KR100506462B1 - Low Melting Point Polyamide Resin Composition - Google Patents
Low Melting Point Polyamide Resin Composition Download PDFInfo
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- KR100506462B1 KR100506462B1 KR1019970077669A KR19970077669A KR100506462B1 KR 100506462 B1 KR100506462 B1 KR 100506462B1 KR 1019970077669 A KR1019970077669 A KR 1019970077669A KR 19970077669 A KR19970077669 A KR 19970077669A KR 100506462 B1 KR100506462 B1 KR 100506462B1
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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
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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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
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
본 발명은 나이론 6 : 15∼55 중량부, 나이론 66 : 5∼40 중량부, 및 나이론 636 : 25∼75 중량부의 3성분 공중합체에 층상규산염이 첨가중합된 것을 특징으로 하는 저융점 폴리아미드 수지 조성물을 제공하는 것으로, 본 발명의 저융점 폴리아미드 수지 조성물은 섬유 봉제용 등의 용도로 분말상으로 이용될 때 분쇄작업성이 우수하여 전기다리미 등에 의해 간단하게 접착될 수 있고, 알콜 등에 용해되기 때문에 용액상으로 접착에 응용할 수 있으며, 분말 코팅재료나 충진제로도 용도 전개가 가능하다.The present invention provides a low melting point polyamide resin, wherein layered silicate is added and polymerized to a three-component copolymer of nylon 6:15 to 55 parts by weight, nylon 66: 5 to 40 parts by weight, and nylon 636: 25 to 75 parts by weight. By providing a composition, the low melting point polyamide resin composition of the present invention has excellent pulverizing property when used in powder form for fiber sewing and the like, can be easily adhered by an electric iron or the like, and is dissolved in alcohol or the like. It can be applied to adhesion in solution and can be used as a powder coating material or filler.
Description
본 발명은 저융점 폴리아미드 수지 조성물에 관한 것으로, 더욱 상세하게는 나이론 6, 나이론 66, 나이론 636의 3성분으로 이루어진 공중합물에 층상규산염을 첨가 중합시켜 분쇄작업성이 우수한 것을 특징으로 하는 저융점 폴리아미드 수지 조성물에 관한 것이다.The present invention relates to a low melting point polyamide resin composition, and more particularly, a low melting point characterized by excellent pulverization by adding a layered silicate to a copolymer composed of three components of nylon 6, nylon 66, and nylon 636. It relates to a polyamide resin composition.
일반적으로 나이론 6, 나이론 66 등의 폴리아미드는 단독으로도 널리 사용되고 있으나, 융점이 비교적 높기 때문에 용도가 제한되는 경우가 적지 않다. 특히 섬유 등의 접착용도에 있어서 심지 등의 용도나 테이프상의 직물 사이에 삽입하여 가압접착하게 되는 접착제로 사용되는 경우에는 가열에 의해 섬유 직물 자체가 열열화되는 일이 있고, 고주파미싱 같은 특수한 장비를 사용해야만 하는 번거로움이 있기 때문에, 이러한 특수 장비를 이용하지 않고도 통상의 전기다리미 등의 간단한 가열 프레스에 의해 용이하게 접착하는 것이 요망되고 있다. 그 때문에 피접착체인 통상의 섬유 직물을 구성하고 있는 섬유 형성 재료의 융점 내지는 분해온도 보다 낮은 융점을 갖고, 유동성이 양호한 폴리아미드 수지 조성물이 요구된다.In general, polyamides such as nylon 6 and nylon 66 are widely used alone, but their use is not limited because of their relatively high melting points. In particular, when the fiber fabric itself is used as a wick or the like, and is used as an adhesive that is interposed between a tape-like fabric and press-bonded, the textile fabric itself may be thermally deteriorated by heating, and special equipment such as a high frequency sewing machine may be used. Since there is the inconvenience of having to use, it is desired to adhere easily by simple heat presses, such as an ordinary electric iron, without using such a special equipment. Therefore, the polyamide resin composition which has melting | fusing point lower than melting | fusing point or decomposition temperature of the fiber forming material which comprises the normal fiber fabric which is a to-be-adhered body, and has favorable fluidity | liquidity is calculated | required.
그러나 너무 융점이 저온이고 유동성이 큰 접착제이면 가열압착공정에서 접착제가 직물의 조직중에 너무 침투하여 직물의 촉감을 단단하게 하거나, 유효접착면적을 감소시켜 접착강도를 저하시키므로, 150℃ 이하의 저융점을 갖고 접착강도가 높으며, 필름 접착시 성형성이 우수한 폴리아미드 수지 조성물이 요구된다.However, if the melting point is too low and the fluidity is high, the adhesive melts in the fabric of the fabric in the heat compression process so as to harden the feel of the fabric or lower the adhesive strength by reducing the effective bonding area. There is a need for a polyamide resin composition having a high adhesive strength and excellent moldability upon film adhesion.
