KR100697868B1 - Composite for Bulk mold compound - Google Patents

Composite for Bulk mold compound Download PDF

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KR100697868B1
KR100697868B1 KR1020050038168A KR20050038168A KR100697868B1 KR 100697868 B1 KR100697868 B1 KR 100697868B1 KR 1020050038168 A KR1020050038168 A KR 1020050038168A KR 20050038168 A KR20050038168 A KR 20050038168A KR 100697868 B1 KR100697868 B1 KR 100697868B1
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weight
parts
mold compound
unsaturated polyester
bulk mold
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KR20060115545A (en
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김성룡
권기준
김대훈
김홍경
김경민
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충주대학교 산학협력단
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/06Unsaturated polyesters
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24Acids; Salts thereof
    • C08K3/26Carbonates; Bicarbonates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/02Halogenated hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/49Phosphorus-containing compounds
    • C08K5/51Phosphorus bound to oxygen
    • C08K5/52Phosphorus bound to oxygen only
    • C08K5/521Esters of phosphoric acids, e.g. of H3PO4
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/02Fibres or whiskers
    • C08K7/04Fibres or whiskers inorganic
    • C08K7/14Glass
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02Homopolymers or copolymers of hydrocarbons
    • C08L25/04Homopolymers or copolymers of styrene
    • C08L25/06Polystyrene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2227Oxides; Hydroxides of metals of aluminium
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/02Flame or fire retardant/resistant
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group

Abstract

벌크 몰드 컴파운드 조성물이 제공된다. 벌크 몰드 컴파운드 조성물은 불포화 폴리에스테르 수지와 폴리스티렌계 수지가 100 중량부가 되도록 혼합된 고분자 수지에 대하여, 1.0~15.0㎛의 입경을 가지는 수산화알미늄 170~400 중량부, 0.1~8.0㎛의 입경을 가지는 중질탄산칼슘 20~200 중량부, 염소화 파라핀 10~30 중량부, 삼산화안티몬 10~30 중량부, 계면활성제를 0.5~5중량부를 포함한다.Bulk mold compound compositions are provided. The bulk mold compound composition is 170 to 400 parts by weight of aluminum hydroxide having a particle size of 1.0 to 15.0 μm and a heavy particle size of 0.1 to 8.0 μm with respect to the polymer resin mixed so that the unsaturated polyester resin and the polystyrene resin are 100 parts by weight. 20 to 200 parts by weight of calcium carbonate, 10 to 30 parts by weight of chlorinated paraffin, 10 to 30 parts by weight of antimony trioxide, and 0.5 to 5 parts by weight of surfactant.

벌크 몰드 컴파운드, 불포화 폴리에스테르, 유리섬유, 계면 활성제, 난연성 Bulk Mold Compounds, Unsaturated Polyester, Fiberglass, Surfactants, Flame Retardant

Description

벌크 몰드 컴파운드 조성물{Composite for Bulk mold compound}Bulk mold compound composition

본 발명은 벌크 몰드 컴파운드 조성물에 관한 것으로서, 보다 상세하게는 분산성, 표면거칠기, 외관, 난연성이 우수한 불포화폴리에스테르계 벌크 몰드 컴파운드 조성물에 관한 것이다.The present invention relates to a bulk mold compound composition, and more particularly, to an unsaturated polyester bulk mold compound composition having excellent dispersibility, surface roughness, appearance, and flame retardancy.

벌크 몰드 컴파운드(Bulk Mold Compound) 조성물은 일정한 벌크의 형태로 되어 성형틀(Mold)에 삽입되어 소정의 온도와 압력을 가하여 가정용품, 장난감, 전기제품, 자동차 용품 등을 생산하는데 응용되고 있다. Bulk Mold Compound (Bulk Mold Compound) The composition is in the form of a certain bulk is inserted into a mold (Mold) is applied to produce a household goods, toys, electrical appliances, automotive articles, etc. by applying a predetermined temperature and pressure.

이러한 벌크 몰드 컴파운드 조성물은 일반적으로 불포화 폴리에스테르 수지를 주성분으로 하고 무기 충전재, 유리섬유, 경화제 및 기타 첨가제를 포함하고 있으며, 전기적, 내화학성, 내열성이 우수하여 논퓨즈브레이크, 절연판과 같은 전기 절연재료에 많이 사용되고 있다.Such bulk mold compound compositions are generally composed of unsaturated polyester resins, and include inorganic fillers, glass fibers, hardeners, and other additives, and are excellent in electrical, chemical, and heat resistance, such as non-fuse brakes and insulating plates. It is used a lot in.

