WO2014192283A1 - Cuir synthétique - Google Patents

Cuir synthétique Download PDF

Info

Publication number
WO2014192283A1
WO2014192283A1 PCT/JP2014/002769 JP2014002769W WO2014192283A1 WO 2014192283 A1 WO2014192283 A1 WO 2014192283A1 JP 2014002769 W JP2014002769 W JP 2014002769W WO 2014192283 A1 WO2014192283 A1 WO 2014192283A1
Authority
WO
WIPO (PCT)
Prior art keywords
synthetic leather
adhesive
thermally expandable
polyurethane resin
fine particles
Prior art date
Application number
PCT/JP2014/002769
Other languages
English (en)
Japanese (ja)
Inventor
祥太郎 池田
俊幸 森
佐藤　正樹
Original Assignee
アキレス株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by アキレス株式会社 filed Critical アキレス株式会社
Priority to JP2015519644A priority Critical patent/JP6433423B2/ja
Publication of WO2014192283A1 publication Critical patent/WO2014192283A1/fr

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0043—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers
    • D06N3/005—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers obtained by blowing or swelling agent
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • D06N3/145—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes two or more layers of polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/554—Wear resistance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/582—Tearability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2479/00—Furniture
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B32B2605/003—Interior finishings
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2211/00—Specially adapted uses
    • D06N2211/12—Decorative or sun protection articles
    • D06N2211/14—Furniture, upholstery
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2211/00—Specially adapted uses
    • D06N2211/12—Decorative or sun protection articles
    • D06N2211/26—Vehicles, transportation

