JP6433423B2 - Synthetic leather - Google Patents
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- JP6433423B2 JP6433423B2 JP2015519644A JP2015519644A JP6433423B2 JP 6433423 B2 JP6433423 B2 JP 6433423B2 JP 2015519644 A JP2015519644 A JP 2015519644A JP 2015519644 A JP2015519644 A JP 2015519644A JP 6433423 B2 JP6433423 B2 JP 6433423B2
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- 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
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- 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
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)
Description
本発明は合成皮革に関する。 The present invention relates to synthetic leather.
車輌用シートや家具用シートとして、従来より高耐久性合成皮革が用いられている。高耐久性合成皮革は、離型紙等の離型性担体上にポリオール、イソシアネート、鎖伸長剤、溶媒を含むポリウレタン樹脂材料を塗布した後、必要に応じて加熱して樹脂材料中の溶媒を蒸発させるとともに、樹脂の架橋反応を起こさせて表皮層を形成し、更に必要に応じてポリウレタン樹脂の中間層を形成し、更に接着層、生布を順次積層した後、加熱して接着剤を硬化させて生布と表皮層や中間層等のポリウレタン樹脂層とを一体化する乾式法により一般に製造されている(特許文献1)。 Conventionally, highly durable synthetic leather has been used as a vehicle seat or furniture seat. For high durability synthetic leather, 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. In addition, 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. Further, 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).
高耐久性合成皮革の表皮層や中間層は、1液型や2液型のポリウレタン樹脂により構成され、特に高耐久性が求められる場合、表皮層にはポリカーボネート系ウレタン樹脂が用いられる。一方、車輌用シート、家具用シートに要求される外観、質感(風合い)、耐摩耗性、剥離強度を得る目的で、高耐久性合成皮革の生布として、従来は目付が200g/m2以上の編布、織布、不織布等が使用されている。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. When high durability is particularly required, a polycarbonate urethane resin is used for the skin layer. On the other hand, in order to obtain the appearance, texture (texture), abrasion resistance, and peel strength required for vehicle seats and furniture seats, 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.
近年、車の燃費向上の目的で各部品ともグラム単位での軽量化が検討されており、高耐久性合成皮革等の車輌用内装材にも軽量化が要求されつつある。従来の高耐久性合成皮革は、生布が合成皮革重量の6〜8割を占めているため、目付が200g/m2未満の生布を用いることにより、容易に軽量化の目的を達成できるとともに、コストダウンも図ることができる。しかしながら、目付が200g/m2未満という従来に比して軽量の生布を用いて乾式法で製造された合成皮革は、薄くなって質感が得られ難く、耐摩耗性も低下するという問題があった。また質感の低下をポリウレタン樹脂層を厚くすることで補おうとすると、合成皮革の風合いが硬くなってしまうとともに、軽量化の目的を達成できなくなるという問題があった。更に、従来の合成皮革では、ポリオールとイソシアネートとを含む2液型のウレタン系接着剤により接着層を形成しているが、ウレタン系接着剤を塗布して生布と張り合わせた後、硬化させるために50℃で48時間程度の養生が必要となるため、合成皮革の製造効率が低く、製造コストが高くつくという問題があった。In recent years, for the purpose of improving the fuel efficiency of a vehicle, weight reduction of each part has been studied in gram units, and the weight reduction of vehicle interior materials such as high durability synthetic leather is being demanded. In conventional high-durability synthetic leather, raw fabric occupies 60 to 80% of the weight of synthetic leather. Therefore, the use of raw fabric with a basis weight of less than 200 g / m 2 can easily achieve the purpose of weight reduction. At the same time, the cost can be reduced. However, synthetic leather manufactured by a dry method using a lighter weight fabric than the conventional one having a basis weight of less than 200 g / m 2 has a problem that it is difficult to obtain a texture due to thinness and wear resistance is also reduced. there were. Further, if it is attempted to compensate for the deterioration of the texture by increasing the thickness of the polyurethane resin layer, there is a problem that the texture of the synthetic leather becomes hard and the purpose of reducing the weight cannot be achieved. Furthermore, in the conventional synthetic leather, 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 In addition, 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.
本発明者等は、上記の課題を解決すべく鋭意研究した結果、特定のウレタン系接着剤を用いることにより、目付が200g/m2未満という軽量の生布を用いても、従来と同等の外観、質感(風合い)、耐摩耗性、剥離強度を有し、しかも生布との接着時間が極めて短時間で済み、合成皮革の製造効率を大幅に向上できることを見出し、本発明を完成するに至った。As a result of earnest research to solve the above problems, 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.
