylene-based polymerization as a raw material, and the like is a hygroscopic particle in the present month. 0% by mass or more (preferably 7 〇 mass, ^ 里 / 〇 U above 'more preferably 90% by mass or more) with yttrium acrylate crosslinked polymer as the two original enthalpy; the hygroscopic fine particles only contain acrylic acid It is preferred that the crosslinked polymer is a raw material. - "My acrylic cross-linked polymer" refers to a cross-linked structure which is introduced into an acryl-based poly-polymer. 'The internal olefinic polymer-based polymer (曱基) 201245539 acrylic acid; (meth) methacrylate An acrylic monomer such as ethyl (meth)acrylate; an acrylic monomer such as (meth)acrylic acid amide; or an acrylic acid having at least a polymerizable vinyl group and a nitrile group such as (fluorenyl) acrylonitrile. The monomer is copolymerized with a copolymerized monomer composition to which other copolymerized monomers are added as needed. The acrylic monomer or the acrylonitrile monomer used in the acrylic polymer may be used singly or in combination of two or more. Further, the other copolymerizable monomer is not particularly limited as long as it does not impair the action of the finally obtained hygroscopic fine particles, and for example, a monomer containing a sulfonic acid such as a halogenated ethylene, a vinylidene halide or a p-styrenesulfonate can be used. And a salt thereof, a vinyl compound such as styrene or vinyl acetate, or a vinylidene compound. The introduction of the crosslinked structure may be carried out by further adding a compound having two or more polymerizable vinyl groups as a copolymerization component forming a crosslinked structure to the above copolymerized monomer composition, followed by copolymerization. As the compound having two or more polymerizable vinyl groups, triallyl isocyanurate, triallyl cyanurate divinylbenzene, ethylene glycol di(meth)acrylate, or the like can be preferably used. Bismuth acrylamide and the like. In addition, when the acrylic polymer is an acrylonitrile-based polymer obtained by copolymerizing a copolymerized monomer composition in which an acrylonitrile-based monomer is added with other copolymerized monomers as needed, it can be treated with a lanthanoid compound. Import cross-linked structures. Examples of the oxime-based compound which can be used at this time include hydrazine hydrate, cesium sulfate, guanidine hydrochloride, cerium nitrate, cerium bromide, cerium carbonate, and the like; ethylenediamine, barium sulfate, guanidine hydrochloride, and nitric acid. Anthracene derivatives such as ruthenium, ruthenium phosphate and melamine. -16- 201245539 The base olefin is the same as the above-mentioned bis, or it can be combined with a single one or a single one, and the individual can be combined and aggregated. The above-mentioned acrylic cross-linked polymer has a plurality of groups, or has a functional group which can be modified into a slow group. By chemically converting the carboxyl group or a functional group which can be modified into a thiol group into a salt-type carboxyl group, Suction and release wet particles can be obtained. The acrylonitrile-based crosslinked polymer in which the crosslinked structure is introduced into the acrylonitrile-based polymer via the oxime-based compound, wherein the acrylonitrile-based polymer contains 50% by mass or more a copolymerization of a monomeric monomer composition of acrylonitrile; or a chemical conversion of a nitrile group of an acrylonitrile-based crosslinked polymer to a salty carboxyl group by hydrolysis, that is, a carboxyl group having a carboxyl group content of 1.0 mmol/g or more The acrylonitrile-based crosslinked polymer is obtained by copolymerizing a copolymerized monomer composition containing 50% by mass or more of acrylonitrile and further containing a compound having two or more polymerizable vinyl groups. As a more preferable form, (A) the acetonitrile group remaining in the acrylonitrile-based crosslinked polymer is converted into a salt form carboxyl group by hydrolysis chemical conversion, that is, the absorption and release of the salt type carboxyl group having 1.0 mmol/g or more. The wet fine particles, wherein the acrylonitrile-based crosslinked polymer is treated with a lanthanoid compound to increase the nitrogen content by 0.1 to 15% by mass, and the crosslinked structure is introduced into the copolymerization of acrylonitrile containing 85% by mass or more. (B) converting the nitrile group of the acrylonitrile-based crosslinked polymer into a salt form carboxyl group by hydrolysis chemical reaction, that is, containing 2. 〇mm〇1/g; The above-mentioned salt-type carboxyl group-releasing moisture-releasing fine particles or the like, wherein the acrylonitrile-based crosslinked polymer system contains 50% by mass or more of acrylonitrile, and further contains η 201245539 ethylene acetyl or isomeric cyanuric acid The copolymerized monomer composition of allyl ester and other copolymerized monomers is copolymerized to introduce a crosslinked structure. In addition, the "increased nitrogen content" in the moisture-absorbing fine particles of (A) refers to the nitrogen content (% by mass) in the acrylonitrile-based polymer as a raw material, and the introduction of the crosslinked structure into the resin via the treatment of the arrogant compound. The difference in nitrogen content (Berry 〇 / 〇). If the nitrogen content is less than the above range, the organic fine particles are dissolved in the hydrolysis step, and the salty carboxyl group cannot be introduced. On the other hand, when it is larger than the above range, the nitrile group of 丨Ommol/g or more cannot be converted into a salt form carboxyl group. In addition, the method of introducing the cross-linking into the acrylonitrile-based polymer via the oxime-based compound is not particularly limited as long as the nitrogen content of the cross-linking increases by 0.1 to 15.0% by mass, but the concentration of the lanthanoid compound is 1~ 80% by mass and a temperature of 50 to 12 (the method of rct application for 2 to 1 hour is industrially preferable. As the hygroscopic fine particles, in addition to the above-mentioned acrylonitrile-based crosslinked polymer as a raw material, It is preferable to use a hygroscopic fine particle in which a part of the acrylate-based crosslinked polymer is converted into a salt-form carboxyl group by hydrolysis chemistry, that is, a hygroscopic fine particle containing 1.0 mol/g or more of the salt-form carboxyl group, and the like. The copolymerized polymer is obtained by containing 5% by mass or more of acrylate, further containing divinylbenzene or triallyl cyanurate, and other copolymerized monofluorene (tetra) polymerizable monomer composition into a crosslinked structure. In the case of the surface material of the seat, the