KR101313713B1 - compositions of polyurethane resin has anti-hydrolysis property, Manufacturing method of polyurethane resin using the same and polyurethane adhesive with polyurethane resin - Google Patents

compositions of polyurethane resin has anti-hydrolysis property, Manufacturing method of polyurethane resin using the same and polyurethane adhesive with polyurethane resin Download PDF

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KR101313713B1
KR101313713B1 KR1020110121747A KR20110121747A KR101313713B1 KR 101313713 B1 KR101313713 B1 KR 101313713B1 KR 1020110121747 A KR1020110121747 A KR 1020110121747A KR 20110121747 A KR20110121747 A KR 20110121747A KR 101313713 B1 KR101313713 B1 KR 101313713B1
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KR20130056025A (en
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이재년
서석훈
최필준
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한국신발피혁연구원
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/54—Aqueous solutions or dispersions

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Abstract

본 발명은 내수성이 우수한 수성 폴리우레탄 수지 조성물과 이를 이용한 수성 폴리우레탄 수지의 제조방법에 관한 것으로, 보다 구체적으로는 내가수분해성이 우수한 폴리(테트라메틸렌 글리콜)(PTMG)와 물리적 특성이 우수한 폴리카보네이트디올, 유연성과 저온굴곡성이 우수한 1,3-Propandiol과 내광성이 우수한 지방족 디이소시아네이트 조성물을 프리폴리머(pre-polymer) 합성법을 이용하여 중합시킨 폴리우레탄 수분산 수지로서, 내구성, 내수성, 내약품성, 내광성, 마모강도, 기계적 물성, 유연성, 접착력 등의 물성이 우수하여 섬유 원단에 사용되는 접착제 용도에 적합한 것을 특징으로 하는 내수성이 우수한 폴리우레탄 수지 조성물과 이를 이용한 수성 폴리우레탄 수지의 제조방법 및 이 방법에 의해 제조된 수성 폴리우레탄 수지는 내수성이 우수하므로 섬유용 접착제, 벽지용 접착제, 자동차 시트용 접착제, 인공피혁용 접착제, 합성피혁용 접착제, 가방 원단용 접착제, 의류용 원단용 접착제, 신발 원단용 접착제, 합성피혁 및 인공피혁용 코팅제, 목재용 코팅제, 전자부품 코팅제, 바닥재 코팅제, 도료 등과 같이 다양한 분야에 적용될 수 있다.The present invention relates to an aqueous polyurethane resin composition having excellent water resistance and a method for producing an aqueous polyurethane resin using the same, and more specifically, poly (tetramethylene glycol) (PTMG) having excellent hydrolysis resistance and a polycarbonate having excellent physical properties. Diol, a polyurethane water dispersion resin obtained by polymerizing 1,3-propanediol having excellent flexibility and low temperature bendability and aliphatic diisocyanate composition having excellent light resistance using a prepolymer synthesis method, and having durability, water resistance, chemical resistance, light resistance, It is excellent in water resistance, mechanical properties, flexibility, adhesive strength and the like, and is suitable for adhesives used in textile fabrics. The prepared water-based polyurethane resin has excellent water resistance Adhesive for textiles, Adhesive for wallpaper, Adhesive for automobile seats, Adhesive for artificial leather, Adhesive for synthetic leather, Adhesive for bag fabrics, Adhesive for garment fabrics, Adhesive for footwear fabrics, Coating for synthetic leather and artificial leather, Coating for wood It can be applied to various fields such as electronic component coatings, floor coatings, paints and the like.

Description

내수성이 우수한 폴리우레탄 수분산 수지 조성물, 이를 이용한 폴리우레탄 수분산 수지의 제조방법 및 이 제조방법에 의해 제조된 폴리우레탄 수분산 수지를 포함하는 폴리우레탄 수분산 접착제{compositions of polyurethane resin has anti-hydrolysis property, Manufacturing method of polyurethane resin using the same and polyurethane adhesive with polyurethane resin}Polyurethane water dispersion resin composition having excellent water resistance, a method for preparing a polyurethane water dispersion resin using the same, and a polyurethane water dispersion adhesive comprising a polyurethane water dispersion resin prepared by the method property, Manufacturing method of polyurethane resin using the same and polyurethane adhesive with polyurethane resin}

본 발명은 내수성이 우수한 폴리우레탄 수분산 수지 조성물, 이를 이용한 폴리우레탄 수분산 수지의 제조방법 및 이 제조방법에 의해 제조된 폴리우레탄 수분산 수지를 포함하는 폴리우레탄 수분산 접착제에 관한 것으로, 구체적으로는 내가수분해성이 우수한 폴리(테트라메틸렌 글리콜)(PTMG)과 폴리카보네이트 디올, 1,3-Propandiol 혼합물로 이루어지고, 이 혼합물을 디이소시아네이트 화합물과 반응시켜 프리폴리머로 합성한 후 최종적으로 쇄연장제로 합성함으로써, 내구성, 내약품성, 내광성, 마모강도, 기계적 물성, 유연성, 접착력 등의 물성이 우수하도록 하는 내수성이 우수한 폴리우레탄 수분산 수지 조성물, 이를 이용한 폴리우레탄 수분산 수지의 제조방법 및 이 제조방법에 의해 제조된 폴리우레탄 수분산 수지를 포함하는 폴리우레탄 수분산 접착제에 관한 것이다.
The present invention relates to a polyurethane water dispersion resin composition having excellent water resistance, a method for preparing a polyurethane water dispersion resin using the same, and a polyurethane water dispersion adhesive including a polyurethane water dispersion resin prepared by the production method. Is composed of a mixture of poly (tetramethylene glycol) (PTMG) with excellent hydrolysis resistance, polycarbonate diol, and 1,3-propanediol, and the mixture is reacted with a diisocyanate compound to synthesize a prepolymer and finally synthesized as a chain extender. Thus, the polyurethane water dispersion resin composition having excellent water resistance to be excellent in physical properties such as durability, chemical resistance, light resistance, wear strength, mechanical properties, flexibility, adhesion, and the like, and a method for producing a polyurethane water dispersion resin using the same Polyurethane Water Dispersion Contact Including Polyurethane Water Dispersion Resin It is about a complex.

일반적으로 폴리우레탄 수지는 분자중에 우레탄 결합을 가지는 것으로써, 주로 디이소시아네이트(diisocyanate)류와 폴리올(polyol) 화합물과의 반응에 의해 합성된 고분자 화합물이며, 내마모성, 내유성 및 내용제성에 뛰어나고, 탄성이 우수하여 접착제, 코팅제, 사출물, 페인트, 잉크, 도료, 발포체, 신발부품, 의류, 의료용 고분자 등 다양한 분야에서 적용되어지고 있다.
In general, a polyurethane resin is a polymer compound having a urethane bond in a molecule and mainly synthesized by a reaction between diisocyanates and a polyol compound, and excellent in wear resistance, oil resistance and solvent resistance, and elasticity. It is excellent and is applied in various fields such as adhesives, coatings, injection moldings, paints, inks, paints, foams, footwear parts, clothing, medical polymers.

그리고 폴리우레탄 접착제의 경우에는 거의 대부분이 가격이 저렴한 폴리에스테르 디올을 주재료로 사용하여 합성하고 있다. 최근 자동차 및 전자재료 코팅제, 각종 산업자재용 접착제로서 고내구성 및 고내수성의 폴리우레탄 수지의 사용량이 증가하고 있는 추세이다.
In the case of polyurethane adhesives, most of them are synthesized using inexpensive polyester diol as a main material. Recently, the use of polyurethane resins for automotive and electronic materials and adhesives for various industrial materials is increasing in durability and water resistance.

여기서, 상기 고내구성 및 고내수성 폴리우레탄 수지란 기존의 코팅 수지에 비하여 내가수분해성 및 기계적 물성이 10~30% 이상 높고, 열적 특성이 우수하여 내광성이 우수하며, 마찰에 의한 내마모강도가 우수하며, 접착 혹은 코팅 후 제품의 물리적 특성이 오랜 기간 발현되는 수지를 말한다.
Here, the high durability and high water resistance polyurethane resin is 10 ~ 30% higher hydrolysis resistance and mechanical properties than the conventional coating resin, excellent thermal properties, excellent light resistance, excellent wear resistance by friction It refers to a resin in which the physical properties of the product are expressed for a long time after adhesion or coating.

한편, 폴리카보네이트 디올(polycarbonate diol)은 폴리에스테르 디올(polyester diol), 폴리에테르 디올(polyether diol), 폴리카프로락톤 디올(lycaprolactone diol) 및 트리올(triol), 폴리올(polyol)에 비해 기계적 물성, 내약품성, 내화학성, 내가수분해성, 내광성, 내열성이 우수한 특수 폴리올로서 폴리카보네이트 디올(polycarbonate diol)에 대한 수요가 증가하고 있으며, 특히 특수 폴리올은 고내구성을 요구하는 자동차 용품, 전자재료, 산업자재 영역에서 사용되고 있다.
On the other hand, polycarbonate diol (polycarbonate diol), compared to polyester diol (polyester diol), polyether diol (polyether diol), polycaprolactone diol (lycaprolactone diol) and triol (triol), polyol (polyol), As a special polyol having excellent chemical resistance, chemical resistance, hydrolysis resistance, light resistance, and heat resistance, demand for polycarbonate diol is increasing. In particular, special polyol is used for automobile products, electronic materials, and industrial materials requiring high durability. It is used in the area.

관련 선행기술로써, 국내 특허의 경우에는 국내 등록특허공보 제10-0785349호에 내용제성이 우수한 수분산 폴리우레탄 수지의 제조방법과, 국내 공개특허공보 제10-2008-0057276호에 폴리우레탄 엘라스토머 및 국내 등록특허공보 제10-0131833호에 폴리우레탄 탄성섬유 제조방법에 대한 내용 등을 기술하고 있다.
As a related prior art, in the case of a domestic patent, a method for producing a water-dispersible polyurethane resin having excellent solvent resistance in Korean Patent Publication No. 10-0785349, and a polyurethane elastomer and a domestic Patent Publication No. 10-2008-0057276 Korean Patent Publication No. 10-0131833 describes the contents of the polyurethane elastic fiber manufacturing method and the like.

하지만, 상기와 같은 종래의 기술은 내구성, 내구성, 내약품성, 내광성, 마모강도, 기계적 물성, 유연성, 접착력 등의 물성이 만족할만한 수준에 못미치고 있으며 특히, 섬유 원단에 사용되는 접착제 용도에 적합하지 못하는 문제점이 있었다.
However, the prior art as described above is not satisfactory to the physical properties such as durability, durability, chemical resistance, light resistance, wear strength, mechanical properties, flexibility, adhesive strength, and is not particularly suitable for adhesive applications used in textile fabrics. There was a problem.

