KR20140075953A - DCPD Modified Unsaturated Polyester Composition and Manufacturing the Same - Google Patents

DCPD Modified Unsaturated Polyester Composition and Manufacturing the Same Download PDF

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KR20140075953A
KR20140075953A KR1020120143731A KR20120143731A KR20140075953A KR 20140075953 A KR20140075953 A KR 20140075953A KR 1020120143731 A KR1020120143731 A KR 1020120143731A KR 20120143731 A KR20120143731 A KR 20120143731A KR 20140075953 A KR20140075953 A KR 20140075953A
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unsaturated polyester
weight
dicyclopentadiene
polyester resin
resin composition
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KR101425403B1 (en
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정훈상
박형남
이광희
김학준
정의민
최광식
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애경화학 주식회사
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    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/46—Polyesters chemically modified by esterification
    • C08G63/47—Polyesters chemically modified by esterification by unsaturated monocarboxylic acids or unsaturated monohydric alcohols or reactive derivatives thereof
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/87—Non-metals or inter-compounds thereof
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    • 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
    • C08K3/32—Phosphorus-containing compounds
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    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/01—Hydrocarbons
    • 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
    • C08K5/00—Use of organic ingredients
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    • C08K5/07—Aldehydes; Ketones
    • C08K5/08—Quinones
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    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/06—Unsaturated polyesters

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Abstract

The present invention relates to a dicyclopentadiene (DCPD)-modified unsaturated polyester resin composition and a manufacturing method thereof and, more particularly, to a dicyclopentadiene (DCPD)-modified unsaturated polyester resin composition and a manufacturing method thereof wherein the dicyclopentadiene (DCPD)-modified unsaturated polyester resin composition is manufactured by the polycondensation reaction of propylene glycol (PG), neopentyl glycol (NPG), dipropylene glycol (DPG), maleic anhydride (MA), and dicyclopentadiene (DCPD), which is a modifier, to have a doubled to quadrupled final thickening property compared with existing unsaturated polyester while exhibiting initial low thickening behavior and to have improved gloss and weather resistance. The dicyclopentadiene-modified unsaturated polyester resin composition according to the present invention comprises: 10 to 40 wt% of propylene glycol (PG); 0.1 to 50 wt% of neopentyl glycol (NPG); 0.1 to 20 wt% of dipropylene glycol (DPG); 20 to 80 wt% of maleic anhydride (MA); 0.1 to 20 wt% of dicyclopentadiene (DCPD); 0.1 to 3 wt% of a polymerization inhibitor; 0.1 to 1 wt% of a polycondensation catalyst; 0.1 to 1 wt% of a dispersant and a phase separation inhibitor; and 0.1 to 1 wt% of a heat generation inhibitor.

Description

디사이클로펜타디엔으로 개질된 불포화폴리에스테르수지 조성물 및 그 제조방법{DCPD Modified Unsaturated Polyester Composition and Manufacturing the Same}[0001] The present invention relates to an unsaturated polyester resin composition modified with dicyclopentadiene and a process for producing the unsaturated polyester resin composition,

본 발명은 디사이클로펜타디엔(DCPD ; Dicyclopentadiene)으로 개질된 불포화폴리에스테르수지 조성물 및 그 제조방법에 관한 것으로, 더욱 상세하게는 프로필렌글리콜(PG), 네오펜틸글리콜(NPG), 디프로필렌글리콜(DPG), 무수말레인산(MA) 및 Modifier(개질제)인 디사이클로펜타디엔(DCPD)을 Polycondensation 반응시켜 초기 낮은 증점 거동을 보이면서도 말기 증점이 기존 불포화폴리에스테르보다 2~4배 향상되고, 광택 및 내후성이 향상된 디사이클로펜타디엔(DCPD ; Dicyclopentadiene) 으로 개질된 불포화폴리에스테르수지 조성물 및 그 제조방법에 관한 것이다.
The present invention relates to an unsaturated polyester resin composition modified with dicyclopentadiene (DCPD) and a method of preparing the same. More specifically, the present invention relates to a composition for preparing an unsaturated polyester resin composition comprising propylene glycol (PG), neopentyl glycol (NPG), dipropylene glycol ), Dicyclopentadiene (DCPD) as a modifier (maleic anhydride (MA)) and modifier (modifier) were initially subjected to polycondensation reaction to show an initial low viscosity behavior and a 2- to 4-fold improvement in the terminal viscosity of the unsaturated polyester, The present invention relates to an unsaturated polyester resin composition modified with dicyclopentadiene (DCPD) and a method for producing the same.