average particle size of the particles of the moisture-absorbing fine particles is not particularly limited as long as the mechanical properties of the leather are not impaired. If used for The surface roughness of the steering wheel that is directly touched by the body may not be as good as the consumer's good 201245539, 50μιη or less, more preferably 3〇μηι or less, and even more preferably 2〇^m or less. In addition, the average particle size of the hygroscopic particles The lower limit of the diameter is not particularly limited, but is preferably 1 μm or more. The content of the hygroscopic fine particles in the resin layer of synthetic leather for automotive interiors (when the resin layer is a plurality of layers, it is contained in the entire resin layer) The total content is preferably 2 g/m 2 or more, more preferably 5 g/m 2 or more. The content containing 2 g/m 2 or more 'when the human body touches the interior of the automobile, the moisture existing between the skin and the inner material ( Khan) is quickly absorbed by synthetic leather, and can be obtained without feeling sticky. The content is not particularly limited, but is preferably 5 〇 g/m 2 or less, more preferably 5 〇 g/m 2 or less, in terms of completeness and cost efficiency of synthetic leather. Preferably, it is 30 g/m2 or less, and more preferably 2 g/m2 or less. The hygroscopic particles are only required to be contained in at least one layer of the resin layer. When the resin layer is a plurality of layers, the hygroscopic particles may be contained only in Any layer, which may also be contained in two or more layers. The layered tree of apricot When the enamel layer is a plurality of layers, the content of the hygroscopic fine particles in the outermost layer is preferably 2 〇g/m or less, more preferably 10 g/m 2 or less, and even more preferably 5 g / 交 / 2 3 . M2 or less. By the poetry of the poetry, the moisture absorption in the surface layer is reduced by 3, and the moist feeling of the leather is better. In addition, if the outermost layer contains hygroscopicity When the particles are hygroscopic, the particles of the right-handed sputum such as &amp; a, the total content of the 糸 增 粒 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 总计 总计 总计 总计 总计 总计 总计 总计 总计 总计 总计 总计 总计 总计 总计 总计 总计 总计 总计 总计It is better to be 2 〇g/m2 or less. Therefore, the number of particles in the outermost layer is not excessive, and the thickness of the leather can be further reduced by 80%. When the layer of the Hetian resin layer is reduced to a plurality of layers, the hygroscopicity is limited to 'the best one is that the outer layer of the outer layer is not particularly contained in the layer other than the layer (the most wettable particles).昙主a 增木3 has a better absorption for the adjacent layer of the outermost layer. In addition, - ^□Γ -19- 201245539 when the outermost layer does not contain hygroscopic particles, it is formed on the layer of eight The resin layer preferably has a moisture permeability or moisture absorption property, and is infiltrated into the resin layer to be absorbed by the hygroscopic fine particles. [Organic Microparticles] The organic microparticles may be a compound containing a basic skeleton of the I structure. Various organic fine particles such as amino phthalate ester, rabbit dragon, olefin, or polytetrafluoroethylene, and other organic fine particles are not particularly limited. However, oxygen and the hygroscopic microparticle phase # The hygroscopicity is low. 1 is 5% by mass, preferably 3% by mass or less. 'A and ^' In the present invention, the radix of the organic fine particles is preferably -1 〇C or less. More preferably _2 (rc or less. Transfer point (five) as long as it is in the above range, not only = wet of synthetic leather for loading It can also be obtained, T-double-sided, and can be further improved by design. In addition, if gas particles are used instead of organic particles, the surface of the surface can be smooth and smooth. The glass transition point (Tg) of the photoorganic fine particles and the glass transition point (Tgr) of the resin constituting the resin layer of the scoop particles are preferably - l〇〇〇c to + 60 〇C. If it is within this range, '乂, 八' body

It is preferable to form resistance. The above difference (Tg_T -4 (rc ~ +3 (rc, more preferably _2 (rc ~ 2 〇 it. If ^' this), the human body feels less discomfort when touched, the moisturizing feeling is increased and the ten is formed Synthetic resin of the layer of organic fine particles =: (^ x ~ glass: jade g is preferably -80 ° C or more, more preferably _6 〇 or more, wet microparticles, water atom as acid system, nitane It is a system of microparticles, a glass with a moisture absorption point (Tg) particle and an internal light effect of a car, and other inorganic effects, but it is difficult to have a Tg-Tgr touch, but in addition, k. More preferably from the transfer point of '20-201245539 -50 C or more, preferably 〇.. to -lot or less. More preferably _5C or less, and even better to describe the particle size of organic particles into a leather The mechanical properties, etc., are not edited: No. 4: In-vehicle loading is selected. However, if it is used directly in the human body =:, when the visible use is not properly selected, the surface roughness is more Preferably, the average particle diameter is 20:::: the average particle diameter is 3 - the particle core 2: the lower part. In addition, the organic system. The lower limit is not particularly limited, but preferably the claw is When the organic microlayer of the enamel resin layer is a plurality of layers, the total amount contained in the all-resin layer is: (=: gas or less. Although the content is not particularly limited, it is (4) 5 ° 〆 cost efficiency 簟 a quasi-β leather The completeness, cost-effective sheep, etc., more preferably 3 〇 * 2 or less. Further, the above-mentioned content of the organic fine particles is preferably 0. W or more, more preferably lg / i; And = not limited to 3g / m2 or more. It is better to obtain a more moist touch through the cover. The sub-touch "the shape of the organic particles in the instant of leather is not particularly regular, amorphous, aspect ratio obvious phase It is used in the same way as the problem. In addition, as long as the glass transition point does not disappear, it is also added to give solvent resistance. In addition, the (four)-based fine particles are subjected to surface treatment with a fatty acid, a coupling agent, and the like. The organic fine particles are contained in the resin layer which is the outermost skin, that is, the outer resin layer contains organic fine particles, but it is preferably contained only in the outermost resin layer. ~ -2 1- 201245539 As the automobile interior of the present invention The form of synthetic leather for the material