Definitions

  • the present invention relates to synthetic leather.
  • Highly durable synthetic leather has been used as a vehicle seat or furniture seat.
  • a polyurethane resin material containing polyol, isocyanate, chain extender and solvent is coated on a releasable carrier such as release paper, and then heated as necessary to evaporate the solvent in the resin material.
  • a cross-linking reaction of the resin is caused to form a skin layer, and if necessary, an intermediate layer of polyurethane resin is formed.
  • an adhesive layer and a raw cloth are sequentially laminated, and then the adhesive is cured by heating. It is generally manufactured by a dry method in which a raw cloth and a polyurethane resin layer such as a skin layer or an intermediate layer are integrated (Patent Document 1).
  • the skin layer and the intermediate layer of the highly durable synthetic leather are composed of a one-pack type or two-pack type polyurethane resin.
  • a polycarbonate urethane resin is used for the skin layer.
  • the conventional fabric weight is 200 g / m 2 or more as a raw fabric of high durability synthetic leather. Knitted fabric, woven fabric, non-woven fabric, etc. are used.
  • the adhesive layer is formed by a two-component urethane adhesive containing polyol and isocyanate. In order to cure after applying the urethane adhesive and pasting it together with the raw cloth, since curing at 50 ° C. for about 48 hours is required, the production efficiency of synthetic leather is low and the production cost is high.
  • the present inventors have used a specific urethane-based adhesive, and even if a lightweight raw cloth with a basis weight of less than 200 g / m 2 is used, it is equivalent to the conventional one. To find out that it has appearance, texture (texture), abrasion resistance, peel strength, and requires only a very short time for bonding to a green fabric, which can greatly improve the production efficiency of synthetic leather. It came.
  • the present invention (1) Synthetic leather formed by laminating a polyurethane resin layer on a raw cloth through an adhesive layer, and the raw cloth has a basis weight of less than 200 g / m 2 , and the adhesive layer has a terminal isocyanate group blocking agent.
  • a urethane adhesive containing a blocked urethane prepolymer, an amine-based cross-linking agent, and heat-expandable fine particles is heated to foam the heat-expandable fine particles, and the urethane prepolymer and the amine-based cross-linking agent are subjected to a cross-linking reaction.
  • Synthetic leather comprising a formed polyurethane resin containing foamed thermally expandable fine particles, (2) A urethane system in which the adhesive layer includes a urethane prepolymer in which terminal isocyanate groups that are deblocked at 120 to 180 ° C. are blocked, an amine-based crosslinking agent, and thermally expandable fine particles having a maximum expansion temperature of 120 to 180 ° C.
  • the synthetic leather according to the above (1) which is formed by heating the adhesive at 120 to 180 ° C. to foam the thermally expandable fine particles and cross-linking the urethane prepolymer and the amine-based cross-linking agent.
  • the synthetic leather of the present invention is lightweight but excellent in appearance, texture (texture), abrasion resistance and peel strength, and has high durability that can be used as a vehicle seat, furniture seat, and the like.
  • the synthetic leather of the present invention can be produced in an extremely short time as compared with conventional synthetic leather, and has high production efficiency, so that the production cost can be reduced.
  • FIG. 4 is an electron micrograph of a cross section of a synthetic leather of Comparative Example 2.
  • 4 is an electron micrograph of a cross section of a synthetic leather of Comparative Example 3.
  • 6 is an electron micrograph of a cross section of a synthetic leather of Comparative Example 4.
  • a raw cloth 2 and a skin layer 3 which is a polyurethane resin layer are laminated and integrated through an adhesive layer 4, and a surface treatment layer 5 is provided on the surface of the skin layer 3. It is provided and configured.
  • the adhesive layer 4 contains foamed thermally expandable fine particles 7.
  • the raw fabric 2 includes synthetic fibers such as polyester, polyamide and polyacrylonitrile, natural fibers such as cotton and hemp, knitted fabrics, woven fabrics and non-woven fabrics made of recycled fibers such as rayon, suf and acetate alone or a mixed fiber thereof. Any of those conventionally used as a raw fabric for synthetic leather can be used. Among these, those having a basis weight of less than 200 g / m 2 are used. The raw cloth 2 may be raised or may not be raised. The raw fabric 2 preferably has a basis weight of 190 g / m 2 or less, and particularly preferably has a basis weight of 100 to 180 g / m 2 . Further, those having a tensile strength of 200 N / 3 cm or more (JIS K6772) and a tear strength of 20 N or more (JIS K6772) are preferable.
  • synthetic fibers such as polyester, polyamide and polyacrylonitrile, natural fibers such as cotton and hemp, knitted fabrics, woven fabrics and non-woven fabrics made
  • any of those conventionally used for the skin layer of synthetic leather can be used.