即ち本発明は、
(1)生布に接着層を介してポリウレタン樹脂層を積層してなる合成皮革であって、生布は目付が200g/m2未満であるとともに、接着層が末端イソシアネート基をブロック化剤でブロックされたウレタンプレポリマーとアミン系架橋剤と熱膨張性微粒子とを含むウレタン系接着剤を加熱して熱膨張性微粒子を発泡させるとともに、ウレタンプレポリマーとアミン系架橋剤とを架橋反応させて形成された、発泡した熱膨張性微粒子を含むポリウレタン樹脂よりなることを特徴とする合成皮革、
(2)上記アミン系架橋剤と架橋反応する上記ウレタンプレポリマーは、上記加熱により脱ブロック化されたウレタンプレポリマーである上記(1)に記載の合成皮革、
(3)ウレタン系接着剤中における熱膨張性微粒子の含有量(溶剤を除く接着剤成分中の割合)は、1.5〜5重量%である上記(1)記載の合成皮革、
(4)前記アミン系架橋剤が、脂肪族ジアミン、脂肪族トリアミン、又は脂肪族ジアミンと脂肪族トリアミンの混合物である上記(1)記載の合成皮革、
を要旨とするものである。
That is, 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) The synthetic leather according to (1), wherein the urethane prepolymer that undergoes a crosslinking reaction with the amine-based crosslinking agent is a urethane prepolymer that has been deblocked by the heating .
(3) The synthetic leather according to (1), wherein the content of thermally expandable fine particles in the urethane-based adhesive (ratio in the adhesive component excluding the solvent) is 1.5 to 5% by weight,
(4) The synthetic leather according to (1), wherein the amine-based crosslinking agent is an aliphatic diamine, an aliphatic triamine, or a mixture of an aliphatic diamine and an aliphatic triamine,
Is a summary.
本発明の合成皮革は、軽量でありながら外観、質感(風合い)、耐摩耗性、剥離強度に優れ、車輌用シート、家具用シート等として利用することができる高耐久性を有する。また本発明の合成皮革は、従来の合成皮革に比して、極めて短時間で製造することができ、製造効率が高いため、製造コスト削減を図ることができる等の効果を奏する。 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, a furniture seat, and the like. In addition, 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.
図1に示す本発明の合成皮革1は、生布2とポリウレタン樹脂層である表皮層3とが、接着層4を介して積層一体化され、表皮層3の表面には表面処理層5を設けて構成されている。接着層4には、発泡した熱膨張性微粒子7が含有されている。 In the synthetic leather 1 of the present invention shown in FIG. 1, 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.
生布2としては、ポリエステル、ポリアミド、ポリアクリロニトリル等の合成繊維、綿、麻等の天然繊維、レーヨン、スフ、アセテート等の再生繊維の単独あるいはこれらの混紡繊維よりなる編布、織布、不織布等、従来より合成皮革の生布として利用されているものであれば何れも使用できるが、これらのなかから目付が200g/m2未満のものを用いる。生布2は起毛したものであっても、起毛していないものであっても良い。生布2としては、目付が190g/m2以下のものが好ましいが、特に目付が100〜180g/m2のものが好ましい。また引張強度が200N/3cm以上(JIS K6772)、引裂強度が20N以上(JIS K6772)のものが好ましい。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, but preferably has a basis weight of 190 g / m 2 or less, particularly the basis weight is preferably from 100~180g / 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.
表皮層3を構成するポリウレタン樹脂としては、従来から合成皮革の表皮層に用いられているものであればいずれも使用できる。具体的には、ポリエステル系ポリウレタン樹脂、ポリエーテル系ポリウレタン樹脂、ポリカプロラクトン系ポリウレタン樹脂、ポリエステル/ポリエーテル共重合系ポリウレタン樹脂、ポリアミノ酸/ポリウレタン共重合樹脂、ポリカーボネートジオール成分と無黄変型ジイソシアネート成分及び低分子鎖伸長剤等を反応させて得られる無黄変型ポリカーボネート系ポリウレタン樹脂などが挙げられる。また、合成皮革としての諸物性を損なわない範囲であれば、上記のポリウレタン樹脂にポリ塩化ビニル樹脂や合成ゴムなどを混合しても差し支えない。表皮層を形成する上記のポリウレタン樹脂は、ポリオール、ポリイソシアネート、架橋剤を、メチルエチルケトン、トルエン、ジメチルホルムアミドなどの有機溶媒や水等の溶媒に溶解させ、必要に応じて、着色剤、充填剤、光安定剤、紫外線吸収剤、酸化防止剤、難燃剤、架橋剤等の各種添加剤を添加したポリウレタン樹脂溶液を塗布、乾燥、架橋させて形成される。なお、ポリウレタン樹脂溶液は、1液型または2液型のどちらでも採用することができる。表皮層3は10〜60μmの厚みに形成することが好ましく、20〜50μmの厚みに形成することがより好ましい。表皮層3の表面には、絞模様等が付与されていても良い。 Any polyurethane resin can be used as the polyurethane resin constituting the skin layer 3 as long as it is conventionally used for the skin layer of synthetic leather. Specifically, 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, and Examples thereof include non-yellowing polycarbonate polyurethane resins obtained by reacting low molecular chain extenders and the like. In addition, 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 μm, more preferably 20 to 50 μm. A drawing pattern or the like may be provided on the surface of the skin layer 3.