can be exemplified as (1) having a single tree a lipid layer' and the resin layer contains a form of hygroscopic fine particles and organic fine particles; (ii) a resin layer having a plurality of layers containing at least one layer containing hygroscopic fine particles, and the outermost layer containing organic fine particles 彳Ui) having a multilayer resin At least one layer contains no hygroscopic fine particles and organic fine particles, at least one layer contains hygroscopic fine particles, and the outermost layer contains organic fine particles. The synthetic leather for automotive interior materials of the present invention can be used in the substrate layer. The resin layer is formed by a resin layer. The method of forming the resin layer is not particularly limited, and a method of forming a resin layer by drying a solvent by using a synthetic resin obtained by dissolving a solvent may be mentioned, and the resin may be reacted after the liquid resin is applied. The rolling method of forming the method, the laminating method of sticking a resin film containing a synthetic resin, the wet method of applying a liquid resin and then introducing it into a coagulation bath to solidify, and the like, the embossing process can be performed on the surface of the synthetic leather as needed. Texture processing to get the desired appearance. Further, when the above-mentioned layering method is employed, it is preferable to use a polyurethane-based adhesive as an adhesive for adhering the resin film, in consideration of the adhesion to the skin layer. The polyamino phthalate-based adhesive may, for example, be a polyether type, a polyester type, a polycarbonate type, or a composite type thereof. The cured product @100% modulus of the subsequent agent is preferably 〇 5 MPa to 5 MPa, and particularly preferably 0.5 MPa to 3 MPa in consideration of flexibility. The synthetic leather for the interior of this month is a synthetic leather that is made of synthetic leather but can be controlled to have the same degree of humidity in the palm as the leather, and has excellent moisture absorption characteristics, and has a moist touch. . Therefore, if the above characteristics are utilized, it is used for automotive interior materials, especially -22- 201245539 疋 steering wheel skin, storage compartment skin, seat cover, instrument panel

Jl^ I». JC. +Λ J βίρ material, Tianhua board surface material, car seat surface material, etc. Of course, it can be used in combination with other materials capable of performing the desired properties depending on the use, and can be shaped by performing processing without degrading the performance of the present invention. Further, it is also possible to impart functions such as flame retardancy, insect-resistant antibacterial, heat-resistant, water-proof and oil-proof, color, and aromaticity by chemical addition at any stage of product preparation. [Examples] The present invention will be more specifically described by the following examples, but the present invention is not limited to the following examples, and can be appropriately modified within the scope of the foregoing and the following description, and And the like are included in the technical scope of the present invention. The measurement methods used in the examples are as follows. In the following, the "%" and "parts" indicating the content or amount are indicated unless otherwise indicated. 1 -1. Humidity in the palm is measured by a sweating simulation device, with water supply: 140g/m2. Heating plate/dish. 3 7 c, sample-heating plate distance: 〇5 cm, strict temperature and humidity: 20°C X65% RH, sweating mode: 5 minutes and 2 minutes from the start of the test to measure the humidity in the space between the heating plate and the sample. From the results, the amount of humidity (ΔΗ) before the start of the test was determined by the humidity at the time of sweating i minutes. In addition, the sweating simulation device is a heat-generating control device that includes a heat-generating sweating device 1 having a base heating element having a sweating hole, a heat-suppressing device that controls the temperature of the heat-generating body, and a temperature and humidity sensor; Composition. The base system is made of brass and has an area of 12 〇cm2 and has six sweating holes. -23-.201245539 is controlled by a heating element including a planar heater to a constant temperature. The water supply device uses a tube pump to deliver a fixed amount of water to the sweat hole of the substrate. The surface of the substrate was adhered with a simulated skin comprising a polyester multifilament fabric having a thickness of 1 mm, whereby water discharged from the perspiration holes was spread over the surface of the substrate to make a dry state. A frame with a height of 0.5 · 5 m is placed around the substrate to hold the sample at a distance of 0.5 cm from the substrate. The temperature and humidity sensor is placed in a space between the substrate and the sample (synthetic leather) to measure the humidity of the "space surrounded by the substrate, the sample and the outer frame" when the substrate is in a sweat state. 1 -2·Average surface friction coefficient (special method) The surface friction coefficient measuring device (KES-SE, manufactured by KATO TECH) is used to measure the average surface friction coefficient (MIU). Determination of conditions. It is also a rubbing material (fingerprint type), a load of N47N/cm2 (15〇gf/cm), and a sensitivity L (sensitivity 1 〇〇g/V). Other conditions such as friction distance and friction speed are in accordance with the device specifications (friction distance 3 〇 mm, analysis distance 20 mm, sample moving speed 1 mm/sec). 1 -3 . Compression displacement at low load (〇.〇98N/cm2) The compressive displacement of the test material is measured by a compression tester ("KES-FB3" manufactured by KATO TECH Co., Ltd.). The pressurizing plate used was a circular shape of 2 cm 2 and was compressed to 〇.49 N/cm 2 at a rate of 0.02 mm/sec, and the amount of displacement at the time of compression of 0.09 8 N/cm 2 at that time was measured. 1 -4. Surface Roughness (SMD) The surface tester (} (8 11 €0 €! 11 ("3") is used to test the upper and lower thickness variations of the surface of the test material. The measurement conditions were such that a load of 〇〇98N was applied to a piano line having a width of 5 mm and a diameter of 〇·5 mm, a friction distance of 30 mm, an analysis distance of 20 mm, and a sample moving speed of imm/sec. -24 - 201245539 卜 5. According to a commentator (monitor) The paired comparison of the sticky feeling, the softness of the softness, and the moist feeling was judged by 10 commentators based on the pairwise comparison method to judge the stickiness, softness, roughness, and moist feeling of the sample. The seats are placed in a constant temperature and humidity room controlled by an environment of 2 5, 6 〇 % RH; the left and right seats of the car seat are each provided with two samples for comparison. Secondly, comments are made. The left and right palms are placed on the left and right samples on the seat surface of the car for a minute. After that, the commentator judges the sticky feeling, softness, and feeling of dying after 1 minute and the moist feeling as a comprehensive evaluation; And ask them to decide which of the left and right - the test is less sticky, softer, more Not dry, even as a comprehensive assessment, 浐