  • polyester polyurethane resin, polyether polyurethane resin, polycaprolactone polyurethane resin, polyester / polyether copolymer polyurethane resin, polyamino acid / polyurethane copolymer resin, polycarbonate diol component and non-yellowing diisocyanate component examples thereof include non-yellowing polycarbonate polyurethane resins obtained by reacting low molecular chain extenders and the like.
  • polyvinyl chloride resin or synthetic rubber may be mixed with the above polyurethane resin as long as various physical properties as synthetic leather are not impaired.
  • the polyurethane resin forming the skin layer is prepared by dissolving a polyol, polyisocyanate, and a crosslinking agent in an organic solvent such as methyl ethyl ketone, toluene, dimethylformamide, or a solvent such as water, and if necessary, a colorant, a filler, It is formed by applying, drying, and crosslinking a polyurethane resin solution to which various additives such as a light stabilizer, an ultraviolet absorber, an antioxidant, a flame retardant, and a crosslinking agent are added.
  • the polyurethane resin solution can be either a one-component type or a two-component type.
  • the skin layer 3 is preferably formed to a thickness of 10 to 60 ⁇ m, more preferably 20 to 50 ⁇ m. A drawing pattern or the like may be provided on the surface of the skin layer 3.
  • the synthetic leather 1 of the present invention is provided with an intermediate layer 6 between the skin layer 3 and the adhesive layer 4 as shown in FIG.
  • the layer 3 and the intermediate layer 6 may be used.
  • the polyurethane resin constituting the intermediate layer 6 the same polyurethane resin as that constituting the skin layer 3 can be used.
  • the intermediate layer 6 may have a foam structure.
  • the thickness of the intermediate layer 6 is preferably 10 to 100 ⁇ m for the non-foamed structure and 50 to 1000 ⁇ m for the foamed structure.
  • the intermediate layer 6 is not limited to one layer, and two or more layers can be provided.
  • the adhesive layer 4 for bonding the polyurethane resin layer such as the skin layer 3 and the intermediate layer 6 and the raw cloth 2 is composed of a urethane prepolymer in which a terminal isocyanate group is blocked with a blocking agent, an amine-based crosslinking agent, and a thermal expansion property.
  • the urethane adhesive containing fine particles is heated to foam the thermally expandable fine particles, and is formed by a polyurethane resin containing foamed thermally expandable fine particles, which is obtained by crosslinking the urethane prepolymer and the amine crosslinking agent. Yes.
  • Examples of the urethane prepolymer in which the terminal isocyanate group used in the urethane adhesive is blocked with a blocking agent include aliphatic diol and phosgene, diallyl carbonate, or the like described in JP-A-2006-70059. What blocked the terminal isocyanate group of the urethane prepolymer obtained from the polycarbonate diol liquid at 25 degreeC which is a reaction material with a cyclic carbonate, and organic diisocyanate with the blocking agent is mentioned.
  • those conventionally used as polyurethane raw materials can be used, for example, polyols such as ethylene glycol, propylene glycol, butylene glycol, and dicarboxylic acids such as succinic acid, maleic acid, and adipic acid.
  • Polyester diol which is a dehydration condensate of the above; polyether diol which is ethylene oxide, propylene oxide, butylene oxide alone or two or more kinds of ring-opening polymers.
  • organic diisocyanate conventionally known polyurethane raw materials can be used, and are not particularly limited.
  • 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate.
  • Examples of the blocking agent for blocking the terminal isocyanate group of the urethane prepolymer obtained by reacting polycarbonate diol and organic diisocyanate so that the terminal is an isocyanate group include ketoximes, lactams, phenols, pyrazoles, and active methylene compounds. Among them, ketoximes and lactams that can easily block an isocyanate group and can be deblocked at 120 to 180 ° C. are preferable.
  • the ketoximes include methyl ethyl ketoxime, cyclohexanone oxime, acetone oxime, 3-methyl-2-butanone oxime, 2-pentanone oxime, 3-pentanone oxime, 4-methyl-2-pentanone oxime, 2-heptanone oxime, 3 -Heptanone oxime and acetophenone oxime are preferred, and as the lactam, ⁇ -caprolactam is preferred.
  • the urethane-based adhesive for constituting the adhesive layer 4 contains an amine-based crosslinking agent and thermally expandable fine particles together with the urethane prepolymer whose terminal isocyanate group is blocked with the blocking agent.
  • Aliphatic polyamines are used as amine-based crosslinking agents, such as ethylenediamine, 1,2-propanediamine, 1,3-propylenediamine, 1,6-hexamethylenediamine, piperazine, 2-methylpiperazine, 2,5-dimethyl.
  • Piperazine N, N′-diaminopiperazine, isophoronediamine, 4,4′-diaminocyclohexylmethane, 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane, 1,2-cyclohexanediamine, 1,4- Cyclohexanediamine, aminoethylethanolamine, aminopropylethanolamine, aminohexylethanolamine, aminoethylpropanolamine, aminopropylpropanolamine, aminohexylpropanolamine, 2,5-bis (aminomethyl) bisi (B) Aliphatic diamines such as [2,2,1] heptane and 2,6-bis (aminomethyl) bicyclo [2,2,1] heptane, aliphatic triamines such as diethylenetriamine and dipropylenetriamine, triethylenetetramine and hydrazine And acid hydrazides.