종래에는 저융점 폴리아미드 수지 조성물을 용이하게 수득하기 위해 나이론 6, 나이론 66, 나이론 610의 3원을 공중합하거나 또는 상기 3성분 이외에 나이론 12를 일정량 첨가하여 4원 공중합(일본특개소 50-22034호)하여 저융점을 갖는 폴리아미드 수지 조성물을 제조하는 방법 등이 이용되었으나, 일반적으로 사용되고 있는 나이론 6, 나이론 66, 나이론 610 등은 공중합해도 저융점의 폴리아미드를 수득할 수 없는 한계가 있다. Conventionally, in order to easily obtain a low melting point polyamide resin composition, a three-way copolymer of nylon 6, nylon 66, and nylon 610 is copolymerized or a four-way copolymerization is performed by adding a predetermined amount of nylon 12 in addition to the three components (Japanese Patent Application Laid-Open No. 50-22034). However, a method of preparing a polyamide resin composition having a low melting point is used, but nylon 6, nylon 66, nylon 610, and the like, which are generally used, have a limitation in that a low melting point polyamide cannot be obtained.
또 다른 대안으로 가소제를 첨가하는 방법이 있으나, 이는 제품의 강도면에서 좋지 않은 영향을 미치고 가소제가 표면으로 흘러나오는 단점 때문에 사용이 제한되고 있다. Another alternative is to add a plasticizer, but its use is limited due to the disadvantages of adverse effects on the strength of the product and the plasticizer flowing out to the surface.
또한 저융점 폴리아미드 수지 조성물을 섬유 봉제용 등의 용도로 이용하기 위해서는 분말 형태로 가공하는 것이 필요하며, 이를 위해서 일반적으로 냉동분쇄방법이 이용된다. 이러한 냉동분쇄방법은 액체질소 분위기하에서 중합물을 통과시켜 파쇄하는 것인데, 기존의 저융점 중합물은 기존의 나이론에 비해 유연하므로 분쇄작업성이 상당히 떨어지는 문제점을 갖는다. In addition, in order to use the low-melting-point polyamide resin composition for the purpose of sewing fibers, etc., it is necessary to process in powder form, and for this purpose, a freeze grinding method is generally used. The freeze pulverization method is to break through the polymer in a liquid nitrogen atmosphere, the conventional low melting point polymer is flexible compared to the conventional nylon has a problem that the grinding workability is considerably inferior.
본 발명의 목적은 이러한 종래 기술상의 문제점을 극복하는 것으로 저융점을 갖고 접착강도가 높으며, 필름 접착시 성형성이 우수고 분쇄작업성이 우수한 저융점 폴리아미드 수지 조성물을 제공하는 것이다.It is an object of the present invention to provide a low melting point polyamide resin composition having a low melting point, high adhesive strength, excellent moldability and excellent crushability when bonding a film to overcome such problems in the prior art.
즉, 본 발명은 나이론 6 : 15∼55 중량부, 나이론 66 : 5∼40 중량부, 및 나이론 636 : 25∼75 중량부의 3성분 공중합체에 층상규산염이 첨가중합된 것을 특징으로 하는 저융점 폴리아미드 수지 조성물을 제공하는 것이다.That is, the present invention is a low-melting poly, characterized in that the layered silicate is added and polymerized to a three-component copolymer of nylon 6:15 to 55 parts by weight, nylon 66: 5 to 40 parts by weight, and nylon 636: 25 to 75 parts by weight. It is to provide an amide resin composition.
이하 본 발명을 더욱 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in more detail.
본 발명의 공중합 폴리아미드 수지 조성물은 나이론 6 : 15∼55 중량부, 나이론 66 : 5∼40 중량부, 및 나이론 636 : 25∼75 중량부를 공중합하여 수득되며, 이와 같이 3성분을 공중합하면 130∼150℃의 저융점을 갖는 폴리아미드 수지 조성물이 수득된다.The copolymerized polyamide resin composition of the present invention is obtained by copolymerizing nylon 6:15 to 55 parts by weight, nylon 66: 5 to 40 parts by weight, and nylon 636: 25 to 75 parts by weight. A polyamide resin composition having a low melting point of 150 ° C. is obtained.
본 발명에서 상기 나이론 636은 헥사메틸디아민과 탄소수 36개의 식물성 지방산 염의 중합체이고, 나이론 6은 ε-카프로락탐 또는 ε-카프론산의 중합체이며, 나이론 66은 헥사메틸렌디아민과 아디프산염의 중합체이다.In the present invention, the nylon 636 is a polymer of hexamethyldiamine and a 36 fatty acid vegetable fatty acid salt, nylon 6 is a polymer of ε-caprolactam or ε-capronic acid, and nylon 66 is a polymer of hexamethylenediamine and adipic acid salt.