일반적으로 불포화폴리에스테르 수지는 불포화 다염기산과 포화 다염기산을 다가알코올과 축중합 반응시킴으로써 에스테르화한 불포화 폴리에스테르를 공중합 가능한 스티렌 등의 모노머류에 용해하여 제조되는 것이다.
Generally, the unsaturated polyester resin is produced by dissolving an unsaturated polyester esterified by condensation polymerization of an unsaturated polybasic acid and a saturated polybasic acid with a polyhydric alcohol in monomers such as copolymerizable styrene.

상기 불포화 다염기산으로서는 예컨대, 말레산, 무수말레산, 푸마르산, 이타콘산, 무수 이타콘산, 테트라하이드로프탈산, 무수테트라하이드로프탈산, 메틸테트라하이드로 무수프탈산, 테트라브로모 무수프탈산, 테트라클로로 무수프탈산, 무수 헤트산, 무수 하이믹산 등을 들 수 있고, 이들은 1종 또는 2종 이상 병용하여 사용할 수 있다.
Examples of the unsaturated polybasic acids include maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, tetrahydrophthalic acid, anhydrous tetrahydrophthalic acid, methyltetrahydrophthalic anhydride, tetrabromophthalic anhydride, tetrachlorophthalic anhydride, Acid, and anhydrous hymic acid. These may be used alone or in combination of two or more.

또한, 상기 포화 다염기산으로서는, 예컨대, 프탈산, 무수프탈산, 할로겐화무수프탈산, 이소프탈산, 테레프탈산, 헥사하이드로프탈산, 헥사하이드로무수프탈산, 헥사하이드로테레프탈산, 헥사하이드로이소프탈산, 호박산, 말론산, 글루타르산, 아디프산, 세바신산, 1,12-도데칸2산, 2,6-나프탈렌디카르복실산, 2,7-나프탈렌디카르복실산, 2,3-나프탈렌디카르복실산, 2,3-나프탈렌디카르복실산무수물, 4,4'-비페닐디카르복실산, 또한 이들의 디알킬에스테르 등을 들 수 있고, 이들은 1종 또는 2종 이상 병용하여 사용할 수 있다.
Examples of the saturated polybasic acid include phthalic acid, phthalic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, hexahydrophthalic acid, hexahydrophthalic anhydride, hexahydroterephthalic acid, hexahydroisophthalic acid, succinic acid, malonic acid, glutaric acid, Naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid, Naphthalene dicarboxylic acid anhydride, 4,4'-biphenyl dicarboxylic acid, and dialkyl esters thereof. These may be used alone or in combination of two or more.

상기 다가 알코올로서는, 예컨대, 에틸렌 글리콜, 디에틸렌 글리콜, 트리에틸렌 글리콜, 폴리에틸렌 글리콜, 프로필렌 글리콜, 디프로필렌 글리콜, 폴리프로필렌 글리콜, 2-메틸-1,3-프로판디올, 1,3-부탄디올, 네오펜틸 글리콜, 수소화 비스페놀 A, 1,4-부탄디올, 1,6-헥산디올, 1,9-노난디올, 비스페놀 A와 프로필렌 옥시드 또는 에틸렌 옥시드의 부가물, 1,2,3,4-테트라히드록시부탄, 글리세린, 트리메틸올 프로판, 1,3-프로판디올, 1,2-시클로헥산글리콜, 1,3-시클로헥산글리콜, 1,4-시클로헥산 글리콜, 1,4-시클로헥산디메탄올, 파라크실렌 글리콜, 비시클로헥실-4,4'-디올, 2,6-데칼린 글리콜, 2,7-데칼린 글리콜, 비스히드록시에틸 테레프탈레이트 등을 들 수 있고, 이들은 1종 또는 2종 이상 병용하여 사용할 수 있다.
Examples of the polyhydric alcohol include polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 2-methyl-1,3-propanediol, 1,6-hexanediol, 1,9-nonanediol, adducts of bisphenol A with propylene oxide or ethylene oxide, 1,2,3,4-tetra Butylene glycol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, Decyl glycol, 2,7-decalin glycol, and bishydroxyethyl terephthalate. These monomers may be used alone or in combination of two or more. Can be used.

불포화폴리에스테르수지의 종래기술을 살펴 보면, 한국등록특허 10-0574251에 산 10 중량부 및 알코올 11 내지 15 중량부를 축합반응시켜 수득되고, 중량 평균 분자량이 40,000 내지 130,000이고, 불휘발분 산값이 40 이하이며, 점도가 T 내지 Z인 불포화폴리에스테르 수지 조성물이 공지되어 있다.
The unsaturated polyester resin is obtained by a condensation reaction of 10 parts by weight of an acid and 11-15 parts by weight of an alcohol in Korean Patent No. 10-0574251 and has a weight average molecular weight of 40,000 to 130,000 and a non- , And an unsaturated polyester resin composition having a viscosity of T to Z is known.