It determines which is more humid. After pairing and comparing Z 疋 with all the sample combinations, according to the Thurston perfect comparison method, the sticky feeling, the soft sound rough feeling, and the moist feeling were standardized according to -2 to + 2 points, and converted into scores. In addition, the sticky feeling, the higher the score, the less sticky, the softness, the more the two watches are not soft, the higher the feeling, the rougher the feeling, the higher the score, the higher the feeling of not being rough. Those with higher scores are closer to the moist feeling, but they are not individually able to express the sense of moistness, and the assessment is a comprehensive evaluation of the moist feeling. In terms of moist feeling, those with higher scores also indicated that the moist feeling was higher. 1 - 6. Appearance The surface state of the synthetic leather was visually confirmed, and it was confirmed whether there were defects, unevenness, and uneven coating. 1 - 7. Average particle diameter The laser diffraction particle size distribution measuring instrument ("SALD. 2GGV") was used to measure water, and the average particle diameter was determined from the particle size distribution indicated by the volume basis.土' -25- 201245539 1-8. Salt-type refinement scale lg full-dried sample (x(g)), add 2〇〇mi water, and then heat to 50 °C to add lm The aqueous solution of 1/i hydrochloric acid was brought to pH 2, whereby all of the sulfhydryl groups contained in the sample were formed into H-type thiol groups. Next, a titration curve was obtained according to a usual method using an aqueous solution of 0.1 mol/l NaOH. The amount of the total amount of carboxyl groups contained in the sample was calculated from the following equation by determining the consumption of Na0H aqueous solution (Y (ml)) consumed by the oxime-type carboxyl group. (Total slow-acting base I (mmol/g)) = 〇·ιχγ/χ In addition, the titration curve was similarly obtained by adding 1 mol of 1/1 hydrochloric acid aqueous solution to ρΗ2 without performing the above-mentioned total carboxyl group measurement operation. 'And determine the amount of hydrazine-type carboxyl groups contained in the sample. From these results, the amount of the salty carboxyl group was calculated according to the following formula. (Salt type carboxyl group (mmol/g)) = (total carboxyl group amount) - (Η type 绫 basis amount) 1 - 9. Particle moisture absorption rate The particles are sufficiently dried to measure the mass of the dry state (). The next time the particles were conditioned for 24 hours in an environment of 2 〇t and 65% RH, the mass (Wl) of the moisture absorbing state was measured. The moisture absorption rate of the particles was calculated from the mass of each state according to the following formula. Moisture absorption rate of the particles (% by mass) = 100x ( Wi-Wo) / Wo 1-10 · The density of the non-woven fabric is converted into the weight per 1 m 3 by the mass per unit area and thickness determined in accordance with JIS-L 1913 (2010). , as the density shown in g/m3 form. Specifically, the thickness is measured by a thickness measuring device with a load of 2 kPa and the density is obtained by dividing the mass per unit area by the thickness. -26- 201245539 1 -1 1 · Initial stress of non-woven fabric The stress at 5 〇/〇 elongation measured according to m-L 1913 (2010) is used as the initial stress. And the test piece of the wide w,: 2:: and § ′ is prepared for 5 pieces of each month, and the tensile test is performed and the average value is obtained. The tensile test is applied to the fixed speed extension type tensile tester with a tensile speed of 10 cm/min. The load is applied to the test piece to break 1:1. 2. The rupture strength of the non-woven fabric is measured at a constant speed of 2.5 cm. According to JIS-L 1913 (2010) burst strength B method (elongate method). Specifically, take 5 pieces of 8cm diameter test piece, 1〇〇mm/min constant speed, pressurize the front end with a radius of curvature of 1.25cm, and puncture the test piece with a diameter of the putter, and calculate the average of these 1 -1 3 · The bending resistance of non-woven fabrics is based on JIS_L 1913 (2〇1〇) β. Specifically, the full width lm of each direction is taken, and the MD direction is 20 cm and the CD direction is 2, 5: Square test piece, based on 41.5. The cantilever method measures a total of 12 points U and the average of these. This method is the result of MD $ to the bending resistance, and for the m i ° direction, the direction of the test piece is changed to vertical and the result is determined as described above. 2. Preparation of Substrate 2 1 · Non-woven Production Example 1, Substrate of Production Example 12) As an upper substrate, it is prepared from polyamine 6 and polyethylene terephthalate. The undivided short-fiber composite split type non-woven fabric (quality per unit area 8〇g/m2) made by split-type composite fiber (pre-segmented fiber 〇.24dtex). -27- 201245539 The monofilament group was piled up on a resin net adjusted to a mass per unit area of 1〇〇g/m2 by speed; the monofilament group utilizes well-known spinning adhesion to polyethylene terephthalate tree The purpose of the monthly air pressure (hereinafter referred to as "ρΒτ") is to make the fineness of the air to 2.0 dtex and to be stretched. Thereafter, the embossing roll is used to carry out the temporary processing to obtain a spunbonded non-woven fabric. The non-woven fabric is bonded by the spinning. As the underlying substrate, the initial stress of the obtained spunbonded nonwoven fabric was 18.0 N/5 cm in the longitudinal direction and 7 5 N/5 cm in the transverse direction. Thereafter, the upper layer was divided into fibers by a known knitting method to insert the needle by the lower layer of the spunbonded non-woven fabric. The non-woven fabric is mixed with the lower layer of the spunbonded non-woven fabric, thereby obtaining a composite non-woven fabric. Further, the upper layer substrate and the lower layer substrate are subjected to high water pressure treatment by water weaving, and the divided fibers are divided and laminated 'and are not peeled off. The upper layer is made up of the upper layer