또한, 벌크 몰드 컴파운드 조성물은 성형성이 뛰어나 박판성형이 가능하고 시공성이 우수하여 천장재, 바닥재, 벽마감재 등과 같은 건축재료로 점차 사용이 확대되고 있다. 이러한, 벌크 몰드 컴파운드 조성물의 기계적, 물리적 성질은 베이 스가 되는 수지, 첨가제, 셋팅제, 충진재, 강화재 등의 비율을 어떻게 하느냐에 따라 다양하게 조절될 수 있다. 벌크 몰드 컴파운드 및 이와 유사한 시트 몰드 컴파운드(Sheet Mold Compound)에 대한 일반적인 사항은 미국 공개 특허 제5,356,953호, 제5,281,633호 등에 자세하게 기술되어 있다.In addition, the bulk mold compound composition is excellent in formability, thin plate molding is possible and excellent workability has been increasingly used as a building material such as ceiling materials, floor materials, wall finishing materials and the like. The mechanical and physical properties of the bulk mold compound composition may be variously adjusted depending on how the ratio of the resin, the additive, the setting agent, the filler, the reinforcing material, etc., which becomes the base. General details of bulk mold compounds and similar sheet mold compounds are described in detail in US Pat. Nos. 5,356,953, 5,281,633 and the like.

흔히 가장 많이 사용되는 불포화 폴리에스테르계 벌크 몰드 컴파운드는 가격은 저렴하지만 점도가 높은 원재료 등을 상온의 혼련공정을 통하여 혼합하기 때문에 분산의 효과가 불충분하고 표면의 균일성이 상대적으로 좋지 못해 최종 생산된 제품 표면의 광택이 좋지 않아 심미적 효과를 부여하는데 대한 많은 제약이 있어왔다.The most commonly used unsaturated polyester bulk mold compounds are inexpensive but highly viscous raw materials are mixed through a kneading process at room temperature, resulting in insufficient dispersion and relatively poor surface uniformity. The gloss of the product surface has been poor, and there have been many constraints on imparting aesthetic effect.

벌크 몰드 컴파운드 조성물은 일반적으로 열을 받으면 수축하는 성질을 가지는 열경화성플라스틱(일반적으로 불포화 폴리에스테르계를 가장 많이 사용함)을 기본 베이스로 하는데, 열경화성 수지의 열에 의한 수축효과를 보완하기 위하여 저수축(low shrinkage), 저프로파일(low profile)계 열가소성 수지가 사용되어 왔다.The bulk mold compound composition is generally based on a thermosetting plastic (typically the most unsaturated polyester type), which has a property of shrinking when subjected to heat, and low shrinkage (low shrinkage) to compensate for the thermal shrinkage effect of the thermosetting resin. shrinkage, low profile thermoplastics have been used.

이러한, 저수축(low shrinkage), 저프로파일(low profile) 고분자 수지는 일반적으로 폴리스티렌이나 폴리비닐아세테이트와 같은 고분자가 스티렌 단량체와 같은 용매에 분산되어 있거나 용해되어 있는 형태로 불포화 폴리에스테르 수지에 첨가되어 제조된다. 하지만, 저수축제 혹은 저프로파일제를 사용시에는 상분리 현상에 의해 균일한 표면을 가지지 못하여 외관이 좋지 못하거나 색상이 불균일하고 표면의 거칠기가 크게 된다는 문제점이 있다.Such low shrinkage, low profile polymer resins are generally added to unsaturated polyester resins in a form in which a polymer such as polystyrene or polyvinylacetate is dispersed or dissolved in a solvent such as styrene monomer. Are manufactured. However, when a low shrinkage agent or a low profile agent is used, it does not have a uniform surface due to a phase separation phenomenon, so that the appearance is not good or the color is uneven and the surface roughness is large.

이러한 표면의 외관이나 거칠기 성질을 개선하기 위하여 저온에서 경화되는 저프로파일제를 사용하여 수축효과를 조절하는 연구가 많이 진행되었지만 이 경우엔 저온에서 경화가 일어나기 때문에 경화시간이 오래 걸려 생산공정에 채택하기 어렵다는 문제가 있다.In order to improve the appearance or roughness of the surface, many studies have been conducted to control the shrinkage effect by using a low profile agent that is cured at low temperature, but in this case, the curing time takes a long time because curing occurs at low temperature. There is a problem that is difficult.