  • B Aliphatic diamine
  • aliphatic diamines such as heptane and 2,6-bis (aminomethyl) bicyclo [2,2,1] heptane
  • aliphatic triamines such as diethylenetriamine and dipropylenetriamine, and triethylenetetramine.
  • Group triamines and mixtures thereof are preferred.
  • thermally expandable fine particles contained in the urethane-based adhesive examples include microcapsules in which liquid low-boiling hydrocarbons that are vaporized by heating are wrapped with a thermoplastic resin film such as acrylonitrile-based resin.
  • the amount of thermally expandable fine particles added to the urethane-based adhesive is usually 0.5 to 10% by weight, more preferably 1.5 to 5% by weight.
  • the particle size of the microcapsules and the difference in the thermal expansion coefficient of the thermally expandable fine particles are adjusted.
  • the thermally expandable fine particles preferably have a maximum expansion temperature of 120 to 180 ° C. If the maximum expansion temperature is less than 120 ° C, foaming may occur due to heat during preliminary drying when applying and drying the urethane-based adhesive, and if it exceeds 180 ° C, There is a possibility that damage such as shrinkage may be caused to the urethane resin or raw cloth by heat.
  • thermally expandable fine particles for example, Matsumoto Microsphere (trade name) manufactured by Matsumoto Yushi Seiyaku Co., Ltd. can be used.
  • thermally expandable fine particles having a maximum expansion temperature of 120 to 180 ° C. F-30, F36LV, F-36, F-48, F-50, F78K, F-79, F-80S, F-82, F-100, F-102, F-105, F-170, FN-100MD (all Matsumoto Microsphere product number).
  • the surface treatment layer 5 is provided on the surface of the skin layer 3 as necessary for the purpose of polishing the surface of the skin layer 3 or the like.
  • the surface treatment layer can be provided, for example, by coating the surface of the skin layer 3 with a coating liquid in which polyurethane resin, silicon, organic filler, or the like is dispersed in an organic solvent or water.
  • a polyurethane resin solution for constituting the skin layer is applied on the releasable carrier 8 such as a release paper, and the solvent in the applied polyurethane resin solution is evaporated and dried.
  • the skin layer 3 is formed by causing a crosslinking reaction of the resin.
  • a knife coater, a comma doctor, a roll coater, a reverse roll coater, a rotary screen coater, a gravure coater, and other appropriate means are employed.
  • the releasable carrier 8 such as release paper may have a smooth surface on the side on which the polyurethane resin solution is applied, or may have a drawn pattern or the like.
  • the pattern of the releasable carrier 8 is transferred to the surface of the outer skin layer 3 of the synthetic leather 1 to obtain a synthetic leather in which a design by the drawn pattern or the like appears. Can do.
  • an adhesive for forming an adhesive layer is applied on the skin layer 3.
  • a method similar to the application of the polyurethane resin solution for forming the skin layer can be employed.
  • the application amount of the adhesive varies depending on the texture of the target synthetic leather, but it is preferable to apply the adhesive so that the thickness during application (wet) is 100 to 300 ⁇ m.
  • the applied adhesive is dried at a temperature at which the blocking agent in the urethane prepolymer in which the terminal isocyanate group is blocked with the blocking agent is not dissociated, and is preferably dried at 120 ° C. or less to form the adhesive layer 4a.
  • the heat-expandable fine particles in the adhesive layer 4a are foamed by heating and the isocyanate group is blocked.
  • the prepolymer is deblocked to crosslink the urethane prepolymer and the amine-based crosslinking agent, thereby forming the adhesive layer 4 including the foamed thermally expandable fine particles 7 as shown in FIG.
  • the heating temperature after laminating raw fabric 2 varies depending on the type of blocking agent that blocks the terminal isocyanate group of the urethane prepolymer, the type of thermally expandable fine particles, etc., but the maximum expansion temperature is 120 to 180 ° C.
  • the expandable fine particles are selected, and a urethane prepolymer that is blocked so that the deblocking of the urethane prepolymer occurs at 120 to 180 ° C. to cause a reaction between the urethane prepolymer and the amine-based crosslinking agent is selected. Heating at ⁇ 180 ° C. is preferred. The heating time is preferably 1 to 5 minutes.
  • the surface treatment layer 5 can be formed by a method such as a gravure coater, a reverse roll coater, or a spray coater.
  • the intermediate layer 6 is formed by the same method as that for the skin layer 3 after forming the skin layer 3 and before forming the adhesive layer 4 a. It can be manufactured in the same manner as the method shown in FIG.
  • Example 1 20 parts by weight each of dimethylformamide and methyl ethyl ketone as a solvent with respect to 100 parts by weight of one-component non-yellowing polycarbonate polyurethane resin (manufactured by DIC Corporation: trade name “Crisbon NY328FTR”, solid content 20% by weight), black pigment (Dic Co., Ltd .: trade name “Dylac L-1770”) 20 parts by weight were added, mixed and stirred, and applied to the uneven surface of the release paper (Dai Nippon Printing Co., Ltd .: trade name “DE-73”). Then, it was applied so that the thickness after drying was 25 ⁇ 5 ⁇ m, and dried in an oven at 100 ° C. for 3 minutes to form a skin layer having a thickness of 30 ⁇ m.