本発明の合成皮革1は、高耐久性を更に高めるために、図2に示すように必要に応じて、表皮層3と接着層4との間に中間層6を設け、ポリウレタン樹脂層を表皮層3と中間層6とで構成しても良い。中間層6を構成するポリウレタン樹脂としては、表皮層3を構成するポリウレタン樹脂と同様のものを用いることができる。中間層6は発泡構造を有するものであっても良い。中間層6の厚みは非発泡構造の場合10〜100μm、発泡構造の場合50〜1000μmが好ましい。中間層6は、一層に限らず二層以上もうけることもできる。 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. As 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 μm for the non-foamed structure and 50 to 1000 μm for the foamed structure. The intermediate layer 6 is not limited to one layer, and two or more layers can be provided.
表皮層3や中間層6等のポリウレタン樹脂層と、生布2とを接着する接着層4は、末端イソシアネート基をブロック化剤でブロックされたウレタンプレポリマーと、アミン系架橋剤及び熱膨張性微粒子を含むウレタン系接着剤を加熱し、熱膨張性微粒子を発泡させるとともに、ウレタンプレポリマーとアミン系架橋剤とを架橋反応させてなる、発泡した熱膨張性微粒子を含むポリウレタン樹脂により形成されている。上記ウレタン系接着剤に用いられる末端イソシアネート基がブロック化剤でブロックされたウレタンプレポリマーとしては、例えば特開2006−70059号公報に記載されているような、脂肪族ジオールとホスゲン、ジアリルカーボネートもしくは環式カーボネートとの反応物である25℃で液状のポリカーボネートジオールと、有機ジイソシアネートとから得られるウレタンプレポリマーの末端イソシアネート基をブロック化剤でブロックしたものが挙げられる。上記脂肪族ジオールとしては、ポリウレタン原料として従来から使用されているものを用いることができ、例えばエチレングリコール、プロピレングリコール、ブチレングリコール等のポリオールと、コハク酸、マレイン酸、アジピン酸等のジカルボン酸との脱水縮合物であるポリエステルジオール;エチレンオキサイド、プロピレンオキサイド、ブチレンオキサイドの単独又は2種以上の開環重合物であるポリエーテルジオール等が挙げられる。 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, as 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. As the aliphatic diol, 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.
有機ジイソシアネートとしては、従来よりポリウレタン原料として公知のものを用いることができ、特に限定されないが、例えば2,4−トリレンジイソシアネート、2,6−トリレンジイソシアネート、m−フェニレンジイソシアネート、p−フェニレンジイソシアネート、4,4’−ジフェニルメタンジイソシアネート、2,4’−ジフェニルメタンジイソシアネート、3,3’−ジメチル−4,4’−ビフェニレンジイソシアネート、3,3’−ジメトキシ−4,4’−ビフェニレンジイソシアネート、3,3’−ジクロロ−4,4’−ビフェニレンジイソシアネート、1,5−ナフタレンジイソシアネート、1,5−テトラヒドロナフタレンジイソシアネート、キシリレンジイソシアネート、テトラメチルキシリレンジイソシアネート、テトラメチレンジイソシアネート、1,6−ヘキサメチレンジイソシアネート、ドデカメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、1,3−シクロヘキシレンジイソシアネート、1,4−シクロヘキシレンジイソシアネート、1,3−ビス(イソシアナトメチル)−シクロヘキサン、1,4−ビス(イソシアナトメチル)−シクロヘキサン、水素添加キシリレンジイソシアネート、イソホロンジイソシアネート、4,4’−ジシクロヘキシルメタンジイソシアネート、2−イソシアナトシクロヘキシル−2’−イソシアナトシクロヘキシルメタン、4−イソシアナトシクロヘキシル−2’−イソシアナトシクロヘキシルメタン、3,3’−ジメチル−4,4’−ジシクロヘキシルメタンジイソシアネート、2,5−ビシクロ[2,2,1]ヘプタンビス(イソシアナトメチル)、2,6−ビシクロ[2,2,1]ヘプタンビス(イソシアナトメチル)等が挙げられ、これらは単独又は2種以上を併用することができる。 As the organic diisocyanate, conventionally known polyurethane raw materials can be used, and are not particularly limited. For example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate. 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 3,3′-dimethyl-4,4′-biphenylene diisocyanate, 3,3′-dimethoxy-4,4′-biphenylene diisocyanate, 3,3 '-Dichloro-4,4'-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate Tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, 1,3-bis (isocyanatomethyl) -cyclohexane 1,4-bis (isocyanatomethyl) -cyclohexane, hydrogenated xylylene diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 2-isocyanatocyclohexyl-2′-isocyanatocyclohexylmethane, 4-isocyanato Cyclohexyl-2′-isocyanatocyclohexylmethane, 3,3′-dimethyl-4,4′-dicyclohexylmethane diisocyanate, , 5-bicyclo [2,2,1] heptanebis (isocyanatomethyl), 2,6-bicyclo [2,2,1] heptanebis (isocyanatomethyl), etc., and these may be used alone or in combination of two or more. can do.