또한, 벌크 몰드 컴파운드는 난연성을 부여하기 위하여 불포화 폴리에스테르 수지를 주성분으로 브롬계 반응성 에폭시 타입의 난연제와 두종의 수산화알미늄을 사용하여 난연성이 우수한 불포화 폴리에스테르계 벌크 몰드 컴파운드를 제조하는 방법이 국내특허공고번호 제99-25243호에 기재되어 있으나, 이 방법으로는 난연3급 이상의 효과를 얻을 수 없으며, 통상적으로 금형내의 흐름성 때문에 평균 입도가 12㎛ 이하의 무기물을 사용하지만 40~60㎛의 입경을 가진 수산화알미늄을 사용하여 성형시 표면이 불량하다는 단점이 있다.In addition, in order to impart flame retardancy, a method of manufacturing an unsaturated polyester bulk mold compound having excellent flame retardancy by using a brominated reactive epoxy type flame retardant and two kinds of aluminum hydroxide as a main component of an unsaturated polyester resin in order to impart flame retardancy is a domestic patent. Although it is described in Korean Patent No. 99-25243, it is impossible to obtain a flame retardant grade 3 or higher effect by this method, and in general, an inorganic material having an average particle size of 12 μm or less is used because of flowability in a mold, but a particle diameter of 40 to 60 μm When using aluminum hydroxide having a disadvantage that the surface is poor during molding.

본 발명이 이루고자 하는 기술적 과제는 종래의 기술상의 문제점을 고려하여 분산성, 표면거칠기, 치수 안정성, 열적 안정성, 난연성이 우수한 불포화 폴리에스테르계 벌크 몰드 컴파운드 및 이를 이용한 논퓨즈브레이커와 같은 전기재료와 건축물의 천장재, 벽재, 바닥재, 씽크대와 같은 제품을 제공하는데에 있다.The technical problem to be achieved by the present invention is an electrical material and a building such as unsaturated polyester-based bulk mold compound having excellent dispersibility, surface roughness, dimensional stability, thermal stability, flame retardancy in consideration of the conventional technical problems and non-fuse breaker using the same To provide products such as ceilings, walls, floors, and sinks.

본 발명이 이루고자 하는 기술적 과제들은 이상에서 언급한 기술적 과제들로 제한되지 않으며, 언급되지 않은 또 다른 기술적 과제들은 아래의 기재로부터 당업자에게 명확하게 이해될 수 있을 것이다.Technical problems to be achieved by the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned will be clearly understood by those skilled in the art from the following description.

상기의 기술적 과제를 해결하기 위한 본 발명에 따른 벌크 몰드 컴파운드 조성물은 불포화 폴리에스테르 수지와 폴리스티렌계 수지가 100 중량부가 되도록 혼합된 고분자 수지에 대하여, 1~15.0㎛의 입경과 170~400 중량부를 가지는 수산화 알루미늄, 0.1~8.0㎛의 입경과 20~200 중량부를 가지는 중질탄산칼슘, 10~30 중량부를 가지는 염소화파라핀, 10~30 중량부를 가지는 삼산화안티몬, 0.5~5 중량부를 가지는 계면활성제를 포함를 포함한다.The bulk mold compound composition according to the present invention for solving the above technical problem has a particle diameter of 1 ~ 15.0㎛ and 170 ~ 400 parts by weight with respect to the polymer resin mixed so that the unsaturated polyester resin and polystyrene resin 100 parts by weight It includes aluminum hydroxide, heavy calcium carbonate having a particle size of 0.1 ~ 8.0㎛ and 20 to 200 parts by weight, chlorinated paraffin having 10 to 30 parts by weight, antimony trioxide having 10 to 30 parts by weight, surfactant having 0.5 to 5 parts by weight .

기타 실시예들의 구체적인 사항들은 상세한 설명에 포함되어 있다.Specific details of other embodiments are included in the detailed description.

본 발명의 이점 및 특징, 그리고 그것들을 달성하는 방법은 후에 상세하게 후술되어 있는 실시예들을 참조하면 명확해질 것이다. 그러나, 본 발명은 이하에서 개시되는 실시예들에 한정되는 것이 아니라 서로 다른 다양한 형태로 구현될 것이며, 단지 본 실시예들은 본 발명의 개시가 완전하도록 하며, 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자에게 발명의 범주를 완전하게 알려주기 위해 제공되는 것이며, 본 발명은 청구항의 범주에 의해 정의될 뿐이다.Advantages and features of the present invention, and methods of achieving them will be apparent with reference to the embodiments described below in detail. However, the present invention is not limited to the embodiments disclosed below, but may be implemented in various different forms, only the present embodiments to make the disclosure of the present invention complete, and common knowledge in the art to which the present invention pertains. It is provided to fully inform the person having the scope of the invention, which is defined only by the scope of the claims.

본 발명에 따른 벌크 몰드 컴파운드 조성물은 고분자 수지, 수산화 알미늄, 염소화파라핀, 삼산화안티몬, 계면 활성제를 포함한다.The bulk mold compound composition according to the present invention includes a polymer resin, aluminum hydroxide, chlorinated paraffin, antimony trioxide, and a surfactant.

베이스가 되는 고분자 수지는 불포화 폴리에스테르가 60~80 중량%, 폴리스티렌이 40~20 중량%로 되어 있다.The polymer resin used as a base is 60 to 80 weight% of unsaturated polyester and 40 to 20 weight% of polystyrene.