또한, 수분산 폴리우레탄은 도입되는 폴리올의 타입과 분자량, 이소시아네이트, 사슬연장제 등의 변화에 따라 형성되는 기계적, 열적 성질 등이 매우 다르게 나타난다. 일반적으로 고분자 사슬에 이온성기를 도입하여 수분산된 폴리우레탄을 제조하며, 이로 인해 수분산 상에서 입자들이 안정성을 유지하게 되는데, 이러한 도입된 이온성기의 종류 및 함량에 따라서 분산체의 입도와 점도 및 분산안정성 등이 크게 영향을 받는 것으로 보고되고 있다.
In addition, the water-dispersed polyurethane is very different in the mechanical and thermal properties formed by the change of the type and molecular weight of the polyol introduced, isocyanate, chain extender and the like. In general, ionic groups are introduced into the polymer chain to prepare a dispersed polyurethane, and as a result, the particles remain stable in the aqueous dispersion, depending on the type and content of the ionic groups introduced, and the particle size and viscosity of the dispersion. It is reported that dispersion stability is greatly affected.

: 국내 등록특허공보 제10-0785349호 "내용제성이 우수한 수분산 폴리우레탄 및 이의 제조방법": Korean Patent Publication No. 10-0785349 "Water Dispersed Polyurethane with Excellent Solvent Resistance and Its Manufacturing Method" : 국내 공개특허공보 제10-2008-0057276 " 폴리우레탄 엘라스토머": Korean Laid-Open Patent Publication No. 10-2008-0057276 "Polyurethane Elastomer" : 국내 등록특허공보 제10-01361833호 "폴리우레탄 탄성섬유 제조방법": Korean Patent Publication No. 10-01361833 "Polyurethane Elastic Fiber Manufacturing Method"

본 발명은 상기와 같은 문제점을 해결하기 위한 것으로, 내가수분해성이 우수한 폴리(테트라메틸렌 글리콜)(PTMG)과 폴리카보네이트 디올, 1,3-Propandiol 혼합물로 이루어지고, 이 혼합물을 디이소시아네이트 화합물과 반응시켜 프리폴리머로 합성한 후 최종적으로 쇄연장제로 합성함으로써, 내구성, 내구성, 내약품성, 내광성, 마모강도, 기계적 물성, 유연성, 접착력 등의 물성이 우수하도록 하는 내수성이 우수한 폴리우레탄 수분산 수지 조성물, 이를 이용한 폴리우레탄 수분산 수지의 제조방법 및 이 제조방법에 의해 제조된 폴리우레탄 수분산 수지를 제공함을 과제로 한다.
The present invention is to solve the above problems, it is composed of a mixture of poly (tetramethylene glycol) (PTMG), polycarbonate diol, 1,3-propanediol excellent in hydrolysis resistance, the mixture is reacted with a diisocyanate compound And a polyurethane dispersion resin composition having excellent water resistance to be excellent in physical properties such as durability, durability, chemical resistance, light resistance, wear strength, mechanical properties, flexibility, and adhesive strength by synthesizing a prepolymer and finally a chain extender. An object of the present invention is to provide a method for producing a polyurethane water-dispersed resin and a polyurethane water-dispersed resin produced by the production method.

아울러, 상기와 같은 물성이 향상됨에 따라 섬유 원단에 사용되는 접착제 용도에 적합하도록 한 폴리우레탄 수분산 수지를 포함하는 폴리우레탄 수분산 접착제를 제공함을 다른 과제로 한다.
In addition, another object of the present invention is to provide a polyurethane water-dispersion adhesive including a polyurethane water-dispersion resin that is suitable for adhesive use used in textile fabrics as the physical properties are improved.

본 발명은 내수성이 우수한 폴리우레탄 수분산 수지 조성물에 있어서,The present invention is a polyurethane water dispersion resin composition excellent in water resistance,

중량평균분자량이 1,000~2,000인 폴리(테트라메틸렌 글리콜)(PTMG) 10~75 몰%, 중량평균분자량이 1,000~2,000인 폴리카보네이트 디올(polycarbonate diol) 4~10 몰% , 폴리올로써 중량평균분자량이 70~80(76.1 삭제)인 1,3-Propandiol 5~15 몰%, 중량평균분자량이 80~100(90.1 삭제)인 1,4-Butandiol 15~25 몰%, 유화제로써 중량평균분자량이 120~140(134 삭제)인 2,2-Bis(hydroxy methyl) propionic acid(DMPA) 0.5~10 몰%, 중량평균분자량이 60~200인 (저분자량 삭제) 디아민 화합물 또는 디올 화합물 0.5~30 몰%로 이루어진 혼합물 100 중량부에 대하여,10 to 75 mol% of poly (tetramethylene glycol) (PTMG) having a weight average molecular weight of 1,000 to 2,000, 4 to 10 mol% of polycarbonate diol having a weight average molecular weight of 1,000 to 2,000, the weight average molecular weight 5 ~ 15 mol% of 1,3-Propandiol with 70 ~ 80 (76.1 deleted), 15 ~ 25mol% of 1,4-Butandiol with 80 ~ 100 (90.1 deleted), 120 ~ 20 wt% as emulsifier 0.5 to 10 mol% of 2,2-Bis (hydroxy methyl) propionic acid (DMPA) with 140 (134), and 0.5 to 30 mol% of diamine compounds or diol compounds having a weight average molecular weight of 60 to 200 (low molecular weight eliminated) Per 100 parts by weight of the mixture,

촉매로써 디부틸틴디라우레이트(dibutyltin dilaurate, DBTDL) 0.01~0.03 중량부가 포함되고, 상기 폴리올과 디이소시아네이트의 NCO/OH 비가 1.0~1.8이 되도록 디이소시아네이트를 더 포함하여 프리폴리머(pre-polymer) 혼합물을 이루고,0.01 to 0.03 parts by weight of dibutyltin dilaurate (DBTDL) is included as a catalyst, and a prepolymer mixture is further included by further comprising diisocyanate such that the NCO / OH ratio of the polyol and diisocyanate is 1.0 to 1.8. Made up,

상기 프리폴리머 혼합물 65~90 몰%에, 쇄연장제 10~35 몰%가 포함되는 것을 특징으로 하는 내수성이 우수한 폴리우레탄 수분산 수지 조성물을 과제의 해결 수단으로 한다.
The polyurethane water-dispersion resin composition excellent in water resistance is characterized in that the prepolymer mixture is contained in an amount of 65 to 90 mol%, and a chain extender is 10 to 35 mol%.

아울러, 상기 내수성이 우수한 폴리우레탄 수분산 수지 조성물 이용한 폴리우레탄 수분산 수지의 제조방법 및 이 제조방법에 의해 제조된 폴리우레탄 수분산 수지를 포함하는 폴리우레탄 수분산 접착제를 과제의 다른 해결 수단으로 한다.
In addition, a polyurethane water-dispersion adhesive comprising a polyurethane water-dispersion resin prepared by using the polyurethane water-dispersion resin composition having excellent water resistance and a polyurethane water-dispersion resin produced by the production method is another solution to the problem. .

한편, 상기 디아민 화합물은, EDA(ethylene diamine), DETA(diethylene tri amine), Piperazine anhydrous에서 1종 또는 그 이상을 선택하여 사용하며,On the other hand, the diamine compound, EDA (ethylene diamine), DETA (diethylene tri amine), Piperazine anhydrous is used to select one or more,

상기 디올 화합물은, 1,4-butanediol, 1,3-Propandiol, 1,6-hexanediol, ehtylene glycol, diethylene glycol에서 1종 또는 그 이상을 선택하여 사용하는 것이 바람직하다.
The diol compound is preferably used by selecting one or more from 1,4-butanediol, 1,3-Propandiol, 1,6-hexanediol, ehtylene glycol, diethylene glycol.

아울러, 상기 폴리(테트라메틸렌 글리콜)은, 아래 화학식 1과 같은 구조를 가지고,In addition, the poly (tetramethylene glycol) has a structure as shown in Formula 1 below,

상기 폴리카보네이트 디올은, 아래 화학식 2와 같은 1,6-헥산디올과 카보네이트의 합성으로 이루어진 C6 home 타입의 폴리카보네이트 디올, 또는 아래 화학식 3과 같은 1,6-헥산디올과 1,5-펜탄디올의 합성으로 이루어진 C5/C6 copolymer 타입의 폴리카보네이트 디올, 또는 아래 화학식 3과 같은 1,6-헥산디올과 1,4-부탄디올의 합성으로 이루어진 C4/C6 copolymer 타입의 폴리카보네이트 디올 중에서 어느 하나를 선택하여 사용하며,The polycarbonate diol is a C6 home type polycarbonate diol consisting of a synthesis of 1,6-hexanediol and carbonate as shown in Formula 2 below, or 1,6-hexanediol and 1,5-pentanediol as shown in Formula 3 below C5 / C6 copolymer type polycarbonate diol consisting of the synthesis, or C4 / C6 copolymer type polycarbonate diol consisting of the synthesis of 1,6-hexanediol and 1,4-butanediol as shown in Formula 3 below To use,

상기 1,3-Propandiol은, 아래 화학식 5와 같은 구조를 가지며,The 1,3-Propandiol has a structure as shown in Formula 5 below,

상기 쇄연장제는, EDA(ethylene diamine), DETA(diethylene tri amine), Piperazine anhydrous 중에서 1종 또는 그 이상을 선택하여 사용하는 것이 바람직하다.
The chain extender is preferably used by selecting one or more of ethylene diamine (EDA), diethylene tri amine (DETA), and piperazine anhydrous.

Figure 112011092038930-pat00001
(화학식1)
Figure 112011092038930-pat00001
Formula 1

Figure 112011092038930-pat00002
(화학식2)
Figure 112011092038930-pat00002
(Formula 2)

Figure 112011092038930-pat00003
(화학식3)
Figure 112011092038930-pat00003
(Formula 3)

Figure 112011092038930-pat00004
(화학식4)
Figure 112011092038930-pat00004
Formula 4

Figure 112011092038930-pat00005
(화학식5)
Figure 112011092038930-pat00005
(Formula 5)

또한, 상기 디이소시아네이트는, 헥사메틸렌디이소시아네이트(hexamethylene diisocyanate, HDI), 이소프론디이소시아네이트(isophoron diisocyanate, IPDI), 4,4'-디헥실메탄디이소시아네이트(4,4'-dihexyl methane diisocyanate, H12MDI), 수소화 크실릴렌디이소시아네이트(hydronated XDI, H6XDI) 중에서 1종 또는 그 이상을 선택하여 사용하는 것이 바람직하다.
In addition, the diisocyanate is hexamethylene diisocyanate (HDI), isophoron diisocyanate (IPDI), 4,4'-dihexyl methane diisocyanate, H 12 MDI), hydrogenated xylylene diisocyanate (hydronated XDI, H 6 XDI) is preferably used to select one or more.