ポリカーボネートジオールと有機ジイソシアネートとを、末端がイソシアネート基となるように反応させて得たウレタンプレポリマーの末端イソシアネート基をブロックするブロック化剤としては、ケトオキシム、ラクタム、フェノール、ピラゾール、活性メチレン化合物等が挙げられるが、イソシアネート基のブロック化が容易であるとともに、120〜180℃で脱ブロック化が可能なケトオキシム、ラクタムが好ましい。ケトオキシムとしてはメチルエチルケトオキシム、シクロヘキサノンオキシム、アセトンオキシム、3−メチル−2−ブタノンオキシム、2−ペンタノンオキシム、3−ペンタノンオキシム、4−メチル−2−ペンタノンオキシム、2−ヘプタノンオキシム、3−ヘプタノンオキシム、アセトフェノンオキシムが好ましく、ラクタムとしては、ε−カプロラクタムが好ましい。 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. Examples thereof include ketoximes and lactams that can easily block isocyanate groups and can be deblocked at 120 to 180 ° C. 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 preferable, and as a lactam, (epsilon) -caprolactam is preferable.
接着層4を構成するためのウレタン系接着剤は、上記ブロック化剤で末端イソシアネート基をブロックされたウレタンプレポリマーとともに、アミン系架橋剤及び熱膨張性微粒子を含有する。アミン系架橋剤としては脂肪族ポリアミンが用いられ、例えばエチレンジアミン、1,2−プロパンジアミン、1,3−プロピレンジアミン、1,6−ヘキサメチレンジアミン、ピペラジン、2−メチルピペラジン、2,5−ジメチルピペラジン、N,N’−ジアミノピペラジンン、イソホロンジアミン、4,4’−ジアミノシクロヘキシルメタン、3,3’−ジメチル−4,4’−ジアミノジシクロヘキシルメタン、1,2−シクロヘキサンジアミン、1,4−シクロヘキサンジアミン、アミノエチルエタノールアミン、アミノプロピルエタノールアミン、アミノヘキシルエタノールアミン、アミノエチルプロパノールアミン、アミノプロピルプロパノールアミン、アミノヘキシルプロパノールアミン、2,5−ビス(アミノメチル)ビシクロ[2,2,1]ヘプタン、2,6−ビス(アミノメチル)ビシクロ[2,2,1]ヘプタン等の脂肪族ジアミン、ジエチレントリアミン、ジプロピレントリアミン等の脂肪族トリアミン、トリエチレンテトラミン、ヒドラジン類、酸ヒドラジド類等が挙げられる。これらのなかでも、4,4’−ジアミノシクロヘキシルメタン、3,3’−ジメチル−4,4’−ジアミノジシクロヘキシルメタン、イソホロンジアミン、2,5−ビス(アミノメチル)ビシクロ[2,2,1]ヘプタン、2,6−ビス(アミノメチル)ビシクロ[2,2,1]ヘプタン等の脂肪族ジアミン、ジエチレントリアミン、ジプロピレントリアミン等の脂肪族トリアミン、トリエチレンテトラミンが好ましいが、特に脂肪族ジアミン、脂肪族トリアミンやこれらの混合物が好ましい。イソシアネート基をブロックされたウレタンプレポリマーのブロックされたイソシアネート基と、アミン系架橋剤との割合はモル比で、ブロックされたイソシアネート基:アミン系架橋剤=1.35:1.00〜0.95:1.00が好ましく、1.25:1.00〜1.00:1.00が特に好ましい。 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) bis (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. Among these, 4,4′-diaminocyclohexylmethane, 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane, isophoronediamine, 2,5-bis (aminomethyl) bicyclo [2,2,1] Preferred are 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. The ratio between the blocked isocyanate group of the urethane prepolymer blocked with the isocyanate group and the amine crosslinking agent is a molar ratio, blocked isocyanate group: amine crosslinking agent = 1.35: 1.00 to 0.00. 95: 1.00 is preferable, and 1.25: 1.00 to 1.00: 1.00 is particularly preferable.