이중 불포화 폴리에스테르는 가격적으로 저렴하여 많이 쓰이고 있는 Phthalic anhydride (PA)를 주원료로 하는 올소계(Ortho)계, 혹은 이소계(Iso)계, 비스페놀 A(Bisphenol-A)계 등의 것이 사용될 수 있으며 이 중 어떤 것을 사용하더라도 무방하다. 올소계 불포화 폴리에스테르는 불포화도가 30~60%이고, 이소계 불포화 폴리에스테르는 내약품성, 내열성과 같은 물성이 올소계보다 우수하며, 비스페놀A계 불포화 폴리에스테르도 내약품성, 내열수성이 우수하다.Double unsaturated polyesters can be used, such as ortho-based, or iso-based, bisphenol-A, or bisphenol A based on Phthalic anhydride (PA). You can use any of these. The oxo unsaturated polyester has 30 to 60% unsaturation, and the iso unsaturated polyester has superior physical properties such as chemical resistance and heat resistance, and the bisphenol A unsaturated polyester has excellent chemical resistance and hot water resistance.

본 발명에서는 비휘발성(non-volatile) 성분 62% 이상 비스페놀A계의 2액상 불포화 폴리에스테르 수지를 사용하였다.In the present invention, at least 62% of a non-volatile component is used a bisphenol A-based two-liquid unsaturated polyester resin.

이러한, 불포화 폴리에스테르 수지는 일반적으로 7~10 부피%의 체적 수축을 동반하면서 경화되는데 열가소성수지를 불포화 폴리에스테르 수지 중에 미립의 상태로 분산시킴으로써 열팽창에 따른 경화수축을 상쇄시켜 줄 수 있다.In general, the unsaturated polyester resin is cured with a volume shrinkage of 7 to 10% by volume, and by dispersing the thermoplastic resin in a particulate state in the unsaturated polyester resin, the shrinkage due to thermal expansion can be offset.

이와 같이 불포화 폴리에스테르 수지의 수축 억제제로 사용되는 열가소성수지는 그 종류에 특별한 제한은 없는데, 본 발명에서는 폴리스티렌을 전체 불포화폴리에스테르 수지의 40~20 중량%가 되도록 사용하였다.The thermoplastic resin used as a shrinkage inhibitor of the unsaturated polyester resin is not particularly limited in its kind. In the present invention, polystyrene is used to be 40 to 20% by weight of the total unsaturated polyester resin.

수산화 알루미늄(Al(OH)3)은 충진재로 사용된다. 일반적으로 수산화 알루미늄은 원가절감 효과가 있고 연소가스를 억제하며, 250℃, 330℃, 550℃ 근처의 온도에서 수증기를 방출하여 연소점의 열을 빼앗아 연소현상을 억제하는 난연효과도 가지고 있다. 그러나, 수산화 알루미늄을 첨가하게 되면 균일하게 색상을 부여하는 것이 어렵다는 문제점이 있다.Aluminum hydroxide (Al (OH) 3 ) is used as filler. In general, aluminum hydroxide has a cost-saving effect, suppresses combustion gases, and also has a flame retardant effect of suppressing combustion phenomena by dissipating heat at the combustion point by releasing water vapor at temperatures around 250 ° C, 330 ° C, and 550 ° C. However, when aluminum hydroxide is added, it is difficult to give uniform color.

따라서, 본 발명에서는 이러한 문제점을 해결하기 위해 충진재로서 수산화 알루미늄만을 사용하지 아니하고 중질탄산칼슘을 함께 첨가하였다.Therefore, in the present invention, to solve this problem, instead of using only aluminum hydroxide as a filler, heavy calcium carbonate was added together.

또한, 고분자 수지를 100 중량부로 기준하였을때 수산화 알루미늄을 170~400 중량부, 중질탄산칼슘을 20~200 중량부 첨가한다. 이때, 사용된 수산화 알루미늄 및 중질탄산칼슘의 입경은 각각 1~15.0㎛, 0.1~8.0㎛이다.In addition, when the polymer resin is based on 100 parts by weight, 170 to 400 parts by weight of aluminum hydroxide and 20 to 200 parts by weight of heavy calcium carbonate are added. At this time, the particle diameter of the used aluminum hydroxide and heavy calcium carbonate is 1-15.0 micrometers, and 0.1-8.0 micrometers, respectively.

벌크 몰드 컴파운드의 난연성을 부여하기 위한 난연제의 종류로는 크게 인계, 할로겐계, 수산화 금속 화합물, 안티몬계 난연제로 구분된다. Types of flame retardants for imparting flame retardancy of bulk mold compounds are broadly classified into phosphorus-based, halogen-based, metal hydroxide compounds, and antimony-based flame retardants.