본 발명은 내가수분해성이 우수한 폴리(테트라메틸렌 글리콜)(PTMG)과 폴리카보네이트 디올, 1,3-Propandiol 혼합물로 이루어지고, 이 혼합물을 디이소시아네이트 화합물과 반응시켜 프리폴리머로 합성한 후 최종적으로 쇄연장제로 합성함으로써, 내구성, 내구성, 내약품성, 내광성, 마모강도, 기계적 물성, 유연성, 접착력 등의 물성이 우수한 장점이 있다.
The present invention consists of a mixture of poly (tetramethylene glycol) (PTMG) with excellent hydrolysis resistance, polycarbonate diol and 1,3-propanediol, and the mixture is reacted with a diisocyanate compound to synthesize a prepolymer and finally chain extension. By zero synthesis, there is an advantage of excellent physical properties such as durability, durability, chemical resistance, light resistance, wear strength, mechanical properties, flexibility, adhesion.

아울러, 상기와 같은 물성이 향상됨에 따라 섬유 원단에 사용되는 접착제 용도에 적합한 장점이 있다.
In addition, as the physical properties as described above is improved, there is an advantage suitable for adhesive applications used in textile fabrics.

도 1은 본 발명의 일 실시예에 따른 폴리우레탄 수분산 수지의 제조방법을 나타낸 흐름도1 is a flow chart showing a method for producing a polyurethane water dispersion resin according to an embodiment of the present invention.

상기와 같은 효과를 달성하기 위해 본 발명은 내수성이 우수한 폴리우레탄 수분산 수지 조성물, 이를 이용한 폴리우레탄 수분산 수지의 제조방법 및 이 제조방법에 의해 제조된 폴리우레탄 수분산 수지를 포함하는 폴리우레탄 수분산 접착제에 관한 것으로, 이하 본 발명에 따른 바람직한 실시 예를 상세히 설명하되, 하기의 설명에서는 본 발명을 이해하는데 필요한 부분만이 설명되며 그 이외 부분의 설명은 본 발명의 요지를 흩트리지 않도록 생략될 것이라는 것을 유의하여야 한다.
In order to achieve the effects described above, the present invention provides a polyurethane water dispersion resin composition having excellent water resistance, a polyurethane water dispersion method using the same, and a polyurethane water dispersion resin prepared by the method. Regarding the dispersing adhesive, a preferred embodiment according to the present invention will be described in detail below, but only the parts necessary for understanding the present invention will be described in the following description, and the description of other parts will be omitted so as not to distract from the gist of the present invention. It should be noted that.

이하, 본 발명에 따른 내수성이 우수한 수성 폴리우레탄 수지 조성물에 대하여 상세히 설명하면 아래의 다음과 같다.
Hereinafter, the water-based polyurethane resin composition excellent in water resistance according to the present invention will be described in detail as follows.

본 발명은 내수성이 우수한 폴리우레탄 수분산 수지 조성물에 있어서,The present invention is a polyurethane water dispersion resin composition excellent in water resistance,

중량평균분자량이 1,000~2,000인 폴리(테트라메틸렌 글리콜)(PTMG) 10~75 몰%, 중량평균분자량이 1,000~2,000인 폴리카보네이트 디올 4~10 몰% , 폴리올로써 중량평균분자량이 70~80인 1,3-Propandiol 5~15 몰%, 중량평균분자량이 80~100인 1,4-Butandiol 15~25 몰%, 유화제로써 중량평균분자량이 120~140인 2,2-Bis(hydroxy methyl) propionic acid(DMPA) 0.5~10 몰%, 중량평균분자량이 60~200인 디아민 화합물 또는 디올 화합물 0.5~30 몰%로 이루어진 혼합물 100 중량부에 대하여, 10 to 75 mol% of poly (tetramethylene glycol) (PTMG) having a weight average molecular weight of 1,000 to 2,000, 4 to 10 mol% of polycarbonate diol having a weight average molecular weight of 1,000 to 2,000, polyol having a weight average molecular weight of 70 to 80 1,3-Propandiol 5-15 mol%, 1,4-Butandiol having a weight average molecular weight of 80-100, 15-25 mol%, 2,2-Bis (hydroxy methyl) propionic having a weight average molecular weight of 120-140 as an emulsifier per 100 parts by weight of a mixture consisting of 0.5 to 10 mol% of acid (DMPA) and 0.5 to 30 mol% of diamine compounds or diol compounds having a weight average molecular weight of 60 to 200,

촉매로써 디부틸틴디라우레이트(dibutyltin dilaurate, DBTDL) 0.01~0.03 중량부가 포함되고, 상기 폴리올과 디이소시아네이트의 NCO/OH 비가 1.0~1.8이 되도록 디이소시아네이트를 더 포함하여 프리폴리머(pre-polymer) 혼합물을 이루고,0.01 to 0.03 parts by weight of dibutyltin dilaurate (DBTDL) is included as a catalyst, and a prepolymer mixture is further included by further comprising diisocyanate such that the NCO / OH ratio of the polyol and diisocyanate is 1.0 to 1.8. Made up,

상기 프리폴리머 혼합물 65~90 몰%에, 쇄연장제 10~35 몰%가 포함되는 것을 특징으로 한다.
65 to 90 mol% of the prepolymer mixture, characterized in that 10 to 35 mol% chain extender is included.

상기 중량평균분자량이 1,000~2,000인 폴리(테트라메틸렌 글리콜)(PTMG)는, 아래 화학식 1과 같은 구조를 가지는 것으로, 높은 탄성률, 뛰어난 저온 특성, 적은 영구 압축변형, 내가수분해성, 뛰어난 표면 감촉 등이 우수한 화합물로서 폴리우레탄 수지로 제조될 경우 내가수분해성이 우수하여 내수성이 우수한 접착제로 제조할 수 있다. The poly (tetramethylene glycol) (PTMG) having a weight average molecular weight of 1,000 to 2,000 has a structure as shown in Chemical Formula 1 below, and has high elastic modulus, excellent low temperature property, low permanent compression deformation, hydrolysis resistance, and excellent surface feel. When it is made of a polyurethane resin as this excellent compound, it is excellent in hydrolysis resistance and can be produced as an adhesive having excellent water resistance.

한편, 폴리(테트라메틸렌 글리콜) 화합물의 중량평균분자량은 1,000~2,000인 것이 바람직하며, 폴리(테트라메틸렌 글리콜) 화합물의 중량평균분자량이 1,000 미만이 될 경우에는 최종 폴리우레탄 수지의 유연성과 저온 특성이 우수하지 못하고, 폴리(테트라메틸렌 글리콜) 화합물의 중량평균분자량이 2,000을 초과할 경우에는 프리폴리머 합성 시 점도가 높아 겔이 발생할 수 있으며, 인장강도와 100% 모듈러스(modulus)가 낮아질 우려가 있다.On the other hand, the weight average molecular weight of the poly (tetramethylene glycol) compound is preferably 1,000 to 2,000, when the weight average molecular weight of the poly (tetramethylene glycol) compound is less than 1,000, the flexibility and low temperature characteristics of the final polyurethane resin If the weight average molecular weight of the poly (tetramethylene glycol) compound exceeds 2,000, the viscosity may be high due to the synthesis of the prepolymer, and the tensile strength and the 100% modulus may be lowered.

또한 상기 폴리(테트라메틸렌 글리콜)의 혼합량은 10~75 몰%인 것이 바람직하며, 폴리(테트라메틸렌 글리콜)의 혼합량이 10 몰% 미만인 경우에는 내가수분해성이 떨어질 우려가 있고, 폴리(테트라메틸렌 글리콜)의 혼합량이 75 몰%를 초과할 경우에는 내가수분해성은 증가하나 상대적으로 기계적 물성이 저하되는 문제가 있다.
In addition, it is preferable that the mixing amount of the poly (tetramethylene glycol) is 10 to 75 mol%, and when the mixing amount of the poly (tetramethylene glycol) is less than 10 mol%, hydrolysis resistance may be deteriorated, and poly (tetramethylene glycol) may be inferior. When the mixing amount of c) exceeds 75 mol%, hydrolysis resistance is increased, but there is a problem that the mechanical properties are relatively lowered.

Figure 112011092038930-pat00006
(화학식1)
Figure 112011092038930-pat00006
Formula 1

상기 중량평균분자량이 1,000~2,000인 폴리카보네이트 디올(polycarbonate diol)은, 내열성, 내가수분해성, 내구성, 내마모성, 기계적 물성 등이 우수한 화합물로서, 폴리에스테르 디올의 단점인 내열성, 내가수분해성, 내마모성, 기계적 물성 등의 물성을 보완시켜 주는 작용을 하며, 폴리카보네이트디올의 중량평균분자량은 1,000~2,000인 것이 바람직하며, 폴리카보네이트디올의 중량평균분자량이 1,000 미만이 될 경우에는 최종 폴리우레탄 수지의 유연성과 내열성이 우수하지 못하고, 폴리카보네이트디올의 중량평균분자량이 2,000을 초과할 경우에는 프리폴리머 합성 시 점도가 높아 겔이 발생할 수 있으며, 인장강도와 100% 모듈러스(modulus)가 낮아질 우려가 있다. The polycarbonate diol having a weight average molecular weight of 1,000 to 2,000 is a compound having excellent heat resistance, hydrolysis resistance, durability, wear resistance, mechanical properties, and the like, and has disadvantages of polyester diol, such as heat resistance, hydrolysis resistance, abrasion resistance, It supplements physical properties such as mechanical properties, and the weight average molecular weight of the polycarbonate diol is preferably 1,000 to 2,000. When the weight average molecular weight of the polycarbonate diol is less than 1,000, the flexibility of the final polyurethane resin and If the heat resistance is not excellent, and the weight average molecular weight of the polycarbonate diol exceeds 2,000, the gel may occur due to the high viscosity during prepolymer synthesis, and there is a concern that the tensile strength and the 100% modulus are lowered.

한편, 상기 폴리카보네이트 디올의 혼합량은 4~10 몰%인 것이 바람직하며, 폴리카보네이트 디올의 혼합량이 4 몰% 미만인 경우에는 폴리(테트라메틸렌 글리콜)의 단점인 내열성, 내마모성, 기계적 물성 등의 물성을 제대로 보완시키지 못 할 우려가 있고, 폴리카보네이트 디올의 혼합량이 10 몰%를 초과할 경우에는 물리적 특성은 증가하나 상대적으로 제품의 가격이 상승하는 문제가 있다.On the other hand, it is preferable that the mixing amount of the polycarbonate diol is 4 to 10 mol%, and when the mixing amount of the polycarbonate diol is less than 4 mol%, physical properties such as heat resistance, abrasion resistance, and mechanical properties, which are disadvantages of poly (tetramethylene glycol), are There is a concern that it may not be properly supplemented, and when the amount of the polycarbonate diol mixed exceeds 10 mol%, the physical properties increase, but there is a problem that the price of the product increases.