본 발명은 중합물을 냉동분쇄하는 경우에 분쇄작업성을 향상시키기 위하여 중합시에 층상규산염을 첨가하여 중합하는 것을 특징으로 한다. 본 발명에서 층산규산염은 두께가 6∼20Å, 길이가 0.002∼1㎛인 평판상이다. 층산규산염의 원료로서는 규산마그네슘, 규산알루미늄의 층으로 구성되어 있는 층상규산 광물로서 몬트로릴로나이트, 사포나이드, 벤토나이트, 파이테라이트, 논토로나이트, 헥토나이트 등이 있다.The present invention is characterized in that the polymerization by adding a layered silicate during the polymerization in order to improve the pulverization work in the case of freezing grinding the polymer. In the present invention, the layered silicate is in the form of a flat plate having a thickness of 6 to 20 mm 3 and a length of 0.002 to 1 m. As a raw material of the layered silicate, a layered silicate mineral composed of a layer of magnesium silicate and aluminum silicate includes montrylillonite, saponide, bentonite, pyriterite, nontoronite, hectorite and the like.
본 발명에서 이러한 층상규산염의 첨가량은 0.05∼20중량부이고, 바람직하게는 1∼5 중량부이다. 층상규산염의 첨가량이 0.05 중량부 미만이거나 20중량부를 초과하면 본 발명이 의도하는 분쇄작업성의 향상 효과를 수득할 수 없게 된다.The amount of such layered silicate added in the present invention is 0.05 to 20 parts by weight, preferably 1 to 5 parts by weight. If the addition amount of the layered silicate is less than 0.05 parts by weight or more than 20 parts by weight, it is impossible to obtain the effect of improving the grindability intended by the present invention.
본 발명의 공중합 폴리아미드 수지 조성물은 130∼150℃의 저융점을 갖고 필름 접착시 성형성이 뛰어난 이점을 갖는다. 본 발명의 수지 조성물은 비결정성이므로 본원에서 사용되는 경우에 "융점"이라는 용어는 결정성 폴리아미드에서의 융점과는 약간 다른 연화점에 해당하는 의미를 갖는다.The copolymerized polyamide resin composition of the present invention has an advantage of having a low melting point of 130 to 150 ° C. and excellent moldability upon film adhesion. Since the resin composition of the present invention is amorphous, the term "melting point" as used herein has a meaning corresponding to a softening point slightly different from that of the crystalline polyamide.
이하 실시예에 의해 본 발명을 더욱 상세히 설명하나, 본 발명이 하기 실시예에 의하여 제한되는 것은 아니다. Hereinafter, the present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples.
실시예 1∼3Examples 1 to 3
먼저 몬트모릴로나이트 100g을 물 10ℓ에 분산시키고 여기에 134.5g의 6-아미노 카프론산과 24㎖의 염산을 가하여 10분간 교반하고, 스프레이 드라이어를 이용하여 미세분말을 수득하였다. 이러한 비율로 얻은 유기복합체를 표 1에 나타낸 중량부로 넣고 오토클레이브에 헥사메틸렌디아민과 탄소수 36 개인 식물성 지방산을 같은 몰비로 염을 만들고, 나이론 6 성분, 나이론 66 성분을 하기 표 1의 중량부 비율로 배합하고 특히 물을 10 중량부 외첨하여 상온에서 1시간 교반한 후 260℃로 승온하여 3시간 가압교반하였다. 이어서 270℃에서 2시간 반응시켜 카프로락탐의 개환을 진행시킨 후 상압으로 서서히 방압하고, 100∼300 토르의 진공상태로 1시간 교반하여 여분의 수분을 제거하여 중합도를 조절하였다. 수득된 중합체를 지름 2mm, 길이 3mm의 펠렛으로 절단한 후 50℃에서 텀블드라이어를 이용하여 진공건조하여, 본 발명의 저융점 폴리아미드 수지 조성물을 제조하고 액체질소분위기에서 분쇄특성을 평가한 결과를 하기 표 1에 나타내었다. 하기 표 1에서 분쇄속도는 분말이 120㎛ 이하의 것이 나오는 속도를 의미한다.First, 100 g of montmorillonite was dispersed in 10 L of water, and 134.5 g of 6-amino capronic acid and 24 mL of hydrochloric acid were added thereto, followed by stirring for 10 minutes, to obtain a fine powder using a spray dryer. The organic complex obtained in this ratio was added to the weight parts shown in Table 1, and salts were prepared in the same molar ratio of hexamethylenediamine and 36 carbon atoms vegetable fatty acid in an autoclave, and the nylon 6 component and the nylon 66 component were used in the weight ratio of Table 1 below. The mixture was mixed with 10 parts by weight of water, and stirred at room temperature for 1 hour, and then heated to 260 ° C and stirred under pressure for 3 hours. Subsequently, the mixture was reacted at 270 ° C. for 2 hours to proceed with ring opening of caprolactam, and then gradually discharged to normal pressure, and stirred for 1 hour under vacuum at 100 to 300 torr to remove excess water to adjust the degree of polymerization. The obtained polymer was cut into pellets having a diameter of 2 mm and a length of 3 mm, followed by vacuum drying at 50 ° C. using a tumble dryer to prepare a low melting point polyamide resin composition of the present invention and to evaluate the grinding characteristics in a liquid nitrogen atmosphere. It is shown in Table 1 below. In Table 1 below, the grinding speed means a speed at which the powder comes out of 120 μm or less.