또한, 한국공개특허 특2002-0077633에 0.5 - 1.5몰 중량부의 무수프탈산, 프탈산, 이소프탈산, 테레프탈산중 선택된 어느 하나를 포화이염기산 무수물로써 사용하고, 0.5 - 1.5몰 중량부의 α, β- 불포화 이염기산 무수물과 다가알콜로써 0 - 0.5몰 중량부의 프로필렌글리콜, 0.5 - 1.0몰 중량부의 에틸렌글리콜, 0.5 - 1.5몰 중량부의 디에틸렌글리콜, 0.5 - 1.0몰 중량부의 디프로필렌글리콜 이외에 0 - 1.5몰 중량부의 네오펜틸렌그리콜, 0 - 1.5몰 중량부의 비스페놀-A, 0 - 1.5몰 중량부의 수소화비스페놀-A를 반응기에 투입하고, 질소기류하에 에스테르화 반응을 진행시켜 불포화폴리에스테르 수지를 제조하는 방법이 공지되어 있다.
In addition, in Korean Patent Publication No. 2002-0077633, 0.5 to 1.5 mol parts by weight of any one selected from anhydrous phthalic acid, phthalic acid, isophthalic acid and terephthalic acid is used as a saturated dibasic anhydride, and 0.5 to 1.5 mol parts of?,? A dianhydride and a polyhydric alcohol may be used in an amount of 0 to 0.5 mole by mole, in addition to 0 to 1.5 mole parts by weight of propylene glycol, 0.5 to 1.0 mole by mole of ethylene glycol, 0.5 to 1.5 mole by mole of diethylene glycol and 0.5 to 1.0 mole by mole of dipropylene glycol, 0 to 1.5 molar parts by weight of bisphenol-A and 0 to 1.5 molar parts by weight of hydrogenated bisphenol-A are introduced into a reactor and the esterification reaction is carried out in a stream of nitrogen to prepare an unsaturated polyester resin. .

또한, 한국공개특허 10-2011-0075198에 다가 알코올의 알릴에테르 단위를 가지며, 불포화 다염기산을 함유한 다염기산과 다가 알코올의 축합 반응에 의해 생성되는 불포화 폴리에스테르 수지가 공지되어 있다.
Korean Unexamined Patent Publication No. 10-2011-0075198 discloses an unsaturated polyester resin having an allyl ether unit of a polyhydric alcohol and produced by a condensation reaction of a polybasic acid containing an unsaturated polybasic acid and a polyhydric alcohol.

또한, 한국공개특허 10-2011-0135686에 포화염기산인 이소프탈산 120 내지 200중량부, 테레프탈산 40 내지 90중량부와 α,β-에틸렌계 불포화디카르복실산인 무수말레인산 40 내지 70중량부, 푸마르산 150내지 220중량부와 다가알코올인 네오펜틸글리콜 180 내지 200중량부, 프로필렌글리콜 70 내지 90중량부와 반응촉매 0.3 내지 0.6중량부, 비닐단량체인 스틸렌모노머 400 내지 450중량부로 조성되며, 중량평균 분자량이 3,500 내지 6,000이고 불휘발분 55 내지 60중량%이고, 산값이 20이하이며, 점도가 L 내지 N인 불포화 폴리에스테르 수지가 공지되어 있다.
In Korean Patent Laid-open No. 10-2011-0135686, 120 to 200 parts by weight of isophthalic acid as a saturated base acid, 40 to 90 parts by weight of terephthalic acid, 40 to 70 parts by weight of maleic anhydride as?,? Ethylenically unsaturated dicarboxylic acid, fumaric acid 150 And 70 to 90 parts by weight of propylene glycol, 0.3 to 0.6 parts by weight of a reaction catalyst, and 400 to 450 parts by weight of a styrene monomer which is a vinyl monomer, and has a weight average molecular weight An unsaturated polyester resin having an acid value of 20 or less and a viscosity of from L to N is known from 3,500 to 6,000 and 55 to 60% by weight of nonvolatile matter.