아울러, 본 발명에서 사용 가능한 폴리카보네이트 디올 화합물은 디올 화합물과 디알킬카보네이트, 디아릴카보네이트 또는 알킬렌카보네이트 중에서 선택된 카보네이트 화합물을 사용하여 에스테르 교환반응으로 합성하여 제조한 폴리카보네이트디올을 사용하는 것이 바람직하다. In addition, the polycarbonate diol compound usable in the present invention, it is preferable to use a polycarbonate diol prepared by synthesizing by transesterification using a diol compound and a carbonate compound selected from dialkyl carbonate, diaryl carbonate or alkylene carbonate. .

한편, 상기 폴리카보네이트 디올은, 상기 디올의 예는 1,6-헥산디올, 1,5-펜탄디올, 1,4-부탄디올, 1,7-헥탄디올, 1,8-올탄디올, 1,9-노난디올 및 1,10-데칸디올이며, 이들 중에서 1,6-헥산디올, 1,5-펜탄디올, 1,4-부탄디올이 바람직하다.On the other hand, the polycarbonate diol, examples of the diol is 1,6-hexanediol, 1,5-pentanediol, 1,4-butanediol, 1,7- hexanediol, 1,8-oltandiol, 1,9 -Nonanediol and 1,10-decanediol, of which 1,6-hexanediol, 1,5-pentanediol and 1,4-butanediol are preferred.

구체적으로는 아래 화학식 2와 같은 1,6-헥산디올과 카보네이트의 합성으로 이루어진 C6 home 타입의 폴리카보네이트 디올, 또는 아래 화학식 3과 같은 1,6-헥산디올과 1,5-펜탄디올의 합성으로 이루어진 C5/C6 copolymer 타입의 폴리카보네이트 디올, 또는 아래 화학식 4와 같은 1,6-헥산디올과 1,4-부탄디올의 합성으로 이루어진 C4/C6 copolymer 타입의 폴리카보네이트 디올 중에서 어느 것을 사용하여도 무방하다.
Specifically, C6 home type polycarbonate diol consisting of the synthesis of 1,6-hexanediol and carbonate as shown in Formula 2, or 1,6-hexanediol and 1,5-pentanediol as shown in Formula 3 below Any C5 / C6 copolymer type polycarbonate diol, or C4 / C6 copolymer type polycarbonate diol consisting of 1,6-hexanediol and 1,4-butanediol as shown in Chemical Formula 4 may be used. .

Figure 112011092038930-pat00007
(화학식2)
Figure 112011092038930-pat00007
(Formula 2)

Figure 112011092038930-pat00008
(화학식3)
Figure 112011092038930-pat00008
(Formula 3)

Figure 112011092038930-pat00009
(화학식4)
Figure 112011092038930-pat00009
Formula 4

상기 중량평균분자량이 70~80인 1,3-Propandiol은, 폴리올로써 아래 화학식 5와 같은 구조를 가지며, 저온 유연성이 우수하고, 옥수수당으로부터 발효에 의해 생산되는 원료를 사용하여 합성된 제품으로 친환경성이 우수한 화합물로서, 기존의 폴리우레탄 수지의 단점인 저온 유연성 및 친환경성을 보완시켜 주는 역할을 한다.
The 1,3-Propandiol having a weight average molecular weight of 70 to 80 has a structure as shown in Formula 5 below as a polyol, has excellent low temperature flexibility, and is environmentally friendly as a product synthesized using raw materials produced by fermentation from corn sugar. As an excellent compound, it plays a role of complementing the low temperature flexibility and environmental friendliness of the conventional polyurethane resin.

한편, 상기와 같은 1,3-Propandiol의 중량평균분자량이 70 미만일 경우,최종제품의 탄성률이 높아져 딱딱해지고 신장률이 낮아지는 문제가 있고, 80을 초과할 경우, 최종 제품의 탄성률과 인장강도가 낮아지는 문제점이 있다. On the other hand, if the weight average molecular weight of the 1,3-Propandiol as described above is less than 70, there is a problem that the elasticity modulus of the final product is increased and the elongation is lowered, and if it exceeds 80, the elasticity and tensile strength of the final product is low There is a problem losing.

아울러, 1,3-Propandiol의 혼합량은 5~15 몰%인 것이 바람직하며, 1,3-Propandiol의 혼합량이 5 몰% 미만인 경우에는 저온 굴곡성이 떨어질 우려가 있고, 1,3-Propandiol의 혼합량이 15 몰%를 초과할 경우에는 저온 굴곡성 및 친환경성은 증가하나 상대적으로 기계적 물성이 저하되는 문제가 있다. 화학식 5에 1,3-Propandiol의 구조를 나타내었다.
In addition, it is preferable that the mixing amount of 1,3-Propandiol is 5 to 15 mol%, and when the mixing amount of 1,3-Propandiol is less than 5 mol%, there is a possibility that low-temperature flexibility is reduced, and the mixing amount of 1,3-Propandiol is When it exceeds 15 mol%, low temperature flexibility and environmental friendliness increase, but there is a problem in that the mechanical properties are relatively lowered. Formula 5 shows the structure of 1,3-Propandiol.

Figure 112011092038930-pat00010
(화학식5)
Figure 112011092038930-pat00010
(Formula 5)

상기 중량평균분자량이 80~100인 1,4-Butandiol은, 저분자량의 폴리올로서 물리적 특성이 우수한 화합물로써, 폴리우레탄 합성 시 고분자량의 폴리올과 이소시아네이트의 가교점 역할을 하여 기계적 물성을 증가시키는 역할을 한다.. 이때, 상기와 같은 1,4-Butandiol의 중량평균분자량이 80 미만일 경우, 최종제품의 탄성률이 너무 높아져 딱딱해질 문제가 있고, 100을 초과할 경우, 최종제품의 탄성률과 인장강도가 낮아지는 문제점이 있다. The 1,4-Butandiol having a weight average molecular weight of 80 to 100 is a compound having excellent physical properties as a low molecular weight polyol, and serves to increase mechanical properties by acting as a crosslinking point of high molecular weight polyol and isocyanate during polyurethane synthesis. In this case, if the weight average molecular weight of the 1,4-Butandiol as described above is less than 80, the elastic modulus of the final product is too high, there is a problem that it becomes hard, if it exceeds 100, the elastic modulus and tensile strength of the final product There is a problem of being lowered.

아울러, 상기 1,4-Butandiol의 혼합량은 15~25 몰%가 바람직하며, 15 물% 미만인 경우에는 최종제품의 신장률이 높아져 인장강도가 낮아질 우려가 있고, 25 몰%를 초과할 경우에는 탄성률 및 인장강도는 높아지나 유연성이 떨어질 우려가 있다.
In addition, the mixing amount of the 1,4-Butandiol is preferably 15 to 25 mol%, and if the water content is less than 15% by water, the elongation of the final product may be increased and the tensile strength may be lowered. Tensile strength is increased, but there is a fear that flexibility is reduced.

상기 중량평균분자량이 120~140인 2,2-Bis(hydroxy methyl) propionic acid(DMPA)은, 유화제로써, 양말단에 hydroxyl기와 carboxyl기를 가진 화합물로서 hydroxyl기에 의해 우레탄 결합과 carboxyl기에 의해 물에 유화되는 역할을 한다. 이때, 상기와 같은 2,2-Bis(hydroxy methyl) propionic acid(DMPA)의 중량평균분자량이 120 미만일 경우, 물에 유화도기 어렵고 최종제품이 딱딱해지는 문제가 있고, 140을 초과할 경우, 최종제품의 기계적 물성이 떨어지는 문제점이 있다. The 2,2-Bis (hydroxy methyl) propionic acid (DMPA) having a weight average molecular weight of 120 to 140 is an emulsifier, a compound having a hydroxyl group and a carboxyl group at the sock end, emulsified in water by a hydroxyl group and a carboxyl group by a hydroxyl group. Play a role. At this time, if the weight average molecular weight of the 2,2-Bis (hydroxy methyl) propionic acid (DMPA) as described above is less than 120, it is difficult to emulsify in water and the final product is a problem of hardening, if it exceeds 140, the final product There is a problem that the mechanical properties of the fall.

아울러, 상기 2,2-Bis(hydroxy methyl) propionic acid(DMPA)의 혼합량은 0.5~10 몰%가 바람직하며, 0.5 물% 미만인 경우에는 최종 폴리우레탄 수지가 물에 유화되지 않을 우려가 있고, 10 몰%를 초과할 경우에는 유화가 용이하나 최종제품의 내수성이 나빠질 우려가 있다.
In addition, the mixing amount of the 2,2-Bis (hydroxy methyl) propionic acid (DMPA) is preferably 0.5 to 10 mol%, if less than 0.5 water% there is a fear that the final polyurethane resin is not emulsified in water, 10 When the molar percentage is exceeded, the emulsion is easy but the water resistance of the final product may be deteriorated.

상기 중량평균분자량이 60~200인 디아민 화합물 또는 디올 화합물은, 저분자량의 말단에 amine기 또는 hydroxyl기를 가진 화합물로써, 폴리우레탄 합성반응에서 쇄연장제역할을 한다.
The diamine compound or diol compound having a weight average molecular weight of 60 to 200 is a compound having an amine group or a hydroxyl group at a terminal having a low molecular weight, and serves as a chain extender in a polyurethane synthesis reaction.

이때, 상기 디아민 화합물은, EDA(ethylene diamine), DETA(diethylene tri amine), Piperazine anhydrous에서 1종 또는 그 이상을 선택하여 사용하며, 상기 디올 화합물은, 1,4-butanediol, 1,3-Propandiol, 1,6-hexanediol, ehtylene glycol, diethylene glycol 에서 1종 또는 그 이상을 선택하여 사용하는 것이 바람직하다.In this case, the diamine compound, EDA (ethylene diamine), DETA (diethylene tri amine), Piperazine anhydrous is used to select one or more, and the diol compound, 1,4-butanediol, 1,3-Propandiol It is preferable to use one or more selected from 1,6-hexanediol, ehtylene glycol and diethylene glycol.

한편, 상기와 같은 디아민 화합물 또는 디올 화합물의 중량평균분자량이 60미만일 경우, 반응성이 너무 빨라 반응성을 제어하기 힘들고, 최종제품이 딱딱해질 수 있는 문제가 있고, 200을 초과할 경우, 반응성이 느려지고 최종제품의 탄성률이 떨어질 수 있는 문제점이 있다. On the other hand, if the weight average molecular weight of the diamine compound or diol compound as described above is less than 60, the reactivity is too fast to control the reactivity, there is a problem that the final product can be hardened, if it exceeds 200, the reactivity is slow and the final There is a problem that the elastic modulus of the product may fall.