ウレタン系接着剤中に含有される熱膨張性微粒子としては、加熱により気化する液状の低沸点炭化水素を、アクリロニトリル系樹脂等の熱可塑性樹脂膜で包んだマイクロカプセルが挙げられる。ウレタン系接着剤における熱膨張性微粒子の添加量(溶剤を除く接着剤成分中の割合)は、通常、0.5〜10重量%であるが、より好ましくは1.5〜5重量%であり、マイクロカプセルの粒径、熱膨張性微粒子の加熱膨張率の違い等により調整される。例えば粒径が30μm程度で熱膨張率が7倍程度のものでは、0.8〜7重量%が好ましいが、1.5重量%未満では十分な製品厚みが得られにくく、5重量%を超えると十分な剥離強度が得られ難くなるため、添加量は1.5〜5重量%がより好ましい。熱膨張性微粒子は、最大膨張温度が120〜180℃のものが好ましい。最大膨張温度が120℃未満であると、ウレタン系接着剤を塗布、乾燥する際の予備乾燥時の熱で発泡してしまう虞があり、また180℃を超える場合には、加熱発泡させる際の熱でウレタン樹脂や生布に収縮等のダメージを与える虞がある。熱膨張性微粒子としては、例えば松本油脂製薬株式会社製のマツモトマイクロスフェアー(商品名)を用いることができ、最大膨張温度が120〜180℃である熱膨張性微粒子としては、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(いずれもマツモトマイクロスフィアーの商品番号)等が挙げられる。 Examples of the heat-expandable fine particles contained in the urethane-based adhesive 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 (ratio in the adhesive component excluding the solvent) 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. For example, when the particle size is about 30 μm and the coefficient of thermal expansion is about 7 times, 0.8 to 7% by weight is preferable, but if it is less than 1.5% by weight, it is difficult to obtain a sufficient product thickness and exceeds 5% by weight. Therefore, it is difficult to obtain sufficient peel strength, so the addition amount is more preferably 1.5 to 5% by weight. 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. As the thermally expandable fine particles, for example, Matsumoto Microsphere (trade name) manufactured by Matsumoto Yushi Seiyaku Co., Ltd. can be used. As the 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).
表面処理層5は、表皮層3の表面艶出し等の目的で必要に応じて表皮層3の表面に設けられる。表面処理層は、例えばポリウレタン樹脂、シリコン、有機系フィラー等を有機溶媒や水に分散させた塗工液を表皮層3の表面にコーティングすることにより設けることができる。 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.
次に、上記、図1に示した本発明の合成皮革を製造する方法を、図3に基づき説明する。図3(a)に示すように、まず離型紙等の離型性担体8上に表皮層を構成するためのポリウレタン樹脂溶液を塗布し、塗布したポリウレタン樹脂溶液中の溶媒を蒸発乾燥させるとともに、樹脂の架橋反応を生じさせて表皮層3を形成する。ポリウレタン樹脂溶液の塗布には、ナイフコーター、コンマドクター、ロールコーター、リバースロールコーター、ロータリースクリーンコーター、グラビアコーター、その他適宜の手段が採用される。離型紙等の離型性担体8は、ポリウレタン樹脂溶液が塗布される側の表面が平滑なものであっても、絞模様等が付されたものであっても良い。絞模様等が付された離型性担体8を使用すると、離型性担体8の模様が合成皮革1の表皮層3表面に転写され、絞模様等による意匠が現出した合成皮革を得ることができる。 Next, the method for producing the synthetic leather of the present invention shown in FIG. 1 will be described with reference to FIG. As shown in FIG. 3 (a), first, 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. For the application of the polyurethane resin solution, 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. When the releasable carrier 8 with a drawn pattern or the like is used, 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.
次いで図3(b)に示すように、表皮層3の上に接着層形成用の接着剤を塗布する。接着剤の塗布には、表皮層形成用のポリウレタン樹脂溶液の塗布と同様の方法を採用することができる。接着剤の塗布量は、目的とする合成皮革の風合い等によっても異なるが、塗布時の厚み(wet時)が100〜300μmとなるように塗布することが好ましい。塗布した接着剤を、末端イソシアネート基をブロック化剤でブロックされたウレタンプレポリマーにおけるブロック化剤が解離しない温度で乾燥させ、好ましくは120度以下で乾燥させて接着剤層4aを形成する。 Next, as shown in FIG. 3B, an adhesive for forming an adhesive layer is applied on the skin layer 3. For the application of the adhesive, 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 at the time of application (wet time) is 100 to 300 μm. 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.
次に、図3(c)に示すように接着剤層4aに生布2を積層した後、加熱して接着剤層4a中の熱膨張性微粒子を発泡させるとともに、イソシアネート基がブロックされたウレタンプレポリマーの脱ブロック化を生じさせてウレタンプレポリマーとアミン系架橋剤とを架橋させ、図3(d)に示すように、発泡した熱膨張性微粒子7を含む接着層4を形成する。生布2を積層した後の加熱温度は、ウレタンプレポリマーの末端イソシアネート基をブロックするブロック化剤の種類、熱膨張性微粒子の種類等によっても異なるが、最大膨張温度が120〜180℃の熱膨張性微粒子を選択し、かつウレタンプレポリマーの脱ブロック化が120〜180℃で生じてウレタンプレポリマーとアミン系架橋剤との反応が生じるようなブロック化されたウレタンプレポリマーを選択し、120〜180℃で加熱することが好ましい。加熱時間は1〜5分が好ましい。 Next, as shown in FIG. 3 (c), after the green cloth 2 is laminated on 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 the raw cloth 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. Select expandable fine particles and select a urethane prepolymer that is blocked so that the deblocking of the urethane prepolymer occurs at 120 to 180 ° C. and the reaction between the urethane prepolymer and the amine-based crosslinking agent occurs. Heating at ~ 180 ° C is preferred. The heating time is preferably 1 to 5 minutes.