and the lower layer to obtain the target laminate non-woven fabric. The obtained product screen π site, + pre-layer + woven fabric density is 172kg/m3, the bursting strength is 760Ν, bending resistance Α, ιλ 1 ϋ I Wang Feng portrait 11〇mm 'transverse direction 81mm. 2 - 2 · fabric (manufacturing examples 2 to 8, comparative examples 2 to 8 meaning _ material) using 84dtex / 3 6f poly S for monofilament, low A warp knitted fabric having a bit area mass of 300 g/m 2 3. Hygroscopic microparticles 3 -1 · Hygroscopic microparticles No. 1 (average particle diameter: 3 μιη) 450 parts of acrylonitrile and 50 parts of acrylic fiber The ester and η&quot; water were placed in a 2 liter autoclave, and a total of 0.5% of the total amount of the monomer was added as a polymerization initiator. Thereafter, the autoclave was sealed, and polymerization was carried out for 10 minutes with stirring at a pressure of 1 2 (when the reaction was completed, and the mixture was continuously stirred and cooled to -28-201245539 90 °C). That is, a polymer particle having an average particle diameter of 2 μηη is obtained. Secondly, 60 parts of 60% hydrazine hydrate and 850 parts of water are mixed in 100 parts of the obtained polymer particles at a temperature of 90 ° C for 3 hours. The hydrazine treatment was carried out to introduce cross-linking, and further 112 parts of sodium hydroxide was added to 120. (:, 2 hours, the reaction was carried out. The obtained particles were washed with water, washed, and dried. After that, it was classified to obtain acrylic cross-linked polymer microparticles having an average particle diameter of 3 μm. The salt-based base amount of the particles was 7.0 mmol/g, and the increase in the nitrogen content by the hydrazine treatment was 1.5% by mass. The hygroscopic fine particle No. 1 has a moisture absorption rate of 35 to 65 mass%. 3-2. hygroscopic fine particles n〇.2 (average particle diameter: 30 μηι) containing 55 parts of acrylonitrile and 10 parts of yttrium acrylate The ester, 35 parts of distyrene monomer mixture was added to 300 parts of an aqueous solution containing 0.5 parts of persulfate, followed by the addition of 6 parts of sodium metabisulfite, and the polymerization tank with a stirrer was carried out at 65 ° C for 2 hours. polymerization. 15 parts of the obtained particles were dispersed in 85 parts of water, and 1 part of sodium hydroxide was added thereto, and after 9 (TC, 2 hours of hydrolysis reaction, washing, water removal 'drying', the acrylic acid was obtained. The polymer microparticles have an average particle diameter of 30 μm and a salt-based base of 6.3 mm·1 / g. The moisture absorption rate of the obtained hygroscopic microparticles n〇.2 is 35 to 65 mass%. .PMMA particle No. 1 (average particle size: 3μηι) by mixing 90-injured thioglycolic acid vinegar, 1 part of ethylene glycol dimercapto acrylate, 1 part of 2,2,-azo Bis(2,4-dimethylvaleronitrile), 1 part by weight of polyvinyl alcohol, 300 parts of water and stirred with a homogenizer to prepare a monomer dispersion 'polymerized at 50 C for 2 hours. The obtained particles are subjected to water washing, water removal, and drying, and then subjected to classification treatment to obtain polymethyl methacrylate-based fine particles having an average particle diameter of 3 μΐΏ. -29- 201245539 4 · Organic fine particles 4 -1 · Organic fine particles N 〇. 1 (Amino formic acid § is a microparticle, Artperl manufactured by Gensei Industrial Co., Ltd. (registered trademark J series ' Tg : -52 ° C, average particle size: 6 μιη, suction Rate: 3 mass% or less) 4-2. Organic fine particles Νο. 2 (Amino phthalate-based fine particles, Artperl series manufactured by Gensei Industrial Co., Ltd., Tg: -1 3 ° C, average particle diameter: 6 μηι, moisture absorption Rate: 3% by mass or less) 4-3. Organic fine particles Νο.3 (Amino acid-based fine particles, Artperl series manufactured by Gensei Industrial Co., Ltd.), Tg: -52 ° C, average particle diameter: 35 μm, Moisture absorption rate: 3 mass / 〇 )) 5. Inorganic microparticles N 〇. 1 : talc (ni ρ ρ ο η T a 1 c Μ IC ROACE system 歹 ij 'average particle size: 5 μ m ) 6 Synthetic Resin 6-1. Aurethane Resin As the urethane resin, a non-yellowing polycarbonate type polyamine oleic acid vinegar having a modulus of 2 to 1 MPa is used. 2. The high-slip amino phthalate tree is used as a south slip-based oxime ester resin, which is modified by a Xixi oxygen-fired non-yellowing polycarbonate type with a modulus of 5 1 1 OMPa. Amino phthalate (Tgr: -40..~2 〇..) 7 - Manufacture of synthetic leather 7 - 1. Production Example 1 The above-mentioned 彳 之 ; + is impregnated with a Sasaki aqueous solution - Takeout method There is a mass ratio of 18% of the arm of 7 μ ^ u ^ ^ 6 hexenol (P VA ) resin. These are used to exchange the size of the sheet itself and exchange it with the amine. 201245539 of the acid ester resin The polyamino phthalate resin solution was coated with a knife coater, and the PVA resin was exchange-washed with warm water of 60 ° C, and dried by hot air at 120 ° C. After drying, the urethane coating mass per unit area was 80 g/ni2' to obtain a wet synthetic leather. The wet synthetic leather has a total unit area mass of 260 g/m2 and a thickness of 〇8 min. Further, the film as a dry layer is bonded to the wet synthetic leather coated with a predetermined amount of an adhesive, and then the aging treatment is performed to laminate the resin; wherein the film is attached to the release paper, and the touch coating machine is used. The resin in which the hygroscopic fine particle No. 1 was mixed with the urethane resin dissolved in the solvent was applied in a predetermined amount, and dried. Here, the total mass per unit area of the substrate and the resin layer was 3 0 8 g/m 2 and the thickness was i.imm. Further, as the adhesive, a polyamine phthalate-based adhesive is used. Further, the organic fine particles No. 1 is mixed in the high-slip amino phthalate resin, and applied to the above-formed resin layer by gravure coating in a predetermined amount to form the outermost layer. The leather-like texture processing is carried out by using release paper, that is, synthetic leather is obtained. 