아울러, 상기 디아민 화합물 또는 디올 화합물의 혼합량은 0.5~30 몰%가 바람직하며, 0.5 물% 미만인 경우에는 0.5 물% 미만인 경우에는 최종제품의 기계적 물성이 떨어질 우려가 있고, 30 몰%를 초과할 경우에는 최종제품이 기계적 물성은 증가하나 유연성이 떨어질 우려가 있다.
In addition, the mixing amount of the diamine compound or diol compound is preferably 0.5 to 30 mol%, when less than 0.5% by water is less than 0.5% by water, there is a fear that the mechanical properties of the final product is lowered, if it exceeds 30 mol% There is a fear that the final product will have increased mechanical properties but less flexibility.

본 발명에서 사용되는 촉매인 디부틸틴디라우레이트(dibutyltin dilaurate, DBTDL)는 상기 혼합물 100 중량부에 대하여, 0.01~0.03 중량부를 첨가하는 것이 바람직하다. 촉매의 첨가량이 0.01 중량부 미만이 될 경우에는 상기 혼합물과 후술되어질 디이소시아네이트가 제대로 반응되지 않을 우려가 있고, 촉매의 첨가량이 0.03 중량부를 초과할 경우에는 합성반응에 특별한 영향을 미치지 않는다.
Dibutyltin dilaurate (DBTDL), which is a catalyst used in the present invention, is preferably added in an amount of 0.01 to 0.03 parts by weight based on 100 parts by weight of the mixture. If the addition amount of the catalyst is less than 0.01 parts by weight, the mixture and the diisocyanate to be described later may not be properly reacted. If the addition amount of the catalyst exceeds 0.03 parts by weight, the synthesis reaction is not particularly affected.

상기 본 발명에서 사용되는 디이소시아네이트는 상기 폴리올과 디이소시아네이트의 NCO/OH 비가 1.0~1.8이 되도록 디이소시아네이트를 첨가하는 것이 바람직하다.The diisocyanate used in the present invention preferably adds a diisocyanate such that the NCO / OH ratio of the polyol and diisocyanate is 1.0 to 1.8.

여기서 폴리올과 디이소시아네이트의 NCO/OH 비가 1.0~1.8 라는 것은, NCO : OH가 1.0 : 1~ 1.8 : 1라는 것을 말한다.The NCO / OH ratio of polyol and diisocyanate here being 1.0-1.8 means that NCO: OH is 1.0: 1-1.8: 1.

상기에서 NCO/OH 비가 1.0 미만이 될 경우에는 폴리우레탄이 충분히 합성되지 않을 우려가 있고, NCO/OH 비가 1.8을 초과할 경우에는 반응에 참여하지 않은 과량의 디이소시아네이트는 공기 중 수분과 반응하여 쉽게 경화되어질 우려가 있다. In the above case, when the NCO / OH ratio is less than 1.0, the polyurethane may not be sufficiently synthesized. When the NCO / OH ratio exceeds 1.8, the excess diisocyanate that does not participate in the reaction may easily react with moisture in the air. There is a risk of curing.

아울러, 상기 디이소시아네이트는 아리파틱 이소시아네이트(aliphatic isocyanate) 계열의 제품을 사용하는 것이 바람직하며, 상기 제품의 예로는 헥사메틸렌디이소시아네이트(hexamethylene diisocyanate, HDI), 이소프론디이소시아네이트(isophoron diisocyanate, IPDI), 4,4'-디헥실메탄디이소시아네이트(4,4'-dihexyl methane diisocyanate, H12MDI), 수소화크실렌디이소시아네이트(hydronated XDI, H6XDI) 중에서 1종 또는 그 이상을 선택하여 사용하는 것이 바람직하며, 이들 중에서 이소프론디이소시아네이트(isophoron diisocyanate, IPDI)가 특히 바람직하다.
In addition, the diisocyanate is preferably an aliphatic isocyanate-based product, and examples of the product are hexamethylene diisocyanate (HDI), isophoron diisocyanate (IPDI), It is preferable to use one or more selected from 4,4'-dihexyl methane diisocyanate (H 12 MDI) and hydrogenated xylene diisocyanate (hydronated XDI, H 6 XDI). Of these, isophoron diisocyanate (IPDI) is particularly preferred.

본 발명에서 사용되는 상기 쇄연장제는, 선상의 분자쇄를 연장시키고, 폴리우레탄 분자량의 증가와 과량의 이소시아네이트와 함께 가교결합하는 작용을 하는 것으로, 상기 혼합물에 촉매와 디이소시아네이트가 더 포함되어 이루어진 상기 프리폴리머(pre-polymer) 혼합물 65~90 몰%에, 쇄연장제 10~35 몰%가 포함되는 것이 바람직하다. 쇄연장제의 첨가량이 10 몰% 미만이 될 경우에는 소프트 세그멘트(soft segment)의 함량이 증가하여 유연성은 증가하나 기계적 물성이 취약해 질수 있고, 쇄연장제의 첨가량이 35 몰%를 초과할 경우에는 하드 세그멘트(hard segment)의 함량이 증가하여 딱딱해질 우려가 있다. The chain extender used in the present invention extends linear molecular chains and increases the molecular weight of the polyurethane and crosslinks with an excess of isocyanate. The chain extender further comprises a catalyst and a diisocyanate. It is preferable that 10 to 35 mol% of a chain extender is included in 65 to 90 mol% of the prepolymer mixture. If the amount of the chain extender is less than 10 mol%, the content of the soft segment is increased, thereby increasing the flexibility, but the mechanical properties may be weak, and if the amount of the chain extender is more than 35 mol%. There is a fear that the content of the hard segment (hard segment) increases and becomes hard.

한편, 본 발명에서 사용하는 쇄연장제는 EDA(ethylene diamine), DETA(diethylene tri amine), Piperazine anhydrous 중에서 1종 또는 그 이상을 선택하여 사용하는 것이 바람직하다.
On the other hand, the chain extender used in the present invention is preferably used by selecting one or more of EDA (ethylene diamine), DETA (diethylene tri amine), Piperazine anhydrous.

이하, 내수성이 우수한 폴리우레탄 수분산 수지 조성물, 이를 이용한 폴리우레탄 수분산 수지의 제조방법에 대하여, 상세히 설명하면 아래의 다음과 같다.
Hereinafter, a polyurethane water dispersion resin composition having excellent water resistance, and a method for preparing a polyurethane water dispersion resin using the same, will be described in detail as follows.

본 발명에 따른 폴리우레탄 수분산 수지의 제조방법은, 중량평균분자량이 1,000~2,000인 폴리(테트라메틸렌 글리콜)(PTMG) 10~75 몰%, 중량평균분자량이 1,000~2,000인 폴리카보네이트 디올 4~10 몰% , 폴리올로써 중량평균분자량이 70~80인 1,3-Propandiol 5~15 몰%, 중량평균분자량이 80~100인 1,4-Butandiol 15~25 몰%, 유화제로써 중량평균분자량이 120~140인 2,2-Bis(hydroxy methyl) propionic acid(DMPA) 0.5~10 몰%, 중량평균분자량이 60~200인 디아민 화합물 또는 디올 화합물 0.5~30 몰%로 이루어진 혼합물의 수분을 제거하고, 수분을 제거한 상기 혼합물 100 중량부에 대하여, 촉매로써 디부틸틴디라우레이트(dibutyltin dilaurate, DBTDL) 0.01~0.03 중량부를 질소분위기에서 80~90℃에서 25~35분간 혼합하는 단계(S1);The method for producing a polyurethane water dispersion resin according to the present invention is a polycarbonate diol having a weight average molecular weight of 1,000 to 2,000 (PTMG) 10 to 75 mol%, a weight average molecular weight of 1,000 to 2,000 polycarbonate diol 4 ~ 10 mol%, 1 to 3-Propandiol having a weight average molecular weight of 70 to 80 as polyol, 5 to 15 mol%, 1 to 25 mol% of 1,4-Butandiol having a weight average molecular weight of 80 to 100, weight average molecular weight as an emulsifier Remove water from a mixture consisting of 0.5 to 10 mol% of 2,2-Bis (hydroxy methyl) propionic acid (DMPA) having 120 to 140, and a diamine compound having a weight average molecular weight of 60 to 200 or 0.5 to 30 mol% of a diol compound. To 100 parts by weight of the mixture, the water is removed, dibutyltin dilaurate (dibutyltin dilaurate, DBTDL) 0.01 to 0.03 parts by weight in a nitrogen atmosphere for 25 to 35 minutes at 25 to 35 minutes in a mixed atmosphere (S1);

상기 촉매가 혼합된 혼합물에 디이소시아네이트를 투입하여 80~90℃에서 180~300분간 프리폴리머 합성반응을 진행시키는 단계(S2); 및Adding a diisocyanate to the mixture mixed with the catalyst to perform a prepolymer synthesis reaction at 80 to 90 ° C. for 180 to 300 minutes (S2); And

상기 프리폴리머 합성반응에 의한 프리폴리머 혼합물 65~90 몰%에, 쇄연장제 10~35 몰%를 투입하여 80~90℃의 온도에서 120~180 분간 합성반응시키는 단계(S3);를 포함하여 제조되는 것을 특징으로 한다.
Prepared by the step of (S3); the synthesis of 120 to 180 minutes at a temperature of 80 ~ 90 ℃ by adding a chain extender 10 ~ 35 mol% to the prepolymer mixture 65 ~ 90 mol% by the prepolymer synthesis reaction; It is characterized by.

여기서, 상기 프리폴리머(pre-polymer)란, 성형하기 쉽게 하기 위하여 중합 반응(重合反應)을 중도 단계에서 중지시킨, 비교적 중합도(重合度)가 낮은 중합체(重合體)를 말한다.
Here, the said prepolymer means the polymer with comparatively low polymerization degree which stopped the polymerization reaction in the intermediate | middle stage in order to make it easy to shape | mold.

여기서, 상기 각 조성물에 대해서는 이미 상세하게 설명한 바 있으므로 여기서는 그 설명을 생략하기로 한다.
Here, since each composition has already been described in detail, the description thereof will be omitted here.

한편, 상기 폴리우레탄 수분산 수지의 제조방법에 있어서, 각 제조조건의 범위를 벗어날 경우, 물을 투입하여 유화시키기 어렵거나, 물리적 특성이 저하될 우려가 있다.
On the other hand, in the manufacturing method of the said polyurethane water dispersion resin, when it is out of the range of each manufacturing conditions, it may be difficult to add water and emulsify, or a physical property may fall.