인계 난연제는 분리반응으로 탄소가 표면층을 형성하여 물리적으로 표면의 산소를 차폐해 버리는 방식으로 난연효과를 얻게 된다.Phosphorus-based flame retardants obtain a flame retardant effect in that carbon forms a surface layer in a separation reaction and physically shields oxygen on the surface.

염소화 파라핀 등을 포함하는 할로겐계 난연제는 기상에서 기능을 발휘하며 발생된 불연성 가스는 고분자 수지 등의 분해에 의해 발생하는 가연성 가스를 열과 산소로부터 차단해 버린다. 염소화 파라핀과 같은 할로겐계중 염소계 난연제의 난연화 메카니즘은 라디칼 작용에 의해 일어나며, 염소계 난연제의 분해시 Cl 라디칼을 거쳐 HCl을 발생, 연소중에 활성된 수소 라디칼과 히드록시 라디칼을 분리시킨다.Halogen-based flame retardants, including chlorinated paraffin, function in the gas phase, and the non-combustible gas generated blocks the combustible gas generated by decomposition such as polymer resin from heat and oxygen. The flame retardant mechanism of the chlorine-based flame retardant among halogen-based flame retardants such as chlorinated paraffins is caused by radical action and generates HCl through Cl radical during decomposition of the chlorine-based flame retardant to separate the active and hydroxy radicals during combustion.

본 발명에서 염소화 파라핀과 삼산화 안티몬은 각각 난연제와 난연보조제로 사용되었다. 삼산화안티몬은 자체적으로 난연효과를 가지지는 않지만 난연제와 함께 사용되었을 때 우수한 난연효과를 부여한다. 염소화 파라핀과 삼산화 안티몬은 앞서 설명한 고분자 베이스 수지를 100 중량부로 기준하였을 때, 각각 10~30 중량부를 첨가한다.In the present invention, chlorinated paraffin and antimony trioxide were used as flame retardants and flame retardant aids, respectively. Antimony trioxide does not have flame retardant effect on its own but gives excellent flame retardant effect when used with flame retardant. Chlorinated paraffin and antimony trioxide add 10 to 30 parts by weight, respectively, based on 100 parts by weight of the polymer base resin described above.

불포화폴리에스테르 수지는 강도와 탄성율이 낮고 충격성이 좋지 못하므로 섬유를 보강재로 첨가한다. 보강재로는 유리섬유, 카본섬유, 아라미드섬유 등이 사 용될 수 있다. 일반적으로 불포화 폴리에스테르계 벌크 몰드 컴파운드 조성물은 분산성, 표면 거칠기, 외관이 좋지 못하다는 성질을 가지고 있는바, 이러한 단점을 보완하기 위하여 본 발명에서는 길이가 3~12mm인 촙스트랜드 유리섬유를 보강재로 사용한다.Unsaturated polyester resins have low strength and elastic modulus and poor impact properties, so the fibers are added as reinforcing materials. Glass fiber, carbon fiber, aramid fiber, etc. may be used as the reinforcing material. Generally, unsaturated polyester-based bulk mold compound compositions have properties of poor dispersibility, surface roughness, and poor appearance. In order to compensate for these disadvantages, in the present invention, a stranded glass fiber having a length of 3 to 12 mm is used as a reinforcing material. use.

기타 불포화 폴리에스테르를 경화시키기 위해 경화제로 터트-부틸퍼옥시 벤조에이트(t-butyl peroxy benzoate: TBPB)의 유기과산화물이 1~2 중량부 더 포함된다.In order to cure other unsaturated polyesters, an organic peroxide of tert-butyl peroxy benzoate (TBPB) is further included as a curing agent.

상기와 같이 제조한 벌크 몰드 컴파운드 조성물을 일정한 금형(mold)에 넣어 성형한 후, 성형물을 금형과 이탈시키기 위한 이형제로 스테아린산 아연, 스테아린 칼슘과 같은 지방산계 금속 화합물이 2~20 중량부 사용된다.(고분자 수지를 100 중량부로 기준시)After molding the bulk mold compound composition prepared as described above into a predetermined mold (mold), 2 to 20 parts by weight of a fatty acid-based metal compound such as zinc stearate and calcium stearate are used as a release agent for separating the molding from the mold. (Based on 100 parts by weight of polymer resin)

또한, 본 발명에 의한 벌크 몰드 컴파운드에는 난연성, 분산성, 표면 거칠기 등을 향상시키는 계면 활성제가 더 첨가될 수도 있는데, 계면 활성제로는 아래의 화학식을 갖는 포스페이트가 0.1~5 중량부 첨가된다.(고분자 수지를 100 중량부로 기준시)In addition, the bulk mold compound according to the present invention may further be added a surfactant for improving the flame retardancy, dispersibility, surface roughness, etc., 0.1 to 5 parts by weight of the phosphate having the following formula is added as a surfactant. Based on 100 parts by weight of polymer resin)

R-(X)R- (X) nn -OPO-OPO 33 HH 22

여기서, X는 에틸렌옥사이드나 프로필렌옥사이드, n은 0~30, R은 5~40의 탄소수를 가지는 지방족 또는 방향족 그룹X is an ethylene oxide or propylene oxide, n is an aliphatic or aromatic group having 0 to 30, and R is 5 to 40 carbon atoms.