7-2. Production Example 2 A polyvinyl alcohol (PVA) resin having a mass ratio of 1% was adhered to the fabric obtained by the above-described method according to the impregnation-extraction method of the aqueous solution. These are used to impart dimensional stability to the sheet itself and to perform exchange with the amine phthalate resin. The polyamine phthalate resin solution was coated with a knife coater, and the PVA resin was exchange-washed with warm water of 60 ° C, and was 12 Torr. The heat of the wind is dry. After drying, the amine phthalate coating unit had a mass per unit area of 80 g/m2 to obtain a wet synthetic leather. The total unit area of wet synthetic leather is 380g/m in the range of -3 1- 201245539 and the thickness is 〇.7mm. Further, the dry film is pasted with the wet synthetic leather coated with a predetermined amount of an adhesive, and then aged to form a resin layer, wherein the film is coated with a solvent in a predetermined amount by a touch coater. A resin of hygroscopic fine particles No. 1 was mixed with the formic acid resin, and was prepared. Here, the total unit area of the substrate and the resin layer was 428 g/m2, and the thickness was 〇8 mm. Further, the adhesive is a polyacetate-based adhesive. The organic No. 1 was mixed in the above-mentioned high-slip amine phthalate resin and applied to the above-mentioned formation layer by gravure coating in a prescribed amount to form the outermost layer. The leather-like texture is implemented using release paper to obtain a synthetic leather. 7-3. Production Examples 3 to 7 The same procedure as in Production Example 2 except that the amount of the fine particles mixed with the amino phthalate resin was changed and the type of fine particles mixed with the high-slip amine phthalate resin was changed. The way to make synthetic leather. 7-4. Production Example 8 A synthetic leather was obtained in the same manner as in Production Example 2 except that the fine particles were not mixed with the above-described amino phthalate resin and the types and contents of the fine particles of the high-slip amino phthalate resin were mixed. . 7-5. Production Example 9 Synthesis was carried out in the same manner as in Production Example 2 except that the amount of the fine particles mixed with the above-described amino phthalic acid vinegar resin was changed, and the fine particles were not mixed in the high-slip urethane resin. leather. The thin layer of the layer is processed by the resin of the amine-based lanthanum-based fine particles after the desalted amine is dried, and the class, the content, the content of the mixture are changed, and the external system is made of -32-.201245539 7_ 6. Example 10 A film was bonded to the above-mentioned fabric coated with an adhesive, and then subjected to aging treatment to form a resin layer; wherein the film was attached to a release paper, and a solvent dissolved in a solvent was applied in a predetermined amount by a touch coater. The phthalic acid ester resin is mixed with hygroscopic fine particles 1 1. 1. The organic fine particles ν 〇. 1 resin, and dried. Here, the total unit mass of the substrate and the resin layer was 354 g/m 2 and the thickness was 〇 9 mm. The leather is treated with a release paper to obtain a leather-like texture. 7-7. Production Example 11 The film was bonded to the above-mentioned fabric coated with an adhesive, and then subjected to aging treatment to form a resin layer; wherein the film was applied to a release paper and coated in a predetermined amount by a touch coater. The resin of the hygroscopic fine particles N 〇. 1 is mixed with a solvent-soluble amino phthalic acid resin and dried. Here, the total mass per unit area of the substrate and the resin layer was 348 g/m 2 and the thickness was 0.8 mm. The organic fine particle No. 1 ' is mixed with the above-mentioned high-slip amine phthalate resin and applied to the above-formed resin layer by gravure coating in a predetermined amount to form the outermost layer. The leather is processed by using a release paper to obtain a leather-like texture. 7-8. Production Example 12 Sheet 2 The above-obtained fabric was subjected to an impregnation-extraction method of an aqueous solution to which: 1% of polyvinyl alcohol (pv magic resin) was used. These were used to impart dimensional stability to the sheet itself. And carrying out the exchange with the amino phthalate resin. The coating machine is coated with a polyamino carboxylic acid S resin solution, and the PVA resin is exchange cleaned with water, and the heat of 卩 (10) is dried - 33- 201245539. After the 'amino phthalate coating unit area of 80g / m2' to get wet synthetic leather. Wet synthetic leather total unit area of 26 〇g / m2, thickness of 〇. 8mm. Further as a dry layer The film is bonded to the above-mentioned wet synthetic leather coated with a standard 1 adhesive, and then 'curing treatment to laminate the resin layer; wherein the film is attached to the release paper' and is coated with a predetermined amount by a touch coater. A resin of pMMA microparticles N〇 is mixed in a solvent-based amino phthalate resin and dried, and the total mass per unit area of the substrate and the resin layer is 3 0 8 g/m 2 , and the thickness is i. .imm. In addition, the adhesive is based on a polyurethane system. The above-mentioned high-slip urethane resin is supplied to the above-formed resin layer by gravure coating to form the outermost layer. The dermis-like texture processing is performed by using the release paper, thereby obtaining synthetic leather β 7- 9. Production Example 13 The above-obtained fabric was subjected to an impregnation-extraction method of an aqueous solution to which a polyvinyl alcohol (pVA) resin having a mass ratio of 18% was attached. These were used to impart dimensional stability to the sheet itself and to be carried out with an amine. Exchange of urethane resin. The polyurethane resin solution was coated with a knife coater, and the ρ v Α resin was exchange cleaned with 60 ° C of warm water and dried with 12 Torr of hot air. After the 'amino phthalate coating unit area of 8 〇g / m 'wet synthetic leather. Wet synthetic leather total unit area mass of 380g / m2, thickness of 0.7mm. Further as a dry layer of film and The wet synthetic leather coated with a predetermined amount of the adhesive is bonded, and then the aging treatment is performed to laminate the resin layer; wherein the film is attached to the de-34-201245539 molding paper_L' using a touch coater to specify Amount of coated benzoic acid S The resin was mixed with the PMMA fine particles No. 1 and the total amount of the base material and the resin layer was 2 428 g/m and the thickness was 0.8 mm. Further, the adhesive was an acid ester-based adhesive. In the above-mentioned high-slip amine phthalate resin, No. 1 ' is mixed and applied to the above layer by gravure coating to form the outermost layer. The leather is obtained by using a release paper to obtain a synthetic leather. 7 -1 0 -Production Example 1 4 The same procedure as in Production Example 12 was carried out except that the above-mentioned high-slip amine phthalate resin was used, and the film was obtained in the same manner as in Production Example 12. 