한편, 상기와 같은 제조방법에 의해 제조된 폴리우레탄 수분산 수지는 내수성이 우수하므로 섬유용 접착제, 벽지용 접착제, 자동차 시트용 접착제, 인공피혁용 접착제, 합성피혁용 접착제, 가방 원단용 접착제, 의류용 원단용 접착제, 신발 원단용 접착제 등의 폴리우레탄 수분산 접착제 뿐만 아니라, 합성피혁 및 인공피혁용 코팅제, 목재용 코팅제, 전자부품 코팅제, 바닥재 코팅제, 도료 등과 같이 다양한 분야에 적용될 수 있다.
On the other hand, the polyurethane water-dispersed resin produced by the manufacturing method as described above is excellent in water resistance, such as fiber adhesive, wallpaper adhesive, automotive seat adhesive, artificial leather adhesive, synthetic leather adhesive, bag fabric adhesive, clothing It can be applied to various fields such as polyurethane water dispersion adhesives such as adhesives for fabrics and adhesives for shoes, as well as coatings for synthetic leathers and artificial leathers, coatings for wood, electronic component coatings, flooring coatings, paints and the like.

이하, 본 발명의 구성을 아래 실시 예에 의거하여 더욱 상세히 설명하겠는바 본 발명이 하기의 실시 예에 의해서만 반드시 한정되는 것은 아니다.
Hereinafter, the structure of the present invention will be described in more detail based on the following examples, but the present invention is not necessarily limited to the following examples.

1. 내수성이 우수한 폴리우레탄 수분산 수지 조성물을 이용한 폴리우레탄 수분산 수지의 제조
1.Production of polyurethane water dispersion resin using polyurethane water dispersion resin composition having excellent water resistance

(실시예 1)(Example 1)

중량평균분자량이 1000인 폴리(테트라메틸렌 글리콜)(PTMG) 10 몰%, 중량평균분자량이 2000인 폴리카보네이트 디올 10 몰% , 폴리올로써 중량평균분자량이 80인 1,3-Propandiol 15 몰%, 중량평균분자량이 100인 1,4-Butandiol 25 몰%, 중량평균분자량이 140인 2,2-Bis(hydroxy methyl) propionic acid(DMPA) 10 몰%, 중량평균분자량이 200인 디아민 화합물 또는 디올 화합물 30 몰%로 이루어진 혼합물의 수분을 제거하고, 수분을 제거한 상기 혼합물 100 중량부에 대하여, 촉매로써 디부틸틴디라우레이트(dibutyltin dilaurate, DBTDL) 0.03 중량부를 질소분위기에서 80℃에서 35분간 혼합하고(S1), 상기 촉매가 혼합된 혼합물에 상기 폴리올과 디이소시아네이트의 NCO/OH 비가 1.8이 되도록 디이소시아네이트를 투입하여 80℃에서 300분간 프리폴리머 합성반응을 진행시킨 후(S2), 상기 프리폴리머 합성반응에 의한 프리폴리머 혼합물 65 몰%에 대하여, 쇄연장제 35 몰%를 투입하여 80℃의 온도에서 180 분간 합성반응시켜(S3), 폴리우레탄 수분산 수지를 제조하였다.
10 mol% of poly (tetramethylene glycol) (PTMG) having a weight average molecular weight of 1000, 10 mol% of polycarbonate diol having a weight average molecular weight of 2000, 15 mol% of 1,3-Propandiol having a weight average molecular weight of 80 as a polyol, weight 1,4-Butandiol having an average molecular weight of 100 mol moles, 2,2-Bis (hydroxy methyl) propionic acid (DMPA) having a weight average molecular weight of 140 moles, diamine compound or diol compound having a weight average molecular weight of 200 Moisture of the mixture consisting of mol% was removed, and 0.03 parts by weight of dibutyltin dilaurate (DBTDL) as a catalyst was mixed with respect to 100 parts by weight of the mixture from which water was removed (S1) at 80 ° C. for 35 minutes (S1). ), A diisocyanate was added to the mixture of the catalyst so that the NCO / OH ratio of the polyol and the diisocyanate was 1.8, and then the prepolymer synthesis reaction was performed at 80 ° C. for 300 minutes (S2). With respect to the prepolymer mixture of 65% by mole, to synthesize 180 min at a temperature of 80 ℃ by chain extending a first input 35 mol% (S3), to thereby prepare a polyester urethane resin dispersion.

(실시예 2)(Example 2)

중량평균분자량이 1500인 폴리(테트라메틸렌 글리콜)(PTMG) 59 몰%, 중량평균분자량이 1800인 폴리카보네이트 디올 7 몰% , 폴리올로써 중량평균분자량이 76.1인 1,3-Propandiol 8 몰%, 중량평균분자량이 90.1 인 1,4-Butandiol 10 몰%, 중량평균분자량이 134인 2,2-Bis(hydroxy methyl) propionic acid(DMPA) 6 몰%, 중량평균분자량이 150인 디아민 화합물 또는 디올 화합물 10 몰%로 이루어진 혼합물의 수분을 제거하고, 수분을 제거한 상기 혼합물 100 중량부에 대하여, 촉매로써 디부틸틴디라우레이트(dibutyltin dilaurate, DBTDL) 0.02 중량부를 질소분위기에서 85℃에서 30분간 혼합하고(S1), 상기 촉매가 혼합된 혼합물에 상기 폴리올과 디이소시아네이트의 NCO/OH 비가 1.7이 되도록 디이소시아네이트를 투입하여 82℃에서 250분간 프리폴리머 합성반응을 진행시킨 후(S2), 상기 프리폴리머 합성반응에 의한 프리폴리머 혼합물 70 몰%에 대하여, 쇄연장제 30 몰%를 투입하여 82℃의 온도에서 150 분간 합성반응시켜(S3), 폴리우레탄 수분산 수지를 제조하였다.
59 mol% of poly (tetramethylene glycol) (PTMG) having a weight average molecular weight of 1500, 7 mol% of polycarbonate diol having a weight average molecular weight of 1800, 8 mol% of 1,3-Propandiol having a weight average molecular weight of 76.1 as a polyol, weight 10 mol% of 1,4-Butandiol having an average molecular weight of 90.1, 6 mol% of 2,2-Bis (hydroxy methyl) propionic acid (DMPA) having a weight average molecular weight of 134, diamine compound or diol compound having a weight average molecular weight of 150 Moisture of the mixture consisting of mol% was removed, and 0.02 parts by weight of dibutyltin dilaurate (DBTDL) as a catalyst was mixed with respect to 100 parts by weight of the mixture from which the water was removed (S1) at 85 ° C. for 30 minutes (S1). ), A diisocyanate was added to the mixture of the catalyst so that the NCO / OH ratio of the polyol and the diisocyanate was 1.7, and the prepolymer synthesis reaction was performed at 82 ° C. for 250 minutes (S2). With respect to the prepolymer mixture of 70 mol%, by synthesis 150 min at a temperature of 82 ℃ by chain elongation In the claim 30 mol% of (S3), to thereby prepare a polyester urethane resin dispersion.

(실시예 3)(Example 3)

중량평균분자량이 1800인 폴리(테트라메틸렌 글리콜)(PTMG) 62 몰%, 중량평균분자량이 1500인 폴리카보네이트 디올 5 몰% , 폴리올로써 중량평균분자량이 72인 1,3-Propandiol 6 몰%, 중량평균분자량이 85인 1,4-Butandiol 17 몰%, 중량평균분자량이 125인 2,2-Bis(hydroxy methyl) propionic acid(DMPA) 122 몰%, 중량평균분자량이 100인 디아민 화합물 또는 디올 화합물 8 몰%로 이루어진 혼합물의 수분을 제거하고, 수분을 제거한 상기 혼합물 100 중량부에 대하여, 촉매로써 디부틸틴디라우레이트(dibutyltin dilaurate, DBTDL) 0.015 중량부를 질소분위기에서 87℃에서 27분간 혼합하고(S1), 상기 촉매가 혼합된 혼합물에 상기 폴리올과 디이소시아네이트의 NCO/OH 비가 1.3이 되도록 디이소시아네이트를 투입하여 85℃에서 200분간 프리폴리머 합성반응을 진행시킨 후(S2), 상기 프리폴리머 합성반응에 의한 프리폴리머 혼합물 80 몰%에 대하여, 쇄연장제 20 몰%를 투입하여 85℃의 온도에서 130 분간 합성반응시켜(S3), 폴리우레탄 수분산 수지를 제조하였다.
62 mol% of poly (tetramethylene glycol) (PTMG) having a weight average molecular weight of 1800, 5 mol% of a polycarbonate diol having a weight average molecular weight of 1500, 6 mol% of 1,3-Propandiol having a weight average molecular weight of 72 as a polyol, weight the average molecular weight of 85 1,4-Butandiol 17 mol%, a weight average molecular weight of 125 of 2,2-Bis (hydroxy methyl) propionic acid (DMPA) 12 of the diamine compound or diol compound 2 mol%, a weight average molecular weight of 100 To remove the moisture of the mixture consisting of 8 mol%, and 0.015 parts by weight of dibutyltin dilaurate (DBTDL) as a catalyst for 100 parts by weight of the mixture from which water was removed and mixed for 27 minutes at 87 ° C. in a nitrogen atmosphere ( S1), a diisocyanate is added to the mixture of the catalyst so that the NCO / OH ratio of the polyol and the diisocyanate is 1.3, and then a prepolymer synthesis reaction is performed at 85 ° C. for 200 minutes (S2), followed by the prepolymer synthesis reaction. 20 mol% of a chain extender was added with respect to 80 mol% of one prepolymer mixture, and the synthetic reaction was carried out for 130 minutes at the temperature of 85 degreeC (S3), and the polyurethane water dispersion resin was produced.