しかる後、離型性担体8を剥離し、必要に応じて表皮層3表面に表面処理層5を設けることにより、図1に示す合成皮革1を得ることができる。表面処理層5は、グラビアコーター、リバースロールコーター、スプレーコーター等の方法で形成することができる。尚、中間層6を有する図2に示す合成皮革1の場合も、表皮層3を形成した後、接着剤層4aを形成する前に、表皮層3と同様の方法で中間層6を形成する工程を含む以外は、図3に示した方法と同様にして製造することができる。 Thereafter, the releasable carrier 8 is peeled off, and the surface treatment layer 5 is provided on the surface of the skin layer 3 as necessary, whereby the synthetic leather 1 shown in FIG. 1 can be obtained. The surface treatment layer 5 can be formed by a method such as a gravure coater, a reverse roll coater, or a spray coater. In the case of the synthetic leather 1 shown in FIG. 2 having the intermediate layer 6, 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.
以下、具体的な実施例を挙げて、本発明を更に詳細に説明する。 Hereinafter, the present invention will be described in more detail with reference to specific examples.
実施例1
(表皮層)
1液型の無黄変ポリカーボネート系ポリウレタン樹脂(DIC株式会社製:商品名“クリスボンNY328FTR”、固形分20重量%)100重量部に対し、溶剤としてジメチルホルムアミドとメチルエチルケトンを各20重量部、黒顔料(DIC株式会社製:商品名“ダイラックL−1770”)20重量部を添加した後、混合攪拌し、離型紙(大日本印刷株式会社製:商品名“DE−73”)の凹凸絞面に、乾燥後の厚みが25±5μmとなるように塗布し、100℃のオーブン中で3分間乾燥させ、厚さ30μmの表皮層を形成した。Example 1
(Skin layer)
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 “Dilack L-1770”) After adding 20 parts by weight, the mixture is stirred and mixed on 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 μm, and dried in an oven at 100 ° C. for 3 minutes to form a skin layer having a thickness of 30 μm.
(接着剤層)
末端のイソシアネート基がケトオキシムでブロックされたウレタンプレポリマー(DIC株式会社製:商品名“ウレハイパーSU−009”)100重量部に対し、架橋剤として脂肪族ジアミン(BASF社製:商品名“ラロミンC260”)5重量部、熱膨張性微粒子として最大膨張温度160〜180℃、平均粒径30μm、膨張率約7倍の熱膨張性マイクロカプセル(松本油脂製薬株式会社製:商品名“マツモトマイクロスフィアーFN−100MD”)1重量部、溶剤としてジメチルホルムアミド15重量部を配合した接着剤を、表皮層の上に170μm(wet時)となるように塗布し、120℃のオーブンで2分間乾燥し、熱膨張性マイクロカプセルが未発泡状態の接着剤層を形成した。(Adhesive layer)
Aliphatic diamine (manufactured by BASF: trade name “Lalomin C260”) as a crosslinking agent with respect to 100 parts by weight of urethane prepolymer whose terminal isocyanate group is blocked with ketoxime (manufactured by DIC Corporation: trade name “Urehyper SU-009”). ”) 5 parts by weight, thermal expansion microcapsules having a maximum expansion temperature of 160 to 180 ° C., an average particle size of 30 μm, 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, an adhesive containing 15 parts by weight of dimethylformamide as a solvent was applied onto the skin layer so as to have a thickness of 170 µm (when wet), and dried in an oven at 120 ° C for 2 minutes. A thermally expandable microcapsule formed an unfoamed adhesive layer.
(生布との貼り合わせ)
接着剤層の上に、生布として厚み550μm、目付120g/m2の片面メリヤス生地を積層して貼り合わせた後、180℃のオーブンで2分間加熱して熱膨張性マイクロカプセルを発泡させるとともに、ウレタンプレポリマーと架橋剤とが反応硬化した接着層を介して表皮層とメリヤス生地とを接合一体化した。その後、離型紙を剥離して合成皮革を得た。得られた合成皮革の物性を表1に示す。なお、発泡した熱膨張性マイクロカプセルを含むポリウレタン樹脂よりなる接着層の厚みは170μmであった。(Lamination with raw cloth)
On the adhesive layer, a single-sided knitted fabric with a thickness of 550 μm 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 μm.
実施例2
接着剤中の熱膨張性マイクロカプセルを3重量部とし、表皮層の上に170μm(wet時)となるように接着剤を塗布した他は、実施例1と同様にして合成皮革を得た。得られた合成皮革の物性を表1に併せて示す。またこの合成皮革断面の電子顕微鏡写真(日本電子株式会社製の走査型電子顕微鏡:JSM6700F、倍率30倍)を図4に示す。なお、発泡した熱膨張性マイクロカプセルを含むポリウレタン樹脂よりなる接着層の厚みは320μmであった。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 μm (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 μm.