  • one-component non-yellowing polycarbonate polyurethane resin manufactured by DIC Corporation: trade name “Crisbon NY328FTR”, solid content 20% by weight
  • black pigment Dic Co., Ltd .:
  • Aliphatic diamine manufactured by BASF: trade name “Lalomin C260”
  • urethane prepolymer DIRC Corporation: trade name “Urehyper SU-009”
  • Terminal isocyanate group is blocked with ketoxime.
  • thermal expansion microcapsules with a maximum expansion temperature of 160 to 180 ° C., an average particle size of 30 ⁇ m, and an expansion coefficient of about 7 times (manufactured by Matsumoto Yushi Seiyaku Co., Ltd .: trade name“ Matsumoto Microsphere ”) FN-100MD ”) 1 part by weight and an adhesive containing 15 parts by weight of dimethylformamide as a solvent were applied on the skin layer to a thickness of 170 ⁇ m (when wet) and dried in an oven at 120 ° C for 2 minutes.
  • a thermally expandable microcapsule formed an unfoamed adhesive layer.
  • a single-sided knitted fabric with a thickness of 550 ⁇ m and a basis weight of 120 g / m 2 is laminated and bonded as a raw fabric, and then heated in an oven at 180 ° C. for 2 minutes to foam the thermally expandable microcapsules.
  • the skin layer and the knitted fabric were joined and integrated through an adhesive layer in which the urethane prepolymer and the crosslinking agent were reaction-cured. Thereafter, the release paper was peeled off to obtain a synthetic leather.
  • Table 1 shows the physical properties of the obtained synthetic leather.
  • the thickness of the adhesive layer made of a polyurethane resin containing the foamed thermally expandable microcapsules was 170 ⁇ m.
  • Example 2 A synthetic leather was obtained in the same manner as in Example 1 except that the thermally expandable microcapsule in the adhesive was 3 parts by weight, and the adhesive was applied on the skin layer so as to be 170 ⁇ m (wet). Table 1 shows the physical properties of the obtained synthetic leather. Moreover, the electron micrograph (JEOL Co., Ltd. scanning electron microscope: JSM6700F, magnification 30 times) of this synthetic leather cross section is shown in FIG. The thickness of the adhesive layer made of a polyurethane resin containing the foamed thermally expandable microcapsules was 320 ⁇ m.
  • Example 3 A synthetic leather was obtained in the same manner as in Example 1 except that the thermally expandable microcapsule in the adhesive was 5 parts by weight, and the adhesive was applied onto the skin layer so as to be 170 ⁇ m (when wet). Table 1 shows the physical properties of the obtained synthetic leather. The thickness of the adhesive layer made of a polyurethane resin containing the foamed thermally expandable microcapsules was 470 ⁇ m.
  • Example 4 A synthetic leather was obtained in the same manner as in Example 1 except that the heat-expandable microcapsule in the adhesive was 7 parts by weight and the adhesive was applied on the skin layer so that the thickness was 170 ⁇ m (wet). Table 1 shows the physical properties of the obtained synthetic leather.
  • the thickness of the adhesive layer made of a polyurethane resin containing the foamed thermally expandable microcapsules was 720 ⁇ m.
  • Example 5 170 ⁇ m (wet) on the skin layer using an adhesive with 3 parts by weight of thermally expandable microcapsules and 5.54 parts by weight of aliphatic triamine (manufactured by BASF: trade name “Baxodur EC310”) as a crosslinking agent
  • Synthetic leather was obtained in the same manner as in Example 1 except that the coating was applied in the same manner as in Example 1.
  • Table 1 shows the physical properties of the obtained synthetic leather.
  • the thickness of the adhesive layer made of a polyurethane resin containing the foamed thermally expandable microcapsules was 320 ⁇ m.
  • Example 6 3 parts by weight of thermally expandable microcapsules, and 2.25 parts by weight of aliphatic diamine (manufactured by BASF: trade name “Laromin C260”) and aliphatic triamine (manufactured by BASF: trade name “Baxodur EC310” as a crosslinking agent) )
  • Synthetic leather was obtained in the same manner as in Example 1 except that 2.77 parts by weight of the adhesive was applied onto the skin layer so as to be 170 ⁇ m (when wet).
  • Table 1 shows the physical properties of the obtained synthetic leather.
  • the thickness of the adhesive layer made of a polyurethane resin containing the foamed thermally expandable microcapsules was 320 ⁇ m.
  • Comparative Example 1 A synthetic leather was obtained in the same manner as in Example 1 except that an adhesive not containing heat-expandable microcapsules was used and the adhesive was applied on the skin layer so as to have a thickness of 170 ⁇ m (when wet). Table 1 shows the physical properties of the obtained synthetic leather. The thickness of the adhesive layer was 90 ⁇ m.