이러한, 불포화폴리에스테르 수지는 가격이 비교적 저렴하고, 상온에서 단시간 내에 경화되는 작업성과, 뛰어난 내열성, 내식성을 갖고 있으며, 주원료의 다양한 선택에 따라 각종의 물리적, 화학적 특성을 나타낼 수 있기 때문에 다양한 분야에 적용되고 있는데, 예를 들어, 욕조, 정화조와 같은 건축자재, 탱크, 파이프 등과 같은 공업재료, 선박, 자동차 등의 수송기기, 전기절연재료, 겔 코트, 레진 콘크리트, 퍼티도료 등 각종용도로 광범위하게 사용되고 있다.
These unsaturated polyester resins have relatively low cost, workability of curing at room temperature within a short time, excellent heat resistance and corrosion resistance, and they can show various physical and chemical characteristics according to various choices of the main raw materials. For example, in a wide range of applications such as building materials such as bathtubs and septic tanks, industrial materials such as tanks and pipes, transportation devices such as ships and automobiles, electric insulating materials, gelcoats, resin concrete, putty coatings .

한편, 에스엠씨(SMC: Sheet Molding Compound)는 유리섬유강화플라스틱을 제조하기 위한 성형재료의 일종으로서, 적정한 가열 및 가압조건 하에서 이를 성형하면 뛰어난 기계적 특성을 나타낼 뿐만 아니라 내식성 및 성형성이 우수하기 때문에 구조용 및 기능용 소재로 그 활용범위가 광범위하다.
On the other hand, SMC (Sheet Molding Compound) is a type of molding material for producing glass fiber reinforced plastic. When molding it under proper heating and pressurizing conditions, it exhibits excellent mechanical properties and is excellent in corrosion resistance and moldability It has a wide range of applications as structural and functional materials.

이러한 에스엠씨(SMC: Sheet Molding Compound)는 위와 같은 특성으로 인하여 각종 식수용 물탱크나 욕실용 자재 등과 같이 위생 처리가 강하게 요구되는 제품들을 중심으로 널리 사용되고 있으며, 특히 많은 종류의 물탱크들이 에스엠씨 시트로 성형한 패널로 만들어지고 있을 뿐만 아니라, 상기 에스엠씨는 도어, 천정재, 장식판 등의 건축자재와 자동차 헤드램프 및 외장 패널 등의 자동차 부품과 전자제품 등에 널리 사용되고 있다.
Due to the above characteristics, SMC (Sheet Molding Compound) has been widely used for various sanitary products such as various drinking water tanks and bathroom materials. Especially, In addition to being made of a sheet molded panel, the SM is widely used for building materials such as doors, ceiling materials, decorative panels, automobile parts such as automobile head lamps and exterior panels, and electronic products.

상기한 바와 같은 에스엠씨(Sheet Molding Compound)는 일반적으로 불포화폴리에스테르 수지를 주성분으로 하고, 여기에 보강재 및 충진제, 이형제, 안료, 촉매, 경화제, 유리섬유 등의 조성물을 컴파운딩(Compounding)하여 제조되는데 스티렌 단량체(SM: Styrene Monomer)가 35%인 불포화폴리에스테르 수지를 주성분으로 사용하며, 글리콜류는 주로 프로필렌글리콜(Propylene Glycol)과 네오페닐글리콜(Neo Phentyl Glycol)을 사용하고, 포화이염기산으로는 테레프탈산(Tere Phthalic Acid: TPA)과 테트라 하이드로 무수프탈산(Tetra Hydro Phthalic Anhydride: THPA)을 주로 사용하고 있다.
The sheet molding compound as described above is generally produced by compounding an unsaturated polyester resin as a main component and a composition such as a reinforcing material, a filler, a releasing agent, a pigment, a catalyst, a curing agent, The main component is an unsaturated polyester resin in which 35% of styrene monomer (SM: styrene monomer) is used. The glycol is mainly composed of propylene glycol and neopentyl glycol, and is a saturated dibasic acid Terephthalic Acid (TPA) and Tetra Hydro Phthalic Anhydride (THPA).

그러나, 위와 같은 조성물들로 이루어진 에스엠씨(Sheet Molding Compound)는 제조공정중에서 초기 급격한 증점거동으로 인하여 직조된 유리섬유를 투입하는 것은 불가능하고, 성형공정 중에 투입하더라도 유리섬유의 합침이 충분히 되지 않아 보강 효과가 저하되기 쉬우며, 직조된 유리섬유와 수지간의 계면 접착력이 부족하여 복합 재료의 결함으로 작용하는 문제점이 있었다.
However, since the sheet molding compound made of the above-mentioned compositions can not input the woven glass fiber due to the initial sudden thickening behavior in the manufacturing process, it is impossible to insert the glass fiber even during the molding process, There is a problem that the effect is deteriorated and the interfacial adhesion force between the woven glass fiber and the resin is insufficient and acts as a defect of the composite material.