(실시예 4)(Example 4)

중량평균분자량이 2000인 폴리(테트라메틸렌 글리콜)(PTMG) 75 몰%, 중량평균분자량이 1000인 폴리카보네이트 디올 4 몰% , 폴리올로써 중량평균분자량이 70인 1,3-Propandiol 5 몰%, 중량평균분자량이 80인 1,4-Butandiol 15 몰%, 중량평균분자량이 120인 2,2-Bis(hydroxy methyl) propionic acid(DMPA) 0.5 몰%, 중량평균분자량이 60인 디아민 화합물 또는 디올 화합물 0.5 몰%로 이루어진 혼합물의 수분을 제거하고, 수분을 제거한 상기 혼합물 100 중량부에 대하여, 촉매로써 디부틸틴디라우레이트(dibutyltin dilaurate, DBTDL) 0.01 중량부를 질소분위기에서 90℃에서 25분간 혼합하고(S1), 상기 촉매가 혼합된 혼합물에 상기 폴리올과 디이소시아네이트의 NCO/OH 비가 1.0이 되도록 디이소시아네이트를 투입하여 90℃에서 180분간 프리폴리머 합성반응을 진행시킨 후(S2), 상기 프리폴리머 합성반응에 의한 프리폴리머 혼합물 90 몰%에 대하여, 쇄연장제 10 몰%를 투입하여 90℃의 온도에서 120 분간 합성반응시켜(S3), 폴리우레탄 수분산 수지를 제조하였다.
75 mol% of poly (tetramethylene glycol) (PTMG) having a weight average molecular weight of 2000, 4 mol% of polycarbonate diol having a weight average molecular weight of 1000, 5 mol% of 1,3-Propandiol having a weight average molecular weight of 70 as a polyol, weight 15 mol% of 1,4-Butandiol having an average molecular weight of 80, 0.5 mol% of 2,2-Bis (hydroxy methyl) propionic acid (DMPA) having a weight average molecular weight of 120, a diamine compound or a diol compound having a weight average molecular weight of 60 0.5 Moisture of the mixture consisting of mol% is removed, and 0.01 parts by weight of dibutyltin dilaurate (DBTDL) is mixed with a catalyst for 25 minutes at 90 ° C. for 25 minutes with respect to 100 parts by weight of the dehydrated mixture (S1). ), A diisocyanate was added to the mixture of the catalyst so that the NCO / OH ratio of the polyol and the diisocyanate was 1.0, and then the prepolymer synthesis reaction was performed at 90 ° C. for 180 minutes (S2), followed by the prepolymer synthesis reaction. With respect to the prepolymer mixture of 90 mol%, the chain extender added to the 10 mol% was produced (S3), a polyurethane resin dispersion was synthesized 120 min at a temperature of 90 ℃.

(비교예 1)(Comparative Example 1)

폴리(테트라메틸렌 글리콜)(PTMG) 23 몰%, 중량평균분자량이 90.1 인 1,4-Butandiol 8 몰%, 중량평균분자량이 134인 2,2-Bis(hydroxy methyl) propionic acid(DMPA) 6 몰%, 중량평균분자량이 60인 디아민 화합물 또는 디올 화합물 0.5 몰%로 이루어진 혼합물의 수분을 제거하고, 수분을 제거한 상기 혼합물 100 중량부에 대하여, 촉매로써 디부틸틴디라우레이트(dibutyltin dilaurate, DBTDL) 0.01 중량부를 질소분위기에서 85℃에서 30분간 혼합하고(S1), 상기 촉매가 혼합된 혼합물에 디이소시아네이트 45 몰% 투입하여 85℃에서 250분간 프리폴리머 합성반응을 진행시킨 후(S2), 상기 프리폴리머 합성반응에 의한 프리폴리머 혼합물 65 몰%에 대하여, 쇄연장제 35 몰%를 투입하여 80℃의 온도에서 150 분간 합성반응시켜(S3), 폴리우레탄 수분산 수지를 제조하였다.
23 mol% of poly (tetramethylene glycol) (PTMG), 1 mol of 1,4-Butandiol having a weight average molecular weight of 90.1, 6 mol of 2,2-Bis (hydroxy methyl) propionic acid (DMPA) having a weight average molecular weight of 134 %, A diamine compound having a weight average molecular weight of 60, or a molar mixture of 0.5 mol% of a diol compound was removed, and dibutyltin dilaurate (DBTDL) 0.01 was used as a catalyst based on 100 parts by weight of the mixture. After mixing the parts by weight in a nitrogen atmosphere for 30 minutes at 85 ℃ (S1), 45 mol% diisocyanate was added to the mixture mixed with the catalyst to proceed the prepolymer synthesis reaction at 85 ℃ 250 minutes (S2), the prepolymer synthesis reaction With respect to 65 mol% of the prepolymer mixture, 35 mol% of a chain extender was added and synthesized for 150 minutes at a temperature of 80 ° C. (S3) to prepare a polyurethane water dispersion resin.

2. 내구성이 우수한 폴리우레탄 코팅 수지의 평가
2. Evaluation of Durable Polyurethane Coating Resin

실시예 1~4 및 비교예 1의 폴리우레탄 수분산 수지에 대한 물리적 특성을 평가한 결과는 아래 [표 1]의 내용과 같다.
The results of evaluating the physical properties of the polyurethane water dispersion resins of Examples 1 to 4 and Comparative Example 1 are as shown in Table 1 below.

구성 성분Constituent 단위unit 평가방법Assessment Methods 실시예Example 비교예Comparative Example 1One 22 33 44 22 100% 탄성률(modulus)100% modulus kgf/cm2 kgf / cm 2 ASTM D 638ASTM D 638 3535 3535 3737 4141 3333 인장강도(tensile strength)Tensile strength kgf/cm2 kgf / cm 2 ASTM D 638ASTM D 638 177177 181181 184184 192192 172172 인열강도(tear strength)Tear strength kgf/cmkgf / cm ASTM D 624ASTM D 624 6262 6262 6464 6565 5858 마모성(abrasion)Abrasion mg lossmg loss ASTM D 3384ASTM D 3384 4949 4747 4646 4444 5454 내가수분해성(anti-hydrolysis)
(40, 80%, 1hr 후 인장강도)Anti-hydrolysis
(40, 80%, tensile strength after 1hr) kgf/cm2 kgf / cm 2 ASTM D 638ASTM D 638 129129 138138 139139 141141 121121 접착강도(adhesive strength)
(폴리에스테르 원단에 대한 접착강도)Adhesive strength
(Adhesive Strength for Polyester Fabrics) kgf/cmkgf / cm ASTM D 638ASTM D 638 1.41.4 1.51.5 1.51.5 1.61.6 1.11.1
*상기 각 실시예 및 비교예의 중량평균분자량은 GPC(Gel Permeation Chromatography)를 이용하여 측정하였다.
The weight average molecular weights of the above Examples and Comparative Examples were measured using GPC (Gel Permeation Chromatography).

상기 실시예 1~4 및 비교예 1의 폴리우레탄 수분산 수지에 대한 기계적 물성을 시험한 결과, 상기 [표 1]에서와 같이, 실시예 1~4는 비교예 1에 비해 100% 탄성률, 인장강도, 인열강도, 마모성, 내수성 등과 같은 기계적 물성의 성능이 모두 우수함을 확인할 수 있었다.
As a result of testing the mechanical properties of the polyurethane water dispersion resin of Examples 1 to 4 and Comparative Example 1, as shown in Table 1, Examples 1 to 4 are 100% elastic modulus, tensile strength compared to Comparative Example 1 It was confirmed that the performance of mechanical properties such as strength, tear strength, wear resistance, and water resistance were all excellent.

그리고 실시예 1~4의 폴리우레탄 수분산 수지에서, 인장강도, 마모성, 인열강도, 내수성의 경우에는 폴리(테트라메틸렌 글리콜)과 폴리카보네이트디올을 적절한 혼합시켜 합성할 경우에 상기 물성을 향상시킬 수 있음을 알 수 있었다.
In the polyurethane water dispersion resins of Examples 1 to 4, in the case of tensile strength, abrasion resistance, tear strength, and water resistance, the physical properties of the poly (tetramethylene glycol) and polycarbonate diol may be improved by the proper mixing. I could see that.

상술한 바와 같이, 본 발명에 따른 내수성이 우수한 폴리우레탄 수분산 수지 조성물, 이를 이용한 폴리우레탄 수분산 수지의 제조방법 및 이 제조방법에 의해 제조된 폴리우레탄 수분산 수지를 포함하는 폴리우레탄 수분산 접착제을 상기의 바람직한 실시 예를 통해 설명하고, 그 우수성을 확인하였지만 해당 기술분야의 당업자라면 하기의 특허청구범위에 기재된 본 발명의 사상 및 영역으로부터 벗어나지 않는 범위 내에서 본 발명을 다양하게 수정 및 변경시킬 수 있음을 이해할 수 있을 것이다.
As described above, the polyurethane water dispersion resin composition comprising the polyurethane water dispersion resin composition having excellent water resistance according to the present invention, a polyurethane water dispersion resin using the same and a polyurethane water dispersion resin prepared by the production method Although the present invention has been described through the above-described preferred embodiments and its superiority has been confirmed, those skilled in the art can variously modify and change the present invention without departing from the spirit and scope of the present invention as set forth in the claims below. I can understand that.

S1 : 혼합물 제조단계
S2 : 디소시아네이트 투입단계
S3 : 쇄연장제 투입단계S1: Mixture Preparation Step
S2: disocyanate input step
S3: Insertion of chain extender

Claims (7)

내수성이 우수한 폴리우레탄 수분산 수지 조성물에 있어서,
중량평균분자량이 1,000~2,000인 폴리(테트라메틸렌 글리콜)(PTMG) 10~75 몰%, 중량평균분자량이 1,000~2,000인 폴리카보네이트 디올(polycarbonate diol) 4~10 몰% , 폴리올로써 중량평균분자량이 70~80인 1,3-Propandiol 5~15 몰%, 중량평균분자량이 80~100인 1,4-Butandiol 15~25 몰%, 유화제로써 중량평균분자량이 120~140인 2,2-Bis(hydroxy methyl) propionic acid(DMPA) 0.5~10 몰%, 중량평균분자량이 60~200인 디아민 화합물 또는 디올 화합물 0.5~30 몰%로 이루어진 혼합물 100 중량부에 대하여,
촉매로써 디부틸틴디라우레이트(dibutyltin dilaurate, DBTDL) 0.01~0.03 중량부가 포함되고, 상기 폴리올과 디이소시아네이트의 NCO/OH 비가 1.0~1.8이 되도록 디이소시아네이트를 더 포함하여 프리폴리머(pre-polymer) 혼합물을 이루고,
상기 프리폴리머 혼합물 65~90 몰%에, 쇄연장제 10~35 몰%가 포함되는 것을 특징으로 하는 내수성이 우수한 폴리우레탄 수분산 수지 조성물.
In the polyurethane water dispersion resin composition excellent in water resistance,
10 to 75 mol% of poly (tetramethylene glycol) (PTMG) having a weight average molecular weight of 1,000 to 2,000, 4 to 10 mol% of polycarbonate diol having a weight average molecular weight of 1,000 to 2,000, the weight average molecular weight 5 ~ 15 mol% of 1,3-Propandiol with 70 ~ 80, 15 ~ 25mol% of 1,4-Butandiol having weight average molecular weight of 80 ~ 100, 2,2-Bis (120 ~ 140 with weight average molecular weight as emulsifier) Hydroxy methyl) propionic acid (DMPA) with respect to 100 parts by weight of a mixture consisting of 0.5 to 10 mol%, a diamine compound having a weight average molecular weight of 60 to 200 or 0.5 to 30 mol% of a diol compound,
0.01 to 0.03 parts by weight of dibutyltin dilaurate (DBTDL) is included as a catalyst, and a prepolymer mixture is further included by further comprising diisocyanate such that the NCO / OH ratio of the polyol and diisocyanate is 1.0 to 1.8. Made up,
65 to 90 mol% of the prepolymer mixture, 10 to 35 mol% of a chain extender is contained, the polyurethane water dispersion resin composition excellent in water resistance.
제 1항에 있어서,
상기 디아민 화합물은, EDA(ethylene diamine), DETA(diethylene tri amine), Piperazine anhydrous에서 1종 또는 그 이상을 선택하여 사용하며,
상기 디올 화합물은, 1,4-butanediol, 1,3-Propandiol, 1,6-hexanediol, ehtylene glycol, diethylene glycol 에서 1종 또는 그 이상을 선택하여 사용하는 것을 특징으로 하는 내수성이 우수한 폴리우레탄 수분산 수지 조성물.
The method of claim 1,
The diamine compound is selected from one or more selected from ethylene diamine (EDA), diethylene tri amine (DETA), and piperazine anhydrous,
The diol compound is 1,4-butanediol, 1,3-propanediol, 1,6-hexanediol, ehtylene glycol, diethylene glycol selected by using one or more of the water-resistant polyurethane water dispersion, characterized in that used Resin composition.
제 1항에 있어서,
상기 폴리(테트라메틸렌 글리콜)은, 아래 화학식 1과 같은 구조를 가지고,