  • Comparative Example 2 Instead of 1 part by weight of thermally expandable microcapsules, 4 parts by weight of azodicarbonamide powder (manufactured by Eiwa Kasei Co., Ltd .: trade name “Vinole DW # 6”) as a foaming agent and urea powder (Yewa Kasei Co., Ltd.) as a foaming aid Company: Trade name “Cell Paste 101”) 4 parts by weight of adhesive was used, and the adhesive was applied onto the skin layer to a thickness of 170 ⁇ m (when wet) in the same manner as in Example 1. Synthetic leather was obtained. Table 1 shows the physical properties of the obtained synthetic leather. Moreover, the electron micrograph (30 times) of this synthetic leather is shown in FIG. The thickness of the adhesive layer was 160 ⁇ m.
  • Comparative Example 3 instead of 1 part by weight of thermally expandable microcapsules, an adhesive containing 5 parts by weight of 4,4-oxybis (benzenesulfonylhydrazide) powder (manufactured by Eiwa Kasei Co., Ltd .: trade name “Neoselbon N # 5000”) as a foaming agent is used.
  • a synthetic leather was obtained in the same manner as in Example 1 except that it was applied to the outer skin layer so as to have a thickness of 170 ⁇ m (when wet). Table 1 shows the physical properties of the obtained synthetic leather. Moreover, the electron micrograph (30 times) of this synthetic leather is shown in FIG. The thickness of the adhesive layer was 270 ⁇ m.
  • Comparative Example 4 In place of the adhesive of Example 1, 100 parts by weight of a non-yellowing polyurethane resin (manufactured by DIC Corporation: trade name “Chrisbon TA205FT”), a trimethylolpropane addition product of tolylene diisocyanate as a crosslinking agent (Nippon Polyurethane) Kogyo Co., Ltd .: trade name “Coronate L”) 15 parts by weight, 3 parts by weight of thermally expandable microcapsules (Matsumoto Microsphere FN-100MD) as in Example 1, 20 parts each of dimethylformamide and methyl ethyl ketone as solvents Except that it was applied to the outer skin layer to a thickness of 170 ⁇ m (wet) using an adhesive mixed with 5 parts by weight of an amine catalyst (manufactured by DIC Corporation: trade name “Accel HM”).
  • a non-yellowing polyurethane resin manufactured by DIC Corporation: trade name “Chrisbon TA205FT”
  • a synthetic leather was produced in the same manner as in Example 1. However, after applying the raw cloth to the adhesive layer, it was necessary to cure at 50 ° C. for 48 hours until the raw cloth and the skin layer were reliably integrated. Table 1 shows the physical properties of the obtained synthetic leather. Moreover, the electron micrograph (30 times) of this synthetic leather is shown in FIG. The thickness of the adhesive layer made of a polyurethane resin containing the foamed thermally expandable microcapsules was 320 ⁇ m.
  • the adhesive layer foamed state was taken with a scanning electron microscope (manufactured by JEOL Ltd .: JSM6700F, magnification 150 times, width 800 ⁇ m ⁇ length 600 ⁇ m) with a cross section of the obtained synthetic leather (5 points selected arbitrarily).
  • the cell size (longest side) of each heat-expanded microcapsule in the adhesive layer was measured, and the average cell size was calculated. And it evaluated on the following references
  • ⁇ The average cell size is 70 to 150 ⁇ m, and the cell bubbles are closed cells.
  • the average cell size is out of the range of 70 to 150 ⁇ m, or the cell bubbles are not closed cells.
  • the abrasion resistance was evaluated according to the following criteria by performing a taper abrasion test in accordance with JIS K6902 and measuring the number of rotations of the worn wheel until the skin layer of the synthetic leather was worn and the lower layer was exposed.
  • A The number of rotations of the wear wheel until the lower layer is exposed is 5000 times or more.
  • X The number of rotations of the wear wheel until the lower layer is exposed is less than 2000 times.
  • the peel strength was evaluated based on the following criteria by measuring the peel strength based on the method of JIS K6772 peel test. ⁇ : 30 N / 3 cm or more. ⁇ : 20 N / 3 cm or more and less than 30 N / 3 cm. X: Less than 20 N / 3 cm.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne un cuir synthétique qui est léger tout en possédant une excellente apparence, une excellente texture (sensation), une excellente résistance à l'usure, et une excellente résistance au pelage par comparaison avec le cuir synthétique classique, possède une durabilité élevée permettant son utilisation dans des sièges de voiture, des sièges d'ameublement, et similaires, et peut en outre être produit en une période de temps extrêmement courte et peut réduire les coûts de production. Ce cuir synthétique est formé par superposition en couches d'une couche de résine polyuréthane sur un tissu écru par l'intermédiaire d'une couche adhésive, et est caractérisé en ce que la masse surfacique du tissu écru est inférieure à 200 g/m2, et la couche adhésive comprend une résine polyuréthane comprenant des microparticules foamées thermiquement expansibles qui est formée en chauffant un adhésif uréthane comprenant un polymère uréthane possédant un groupe isocyanate terminal bloqué avec un agent bloquant, un agent de réticulation amine, et des microparticules thermiquement expansibles pour foamer les microparticules thermiquement expansibles tout en faisant en sorte que le polymère uréthane et l'agent de réticulation amine subissent une réaction de réticulation.
PCT/JP2014/002769 2013-05-27 2014-05-26 Cuir synthétique WO2014192283A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2015519644A JP6433423B2 (ja) 2013-05-27 2014-05-26 合成皮革