이외에 중합개시제, 안료, 증점제, 습윤 분산제, 항균제, 도트(dot)상의 칩 등의 첨가제가 본 발명에 의한 벌크 몰드 컴파운드 조성물에 첨가될 수 있다.In addition, additives such as polymerization initiators, pigments, thickeners, wet dispersants, antibacterial agents, and chips on the dots may be added to the bulk mold compound composition according to the present invention.

본 발명에 따른 벌크 몰드 컴파운드 조성물은 업계에서 사용하는 일반적인 수단으로 혼련, 합침, 숙성시켜 벌크 형상의 성형재료(Bulk Mold Compound)를 얻는다. 다만, 난연성, 분산성, 표면거칠기 등을 향상시키는 기능이 있는 계면 활성제를 불포화 폴리에스테르 고분자 수지에 첨가시키는 공정이 있다는 것이 다르다.The bulk mold compound composition according to the present invention is kneaded, kneaded, and aged by general means used in the industry to obtain a bulk mold compound. However, there is a difference in that there is a process of adding a surfactant having a function of improving flame retardancy, dispersibility, surface roughness, etc. to the unsaturated polyester polymer resin.

상기 벌크 몰드 컴파운드 조성물은 암수로 이루어진 금형상에 약 120~160℃의 온도에서 금형에 투입된 후 20~150kgf/cm2, 1mm 당 20초 이상의 시간이 경과된 후 원하는 불포화 폴리에스테르 성형제품을 생산할 수 있다.The bulk mold compound composition may be produced into a desired unsaturated polyester molded product after 20 seconds or more after 20 to 150kgf / cm2, 1mm after being put into the mold at a temperature of about 120 ~ 160 ℃ on the mold made of male and female. .

본 발명에 따른 불포화 폴리에스테르 성형제품은 건축물의 바닥장식재, 천장재, 씽크상판, 철도객차 내장재, 선박내장재, 전기용품류, 상판류, 마루굽틀류 등에 이용될 수 있다.Unsaturated polyester molded article according to the present invention can be used for building flooring materials, ceiling materials, sink tops, railway passenger car interiors, ship interiors, electrical appliances, tops, floor coverings.

이하 본 발명의 구체적인 실시예들에 대한 물성을 본 발명에 대한 종래기술들을 비교예로 하여 설명하기로 한다.Hereinafter, the physical properties of specific embodiments of the present invention will be described with reference to the prior art for the present invention.

먼저, 실시예들 및 비교예들에 대한 조성 및 제조 방법에 대해 설명한다.First, the composition and the manufacturing method for Examples and Comparative Examples will be described.

<실시예 1><Example 1>

불포화 폴리에스테르 수지 70 중량부, 폴리스티렌 30 중량부로 이루어진 고분자 수지 100 중량부에 대하여 입경 1~12㎛인 수산화 알루미늄 250 중량부, 계면 활성제로 포스페이트 3중량부, 염소화 파라핀 20 중량부, 삼산화 안티몬 20 중량부, 스테아린산 아연 10 중량부를 니더(kneader)에 40분간 혼련한 후, 6mm 유리단섬유 400 중량부를 넣고 5분간 함침 후 상온에서 숙성한 뒤 성형된 제품을 제조하 였다.250 parts by weight of aluminum hydroxide having a particle diameter of 1 to 12 µm with respect to 100 parts by weight of polymer resin composed of 70 parts by weight of unsaturated polyester resin and 30 parts by weight of polystyrene, 3 parts by weight of phosphate as a surfactant, 20 parts by weight of chlorinated paraffin, and 20 parts of antimony trioxide Part, 10 parts by weight of zinc stearate was kneaded in a kneader for 40 minutes, 400 parts by weight of 6 mm short glass fiber was impregnated for 5 minutes, and then aged at room temperature to prepare a molded product.

<실시예 2><Example 2>

1~12㎛ 수산화 알루미늄 300 중량부, 평균입경 8㎛의 중질탄산칼슘 100 중량부, 6mm 촙스트랜드 유리섬유 500 중량부를 사용한 것을 제외하고는 실시예 1과 동일하다.It is the same as Example 1 except that 300 weight part of 1-12 micrometers aluminum hydroxide, 100 weight part of heavy calcium carbonates with an average particle diameter of 8 micrometers, and 500 weight part of 6 mm chopped strand glass fiber were used.