상기 폴리카보네이트 디올은, 아래 화학식 2와 같은 1,6-헥산디올과 카보네이트의 합성으로 이루어진 C6 home 타입의 폴리카보네이트 디올, 또는 아래 화학식 3과 같은 1,6-헥산디올과 1,5-펜탄디올의 합성으로 이루어진 C5/C6 copolymer 타입의 폴리카보네이트 디올, 또는 아래 화학식 4와 같은 1,6-헥산디올과 1,4-부탄디올의 합성으로 이루어진 C4/C6 copolymer 타입의 폴리카보네이트 디올 중에서 어느 하나를 선택하여 사용하며,

상기 1,3-Propandiol은, 아래 화학식 5와 같은 구조를 가지며,

상기 쇄연장제는, EDA(ethylene diamine), DETA(diethylene tri amine), Piperazine anhydrous 중에서 1종 또는 그 이상을 선택하여 사용하는 것을 특징으로 하는 내수성이 우수한 폴리우레탄 수분산 수지 조성물.

Figure 112013036943250-pat00011
(화학식1)

Figure 112013036943250-pat00012
(화학식2)

Figure 112013036943250-pat00013
(화학식3)


Figure 112013036943250-pat00014
(화학식4)
Figure 112013036943250-pat00015
(화학식5)
The method of claim 1,
The poly (tetramethylene glycol) has a structure as shown in Formula 1 below,

The polycarbonate diol is a C6 home type polycarbonate diol consisting of a synthesis of 1,6-hexanediol and carbonate as shown in Formula 2 below, or 1,6-hexanediol and 1,5-pentanediol as shown in Formula 3 below C5 / C6 copolymer type polycarbonate diol, or C4 / C6 copolymer type polycarbonate diol consisting of 1,6-hexanediol and 1,4-butanediol as shown in Formula 4 below To use,

The 1,3-Propandiol has a structure as shown in Formula 5 below,

The chain extender is a polyurethane water dispersion resin composition having excellent water resistance, characterized in that one or more selected from EDA (ethylene diamine), DETA (diethylene tri amine), Piperazine anhydrous used.

Figure 112013036943250-pat00011
Formula 1

Figure 112013036943250-pat00012
(Formula 2)

Figure 112013036943250-pat00013
(Formula 3)


Figure 112013036943250-pat00014
Formula 4
Figure 112013036943250-pat00015
(Formula 5)
제 1항에 있어서,
상기 디이소시아네이트는,
헥사메틸렌디이소시아네이트(hexamethylene diisocyanate, HDI), 이소프론디이소시아네이트(isophoron diisocyanate, IPDI), 4,4'-디헥실메탄디이소시아네이트(4,4'-dihexyl methane diisocyanate, H12MDI), 수소화 크실릴렌디이소시아네이트(hydronated XDI, H6XDI) 중에서 1종 또는 그 이상을 선택하여 사용하는 것을 특징으로 하는 내수성이 우수한 폴리우레탄 수분산 수지 조성물.
The method of claim 1,
The diisocyanate is,
Hexamethylene diisocyanate (HDI), isophoron diisocyanate (IPDI), 4,4'-dihexyl methane diisocyanate (H 12 MDI), hydrogenated xylyl Polyurethane water dispersion resin composition excellent in water resistance, characterized in that one or more selected from the use of rendiisocyanate (hydronated XDI, H 6 XDI).
폴리우레탄 수분산 수지의 제조방법에 있어서,
중량평균분자량이 1,000~2,000인 폴리(테트라메틸렌 글리콜)(PTMG) 10~75 몰%, 중량평균분자량이 1,000~2,000인 폴리카보네이트 디올 4~10 몰% , 폴리올로써중량평균분자량이 70~80인 1,3-Propandiol 5~15 몰%, 중량평균분자량이 80~100인 1,4-Butandiol 15~25 몰%, 유화제로써 중량평균분자량이 120~140인 2,2-Bis(hydroxy methyl) propionic acid(DMPA) 0.5~10 몰%, 중량평균분자량이 60~200인 디아민 화합물 또는 디올 화합물 0.5~30 몰%로 이루어진 혼합물의 수분을 제거하고, 수분을 제거한 상기 혼합물 100 중량부에 대하여, 촉매로써 디부틸틴디라우레이트(dibutyltin dilaurate, DBTDL) 0.01~0.03 중량부를 질소분위기에서 80~90℃에서 25~35분간 혼합하는 단계(S1);
상기 촉매가 혼합된 혼합물에 디이소시아네이트를 투입하여 80~90℃에서 180~300분간 프리폴리머 합성반응을 진행시키는 단계(S2); 및
상기 프리폴리머 합성반응에 의한 프리폴리머 혼합물 65~90 몰%에, 쇄연장제 10~35 몰%를 투입하여 80~90℃의 온도에서 120~180 분간 합성반응시키는 단계(S3);를 포함하여 제조되는 것을 특징으로 하는 폴리우레탄 수분산 수지의 제조방법
In the manufacturing method of polyurethane water dispersion resin,
10 to 75 mol% of poly (tetramethylene glycol) (PTMG) having a weight average molecular weight of 1,000 to 2,000, 4 to 10 mol% of polycarbonate diol having a weight average molecular weight of 1,000 to 2,000, and a weight average molecular weight of 70 to 80 as a polyol 1,3-Propandiol 5-15 mol%, 1,4-Butandiol having a weight average molecular weight of 80-100, 15-25 mol%, 2,2-Bis (hydroxy methyl) propionic having a weight average molecular weight of 120-140 as an emulsifier acid (DMPA) 0.5-10 mol%, the weight average molecular weight of 60-200 diamine compound or diol compound 0.5-30 mol% of water mixture is removed, the water is removed 100 parts by weight of the mixture as a catalyst Dibutyltin dilaurate (dibutyltin dilaurate, DBTDL) 0.01 to 0.03 parts by weight of the mixed 25 to 35 minutes at 80 ~ 90 ℃ in a nitrogen atmosphere (S1);
Adding a diisocyanate to the mixture mixed with the catalyst to perform a prepolymer synthesis reaction at 80 to 90 ° C. for 180 to 300 minutes (S2); And
Prepared by the step of (S3); the synthesis of 120 to 180 minutes at a temperature of 80 ~ 90 ℃ by adding a chain extender 10 ~ 35 mol% to the prepolymer mixture 65 ~ 90 mol% by the prepolymer synthesis reaction; Method for producing a polyurethane water dispersion resin, characterized in that
제 5항에 있어서,
상기 디이소시아네이트는,
상기 폴리올과 디이소시아네이트의 NCO/OH 비가 1.0~1.8이 되도록 투입되는 것을 특징으로 하는 폴리우레탄 수분산 수지의 제조방법
6. The method of claim 5,
The diisocyanate is,
Method for producing a polyurethane water dispersion resin, characterized in that the NCO / OH ratio of the polyol and diisocyanate is 1.0 to 1.8
제 5항의 제조방법에 의해 제조된 폴리우레탄 수분산 수지를 포함하는 내수성이 우수한 폴리우레탄 수분산 접착제.
Polyurethane water-dispersion adhesive excellent in water resistance comprising a polyurethane water-dispersion resin prepared by the manufacturing method of claim 5.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107722251A (en) * 2012-12-26 2018-02-23 三菱化学株式会社 Polyurethane obtained from PCDL and use PCDL

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101480802B1 (en) * 2013-08-22 2015-01-09 동광산업주식회사 Method for producing of waterborne urethane binder for surface coating materials
WO2016103283A1 (en) 2014-12-23 2016-06-30 Council Of Scientific & Industrial Research Bio-based aromatic diisocyanates for preparation of polyurethanes
KR102145147B1 (en) * 2020-03-27 2020-08-14 이흥수 Coating material for eco-friendly leather products and including them
CN115873204A (en) * 2022-12-14 2023-03-31 合肥安利聚氨酯新材料有限公司 High-wear-resistance polyurethane resin for velvet foamed leather and preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01210414A (en) * 1988-02-19 1989-08-24 Furukawa Electric Co Ltd:The Preparation of polyurethane resin
KR970001538B1 (en) * 1992-12-31 1997-02-11 고려화학 주식회사 Method for manufacturing water dispersion resin and water-soluble paints composition containing the same
US20040236059A1 (en) 2001-07-27 2004-11-25 Piqueras Jose Ayuso Ionomer polyurethane thermoplastic
KR101027663B1 (en) 2010-03-18 2011-04-12 한국신발피혁연구소 High durable polyurethane coating resin composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01210414A (en) * 1988-02-19 1989-08-24 Furukawa Electric Co Ltd:The Preparation of polyurethane resin
KR970001538B1 (en) * 1992-12-31 1997-02-11 고려화학 주식회사 Method for manufacturing water dispersion resin and water-soluble paints composition containing the same
US20040236059A1 (en) 2001-07-27 2004-11-25 Piqueras Jose Ayuso Ionomer polyurethane thermoplastic
KR101027663B1 (en) 2010-03-18 2011-04-12 한국신발피혁연구소 High durable polyurethane coating resin composition

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107722251A (en) * 2012-12-26 2018-02-23 三菱化学株式会社 Polyurethane obtained from PCDL and use PCDL
US11220572B2 (en) 2012-12-26 2022-01-11 Mitsubishi Chemical Corporation Polycarbonate diol and polyurethane using same

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