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013-111283 2013-05-27
JP2013111283 2013-05-27

Publications (1)

Publication Number Publication Date
WO2014192283A1 true WO2014192283A1 (fr) 2014-12-04

Family

ID=51988335

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/002769 WO2014192283A1 (fr) 2013-05-27 2014-05-26 Cuir synthétique

Country Status (2)

Country Link
JP (1) JP6433423B2 (fr)
WO (1) WO2014192283A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105365838A (zh) * 2015-11-24 2016-03-02 唐山轨道客车有限责任公司 座椅面板和座椅
KR20180037990A (ko) 2015-09-02 2018-04-13 디아이씨 가부시끼가이샤 습기 경화형 핫멜트 우레탄 조성물, 그 발포 경화물의 제조 방법, 합성 피혁, 및, 그 제조 방법
TWI623443B (zh) * 2016-09-20 2018-05-11 Huang Min San Graphical thermal transfer structure
CN112409562A (zh) * 2020-11-21 2021-02-26 华大化学(安徽)有限公司 一种软质篮球革专用聚氨酯树脂及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6128079A (ja) * 1984-07-11 1986-02-07 Komatsu Seiren Kk 合成皮革の製造方法
JPS6182993U (fr) * 1984-11-01 1986-06-02
JPS63249787A (ja) * 1987-03-31 1988-10-17 Bando Chem Ind Ltd 合成皮革の製造方法
JP2005171392A (ja) * 2003-12-08 2005-06-30 Teijin Cordley Ltd 皮革様シート状物の製造方法
JP2005248415A (ja) * 2004-03-01 2005-09-15 Carl Freudenberg Kg 耐光堅牢度の高い人工皮革の製造方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60199087A (ja) * 1984-03-22 1985-10-08 Seiko Kasei Kk 合成皮革用接着剤
JP4190604B2 (ja) * 1997-09-24 2008-12-03 旭化成せんい株式会社 合成皮革

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6128079A (ja) * 1984-07-11 1986-02-07 Komatsu Seiren Kk 合成皮革の製造方法
JPS6182993U (fr) * 1984-11-01 1986-06-02
JPS63249787A (ja) * 1987-03-31 1988-10-17 Bando Chem Ind Ltd 合成皮革の製造方法
JP2005171392A (ja) * 2003-12-08 2005-06-30 Teijin Cordley Ltd 皮革様シート状物の製造方法
JP2005248415A (ja) * 2004-03-01 2005-09-15 Carl Freudenberg Kg 耐光堅牢度の高い人工皮革の製造方法

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20180037990A (ko) 2015-09-02 2018-04-13 디아이씨 가부시끼가이샤 습기 경화형 핫멜트 우레탄 조성물, 그 발포 경화물의 제조 방법, 합성 피혁, 및, 그 제조 방법
US10947336B2 (en) 2015-09-02 2021-03-16 Dic Corporation Moisture curable hot melt urethane composition, method for producing cured foam of same, synthetic leather and method for producing synthetic leather
CN105365838A (zh) * 2015-11-24 2016-03-02 唐山轨道客车有限责任公司 座椅面板和座椅
CN105365838B (zh) * 2015-11-24 2018-04-24 中车唐山机车车辆有限公司 座椅面板和座椅
TWI623443B (zh) * 2016-09-20 2018-05-11 Huang Min San Graphical thermal transfer structure
CN112409562A (zh) * 2020-11-21 2021-02-26 华大化学(安徽)有限公司 一种软质篮球革专用聚氨酯树脂及其制备方法

Also Published As

Publication number Publication date
JPWO2014192283A1 (ja) 2017-02-23
JP6433423B2 (ja) 2018-12-05

Similar Documents

Publication Publication Date Title
ES2804030T3 (es) Cuero artificial con propiedades de resistencia a la flexión mejoradas
US20180072027A1 (en) Multi-layer composite materials comprising a textile sheet material, production and corresponding method of use thereof
JP6433423B2 (ja) 合成皮革
WO2016063761A1 (fr) Article du type feuille
JP4515841B2 (ja) ウレタンポリオールプレポリマー、多孔性ポリウレタン体及びその製造方法
KR101816392B1 (ko) 자동차 내장재용 인조가죽 및 그의 제조방법
US11155960B2 (en) Artificial leather having water-based polyurethane foam layer and method of manufacturing the same
JP4866091B2 (ja) ポリウレタン微多孔膜を備えた高発泡布帛及びその製造方法
JP7314267B2 (ja) 合成皮革製品およびその調製方法
WO2007086128A1 (fr) Composition de resine de polyurethanne pour feuille impermeable a l’eau permeable a l’humidite durable, feuille impermeable a l’eau permeable a l’humidite et son procede de fabrication
JP6508519B2 (ja) ウレタン樹脂組成物、及び、皮革様シート
EP1977883B1 (fr) Tissu avec couche fortement expansée et son procede de fabrication
KR20180078057A (ko) 크래쉬 패드용 인조피혁 및 이를 포함하는 크래쉬 패드
TWI466778B (zh) 聚胺甲酸酯積層體之製造方法及由該製造方法所獲得的聚胺甲酸酯積層體
JPWO2011132581A1 (ja) ポリウレタン樹脂水性分散体、無孔質フィルム、並びに、透湿性防水布帛及びその製造方法
WO2004092240A1 (fr) Composite a base de polyurethanne aqueux et cuirs synthetiques possedant une structure nouvelle
JP5940336B2 (ja) 合成皮革の製造方法
JP2014129622A (ja) 合成皮革
TW201408837A (zh) 胺基甲酸酯樹脂組成物、仿皮革片材及積層體
US20050026525A1 (en) Composite material with synthetic composite matrix, method for producing said material, and its application
JP2008057062A (ja) 皮革様シート状物およびその製造方法
TW202306775A (zh) 包含發泡粒子之多層複合材料
JP5779424B2 (ja) 銀付調皮革様シート
JP5350316B2 (ja) 耐久性のある透湿性防水シート用ポリウレタン樹脂組成物、透湿性防水シートおよびその製造方法
WO2022185689A1 (fr) Cuir synthétique

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14804281

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2015519644

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14804281

Country of ref document: EP

Kind code of ref document: A1