<실시예 3><Example 3>

평균입경 8㎛의 중질탄산칼슘 250 중량부를 사용한 것을 제외하고는 실시예 1과 동일하다.It is the same as Example 1 except using 250 weight part of heavy calcium carbonates whose average particle diameter is 8 micrometers.

<실시예 4><Example 4>

불포화 폴리에스테르 수지로만 이루어진 고분자 수지 100 중량부, 입경 1~12㎛ 수산화 알루미늄 250 중량부, 계면 활성제로서 포스페이트 3 중량부, 염소화 파라핀 20 중량부, 삼산화 안티몬 20 중량부, 스테아린산 아연 10 중량부를 니더(kneader)에 40분간 혼련후 6mm 유리 단섬유 400 중량부를 넣고 5분간 함침 후 상온에서 숙성시킨 뒤 성형된 제품을 제조하였다.100 parts by weight of a polymer resin composed only of an unsaturated polyester resin, 250 parts by weight of aluminum hydroxide with a particle size of 1 to 12 μm, 3 parts by weight of phosphate as a surfactant, 20 parts by weight of chlorinated paraffin, 20 parts by weight of antimony trioxide, and 10 parts by weight of zinc stearate kneader) was kneaded for 40 minutes, and then 400 parts by weight of short 6 mm glass fibers were impregnated for 5 minutes and aged at room temperature to prepare a molded product.

<비교예 1>Comparative Example 1

불포화 폴리에스테르 수지만으로된 고분자 수지 100 중량부를 사용하고, 계 면활성제를 사용하지 않은 것을 제외하고는 실시예 1과 동일하다.It is the same as Example 1 except using 100 weight part of polymer resins which consist only of unsaturated polyester resin, and not using surfactant.

<비교예 2>Comparative Example 2

불포화 폴리에스테르 수지만으로된 고분자 수지 100 중량부를 사용하고, 계면활성제를 사용하지 않은 것을 제외하고는 실시예 3과 동일하다.It is the same as Example 3 except using 100 weight part of polymer resins which consist only of unsaturated polyester resin, and not using surfactant.

<비교예 3>Comparative Example 3

불포화 폴리에스테르 수지 70 중량부, 폴리스티렌 30 중량부로 이루어진 고분자 수지, 계면활성제를 사용하지 않은 것을 제외하고는 실시예 1과 동일하다.It is the same as Example 1 except not using a polymeric resin which consists of 70 weight part of unsaturated polyester resins, 30 weight part polystyrene, and surfactant.

Figure 112005023989347-pat00001
Figure 112005023989347-pat00001

고분자 수지: 스티렌이 용해되어 있는 비스페놀-A 계 불포화 폴리에스테르로서 점도 1000mPa/sPolymer resin: Bisphenol-A unsaturated polyester in which styrene is dissolved, viscosity 1000 mPa / s

수축억제제: 스티렌 단량체에 용해되어 있는 폴리스티렌로서 점도 7000mPa?sShrinkage inhibitor: Polystyrene dissolved in styrene monomer, viscosity 7000 mPa? S

수산화 알루미늄: 입경 1~12㎛Aluminum hydroxide: particle size 1-12㎛

중질탄산칼슘: 평균입경 4㎛, BET 표면적: 1.7m2/gHeavy calcium carbonate: Average particle size 4㎛, BET surface area: 1.7m 2 / g

계면활성제 A :(tris-ethyl-phenyl)-phenyl-polyethyloxy-phosphateSurfactant A: (tris-ethyl-phenyl) -phenyl-polyethyloxy-phosphate

계면활성제 B : butyl-phenyl-polyethyloxy-phosphateSurfactant B: Butyl-phenyl-polyethyloxy-phosphate

스테아린산 아연: 분말상Zinc Stearate: Powder

유리섬유: 직경 6mmFiberglass: Diameter 6mm

TBPB: tert-butyl-peroxy benzoateTBPB: tert-butyl-peroxy benzoate

표면거칠기: 성형제품의 표면거칠기를 말함Surface Roughness: Refers to the surface roughness of molded products

외관: 250×250×1.5mm 시험편에 의한 육안 확인Appearance: Visual check by 250 × 250 × 1.5mm test piece

수축율: ASTM D-955에 의한 실험Shrinkage: Experiment by ASTM D-955

이상 첨부된 표를 참조하여 본 발명의 실시예들을 설명하였으나, 본 발명은 상기 실시예들에 한정되는 것이 아니라 서로 다른 다양한 형태로 제조될 수 있으며, 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자는 본 발명의 기술적 사상이나 필수적인 특징을 변경하지 않고서 다른 구체적인 형태로 실시될 수 있다는 것을 이해할 수 있을 것이다. 그러므로 이상에서 기술한 실시예들은 모든 면에서 예시적인 것이며 한정적이 아닌 것으로 이해해야만 한다. While the embodiments of the present invention have been described with reference to the accompanying tables, the present invention is not limited to the above embodiments, but may be manufactured in various forms, and having ordinary skill in the art to which the present invention pertains. It will be understood by those skilled in the art that the present invention may be embodied in other specific forms without changing the technical spirit or essential features of the present invention. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive.