비교예 1Comparative Example 1
오토클레이브에 층상규산염을 첨가하지 않은 것을 제외하고는 실시예 1과 동일한 방법으로 중합 및 건조하여 저융점 폴리아미드 수지 조성물을 제조하고 그 분쇄특성을 측정한 결과를 하기 표 1에 함께 나타내었다.Except that the layered silicate was not added to the autoclave was polymerized and dried in the same manner as in Example 1 to prepare a low melting point polyamide resin composition and the results of measuring the grinding properties are shown in Table 1 together.
본 발명의 저융점 폴리아미드 수지 조성물은 낮은 온도 및 냉각후에 높은 결합력을 가지며 분쇄특성이 우수할 뿐만 아니라, 분말상이라도 저융점에서 성형성이 양호하므로 전기 다리미 등에 의해 간단하게 접착될 수 있으며, 알콜 등에 용해되기 때문에 용액상으로 접착에 응용해도 좋고, 분말 코팅재료나 충진제로도 용도 전개가 가능하다.The low melting point polyamide resin composition of the present invention has a high bonding strength after low temperature and cooling and is excellent in pulverization characteristics, and can be easily adhered by an electric iron or the like because it has good moldability even at a low melting point even in powder form. Since it melt | dissolves, it may apply to adhesion | attachment in solution form, and application development is possible also as a powder coating material and a filler.
Claims (4)
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| KR1019970077669A KR100506462B1 (en) | 1997-12-30 | 1997-12-30 | Low Melting Point Polyamide Resin Composition |
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| Publication Number | Publication Date |
|---|---|
| KR19990057606A KR19990057606A (en) | 1999-07-15 |
| KR100506462B1 true KR100506462B1 (en) | 2005-10-13 |
Family
ID=37305398
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1019970077669A KR100506462B1 (en) | 1997-12-30 | 1997-12-30 | Low Melting Point Polyamide Resin Composition |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR100506462B1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180129300A (en) * | 2017-05-26 | 2018-12-05 | 현대자동차주식회사 | Polyamide resin composition having high elasticity modulus and stability and molded articles thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR910008787A (en) * | 1989-10-16 | 1991-05-31 | 도미다 구니오 | Discharge method and compact fluorescent lamp using this discharge method |
| JPH0522034A (en) * | 1990-12-28 | 1993-01-29 | Raytheon Co | Saw device and manufacture thereof |
| JPH07243149A (en) * | 1994-03-07 | 1995-09-19 | Toray Ind Inc | Woven fabric for one direction reinforcement |
| JPH07243150A (en) * | 1994-03-07 | 1995-09-19 | Toray Ind Inc | Mesh woven fabric for reinforcement and production thereof |
-
1997
- 1997-12-30 KR KR1019970077669A patent/KR100506462B1/en not_active IP Right Cessation
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR910008787A (en) * | 1989-10-16 | 1991-05-31 | 도미다 구니오 | Discharge method and compact fluorescent lamp using this discharge method |
| JPH0522034A (en) * | 1990-12-28 | 1993-01-29 | Raytheon Co | Saw device and manufacture thereof |
| JPH07243149A (en) * | 1994-03-07 | 1995-09-19 | Toray Ind Inc | Woven fabric for one direction reinforcement |
| JPH07243150A (en) * | 1994-03-07 | 1995-09-19 | Toray Ind Inc | Mesh woven fabric for reinforcement and production thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180129300A (en) * | 2017-05-26 | 2018-12-05 | 현대자동차주식회사 | Polyamide resin composition having high elasticity modulus and stability and molded articles thereof |
| KR102298964B1 (en) | 2017-05-26 | 2021-09-06 | 현대자동차주식회사 | Polyamide resin composition having high elasticity modulus and stability and molded articles thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR19990057606A (en) | 1999-07-15 |
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