7 -11 - Production Example 1 5 The fabric obtained above was obtained. Impregnation with aqueous solution _ Polyvinyl alcohol (Pva) resin with a ratio of 1 8 〇 / 〇. This sheet itself imparts dimensional stability and is subjected to amine group exchange. Coating the polyurethane with the knife coater 6 (W warm water of TC is exchanged and cleaned with PVA tree... Air dried. After drying 'Amino acid can coat unit 8W' #wet synthetic leather. Wet The amount is 380 g/m 2 and the thickness is 〜7 mm. The film is coated with a predetermined amount of the above-mentioned wet synthetic skin, and then aged to form a resin layer; And the dry area quality is processed by the resin texture formed by the polyamino-based organic fine particles, and the fine particles are obtained by the synthetic skin extraction method, etc., which is used for the lipolysis solution of the ester resin, and is L 12 〇 °c The heat φ product is a thin leather bonded to the unit area of the dry layer, and the film is attached to the mold paper of De-35-201245539, and is mixed with a urethane resin dissolved in a solvent by a predetermined amount using a touch coater. A resin having hygroscopic fine particles No. 1 was prepared and dried, and the total basis weight of the substrate and the resin layer was 428 g/m 2 and the thickness was 〇 8 mm. Further, the adhesive was a polyamine. Carbamate-based adhesive. The inorganic urethane resin is mixed with the inorganic fine particles No. 1 ' and applied to the resin layer formed as described above by gravure coating to form the outermost layer. The leather-like texture processing is carried out by using the release paper to obtain a synthetic leather. 7 - 1 2. Production Example 1 6 A synthetic leather was obtained in the same manner as in Production Example 15 except that the fine particles were not mixed with the above-mentioned high-slip amine phthalate resin. 7 -1 3 . 1 7 was prepared in the same manner as in Production Example 15 except that the fine particles were not mixed with the above-mentioned amino phthalate resin, and the organic fine particles N〇.丨 were mixed in the high-slip urethane resin. 7-14. Production Example 18 A synthetic method was prepared in the same manner as in Production Example 5 except that the fine particles were not mixed with the above-mentioned urethane resin or high-slip amino phthalate. Leather The composition of the synthetic leather obtained in the above Production Examples 1 to 18 and the evaluation results of the average moisture surface friction coefficient, the surface roughness, and the compression displacement amount at the time of low load are shown in Table 1. -36- 201245539 Synthetic Leather SMD (μηι) 〇〇- v£&gt; P p »nm P ρ P r^ rl ρ ρ ρ -It I 牮趔 beam 1 sS (Ν CS 〇(S CS 〇σΝ 〇〇〇&lt;N &lt;N Ο fN &lt;N Ο rJ ο 〇卜〇〇〇〇w- &gt; 〇Γ4 CN dm Ο f^&gt; Ο *Λ 〇〇ΚΓ» 〇DS ΓΛ en 〇m ΡΟ Ο &gt;r&gt;&lt;N Ο d 〇CM 〇dw*&gt;&lt;N 〇VO (N 0 〇m 〇 〇 〇 fO ΓΛ Ο UJ ο VI d Γ- d CS r〇Ο 〇 v〇ν〇Ό v〇\〇iS 卜寸 v〇CS v£&gt; v〇喵φίρ ^ J 蚌婼忽 m Inch inch S inch inch inch inch inch m art m 〇〇 (N inch?: rf inch? SO 〇 inch l resin layer &lt; uniform: enough sea 3 s ^ i mildew O W> (N (N 锣 for raspberry i mold OO v〇3 filled with ''aUU Zhao 2l into $ 彘鸾铉 cup \ 瞍 for i s S 铿 S S, 靼 荜 荜 雔 for i s 锣 i 逛 逛 逛 逛 靼 # # # ^6 M 蕤鸾杯&lt;Ν^Ο 怼葙鸾杯m _〇窠成m Cup0^ 怼U 鸾d 6 Z 2 怼刍 葙唉鸾UU \ ό 2 Μ Μ Cup O is cut \ 6 2 怼轾成% cup\ 莓WX 孙乡甾车 W. &amp;- 锘耷趄遛想想6· &lt; S吟以Ο 〇 ^ ^ 〇〇ο ο fS fS ΙΓ&gt; ....ΓΜ Tea Beer 1 β 珠 $$ Ο 〇^ ^ 〇〇5%^ 5 雄佑~ SSW ^ 球佑00 ν〇ϊ_ Ο 〇&lt;Ν &lt;Ν 〇φ 球 Μ 〇 〇 CM fS ^ '&lt; 1 SS ♦X 绅 为 为 为 靡 £ £ £ £ £ £ £ £ £ £ £ d d d d d d d ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ Δί« 封〇魄2 磁—&lt; 6 S 2 CU is Μ -^ ό Z Z 耷贱 « « « « ^ ^ ^ ^ ^ κ ^ δ g g g g g g g 键 键 键 键 键 键 键 键 键 键 键 键 键 键 键 键 键 键 键 键183 \ 钽 chain S- 硪甾 substrate ν® ΦΊ&lt;~&quot; 蚌婼今1 ο m | 〇m 鞔想样· K- 吞兹怜兹钣ΓΜ child m -t child*/&gt; child 00 On 〇铋rj 铋 铋 - Tibetan Mastiff 〇 - 0 -Lz_ 201245539 In addition, according to the subjective evaluation results of the commentator's sticky feeling, softness, rough feeling, and moist feeling are shown in Table 2. The stickiness score is positive, indicating that the feeling of stickiness is not sticky, and the scores of softness and moistness are positive, respectively, indicating that a soft feeling and a moist feeling can be obtained, and a score of a rough feeling is positive, indicating that a feeling of not being rough is obtained. Table 2: Softness, softness, roughness, wetness, manufacturing Example 1 1.4 1.1 1.4 1.6 Manufacturing Example 2 1.5 1.1 1.4 1.6 Manufacturing Example 3 1.5 0.9 : 1.2 1.1 Manufacturing Example 4 1.2 1.3 0.8 1.2 Manufacturing Example 5 1,2 1.5 0.6 1.5 Production Example 6 1.8 1.1 1.4 1.7 Manufacturing Example 7 1.1 1.1 1.4 1.5 Manufacturing Example 8 1.7 1.0 0.7 1.2 Manufacturing Example 9 1.6 1.0 1.0 1.0 Manufacturing Example 10 1.5 0.7 1.0 0.8 Manufacturing Example 11 1.5 0.8 1.4 1.0 Manufacturing Example 12 -1.5 -0.1 1.4 -0.5 Manufacturing Example 13 - 1.2 1.1 1.4 - 0.1 Manufacturing Example 14 - 1.1 - 0.4 1.1 - 0.7 Manufacturing Example 15 1.4 - 0.4 1.1 - 0.8 Manufacturing Example 16 1.4 - 0.1 1.4 - 0.6 Manufacturing Example 17 - 1.2 1.1 1.4 - 0.1 Manufacturing Example 18 - 1.7 - 0.1 1.4 - 0.5 It can be confirmed from Table 1 that the rise amount (ΔΗ) of the humidity in the palm of the manufacturing examples 1 to Π, 15 and 16 after 1 minute is 18% RH or less. Among the subjective evaluations of the reviewers in Table 2, the feelings of non-stickiness were obtained in Production Examples 1 to 1 1, 15 and 16. On the other hand, in the production examples 12, 13, 14, 17, and 18 in which the hygroscopic fine particles were not mixed, the amount of rise in the palm humidity (ΔΗ) after one minute was greater than 1 8% RH, in the commentator. In the subjective assessment, it is also seen that the tendency to assess the stickiness is poor. The average coefficient of friction (MIU) showed a value of 0.2 or more in Production Examples 1 to 1 1, 1 3, and 1 7 , and it was found that the surface having a feeling of resistance was completed and finished to a surface having a moist feeling. On the other hand, the manufacturing examples 12, 14, 1 5 - 38 - 201245539 and the heart 18 Yin _ are smaller than 〇 · 2. Because organic has the effect of improving mu, there is no such thing as a softness and a particle. The MIU has a lower effect, and there is a tendency for the inorganic to be dry and smooth, and the completion is not completed. In the case of inorganic particles, the surface roughness (SMD) is the value of 2.5_ or less in the full-manufacturing example in the case of the whole grain, and all the samples are completed. Yuping ~g &amp; ± % into a good surface roughness fruit. In the main... of the shell, it is also possible to obtain a low-load and a small displacement, and the manufacturing example i~&quot;, η, 颂 is not 0.1 6 mm or more, and the system is known. In the case of Yuping a member &amp; + &amp; load compression, the displacement is larger. 2: In the main evaluation, in the manufacturing example U~U, 13, and 17, the 牟 softness system is generally ϋ ^ 柔, ΐ 5, ΐ 6, " The medium displacement is lower than the V, and the scores for the examples 12 and 14 are also determined. ^ The commentator's subjective assessment can make the compression displacement of the low load two: soft:::, because the organic particles are more 槲' The silk 5 is forbearing and the sheep is soft... The dispersion in the resin causes the stress to be dispersed so that it cannot be seen. The force:: the inorganic particles can be dispersed but hard, _ divided by two (△,: 1 minute after the palm The amount of humidity rise; Syrian batch # . , / the average surface friction coefficient of the service; SMD: surface • 22 low load compression displacement; sticky feeling · softness · rough feelings of the second '· according to the subjective opinion of the commentator As a result, the appearance, the efficiency of I, and the fourth-order