본 발명의 실시예들에 의하며 성형제품을 제조하더라도 분산성이 좋고, 표면 거칠기가 작고, 수축율이 낮으며, 난연성이 우수한 벌크 몰드 컴파운드를 제조할 수 있다.According to embodiments of the present invention, even if a molded product is manufactured, a bulk mold compound having good dispersibility, small surface roughness, low shrinkage rate, and excellent flame retardancy may be manufactured.

Claims (3)

불포화 폴리에스테르 수지와 폴리스티렌계 수지가 100 중량부가 되도록 혼합된 고분자 수지에 대하여, 1~15.0㎛의 입경과 170~400 중량부를 가지는 수산화 알루미늄, 0.1~8.0㎛의 입경과 20~200 중량부를 가지는 중질탄산칼슘, 3~12mm의 길이를 가진 유리섬유 5.0~30 중량부, 10~30 중량부를 가지는 염소화파라핀, 10~30 중량부를 가지는 삼산화안티몬, 0.5~5 중량부를 가지는 계면활성제를 포함하는 벌크 몰드 컴파운드 조성물.Aluminum hydroxide having a particle size of 1 to 15.0 μm and 170 to 400 parts by weight, a particle diameter of 0.1 to 8.0 μm and a heavy weight having 20 to 200 parts by weight, based on the polymer resin mixed so that the unsaturated polyester resin and the polystyrene resin are 100 parts by weight. Bulk mold compound comprising calcium carbonate, 5.0-30 parts by weight of glass fiber having a length of 3-12 mm, chlorinated paraffin having 10-30 parts by weight, antimony trioxide having 10-30 parts by weight, and surfactant having 0.5-5 parts by weight Composition. 제 1 항에 있어서,The method of claim 1, 난연성, 표면거칠기, 분산성 등을 향상시키는 상기 계면활성제는 포스페이트계로 (1)과 같은 구조를 갖는 벌크 몰드 컴파운드 조성물 The surfactant, which improves flame retardancy, surface roughness, dispersibility, and the like, is a bulk mold compound composition having a structure as in (1) based on phosphate. R-(X)n-OPO3H2 - (1)R- (X) n -OPO 3 H 2- (1) 여기서 X: 에틸렌 옥사이드 또는 프로필렌옥사이드Where X: ethylene oxide or propylene oxide n: 0 ~ 30n: 0 to 30 R: 지방족 또는 방향족 그룹으로 5~40 개의 탄소수를 가짐R is an aliphatic or aromatic group having 5 to 40 carbon atoms 제 1 항에 있어서,The method of claim 1, 불포화 폴리에스테르 수지와 폴리스티렌계 저수축제의 혼합비율은 100미만 : 0 초과 ~ 60이상 : 40이하의 범위를 가지는 것을 특징으로 하는 벌크 몰드 컴파운드 조성물.The mixing ratio of the unsaturated polyester resin and the polystyrene-based low shrinkage agent is less than 100: the bulk mold compound composition, characterized in that it has a range of more than 0 ~ 60 or more: 40 or less.
KR1020050038168A 2005-05-06 2005-05-06 Composite for Bulk mold compound KR100697868B1 (en)

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KR100885647B1 (en) * 2008-11-11 2009-02-25 세왕에스엔에스(주) Bulk molding compound for a sink panel and method for producing thereof
CN109836791A (en) * 2019-01-22 2019-06-04 西原环保工程(上海)有限公司 A kind of composite material and preparation method

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KR800001656B1 (en) * 1976-04-27 1980-12-31 원본미기재 Sheet or bulk molding composition
JPH0827364A (en) * 1994-07-18 1996-01-30 Sumitomo Bakelite Co Ltd Unsaturated polyester resin molding material
KR20040068560A (en) * 2001-11-29 2004-07-31 브로민 콤파운드 리미티드 Fire Retarded Polymer Composition
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KR20160044390A (en) * 2014-10-15 2016-04-25 합자회사 거광산업 Architectural materiels for the ceiling, and the method of making thereof
KR101630201B1 (en) 2014-10-15 2016-07-07 주식회사 거광이엔지 Architectural materiels for the ceiling, and the method of making thereof

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