実施例3
接着剤中の熱膨張性マイクロカプセルを5重量部とし、表皮層の上に170μm(wet時)となるように接着剤を塗布した他は、実施例1と同様にして合成皮革を得た。得られた合成皮革の物性を表1に併せて示す。なお、発泡した熱膨張性マイクロカプセルを含むポリウレタン樹脂よりなる接着層の厚みは470μmであった。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 μm (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 μm.
実施例4
接着剤中の熱膨張性マイクロカプセルを7重量部とし、表皮層の上に170μm(wet時)となるように接着剤を塗布した他は、実施例1と同様にして合成皮革を得た。得られた合成皮革の物性を表1に併せて示す。なお、発泡した熱膨張性マイクロカプセルを含むポリウレタン樹脂よりなる接着層の厚みは720μmであった。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 μm (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 μm.
実施例5
熱膨張性マイクロカプセルを3重量部とし、更に架橋剤として脂肪族トリアミン(BASF社製:商品名“Baxxodur EC310”)5.54重量部とした接着剤を用いて表皮層の上に170μm(wet時)となるように塗布した他は、実施例1と同様にして合成皮革を得た。得られた合成皮革の物性を表1に併せて示す。なお、発泡した熱膨張性マイクロカプセルを含むポリウレタン樹脂よりなる接着層の厚みは320μmであった。Example 5
170 μm (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 μm.
実施例6
熱膨張性マイクロカプセルを3重量部とし、更に架橋剤として脂肪族ジアミン(BASF社製:商品名“ラロミンC260”)2.25重量部及び脂肪族トリアミン(BASF社製:商品名“Baxxodur EC310”)2.77重量部とした接着剤を用いて表皮層の上に170μm(wet時)となるように塗布した他は、実施例1と同様にして合成皮革を得た。得られた合成皮革の物性を表1に併せて示す。なお、発泡した熱膨張性マイクロカプセルを含むポリウレタン樹脂よりなる接着層の厚みは320μmであった。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 μm (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 μm.
比較例1
熱膨張性マイクロカプセルを含まない接着剤を用い、表皮層の上に170μm(wet時)となるように接着剤を塗布した他は、実施例1と同様にして合成皮革を得た。得られた合成皮革の物性を表1に併せて示す。なお、接着層の厚みは90μmであった。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 μm (when wet). Table 1 shows the physical properties of the obtained synthetic leather. The thickness of the adhesive layer was 90 μm.
比較例2
熱膨張性マイクロカプセル1重量部に代えて、発泡剤としてアゾジカルボンアミド粉末(永和化成株式会社製:商品名“ビニホールDW#6”)4重量部、及び発泡助剤として尿素粉末(永和化成株式会社製:商品名“セルペースト101”)4重量部とした接着剤を用い、表皮層の上に170μm(wet時)となるように接着剤を塗布した他は、実施例1と同様にして合成皮革を得た。得られた合成皮革の物性を表1に併せて示す。またこの合成皮革の電子顕微鏡写真(30倍)を図5に示す。なお、接着層の厚みは160μmであった。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 μm (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 μm.
比較例3
熱膨張性マイクロカプセル1重量部に代えて、発泡剤として4,4−オキシビス(ベンゼンスルホニルヒドラジド)粉末(永和化成株式会社製:商品名“ネオセルボンN#5000”)5重量部とした接着剤を用い、表皮層の上に170μm(wet時)となるように塗布した他は、実施例1と同様にして合成皮革を得た。得られた合成皮革の物性を表1に併せて示す。またこの合成皮革の電子顕微鏡写真(30倍)を図6に示す。なお、接着層の厚みは270μmであった。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 Chemical 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 μm (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 μm.
比較例4
実施例1の接着剤に代えて、無黄変ポリウレタン樹脂(DIC株式会社製:商品名“クリスボンTA205FT”)100重量部に対し、架橋剤としてトリレンジイソシアネートのトリメチロールプロパン付加生成物(日本ポリウレタン工業株式会社製:商品名“コロネートL”)15重量部、実施例1と同様の熱膨張性マイクロカプセル(マツモトマイクロスフィアーFN−100MD)3重量部、溶剤としてジメチルホルムアミドとメチルエチルケトンを各20重量部、アミン系触媒(DIC株式会社製:商品名“アクセルHM”)5重量部を添加混合した接着剤を用い、表皮層の上に170μm(wet時)となるように塗布した他は、実施例1と同様にして合成皮革を製造した。但し、接着剤層に生布を貼り付けた後、生布と表皮層とが確実に一体化されるまでに、50℃で48時間の養生が必要であった。得られた合成皮革の物性を表1に併せて示す。またこの合成皮革の電子顕微鏡写真(30倍)を図7に示す。なお、発泡した熱膨張性マイクロカプセルを含むポリウレタン樹脂よりなる接着層の厚みは320μmであった。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 μm (wet) using an adhesive mixed with 5 parts by weight of an amine catalyst (manufactured by DIC Corporation: trade name “Accel HM”). 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 μm.