• Slave (◎: very good, 〇: good, △: normal, X bad) is assessed. The results are shown in Table 3. -39- 201245539 e^ Cost efficiency 〇〇〇〇&lt;] 〇〇◎ ◎ ◎ 〇〇〇〇〇〇〇 Appearance ◎ ◎ ◎ ◎ 0 ◎ ◎ ◎ ◎ ◎ ◎ X ◎ ◎ ◎ X ◎ X Wet ◎ ◎ 〇〇 ◎ ◎ ◎ 〇〇 &lt;3 0 XXXXXXX Rough ◎ ◎ ◎ 〇 &lt;] &lt;3 ◎ ◎ &lt;3 〇〇 ◎ ◎ ◎ 0 〇 ◎ ◎ ◎ Softness 0 〇 &lt;] ◎ ◎ 0 0 0 0 &lt;] X 〇 XXX 0 X sticky feeling ◎ ◎ ◎ 〇 0 ◎ 〇 ◎ ◎ ◎ ◎ XXX ◎ ◎ XX SMD ◎ ◎ ◎ 0 〇 ◎ ◎ 〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Low load compression Displacement amount ◎ ◎ 0 〇 ◎ ◎ ◎ 0 〇 &lt;&lt;] X ◎ XXX ◎ X MIU ◎ ◎ 〇 ◎ ◎ ◎ 0 〇 0 〇 ◎ X ◎ X : &lt; X ◎ X ◎ ◎ ◎ ◎ ◎ ◎ ◎ 〇 ◎ ◎ ◎ ◎ XXX ◎ ◎ XX Manufacturing Example 1 Manufacturing Example 2 Manufacturing Example 3 Manufacturing Example 4 Manufacturing Example 5 Manufacturing Example 6 Manufacturing Example 7 Manufacturing Example 8 Manufacturing Example 9 Manufacturing Example 11 Manufacturing Example 12 Manufacturing Example 13 Manufacturing Example 14 Manufacturing Example 15 Manufacturing Example 16 Manufacturing Example 17 Manufacturing Example 18 w^x * ιϊφν · Cable ^璁© , 0 inch · 2012455 39 It can be seen from Table 3 that in Production Examples 1 to 11, the amount of increase in humidity in the palm after 1 minute (ΔΗ) is 18% RH or less, and the average friction coefficient (MIU) is 0.2 or more. Surface roughness (SMD) Below 2.5μπι, the low-load compression displacement is 〇.16mm or more, and there is no problem in appearance and cost efficiency. In the subjective assessment of the commentator, there is no sticky feeling, softness, no rough feeling and moist feeling. . On the other hand, in the production examples 1, 2, 14, and 18, the SMD system showed a good value and no rough feeling, but the rise amount of δη was high, the stickiness was felt, and the MIU value was low, so that the surface was finished to be dry, The low load compression displacement amount is small without flexibility, and a moist feeling cannot be obtained. In Production Examples 13 and 17, the MIU value, the SMD value, and the low-load compression displacement amount showed good values, and the tendency was not to be rough and soft, but the amount of rise was high and the feeling of stickiness was not good, and the wet feeling could not be obtained. In the manufacturing examples I5 and 16, the ΔΗ and SMD also showed good values, and the finished product was not sticky or rough, but the MIU and the low load compression displacement were small and felt dry and not soft, and the wet feeling could not be obtained. [Industrial Applicability] The synthetic leather for automotive interior materials of the present invention is used for automotive interior materials, particularly steering wheel skins, storage compartment skins, seat covers, instrument panels, door trim panels, and ceiling skin materials. , car seat surface material, etc. [Simple description of the diagram] Benefits 〇 [Main component symbol description] fe 〇 -4 1-

Claims (1)

201245539 VII. Patent application scope: 1. A synthetic leather for automotive interior materials, which is formed on a substrate layer having a single or multi-layer structure of non-woven fabric or woven fabric, and formed with a resin layer containing a single layer or a plurality of layers of synthetic resin. The synthetic leather is characterized in that at least one layer of the resin layer contains hygroscopic fine particles, and the outermost skin resin layer contains organic fine particles, and the juice simulation device measures the measured humidity of the palm in the palm after the start of sweating for one minute. (ΔΗ) is 18% RH or less, and the average surface friction coefficient (miu) at a load of 1.47 N/cm 2 is 0.20 or more, the surface roughness (SMD) is 2.5 μm or less, and the compression displacement at a low load (0.098 N/cm 2 ). The amount is 0 16mm or more. 2. If the application is before the first 3. If the application is before the first 4 · If the application is before the 5th, if the application is before the 6th, if the application is before the 6th, if the application is before the seventh. For the organic fine particles, please refer to the patent range of the resin layer. The above-mentioned patented range, the hygroscopic fine particles, the patent range, the resin layer, the patented range, and the hygroscopic particulate matter. One item of synthetic leather for automotive interiors has a glass transition point (Tg) of -lot: or less. A synthetic leather for automotive interior materials having an average particle diameter of Ιμιη~30μιη. One item of synthetic leather for automotive interiors, the content of which is from 0.5 g/m2 to 50 g/m2. A synthetic leather for automotive interior materials having an average particle size of 1 μηι to 5 0 μιη. A synthetic leather for automotive interior materials having a flat particle content of 2 g/m2 to 50 g/m2. 1 item of synthetic leather for automotive interior materials, 50% by mass or more of which is based on acrylic cross-linking -42-201245539 8. As in the patented scope, the synthetic leather for automotive interior materials, the aforementioned substrate The layer has a two-layer structure woven fabric in which the fiber structure constituting the upper layer and the fiber structure constituting the layer are laminated by mechanical mixing, and the mass per unit area of the upper layer is 4 〇g/m 2 to 50 g/m 2 , and the fibers constituting the layer are The fineness is 〇.〇〇〇ldtex~〇5dtex, the mass per unit area of the lower layer is 40g/m2~200g/m2, and the fineness of the fibers constituting the layer is 1.5dtex~l〇.〇dtex. 9. The synthetic leather for automotive interior materials according to claim 1, wherein the substrate layer has a single layer or a multi-layer structure, and the nonwoven fabric has a density of 12 〇kg/m 3 to 250 kg/m 3 and is strong in rupture. It is 400N~1000N and the bending resistance is imm~120mm. It does not go up and down. -43- 201245539 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the component symbols of this representative figure: None. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: