KR100255339B1 - An artificial leather without organic and solvent and manufacturing process and apparatus thereof - Google Patents

An artificial leather without organic and solvent and manufacturing process and apparatus thereof Download PDF

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Publication number
KR100255339B1
KR100255339B1 KR1019980004230A KR19980004230A KR100255339B1 KR 100255339 B1 KR100255339 B1 KR 100255339B1 KR 1019980004230 A KR1019980004230 A KR 1019980004230A KR 19980004230 A KR19980004230 A KR 19980004230A KR 100255339 B1 KR100255339 B1 KR 100255339B1
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South Korea
Prior art keywords
polyol
solvent
synthetic leather
coating
mixing
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KR1019980004230A
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Korean (ko)
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KR19990069779A (en
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최상태
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이희덕
덕성화학공업주식회사
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Priority to KR1019980004230A priority Critical patent/KR100255339B1/en
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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
    • D06N3/12—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
    • D06N3/0086—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique
    • D06N3/0088—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by directly applying the resin
    • 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
    • D06N2211/28—Artificial leather
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/904—Artificial leather

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  • 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)
  • Polyurethanes Or Polyureas (AREA)

Abstract

PURPOSE: A process for preparing the titled synthetic leather by preparing a polyol-containing mixture and a diisocyanate prepolymer, mixing the same and instantly coating before the reaction of polyurethane is provided, which generates no environmental pollution caused by organic solvents and can produce a product close to natural leather. CONSTITUTION: This process comprises the steps of: preparing a mixture of 40 to 65 parts by weight of a polyol-containing mixture and 35 to 60 parts by weight of a diisocyanate prepolymer; mixing the same in a mole ratio of a chemical equivalent and agitating; and instantly coating on released paper or base material in a liquid state before the formation of strong polyurethane bond. The obtained product has excellent physical properties and touch feeling as compared to conventional synthetic leathers.

Description

무용제(無溶劑) 폴리우레탄 합성피혁과 그 제조방법Solvent-free polyurethane synthetic leather and its manufacturing method

본 발명은 제조공정상 유기용제를 사용하지 않는 무용제(無溶劑) 폴리우레탄(PU) 합성퍼혁과 그 제조방법에 관한 것으로서, 보다 상세하게는 폴리올을 함유 혼합물(원료 A)과 디이소시아네이트 프레폴리머(원료 B)를 각각 만든 후 이들 원료를 고속으로 혼합·교반시키고 폴리우레탄 형성 반응이 시작되기 전에 순간적으로 코팅시켜 폴리우레탄(PU) 합성피혁을 만드는 것을 특징으로 한다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solvent-free polyurethane (PU) synthetic fur and a method for producing the same, which do not use an organic solvent in the manufacturing process. More specifically, a mixture containing polyol (raw material A) and a diisocyanate prepolymer (raw material) After making each B), these raw materials are mixed and stirred at a high speed, and are coated instantaneously before the polyurethane formation reaction is started to make polyurethane (PU) synthetic leather.

폴리우레탄(polyurethane)은 화학구조적으로 우레탄(urethane) 결합(-NHCOO-)을 다수 가지고 있는 고분자화합물의 총칭이며, 우레탄 결합은 다음의 반응식 1과 같이 반응성이 센-NCO기(isocyanate)와 활성수소를 가진 화합물의 -OH기와의 부가반응으로 형성된다.Polyurethane is a generic term for high molecular compounds having a large number of urethane bonds (-NHCOO-) in chemical structure, and urethane bonds are highly reactive with isocyanate and active hydrogen as shown in Scheme 1 below. It is formed by the addition reaction of the compound with -OH group.

대부분의 폴리우레탄은 디이소시아네이트(Diisocyanate), 고분자 폴리올(Polymeric polyol) 및 쇄연장제(Chain extender)의 3 가지 기본출발물질에 의해 만들어지는데, 디이소시아네이트와 고분자 폴리올이 반응하여 연질 세그먼트(segment)를 이루고 디이소시아네이트와 쇄연장제(Chain extender)가 반응하여 경질 세그먼트를 이루어 연질과 경질 세그먼트가 한 분자내에 존재하게 된다.Most polyurethanes are made of three basic starting materials: diisocyanate, polymer polyol, and chain extender. The diisocyanate and polymer polyol react to form a soft segment. And the diisocyanate and chain extender react to form a hard segment so that the soft and hard segments exist in one molecule.

지금까지의 코팅 직물용 폴리우레탄수지는 대부분 용액형으로 보통 1액형수지(또는 스킨), 2액형수지(또는 접착제) 및 가교제로 분류된다. 1액형과 2액형수지는 디이소시아네이트와 거의 같은 몰수의 고분자 디올과 쇄연장제의 중부가반응에 의해 얻어진 선상(linear)의 고분자량체로서 DMF(N,N - Dimethyl formide), MEK(MeHyl ethyl ketone), TOL(Toluene) 등의 유기용제를 주체로 한 “폴리우레탄-유기용제용액”이다. 이하, 본 발명에서 용액형 폴리우레탄수지란 “폴리우레탄-유기용제용액”을 의미한다.Until now, polyurethane resins for coating fabrics are mostly in solution form and are usually classified into one-component resins (or skins), two-component resins (or adhesives), and crosslinking agents. One-component and two-component resins are linear high molecular weights obtained by the polyaddition reaction of polymer diols and chain extenders with about the same moles of diisocyanates as DMF (N, N-Dimethyl formide) and MEK (MeHyl ethyl ketone). ) And "Polyurethane-Organic Solvent Solution" mainly composed of organic solvents such as TOL (Toluene). Hereinafter, in the present invention, the solution type polyurethane resin means “polyurethane-organic solvent solution”.

1액형수지(스킨)는 용제를 제거하면 막을 형성하여 그 자체로서 우수한 피막물성을 나타내게 되는데, 이때 가열건조에 의해 용제를 증발시켜 막을 형성하는 것을 “건식수지”라 하며 수중에 침지하여 용제를 치환시킴으로써 막을 형성하는 것을 “습식수지”라 한다. 습식수지의 용제로는 폴리우레탄에 대한 용해력이 크고 물과 잘섞이는 성질의 DMF가 사용된다.When one-component resin (skin) removes the solvent, it forms a film and shows excellent film properties by itself. At this time, the film is formed by evaporating the solvent by heating and drying to form a film. Submerged in water, the solvent is substituted. By forming a film by means of a "wet resin". As a solvent for wet resins, DMF, which is highly soluble in polyurethane and well mixed with water, is used.

2액형수지(접착제)는 용제를 제거해도 단독으로는 피막을 형성하지 않으며, 가교제를 첨가하여 망상(crosslingked)구조를 만들어야 피막을 형성한다. 일반적으로 2액형수지가 완전히 경화(또는 가교)되려면 50∼60℃에서 약 24∼48 시간이 걸린다.The two-component resin (adhesive) does not form a film alone even if the solvent is removed. A crosslinking agent must be added to form a crosslingked structure to form a film. Generally, it takes about 24 to 48 hours at 50 to 60 ° C for the two-component resin to fully cure (or crosslink).

가교제는 대부분 트리올(Triol)인 TMP(Trimethyl propane) 1 mole에 TDI(2,4,-Toluene diisocyanate)나 IPDI(Isophorone diisocyanate), HDI(Hexamethylene diisocyanate) 3 mole을 부가중합시킨 것으로서 3개의 -NCO기를 가지고 있으므로 말단이 -OH기인 2액형수지와 반응하면 망상구조를 형성하게 된다.The crosslinking agent is the addition of 3 moles of trimethyl propane (TMP), 3 moles of TDI (2,4, -Toluene diisocyanate), IPDI (Isophorone diisocyanate), and HDI (Hexamethylene diisocyanate). Since it has a group, it reacts with a two-component resin whose terminal is -OH to form a network structure.

종래 폴리우레탄 합성피혁의 제조방법은 대부분 용액형 폴리우레탄수지(“폴리우레탄-유기용제 용액”)를 사용하는 공정으로서, 통상 용액형 폴리우레탄수지를 직물, 편물, 부직포 등의 기재위에 또는 이형지위에 도포하여 합성피혁을 제조하는 것이었다. 이러한 종래의 합성피혁 제조방법은 전식법과 습식법로 분류된다.Conventionally, a method of manufacturing a polyurethane synthetic leather is a process using mostly a solution-type polyurethane resin (“polyurethane-organic solvent solution”), usually a solution-type polyurethane resin on a base material such as woven fabric, knitted fabric, nonwoven fabric, or release paper It was applied to produce synthetic leather. Such conventional synthetic leather manufacturing methods are classified into an electrostatic method and a wet method.

건식법은 제1도에 나타난 바와 같이, 이형지에 1액형 폴리우레탄수지를 도포한 후 열실에서 건조하여 용제를 증발시킴으로써 막을 형성하고, 형성된 막위에 2액형 폴리우레탄수지를 도포한 후 백킹소재로 직물, 편물, 부직포 등을 접착시켜 건조한 다음 보온실에서 하루 동안 가교시켜 합성피혁을 제조하는 방법이다.In the dry method, as shown in FIG. 1, a one-component polyurethane resin is applied to a release paper, and then dried in a heat chamber to form a film by evaporating the solvent, and a two-component polyurethane resin is coated on the formed film and then fabricated as a backing material. It is a method of manufacturing synthetic leather by bonding knitted fabrics, nonwoven fabrics and the like and then crosslinking in a warm room for one day.

또한, 습식법은 제2도에 나타난 바와 같이, 1액형 폴리우레탄수지를 백킹소재인 직물, 편물, 부직포 등에 도포한 후 물속을 통과시켜 유기용제를 추출함으로써 폴리우레탄수지가 응고되어 고형체인 막을 형성하고, 이를 열실에서 건조하여 합성피혁을 얻게되는 방법이며, 이때 유기용제가 빠져나온 부분에는 미세한 셀의 미세다공이 형성되게 된다.In addition, in the wet method, as shown in FIG. 2, the one-component polyurethane resin is applied to a backing material such as woven fabric, knitted fabric or nonwoven fabric, and then passed through the water to extract the organic solvent to solidify the polyurethane resin to form a solid film. And, it is a method of obtaining a synthetic leather by drying in a heat chamber, in which the micropore of the fine cell is formed in the portion where the organic solvent escaped.

상술한 바와 같이, 종래의 PU 합성피혁의 제조방법은 그 공정상 필수적으로 유기용제가 사용되고 있으나 이러한 유기용제의 사용은 전세계적으로 환경공해문제를 일으키고 있으며, 또한 유기용제는 발암성물질로 알려져 있어 최종제품인 합성피혁에 잔류하게 될 경우 인체에 유해하다는 문제점이 있었다.As described above, in the conventional method for manufacturing PU synthetic leather, organic solvents are essentially used in the process, but the use of such organic solvents causes environmental pollution problems worldwide, and organic solvents are known as carcinogenic substances. There was a problem in that it is harmful to the human body if it remains in the final product synthetic leather.

따라서 무용제 PU 합성피혁의 제조에 관해 전세계적으로 연구가 진행되고 있으나, 적당한 원료제조의 어려움, 원료의 빠른 경화로 인한 제조공정상의 어려움, 제품의 불균일성, 종래 합성피혁과 비교시 제품의 질 저하 등의 문제로 실용화되지 못하고 있는 실정이었다.Therefore, although research is being conducted worldwide on the manufacture of solvent-free PU synthetic leather, it is difficult to manufacture a suitable raw material, difficulty in manufacturing process due to rapid curing of the raw material, product non-uniformity, deterioration of product quality compared to conventional synthetic leather, etc. The situation was not practical because of the problem.

이에 본 발명은 제조공정상 유기용제를 사용하지 않는 무용제 PU 합성피혁과 그 제조방법을 제공하고자 한다. 또한 본 발명은 유기용제를 사용하는 종래의 합성피혁과 비교할 때 물성, 질감, 감촉면에서 우수하고 보다 천연피혁에 가까운 무용제 PU 합성피혁과 그 제조방법을 제공하고자 한다. 이를 위해 본 발명에서는 유기용제를 사용하지 않고 원료인 폴리머 혼합물(원료 A)과 디이소시아네이트 프레폴리머(원료 B)를 만든 후, 유기용제가 없는 조건하에서 이들 원료를 직접 반응시켜 강력한 폴리우레탄결함을 형성시키며 원료의 혼합·교반 후 반응이 시작되기전 액체상태일 때 순간적으로 코팅하여 합성피혁을 만든다.Accordingly, the present invention is to provide a solvent-free PU synthetic leather that does not use an organic solvent in the manufacturing process and its manufacturing method. In addition, the present invention is to provide a non-solvent PU synthetic leather and its manufacturing method which is excellent in physical properties, texture, texture and more close to natural leather compared to conventional synthetic leather using an organic solvent. To this end, the present invention forms a polymer mixture (raw material A) and a diisocyanate prepolymer (raw material B) as raw materials without using an organic solvent, and then reacts these raw materials directly under an organic solvent-free condition to form a strong polyurethane defect. After mixing and stirring the raw materials, the coating is instantaneously made in the liquid state before the reaction starts to make synthetic leather.

또한, 본 발명은 원료를 순간적으로 고속 혼합·교반·코팅할 수 있는 특정한 장치를 사용함으로써 작업공정이 단순화된 무용제 PU 합성피혁의 제조방법을 제공하고자 한다.In addition, the present invention is to provide a method for producing a solvent-free PU synthetic leather with a simplified work process by using a specific device capable of instantaneous high-speed mixing, stirring, and coating of raw materials.

제1도는 종래의 건식법에 따른 PU 합성피혁의 제조공정을 나타낸 공정도.1 is a process chart showing a manufacturing process of PU synthetic leather according to the conventional dry method.

제2도는 종래의 습식법에 따른 PU 합성피혁의 제조공정을 나타낸 공정도.Figure 2 is a process chart showing the manufacturing process of PU synthetic leather according to the conventional wet method.

제3도는 본 발명에 따른 무용제(無溶劑) PU 합성피혁의 제조방법에 따른 코팅공정을 나타낸 공정도.3 is a process chart showing a coating process according to the manufacturing method of a solvent-free PU synthetic leather according to the present invention.

제4(a)도는 롤 코터를 이용한 코팅공정의 예시도.Figure 4 (a) is an illustration of a coating process using a roll coater.

제4(b)도는 본 발명에 따른 변형된 롤 코터를 이용한 코팅공정의 예시도.Figure 4 (b) is an illustration of a coating process using a modified roll coater according to the present invention.

제4(c)도는 본 발명에 따른 이형지 코터를 이용한 코팅공정의 예시도.Figure 4 (c) is an illustration of a coating process using a release paper coater according to the present invention.

제4(d)도는 본 발명에 따른 벨트형 이형지 코터를 이용한 코팅공정의 예시도.Figure 4 (d) is an illustration of a coating process using a belt type release paper coater according to the present invention.

제5도는 본 발명에 따른 혼합장치의 블록도.5 is a block diagram of a mixing apparatus according to the present invention.

제6도는 본 발명에 따른 혼합장치의 혼합챔버 부분을 나타낸 정면도.6 is a front view showing the mixing chamber portion of the mixing device according to the present invention.

제7(a)도는 본 발명에 따른 혼합장치의 토출구 부분을 나타낸 정면도.7 (a) is a front view showing the discharge port portion of the mixing apparatus according to the present invention.

제7(b)도는 본 발명에 따른 혼합장치의 토출구 부분을 나타낸 측면도이다.7 (b) is a side view showing the discharge port portion of the mixing apparatus according to the present invention.

* 도면의 주요부분에 대한 부호의 설명* Explanation of symbols for main parts of the drawings

11 : 코터 12a : 1액형 폴리우레탄수지(스킨)11: coater 12a: one-component polyurethane resin (skin)

12b : 2액형 폴리우레탄수지(접착제)12b: 2-component polyurethane resin (adhesive)

13 : 본 발명에 따른 원료 혼합액(원료A + 원료B)13: raw material mixture according to the present invention (raw material A + raw material B)

14 : 이형지 15 : 기재14: release paper 15: substrate

16 : 열실 17 : 폴리우레탄 성형 막16: heat seal 17: polyurethane molding film

18 : 응고조(DMF 수용액) 19 : 터닝롤18: coagulation tank (DMF aqueous solution) 19: turning roll

20 : 수세조(물) 21 : 혼합장치20: washing tank (water) 21: mixing device

22 : 롤 코터 23a : 변형된 롤 코터22: roll coater 23a: deformed roll coater

23b : 이형지 코터 23c : 벨트형 이형지 코터23b: Release paper coater 23c: Belt type release paper coater

24 : 혼합 임펠러 25 : 토출구24: mixed impeller 25: discharge port

26 : 혼합원료를 퍼지게 하는 주입구 27 : 혼합 챔버26: inlet for spreading the mixed material 27: mixing chamber

28 : 탱크 A 29 : 탱크 B28: tank A 29: tank B

30 : 스트레이너(straigner) 31 : 원료 이송관30: strainer 31: raw material transfer pipe

32 : 원료 이송 펌프 33 : 사이드 블록32: raw material feed pump 33: side block

34 : 모터 35 : 동력 전달 벨트34: motor 35: power transmission belt

36 : 풀리 37 : 동력 전달 축36: pulley 37: power transmission shaft

38 : 토출되는 혼합원료 39 : 원료 교반용 스크루38: mixed raw material discharged 39: screw for raw material stirring

40 : 질소가스 41 : 속도 변환 모터40: nitrogen gas 41: speed conversion motor

통상적인 용액형 폴리우레탄수지는 디이소시아네이트(diisocyanate)와 고분자 폴리올을 유기용제속에서 반응시켜 얻게된다. 그러나 이와 달리 본 발명에 따른 무용제폴리우레탄수지는, 유기용제를 사용하지 않고 디이소시아네이트와 폴리올을 직접 반응시켜 우레탄결합을 만들며(반응식 2); H2O를 사용하여 가교결합(cross linking)을 형성함으로써 내열성이 강한 열경화성수지를 만들게 된다. H2O는 CO2를 발생시켜 발포제 역할을 하는 동시에 부산물로 -NH2를 산출하며(반응식 3); 산출된 -NH3는 -NCO기와 반응하여 열경화성인 우레아결합을 형성하고(반응식 4); 이 우레아결합(-NHCONH-)은 다시 -NCO기와 뷰렛(biuret)반응을 하여 가교결합을 만들고(반응식 5)(반응식 6); -NCO기는 -NHCOO기(우레탄기)와 알로파네이트(allophanate)반응을 하여 망상구조를 만든다(반응식 7). 가교결합인 이들 결합은 동시에 상호간에도 가교결합을 형성하고(반웅식 8); 또한 결합력이 강한 분자간 수소 결합도 형성하게 된다(반응식 9).Conventional solution type polyurethane resins are obtained by reacting diisocyanate with a polymer polyol in an organic solvent. In contrast, the solvent-free polyurethane resin according to the present invention, without using an organic solvent to directly react the diisocyanate and polyol to make a urethane bond (Scheme 2); By forming cross linking using H 2 O, a thermosetting resin having a high heat resistance is formed. H 2 O generates CO 2 to act as a blowing agent and at the same time yield -NH 2 as a by-product (Scheme 3); The resulting -NH 3 reacts with the -NCO group to form a thermosetting urea bond (Scheme 4); This urea bond (-NHCONH-) is further subjected to biuret reaction with -NCO to form a crosslink (Scheme 5) (Scheme 6); The -NCO group is an allophanate reaction with the -NHCOO group (urethane group) to form a network structure (Scheme 7). These bonds, which are crosslinks, simultaneously form crosslinks with each other (Ref. 8); In addition, a strong intermolecular hydrogen bond is formed (Scheme 9).

상기 반응 결과, 전체적으로 -OH와 -NCO의 우레탄결합, 우레아결합, 가교 결할 및 분자간 수소결합이 공존하게 되므로 분자간 결합이 강한 열경화성의 고분자물질을 형성하게 된다.As a result of the reaction, urethane bonds, urea bonds, crosslinking defects, and intermolecular hydrogen bonds of -OH and -NCO coexist as a whole, thereby forming a thermosetting polymer material having strong intermolecular bonds.

따라서 본 발명에 따른 무용제 폴리우레탄수지는, 선상(linear)으로 우레탄결합이 형성된 열가소성 수지인 용액형 폴리우레탄수지에 비해 뛰어난 내열성, 내마모성, 고탄성의 특징을 나타내게 된다.Accordingly, the solvent-free polyurethane resin according to the present invention exhibits excellent heat resistance, wear resistance, and high elasticity as compared with a solution-type polyurethane resin, which is a thermoplastic resin in which a urethane bond is linearly formed.

본 발명에서는 먼저 무용제 폴리우레탄 원료인 폴리올 함유 혼합물(원료 A)과 디이소시아네이트 프레폴리머(원료 B)를 만든 후, 이들을 혼합·교반시키며, 교반 후 강력한 폴리우레탄 결합이 형성되어 경화되기 전인 액체상태일 때 단시간내에 이형지 또는 기재위에 코팅시킴으로써 무용제 PU 합성피혁을 만든다.In the present invention, first, a polyol-containing mixture (raw material A) and a diisocyanate prepolymer (raw material B), which are solvent-free polyurethane raw materials, are prepared, and then mixed and agitated, and agitated in a liquid state before a strong polyurethane bond is formed and cured. Solvent-free PU synthetic leather is produced by coating on a release paper or a substrate in a short time.

본 발명의 무용제 PU 합성피혁의 제조방법은 크게 3 가지 공정 즉, (1) 폴리올 혼합물(원료 A)과 디이소시아네이트 프레폴리머(원료 B)를 만드는 공정; (2) 원료 A, B를 화학당량 몰비로 혼합·교반하는 공정 및 (3) 코팅하는 공정으로 이루어진다. 이하, 각 공정별로 상세하게 설명한다.The manufacturing method of the solvent-free PU synthetic leather of this invention is largely three processes, (1) Process of making a polyol mixture (raw material A) and a diisocyanate prepolymer (raw material B); (2) mixing and stirring raw materials A and B in a chemical equivalent molar ratio, and (3) coating. Hereinafter, each process is explained in full detail.

(1) 플리올 혼합물(원료 A)과 디이소시아네이트 프레폴리머(원료 B)의 제조공정(1) Process for producing a polyol mixture (raw material A) and a diisocyanate prepolymer (raw material B)

무용제 폴리우레탄 원료인 폴리올 함유 혼합물(원료 A)과 디이소시아네이트 프레폴리머(원료 B)를 각각 제조한다.A polyol-containing mixture (raw material A) and a diisocyanate prepolymer (raw material B), which are solvent-free polyurethane raw materials, are prepared, respectively.

1) 폴리올 함유 혼합물(원료 A)의 제조1) Preparation of Polyol-Containing Mixture (Raw A)

분자량 100~10000의 하이드록실기를 함유한 폴리에스테르 폴리올, 폴리에테르 폴리올, 변형된 폴리에테르 폴리올, 폴리치오에테르 폴리올 및 이들을 2이상 혼합한 폴리올중에서 선택된 폴리올에 촉매 및 소량의 물을 혼합하여 원료 A인 폴리올 함유 혼합물을 만든다. 이때 촉매는 폴리올과 디이소시아네이트를 반응시키기 위한 것으로서 TEDA(Triethylene thiamine) 같은 3차 아민류 촉매 또는 Sn 같은 금속촉매 등의 통상적인 촉매가 사용될 수 있다.Raw material A by mixing a catalyst and a small amount of water in a polyol selected from a polyester polyol containing a hydroxyl group having a molecular weight of 100-10000, a polyether polyol, a modified polyether polyol, a polythioether polyol and a polyol mixed with two or more thereof A phosphorus polyol containing mixture is made. In this case, as the catalyst is used to react the polyol and diisocyanate, a conventional catalyst such as a tertiary amine catalyst such as TEDA (Triethylene thiamine) or a metal catalyst such as Sn may be used.

그러나 이러한 통상적인 촉매를 사용할 경우, 폴리올과 디이소시아네이트 프레폴리머(원료 B) 간의 반응이 급격하게 진행되어 혼합·교반후 약 5-8초 후에 혼합액의 점도와 형태가 변화하기 시작하므로 코팅이 아주 단시간내에 이루어져야 한다. 따라서 본 발명에서는 이러한 통상적인 촉매보다는 폴리올과 디이소시아네이트 프레폴리머간의 반응을 보다 지연시킬 수 있는 지연형 촉매를 사용하는 것이 바람직하다.However, when using such a conventional catalyst, the reaction between the polyol and the diisocyanate prepolymer (raw material B) proceeds rapidly and the viscosity and form of the mixed solution begin to change after about 5-8 seconds after mixing and stirring, so that the coating is very short. Must be done within Therefore, in the present invention, it is preferable to use a delayed catalyst that can delay the reaction between the polyol and the diisocyanate prepolymer more than such a conventional catalyst.

이러한 지연형 촉매로는 시클릭 아미딘(cyclic amidine) 계열의 촉매 등이 사용될 수 있으며, 지연형 촉매는 원료의 우레탄반응(urethane reaction), 발포반응(foaming reaction) 및 가교반응(cross linking reaction)을 지연시킨다. 본 발명에서는 이러한 지연형 촉매를 사용하여 혼합·교반 후 약 20∼30초 후에 반응이 일어나도록 하는 것이 바람직하다.As such a delayed catalyst, a cyclic amidine-based catalyst may be used, and the delayed catalyst may be a urethane reaction, a foaming reaction, and a cross linking reaction of a raw material. Delay. In the present invention, it is preferable to use the delayed catalyst so that the reaction occurs after about 20-30 seconds after mixing and stirring.

폴리올 함유 혼합물 중에 포함된 물(H2O)은 디이소시아네이트와 반응하여 CO2를 발생시키므로 발포제 역할을 하게 되며 동시에 부산물로 -NH2를 산출하게 된다(반응식 3).Water (H 2 O) contained in the polyol-containing mixture reacts with diisocyanate to generate CO 2 and thus acts as a blowing agent, and at the same time yields -NH 2 as a by-product (Scheme 3).

또한, 폴리올 함유 혼합물에는 코팅시의 두께를 조정하기 위하여 적당한 발포제를 추가로 혼합할 수 있다. 또한, 형성되는 셀의 크기 및 구조를 조정하기 위하여 정포제를 첨가할 수 있으며, 정포제로는 주로 실리콘계열의 계면활성제등이 사용될 수 있다. 이 밖에도, 유연성(softness), 경화시간 등을 조절하기 위하여 쇄연장제를 첨가할 수 있으며, 원하는 기능 및 기호에 따라 여러 가지 종류의 폴리올, 쇄연장제, 색소 등을 선택적으로 첨가함으로써 다양한 PU 합성피혁을 제조할 수 있다.In addition, the polyol-containing mixture may further be mixed with a suitable blowing agent in order to adjust the thickness at the time of coating. In addition, a foam stabilizer may be added to adjust the size and structure of the cell to be formed. As the foam stabilizer, a silicone-based surfactant may be mainly used. In addition, a chain extender may be added to control softness, curing time, and the like, and various PU synthesis may be selectively added by adding various types of polyols, chain extenders, and pigments according to desired functions and preferences. Leather can be manufactured.

2) 디이소시아네이트 프레폴리머(원료 B)의 제조2) Preparation of Diisocyanate Prepolymer (Raw B)

폴리올과 유기 폴리이소시아네이트(organic polyisocyanate)를 일부 반응시켜 말단의 유리(free) NCO 함량이 10∼20%인 디이소시아네이트 프레폴리머를 만든다(반응식 10). 이때 폴리올로는 분자량 100∼10000의 하이드록실기를 함유한 폴리에스테르 폴리올, 폴리에테르 폴리올, 변형된 폴리에테르 폴리올, 폴리치오에테르 폴리올 또는 이들을 2 가지 이상 혼합한 폴리올 등이 사용될 수 있다. 유기 폴리이소시아네이트로는 지방족, 방향족, 고리형 지방족, 아랄리파틱(araliphatic) 폴리이소시아네이트 등이 사용될 수 있는데, 이 중 반응성이 좋은 알켄 디이소시아네이트, 방향족 디이소시아네이트, 고리형 지방족 디이소시아네이트, 아랄리파틱(araliphatic) 디이소시아네이트를 사용하는 것이 보다 바람직하다.Partial reaction of the polyol with organic polyisocyanate yields a diisocyanate prepolymer having a free NCO content of 10-20% at the end (Scheme 10). In this case, a polyester polyol containing a hydroxyl group having a molecular weight of 100 to 10000, a polyether polyol, a modified polyether polyol, a polythioether polyol, or a polyol mixed with two or more thereof may be used. As the organic polyisocyanate, aliphatic, aromatic, cyclic aliphatic, araliphatic polyisocyanate, etc. may be used, among which are highly reactive alkene diisocyanate, aromatic diisocyanate, cyclic aliphatic diisocyanate, araliphatic ( More preferably, araliphatic diisocyanate is used.

(2) 원료 A와 B를 정확한 화학당량 몰비로 혼합·교반하는 공정(2) Process of mixing and stirring raw materials A and B at precise chemical equivalent molar ratio

공정(1)에서 제조한 원료 A(폴리올 함유 혼합물)와 원료 B(디이소시아네이트 프레폴리머)를 정확한 화학당량 몰비로 혼합·교반한다.The raw material A (polyol-containing mixture) and the raw material B (diisocyanate prepolymer) produced in the step (1) are mixed and stirred in an accurate chemical equivalent molar ratio.

원료 A와 B의 혼합·교반은 수작업으로도 할 수 있으나 보다 정확한 혼합·교반을 위해서는 본 발명에 따른 소정의 혼합장치(21)를 이용하여 행하는 것이 바람직하다. 원료를 정확한 화학당량 몰비로 혼합하지 않을 경우 미반응의 원료가 남게되어 제품의 질을 저하시키게 되므로 원료의 혼합은 가급적 정확하게 이루어지도록 해야 한다.Mixing and stirring of the raw materials A and B can be performed by hand, but for more accurate mixing and stirring, it is preferable to use a predetermined mixing device 21 according to the present invention. If raw materials are not mixed in the correct chemical equivalence molar ratio, unreacted raw materials will be left and the quality of the product will be degraded. Therefore, the raw materials should be mixed as accurately as possible.

본 발명에 사용되는 혼합장치(21)의 바람직한 실시예를 제6도에 의거하여 설명한다. 본 발명에 사용되는 혼합장치(21)는 원료를 각각 나누어 투입할 수 있는 두 개 이상의 탱크(28,29), 상기 탱크(28,29)로부터 원료를 혼합챔버(27)로 이송하는 원료이송관(31), 이송된 원료를 교반하는 혼합챔버(27) 및 상기 혼합챔버(27)로부터 교반된 원료를 토출하는 토출구(25)로 이루어진 것으로서, 상기 원료이송관(31)은 상기 탱크(28,29)로부터 각각의 원료를 원하는 양으로 정확하게 이송하기 위한 속도조절기능이 있는 원료 이송용 펌프(32)와 속도변환모터(41)가 부착되어 있으며; 상기 혼합챔버(27)는 원료를 고속으로 혼합·교반하기 위한 혼합임펠러(24)가 구비되어 있으며; 상기 토출구(25)는 상기 혼합챔버(27)로부터 교반된 원료를 토출하는 것을 특징으로 한다. 또한 상기 혼합장치(21)는 반응이 일정하게 일어날 수 있도록 온도 및 압력을 일정하게 유지시킬 수 있다.A preferred embodiment of the mixing apparatus 21 used in the present invention will be described with reference to FIG. The mixing apparatus 21 used in the present invention includes two or more tanks 28 and 29 capable of dividing and feeding the raw materials, and a raw material conveying pipe for transferring the raw materials from the tanks 28 and 29 to the mixing chamber 27 ( 31), the mixing chamber 27 for stirring the transferred raw material and the discharge port 25 for discharging the stirred raw material from the mixing chamber 27, the raw material conveying pipe 31 is the tank (28,29) A raw material conveying pump 32 and a speed converting motor 41 having a speed adjusting function for precisely conveying each raw material in a desired amount from the raw material; The mixing chamber 27 is provided with a mixing impeller 24 for mixing and stirring raw materials at high speed; The discharge port 25 is characterized in that for discharging the stirred raw material from the mixing chamber (27). In addition, the mixing device 21 may maintain a constant temperature and pressure so that the reaction occurs uniformly.

본 발명에서는 상기 혼합장치(21)에 구비된 탱크 A(28)와 탱크 B(29)에 원료 A액과 B액을 각각 투입한 후 정확한 화학당량 몰비로 혼합챔버(27)로 이송시키고, 이를 고속(바람직하게는 5000∼10000 RPM)으로 혼합·교반시킨다. 상기 혼합·교반 공정은 20∼60℃의 일정한 온도 및 1kgf/cm2의 일정한 압력하에서 이루어지는 것이 보다 바람직하다.In the present invention, the raw material A liquid and the liquid B are added to the tank A 28 and the tank B 29 provided in the mixing device 21, respectively, and then transferred to the mixing chamber 27 at an accurate chemical equivalent molar ratio. Mix and stir at high speed (preferably 5000-10000 RPM). As for the said mixing and stirring process, it is more preferable to carry out by the constant temperature of 20-60 degreeC, and the constant pressure of 1 kgf / cm <2> .

원료 A와 B는 상온에서는 액상을 유지하며, 두 원료를 혼합하면 반응하여 고형체를 형성하게 된다. 따라서 혼합·교반후 두 원료가 반응하기 전인 액체상태일 때 코팅을 실시하여야 하므로 혼합·교반·토출이 일체로 신속하게 행해져야 하며, 토출된 혼합액은 기재 또는 이형지위에 투입되어 신속하게 코팅되어야 한다.The raw materials A and B maintain a liquid phase at room temperature, and when the two raw materials are mixed, they react to form a solid. Therefore, after mixing and stirring, the coating should be carried out in the liquid state before the reaction between the two raw materials. Therefore, mixing, stirring, and discharging should be carried out quickly and integrally, and the discharged mixed liquid should be put on the substrate or release paper and coated quickly.

(3) 코팅 공정(3) coating process

공정(2)에서 토출되는 혼합·교반된 원료 혼합액(13)을 이형지 또는 기재위에 투입한 후 이를 코터(11)를 이용하여 코팅시킨다(제3도).The mixed and stirred raw material mixture liquid 13 discharged at the process (2) is put on a release paper or a base material, and this is coated using the coater 11 (FIG. 3).

전술한 바와 같이, 원료의 혼합·교반후 반응이 급격하게 진행되어 강력한 폴리우레탄 결합을 형성하는 고형체로 되므로 반응이 시작되기전 액체 상태일때 단시간내에 코팅을 실시하여야 한다. 만일, 소정의 시간 내에 코팅이 완료되지 않으면 혼합원료의 경화가 진행되어 반고형의 덩어리가 생기게 되므로 코팅면이 불균일하게 되고 코팅 두께도 일정하지 않게 된다.As described above, since the reaction proceeds rapidly after mixing and stirring the raw materials to form a solid polyurethane bond, the coating should be carried out within a short time in the liquid state before the reaction starts. If the coating is not completed within a predetermined time, since the curing of the mixed raw material proceeds to form a semi-solid lump, the coating surface becomes uneven and the coating thickness is not constant.

따라서, 본 발명의 코팅공정에는 보다 신속하게 코팅을 수행할 수 있는 방법이 선택되어야 하며, 원료의 투입과 코팅이 일체로 행해져 원료가 경화되기 전에 완료될 수 있는 코팅방법이면 본 발명의 코팅법으로 적합하다. 또한, 용액형 폴리우레탄수지의 도포에 주로 사용되는 그라비아 프린트(Gravure print) 등의 종래의 코팅방법은 코팅에 소요되는 시간이 길기 때문에 본 발명의 코팅법으로는 적합하지 않다.Therefore, the coating process of the present invention should be selected a method that can perform a coating more quickly, if the coating method that can be completed before the raw material is cured by the addition of the raw material and the coating is integrated into the coating method of the present invention. Suitable. In addition, the conventional coating method such as gravure print mainly used for the application of the solution-type polyurethane resin is not suitable for the coating method of the present invention because the time required for coating is long.

본 발명에 적합한 코팅법의 일례로는 제4(a)도에 도시된 바와 같이, 기재(또는 이형지)위에 원료혼합액(13)을 투입한 후 저속으로 회전하는 롤 코터(22)를 이용하여 코팅하는 방법인 “롤 코터(22)를 이용한 코팅법”을 들 수 있다. 롤 코터(22)는 일반적인 코터의 문제점 즉, 코터에 코팅원료가 남게 되고 이것이 경화되어 코팅면을 불균일하게 하고 코팅두께를 일정하지 않게 한다는 문제점을 해결하기 위하여 본 발명에서 고안한 것으로서, “롤 코터(22)를 이용한 코팅법”은 경화되어가는 코팅원료가 묻은 롤 코터(22)의 아랫부분을 회전시켜 위로 상승시켜서 새로운 부분이 코팅원료와 닿게 함으로써 경화된 원료가 코터를 통과하지 않게 하여 균일한 코팅이 되도록 하는 것을 특징으로 한다.As an example of a coating method suitable for the present invention, as shown in FIG. 4 (a), the raw material mixture 13 is introduced onto a substrate (or a release paper) and then coated using a roll coater 22 rotating at a low speed. "Coating method using a roll coater 22" that is a method. The roll coater 22 is designed in the present invention to solve the problem of a general coater, that is, a coating material is left in the coater and it is hardened to make the coating surface uneven and the coating thickness not constant. (22) "Coating Method" is used to rotate the lower part of the roll coater 22, which is coated with the cured coating material, and to raise the upper part so that the new part is in contact with the coating material so that the cured raw material does not pass through the coater. It is characterized in that the coating.

또한, 본 발명에 적합한 코팅방법으로는, 본 발명에 따른 “변형된 롤 코터(23a)를 이용한 코팅법”(제4b도), “이형지 코터(23b)를 이용한 코팅법”(제4c도), “벨트형 이형지 코터(23c)을 이용한 코팅법”(제4d도) 등을 들 수 있다.Moreover, as a coating method suitable for this invention, the "coating method using the modified roll coater 23a" (FIG. 4B), the "coating method using the release paper coater 23b" (FIG. 4C) according to the present invention. "Coating method using belt type release paper coater 23c" (FIG. 4D), etc. are mentioned.

본 발명의 코팅공정에서는 투입되는 코팅원료의 양과 이형지의 속도가 중요한 요소가 되며, 본 코팅공정에서 원료와 이형지의 바람직한 온도는 20~60℃이다.In the coating process of the present invention, the amount of coating material introduced and the speed of the release paper become important factors, and the preferred temperature of the raw material and the release paper in the present coating process is 20 to 60 ° C.

코팅 후 열실에서 가열하여 1분 30초 정도의 시간이 경과하여 반응온도가 약 120℃ 까지 올라가게 되고 100∼150℃에서 2∼5분간 숙성시키면 완전히 경화된 PU합성피혁 제품을 얻게 된다.After the coating is heated in a heat chamber for about 1 minute and 30 seconds, the reaction temperature rises to about 120 ° C. and when matured at 100 to 150 ° C. for 2 to 5 minutes, a fully cured PU synthetic leather product is obtained.

상기와 같은 방법으로 제조한 무용제 PU 합성피혁에 대해 통상적인 후가공 처리를 함으로써 다양한 외관을 가진 PU 합성피혁을 제조할 수 있다. 즉, 공정(3)에서 최종적으로 얻어진 무용제 PU 합성피혁을 엠보싱로울러로 압착하거나 표면처리로 무늬나 색상을 넣어 표면의 물성 또는 외관을 보강하거나 또는 샌드 페이퍼로 표면을 버핑하여 스웨이드를 만드는 등의 후가공처리를 함으로써 종래의 후가공설비를 그대로 이용하여 다양한 외관을 가진 PU합성피혁을 제조할 수 있다.PU synthetic leather having a variety of appearances can be produced by a conventional post-processing treatment for the solvent-free PU synthetic leather prepared by the above method. That is, after finishing the non-solvent PU synthetic leather obtained in the step (3) by pressing with an embossing roller or by adding a pattern or color by surface treatment to reinforce the physical properties or appearance of the surface or by buffing the surface with sand paper to make suede. By treating, PU synthetic leather having various appearances can be manufactured using the conventional post-processing equipment as it is.

이하, 본 발명을 한정하지 않는 실시예를 통해 본 발명을 보다 상세하게 설명한다.Hereinafter, the present invention will be described in more detail with reference to examples which do not limit the present invention.

[실시예 1]Example 1

원료 A의 제조Preparation of Raw Material A

(1) 제조예 1(1) Preparation Example 1

폴리에스테르 폴리올 64.3 중량부, 실리콘 정포제(silicone surfactant) 0.1 중량부, H2O 0.01 중량부 및 지연형 촉매(시클럭 아미딘계) 0.4 중량부를 혼합, 교반하여 폴리올 혼합물을 만들었다.64.3 parts by weight of polyester polyol, 0.1 part by weight of a silicone surfactant, 0.01 part by weight of H 2 O, and 0.4 part by weight of a delayed catalyst (cyclic amidine-based) were mixed and stirred to prepare a polyol mixture.

(2) 제조예 2(2) Preparation Example 2

폴리에테르 폴리올 49.2 중량부, 실리콘 정포제 0.6 중량부, H2O 0.7 중량부 및 지연형 촉매(시클릭 아미딘계) 0.3 중량부를 혼합, 교반하여 폴리올 혼합물을 만들었다.49.2 parts by weight of polyether polyol, 0.6 parts by weight of a silicon foam stabilizer, 0.7 parts by weight of H 2 O and 0.3 parts by weight of a delayed catalyst (cyclic amidine-based) were mixed and stirred to prepare a polyol mixture.

(3) 제조예 3(3) Preparation Example 3

폴리에스테르 폴리올 55.2 중량부, 실리콘 정포제 1.2 중량부, H2O 0.9 중량부 및 지연형 촉매(시클릭 아미딘계) 0.2 중량부를 혼합, 교반하여 폴리올 혼합물을 만들었다.55.2 parts by weight of polyester polyol, 1.2 parts by weight of a silicon foam stabilizer, 0.9 parts by weight of H 2 O and 0.2 parts by weight of a delayed catalyst (cyclic amidine-based) were mixed and stirred to form a polyol mixture.

[실시예 2]Example 2

원료 B의 제조Preparation of Raw Material B

(1) 제조예 1(1) Preparation Example 1

분자량 100∼10000의 하이드록실기를 함유한 폴리에스테르 폴리올과 방향족 디이소시아네이트(aromatic diisocyanate)를 일부 반응시켜 말단의 유리(free) NCO 함량이 18%인 디이소시아네이트 프레폴리머를 만들었다(반응식 10).A partial reaction of the polyester polyol containing a hydroxyl group having a molecular weight of 100 to 10000 with an aromatic diisocyanate produced a diisocyanate prepolymer having a free NCO content of 18% at the end (Scheme 10).

(2) 제조예 2(2) Preparation Example 2

분자량 100~10000의 하이드녹실기를 함유한 폴리에테르 플리올과 알켄 디이소시아네이트(alkene diisocyanate)를 일부 반응시켜 말단의 유리(free) NCO 함량이 17%인 디이소시아네이트 프레폴리머를 만들었다.The polyether polyol containing a hydroxyl group having a molecular weight of 100-10000 and an alkene diisocyanate were partially reacted to produce a diisocyanate prepolymer having a free NCO content of 17% at the end.

(3) 제조예 3(3) Preparation Example 3

분자량 100∼10000의 하이드록실기를 함유한 폴리에스테르 폴리올과 고리형 지방족 디이소시아네이트(Alkene diisocyanate)를 일부 반응시켜 말단의 유리(free) NCO 함량이 19%인 디이소시아네이트 프레폴리머를 만들었다.A polyester polyol containing a hydroxyl group having a molecular weight of 100 to 10000 was partially reacted with a cyclic aliphatic diisocyanate to prepare a diisocyanate prepolymer having a free NCO content of 19% at the end.

[실시예 3]Example 3

원료 A와 B의 혼합 및 교반Mixing and stirring raw materials A and B

(1) 혼합예 1(1) Mixing example 1

상기 실시예 1의 제조예 1에서 만든 원료 A(폴리올 혼합물 : 폴리에스테르 폴리올 64.3 중량부, 실리콘 정포제 0.1 중량부, H2O 0.01 중량부 및 지연형 촉매(시클릭 아미딘계) 0.4 중량부)를 혼합장치(21)의 탱크 A(28)에 투입하고; 상기 실시예 2의 제조예 1에서 만든 원료 B(디이소시아네이트 프레폴리머) 35.2 중량부를 혼합 장치(21)의 탱크 B(29)에 투입한 후; 이들 원료를 정확한 화학당량 몰비로 혼합챔버(27)로 이송시키고; 혼합 임펠러를 이용하여 고속으로 혼합·교반시켜 무용제 원료의 혼합액을 만들었다. 이때, 혼합 및 교반은 40℃의 일정한 온도 및 1kgf/cm2의 일정한 압력하에서 이루어지도록 했다.Raw material A made in Preparation Example 1 of Example 1 (polyol mixture: 64.3 parts by weight of polyester polyol, 0.1 part by weight of silicon foam stabilizer, 0.01 part by weight of H 2 O and 0.4 part by weight of delayed catalyst (cyclic amidine)) To tank A 28 of mixing device 21; 35.2 parts by weight of raw material B (diisocyanate prepolymer) prepared in Preparation Example 1 of Example 2 was introduced into tank B 29 of the mixing apparatus 21; These raw materials are transferred to the mixing chamber 27 at the correct chemical equivalent molar ratio; A mixed solution of a solvent-free raw material was prepared by mixing and stirring at high speed using a mixed impeller. At this time, mixing and stirring were performed under a constant temperature of 40 ° C. and a constant pressure of 1 kgf / cm 2 .

(2) 혼합예 2(2) Mixing Example 2

혼합장치(21)의 탱크 A(28)에 상기 실시예 1의 제조예 2에서 만든 원료 A(폴리올 혼합물 : 폴리에테르 폴리올 49.2 중량부, 실리콘 정포제 0.6 중량부, H2O 0.7 중량부 및 지연형 촉매(시클릭 아미딘계) 0.3 중량부)을 투입하고; 혼합장치(21)의 탱크 B(29)에 상기 실시예 2의 제조예 2에서 만든 원료 B(디이소시아네이트 프레폴리머) 49.5 중량부를 투입하는 것을 제외하고는, 상기 혼합예 1과 동일한 방법으로 무용제 원료의 혼합액을 만들었다.Raw material A (polyol mixture: 49.2 parts by weight of polyether polyol, 0.6 parts by weight of silicone foam stabilizer, 0.7 parts by weight of H 2 O, and delay) prepared in Preparation Example 2 of Example 1 in tank A 28 of mixing device 21 0.3 part by weight of a type catalyst (cyclic amidine)); Solvent-free raw materials in the same manner as in Mixing Example 1, except that 49.5 parts by weight of raw material B (diisocyanate prepolymer) prepared in Preparation Example 2 of Example 2 was added to tank B 29 of the mixing apparatus 21. Mixed solution was prepared.

(3) 혼합예 3(3) Mixing Example 3

혼합장치(21)의 탱크 A(28)에 상기 실시예 1의 제조예 3에서 만든 원료 A(폴리올 함유 혼합물 : 폴리에스테르 폴리올 55.2 중량부, 실리콘 정포제 1.2 중량부, H2O 0.9 중량부 및 지연형 촉매(시클릭 아미딘계) 0.2 중량부)를 투입하고; 혼합장치(21)의 탱크 B(29)에 상기 실시예 2의 제조예 3에서 만든 원료 B(디이소시아네이트 프레폴리머) 42.5 중량부를 투입하는 것을 제외하고는, 상기 혼합예 1과 동일한 방법으로 무용제 원료의 혼합액을 만들었다.Raw material A (polyol-containing mixture: 55.2 parts by weight of polyester polyol: 1.2 parts by weight of silicone foam stabilizer, 0.9 parts by weight of H 2 O) and the like prepared in Preparation Example 3 of Example 1 in tank A 28 of mixing device 21; 0.2 part by weight of a delayed catalyst (cyclic amidine system); A solvent-free raw material in the same manner as in Mixing Example 1, except that 42.5 parts by weight of the raw material B (diisocyanate prepolymer) prepared in Preparation Example 3 of Example 2 was added to tank B 29 of the mixing apparatus 21. Mixed solution was prepared.

[실시예 4]Example 4

원료 혼합액의 코팅Coating of Raw Material Mixture

(1) “변형된 롤 코터(23a)를 이용한 코팅법”(제4b도)(1) "Coating Method Using Modified Roll Coater 23a" (Fig. 4B)

제4(b)도에 도시된 바와 같이, 이형지(14)(또는 기재)위에 원료 혼합액(13)을 투입한 후 본 발명에 따른 변형된 롤 코터(23a)를 이용하여 코팅시켰다. 변형된 롤 코터(23a)는 하나의 코터에 회전형으로 여러개의 코팅날을 구비한 것으로서, 아랫부분의 코팅날을 이용하여 코팅한 후 코팅원료가 묻은 아랫부분의 코팅날을 위로 회전시키고 새로운 코팅날이 코팅원료와 닿게 함으로써 경화된 원료가 코터를 통과하지 않도록 하는 것을 특징으로 한다.As shown in FIG. 4 (b), the raw material mixture liquid 13 was introduced onto the release paper 14 (or the substrate) and then coated using the modified roll coater 23a according to the present invention. The deformed roll coater 23a is provided with a plurality of coating blades in one coater in a rotatable manner. After coating with the lower coating blade, the coated coating blade is rotated upward and the new coating coating is rotated. By contacting the blade with the coating material is characterized in that the cured raw material does not pass through the coater.

(2) “이형지 코터(23b)를 이용한 코팅법”(제4c도)(2) "Coating Method Using Release Paper Coater 23b" (Fig. 4C)

제4(c)도에 도시된 바와 같이, 이형지(14)(또는 기재)위에 원료 혼합액(13)을 투입한 후 이형지 코터(23b)를 이용하여 코팅시켰다. 이형지 코터(23b)는 본 발명에서 고안한 것으로서, 터닝롤(19)을 이용하여 계속적으로 새로운 이형지를 공급하는 한편, 원료혼합액이 묻은 이형지를 회수하는 것을 특징으로 한다.As shown in FIG. 4 (c), the raw material mixed solution 13 was introduced onto the release paper 14 (or the substrate) and coated using a release paper coater 23b. Release paper coater (23b) is devised in the present invention, it is characterized in that by using the turning roll 19 to continuously supply a new release paper, the release paper on which the raw material mixture solution is deposited.

(3) “벨트형 이형지 코터(23c)를 이용한 코팅법”(제4(d)도)(3) "Coating method using belt type release paper coater 23c" (Fig. 4 (d))

제4(d)도에 도시된 바와 같이, 이형지(14) 위에 원료 혼합액(13)을 투입한 후 벨트형 이형지 코터(23c)를 이용하여 코팅시켰다. 벨트형 이형지 코터(23c)는 상기 이형지 코터(23b)를 개량한 것으로서, 벨트형으로 이형지를 회전시켜 별도로 이형지를 공급, 회수할 필요가 없도록 한 것이며, 이 경우 원료혼합액이 묻은 이형지는 회전시켜 원료혼합액을 경화시킨 후 떼어내고 다시 사용하도록 함으로써 새로운 이형지를 공급한 것과 같은 효과를 주고 있다.As shown in FIG. 4 (d), the raw material mixture solution 13 was introduced onto the release paper 14 and then coated using a belt release paper coater 23c. The belt release paper coater 23c is an improvement on the release paper coater 23b, and the release paper is rotated in a belt form so that it is not necessary to separately supply and recover the release paper. In this case, the release paper with the raw material mixture is rotated and the raw material is rotated. By hardening the mixed solution, removing it and using it again, the same effect as supplying a new release paper is provided.

본 발명에 따르면 유기용제를 사용하지 않고 단 시간 내에 원료를 직접 반응시켜 PU 합성피혁을 제조함으로써 유기용제의 사용에 따른 환경공해가 없으며, 또한 인체에 유해한 유기용제가 합성피혁제품에 잔류할 염려가 없게 된다.According to the present invention, there is no environmental pollution due to the use of the organic solvent by producing a PU synthetic leather by directly reacting the raw materials in a short time without using an organic solvent, and there is a risk that organic solvents harmful to human body remain in the synthetic leather product There will be no.

또한, 본 발명에 따르면 원료의 혼합·교반·코팅이 단시간내에 일체로 이루어지게 되므로 작업공정의 단순화, 작업시간의 단축 및 생산성 향상을 꾀할 수 있으며, 종래의 후가공설비를 그대로 이용하여 다양한 제품을 생산할 수 있다.In addition, according to the present invention, since the mixing, stirring and coating of the raw materials are made in a short time, the work process can be simplified, the working time can be shortened, and the productivity can be improved, and various products can be produced using the conventional post-processing equipment as it is. Can be.

또한, 본 발명에 따르면 열경화성인 폴리우레탄수지가 형성되므로, 열가소성수지를 이용한 기존의 합성피혁제품에 비해 물성과 감촉면에서 우수하며 또한 보다 천연피혁에 가까운 제품을 얻을 수 있다.In addition, according to the present invention, since the thermosetting polyurethane resin is formed, it is superior in terms of physical properties and texture compared to existing synthetic leather products using thermoplastic resins, and more natural leather products can be obtained.

Claims (9)

무용제 폴리우레탄 원료인 폴리올 함유 혼합물과 디이소시아네이트 프레폴리머를 만든 후, 이들을 화학당량 몰비로 혼합·교반시키고, 교반 후 강력한 폴리우레탄 결합이 형성되기 전인 액체상태일 때 이형지 또는 기재위에 코팅시켜 제조되는 무용제 PU 합성피혁으로서; 상기 폴리올 함유 혼합물은 1 이상의 폴리올과 상기 폴리올과 디이소시아네이트간의 반응을 활성화시키는 촉매 및 소량의 물을 포함하며; 상기 디이소시아네이트 프레폴리머는 폴리올과 유기 폴리이소시아네이트(organic polyisocyanate)를 일부 반응시켜 제조한 것으로서 말단의 유리(free) NCO함량이 10∼20%인 것을 특징으로 하는 무용제(無溶劑) 폴리우레탄 합성피혁.Solvent prepared by preparing a polyol-containing mixture and a diisocyanate prepolymer as a solvent-free polyurethane raw material, mixing and stirring them in a chemical equivalent molar ratio, and coating on a release paper or a substrate in a liquid state after stirring before forming a strong polyurethane bond. As PU synthetic leather; The polyol containing mixture comprises a catalyst and a small amount of water to activate a reaction between at least one polyol and the polyol and diisocyanate; The diisocyanate prepolymer is prepared by partially reacting a polyol and an organic polyisocyanate, and is a solvent-free polyurethane synthetic leather, characterized in that the free NCO content of the terminal is 10 to 20%. 제1항에 있어서, 상기 혼합은 상기 폴리올 함유 혼합물 40∼65 중량부와 상기 디이소시아네이트 프레폴리머 35∼60 중량부의 비율로 이루어지는 것임을 특징으로 하는 무용제(無溶劑) 폴리우레탄 합성피혁.The solvent-free polyurethane synthetic leather according to claim 1, wherein the mixing is in a ratio of 40 to 65 parts by weight of the polyol-containing mixture and 35 to 60 parts by weight of the diisocyanate prepolymer. (1) 무용제 폴리우레탄 원료인 폴리올 함유 혼합물과 디이소시아네이트 프레폴리머를 제조하는 공정; (2) 상기 공정 1에서 제조한 폴리올 함유 혼합물과 디이소시아네이트 프레폴리머를 정확한 화학당량 몰비로 혼합·교반하는 공정; 및 (3) 상기 공정 (2)에서 혼합·교반된 원료 혼합액(13)을 이형지 또는 기재위에 투입하여 코팅시키는 공정으로 이루어지는 무용제(無溶劑) 폴리우레탄 합성피혁의 제조방법으로서; 상기 폴리올 함유 혼합물은 1 이상의 폴리올과 상기 폴리올과 디이소시아네이트간의 반응을 활성화시키는 촉매 및 소량의 물을 혼합하여 제조한 것이며; 상기 디이소시아네이트 프레폴리머는 폴리올과 유기 폴리이소시아네이트(organic polyisocyanate)를 일부 반응시켜 제조한 것으로서 말단의 유리(free) NCO 함량이 10∼20%인 것을 특징으로 하는 무용제(無溶劑) 폴리우레탄 합성피혁.(1) step of preparing a polyol-containing mixture and a diisocyanate prepolymer, which are solvent-free polyurethane raw materials; (2) mixing and stirring the polyol-containing mixture and diisocyanate prepolymer prepared in Step 1 in an accurate chemical equivalent molar ratio; And (3) a method of producing a solvent-free polyurethane synthetic leather comprising a step of coating the raw material mixture 13 mixed and stirred in the step (2) on a release paper or a substrate; The polyol-containing mixture is prepared by mixing at least one polyol with a small amount of water and a catalyst that activates the reaction between the polyol and diisocyanate; The diisocyanate prepolymer is prepared by partially reacting a polyol and an organic polyisocyanate, and is a solvent-free polyurethane synthetic leather, characterized in that the free NCO content of the terminal is 10 to 20%. 제3항에 있어서, 상기 폴리올은 분자량 100∼10000의 하이드록실기를 함유한 폴리에스테르 폴리올, 폴리에테르 폴리올, 변형된 폴리에테르 폴리올, 폴리치오에테르 폴리올 및 이들을 2이상 혼합한 폴리올로 이루어진 군으로부터 선택된 어느 하나의 폴리올인 것을 특징으로 하는 무용제(無溶劑) 폴리우레탄 합성피혁의 제조방법.The polyol of claim 3, wherein the polyol is selected from the group consisting of polyester polyols containing hydroxyl groups having a molecular weight of 100 to 10000, polyether polyols, modified polyether polyols, polythioether polyols, and polyols mixed with two or more thereof. A method for producing a solvent-free polyurethane synthetic leather, characterized in that any one polyol. 제3항에 있어서, 상기 촉매는 폴리올과 디이소시아네이트 프레폴러머간의 반응을 보다 지연시킬 수 있는 지연형 촉매인 것을 특징으로 하는 무용제(無溶劑) 폴리우레탄 합성피혁의 제조방법.The method for producing a solvent-free polyurethane synthetic leather according to claim 3, wherein the catalyst is a delayed catalyst capable of further delaying the reaction between the polyol and the diisocyanate prepolymer. 제3항에 있어서, 상기 코팅은 롤 코터(22)를 이용하여 행해지는 것임을 특징으로 하는 무용제(無溶劑) 폴리우레탄 합성피혁의 제조방법.The method for producing a solvent-free polyurethane synthetic leather according to claim 3, wherein the coating is performed using a roll coater (22). 제3항에 있어서, 상기 코팅은 변형된 롤 코터(23a)를 이용하여 행해지는 것임을 특징으로 하는 무용제(無溶劑) 폴리우레탄 합성피혁의 제조방법.The method for producing a solvent-free polyurethane synthetic leather according to claim 3, wherein the coating is performed using a modified roll coater (23a). 제3항에 있어서, 상기 코팅은 이형지 코터(23b)를 이용하여 행해지는 것임을 특징으로 하는 무용제(無溶劑) 폴리우레탄 합성피혁의 제조방법.The method for producing a solvent-free polyurethane synthetic leather according to claim 3, wherein the coating is performed using a release paper coater (23b). 제3항에 있어서, 상기 코팅은 벨트형 이형지 코터(23c)를 이용하여 행해지는 것임을 특징으로 하는 무용제(無溶劑) 폴리우레탄 합성피혁의 제조방법.The method for producing a solvent-free polyurethane synthetic leather according to claim 3, wherein the coating is performed using a belt type release paper coater (23c).
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KR100581330B1 (en) * 2005-10-25 2006-05-22 주식회사 백산 Polyurethane porous structure of non-solvent type and method thereof using for artificial synthetic leather
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