※1
接着層発泡状態は、得られた合成皮革の断面(任意に選んだ5箇所)を走査型電子顕微鏡(日本電子株式会社製:JSM6700F、倍率150倍、横800μm×縦600μmのサイズ)で撮影し、接着層中の加熱膨張した各マイクロカプセルのセル大きさ(一番長い辺)を測定し、セル大きさの平均を算出した。そして、セル大きさの平均と、セル気泡の状態から、以下の基準で評価した。
○:セル大きさの平均が70〜150μmで、セル気泡の状態が独立気泡である。
×:セル大きさの平均が70〜150μmの範囲から外れるか、セル気泡の状態が独立気泡ではない。* 1
The adhesive layer foamed state was taken with a scanning electron microscope (manufactured by JEOL Ltd .: JSM6700F, magnification 150 times, width 800 μm × length 600 μm) 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 | standards from the average of cell size and the state of a cell bubble.
(Circle): The average of cell size is 70-150 micrometers, and the state of a cell bubble is a closed cell.
X: The average cell size is out of the range of 70 to 150 μm, or the cell bubble state is not a closed cell.
※2
合成皮革の外観は、合成皮革表面を指で摘んだ際に発生するシワの状態を目視により観察し、以下の基準で評価した。
○:本皮に近いシワを有している。
×:本皮とは異なるシワ(浮きシワ)を有している。* 2
The appearance of the synthetic leather was evaluated based on the following criteria by visually observing the state of wrinkles generated when the surface of the synthetic leather was picked with a finger.
○: Wrinkles close to real leather.
X: It has wrinkles (floating wrinkles) different from the main skin.
※3
合成皮革の質感は、合成皮革表面を触ったときの柔らかさとボリューム感から、以下の基準で評価した。
○:柔らかく、ボリューム感がある。
△:やや硬いか、ボリューム感がやや劣る。
×:硬いか、ボリューム感が劣る。* 3
The texture of the synthetic leather was evaluated according to the following criteria from the softness and volume when touching the surface of the synthetic leather.
○: Soft and voluminous.
Δ: Slightly hard or slightly inferior in volume.
X: Hard or inferior in volume.
※4
耐摩耗性は、JIS K6902に準拠してテーパー摩耗試験を行い、合成皮革の表皮層が摩耗して下層が露出するまでの摩耗輪の回転数を測定し、以下の基準で評価した。
○:下層が露出するまでの摩耗輪の回転数が5000回以上。
△:下層が露出するまでの摩耗輪の回転数が2000回以上、5000回未満。
×:下層が露出するまでの摩耗輪の回転数が2000回未満。* 4
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.
(Triangle | delta): The rotation speed of the wear ring until a lower layer is exposed is 2000 times or more and less than 5000 times.
X: The number of rotations of the wear wheel until the lower layer is exposed is less than 2000 times.
※5
剥離強度は、JIS K6772剥離試験の方法に基いて剥離強度を測定し、以下の基準で評価した。
○:30N/3cm以上。
△:20N/3cm以上、30N/3cm未満。
×:20N/3cm未満。* 5
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.
Δ: 20 N / 3 cm or more and less than 30 N / 3 cm.
X: Less than 20 N / 3 cm.
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PCT/JP2014/002769 WO2014192283A1 (en) | 2013-05-27 | 2014-05-26 | Synthetic leather |
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EP3327054B1 (en) | 2015-09-02 | 2020-11-11 | DIC Corporation | Moisture curable hot melt urethane composition, method for producing cured foam of same, synthetic leather and method for producing synthetic leather |
CN105365838B (en) * | 2015-11-24 | 2018-04-24 | 中车唐山机车车辆有限公司 | Seat panel and seat |
TWI623443B (en) * | 2016-09-20 | 2018-05-11 | Huang Min San | Graphical thermal transfer structure |
CN112409562A (en) * | 2020-11-21 | 2021-02-26 | 华大化学(安徽)有限公司 | Polyurethane resin special for soft basketball leather and preparation method thereof |
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JPS60199087A (en) * | 1984-03-22 | 1985-10-08 | Seiko Kasei Kk | Adhesive for synthetic leather |
JPS6128079A (en) * | 1984-07-11 | 1986-02-07 | Komatsu Seiren Kk | Manufacture of synthetic leather |
JPH0351354Y2 (en) * | 1984-11-01 | 1991-11-01 | ||
JPH086261B2 (en) * | 1987-03-31 | 1996-01-24 | バンドー化学株式会社 | Synthetic leather manufacturing method |
JP4190604B2 (en) * | 1997-09-24 | 2008-12-03 | 旭化成せんい株式会社 | Synthetic leather |
JP4369213B2 (en) * | 2003-12-08 | 2009-11-18 | 帝人コードレ株式会社 | Method for producing leather-like sheet |
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