또한, 불포화폴리에스테르 수지는 상기에 기재한 바와 같이 기계적인 물성은 양호하나 내자외선성(내후성), 광택성이 좋지 않고, 이에 따라 표면에 스크린 인쇄 및 전사 등이 잘 이루어지지 않는 단점이 있었다.
As described above, the unsaturated polyester resin has good mechanical properties but has poor ultraviolet resistance (weatherability) and glossiness, and thus has a disadvantage in that screen printing and transfer are not well performed on the surface.

이에 본 발명자들은 프로필렌글리콜(PG), 네오펜틸글리콜(NPG), 디프로필렌글리콜(DPG), 무수말레인산(MA)과 디사이클로펜타디엔(DCPD)을 Polycondensation 반응시켜 불포화폴리에스테르 수지를 제조할 경우 초기 낮은 증점 거동을 보이면서도 말기 증점이 기존 불포화폴리에스테르보다 2~4배 향상되고, 광택 및 내후성이 향상된다는 것을 확인하고 본 발명을 완성하게 되었다.
Accordingly, the present inventors have found that when an unsaturated polyester resin is produced by a polycondensation reaction of propylene glycol (PG), neopentyl glycol (NPG), dipropylene glycol (DPG), maleic anhydride (MA) and dicyclopentadiene It is confirmed that the late thickening behavior is improved by 2 to 4 times as compared with the conventional unsaturated polyester, and gloss and weatherability are improved. Thus, the present invention has been completed.

본 발명은 프로필렌글리콜(PG), 네오펜틸글리콜(NPG), 디프로필렌글리콜(DPG), 무수말레인산(MA)을 Modifier(개질제)인 디사이클로펜타디엔(DCPD)과 함께 Polycondensation 반응시켜 초기 낮은 증점 거동을 보이면서도 말기 증점이 기존 불포화폴리에스테르보다 2~4배 향상되고, 광택 및 내후성이 향상된 디사이클로펜타디엔(DCPD ; Dicyclopentadiene)으로 개질된 불포화폴리에스테르수지 조성물을 제공하는 것을 해결하고자 하는 과제로 한다.
The present invention relates to a process for producing a polyphenylene sulfide resin by polycondensation reaction of propylene glycol (PG), neopentyl glycol (NPG), dipropylene glycol (DPG) and maleic anhydride (MA) with dicyclopentadiene (DCPD) (Dicyclopentadiene) modified with an unsaturated polyester resin having an increased viscosity of 2 to 4 times higher than that of a conventional unsaturated polyester while having improved gloss and weatherability, and an object of the present invention is to provide an unsaturated polyester resin composition modified with dicyclopentadiene .

상기 과제의 해결을 위하여, 본 발명은 프로필렌글리콜(PG) 10~40중량부, 네오펜틸글리콜(NPG) 0.1~50중량부, 디프로필렌글리콜(DPG) 0.1~20중량부, 무수말레인산(MA) 20~80중량부, 디사이클로펜타디엔(DCPD) 0.1~20중량부, 중합금지제 0.1~3중량부, 중축합촉매 0.1~1중량부, 분산제 및 상분리방지제 0.1~1중량부, 발열억제제 0.1~1중량부를 포함하여 구성되는 디사이클로펜타디엔(DCPD ; Dicyclopentadiene)으로 개질된 불포화폴리에스테르수지 조성물을 과제의 해결수단으로 한다.
(DPG), 0.1 to 20 parts by weight of neopentyl glycol (NPG), 0.1 to 20 parts by weight of maleic anhydride (MA), and 0.1 to 20 parts by weight of propylene glycol 0.1 to 3 parts by weight of a polymerization inhibitor, 0.1 to 1 part by weight of a polycondensation catalyst, 0.1 to 1 part by weight of a dispersant and a phase separation inhibitor, 0.1 to 1 part by weight of a heat inhibitor 0.1, To 1 part by weight of an unsaturated polyester resin composition modified with dicyclopentadiene (DCPD).

또한, 상기 중합금지제는 하이드로퀴논, 메틸에테르하이드로퀴논, 2,5-다이부틸하이드로퀴논, 3,5-다이-3급-부틸-4-하이드록시톨루엔, 메틸-다이-3급-부틸페놀, 2,6-다이-3급-부틸-p-크레졸 중에서 1종 이상 선택되는 디사이클로펜타디엔으로 개질된 불포화폴리에스테르수지 조성물을 과제의 해결수단으로 한다.
The polymerization inhibitor may be at least one selected from the group consisting of hydroquinone, methyl ether hydroquinone, 2,5-dibutyl hydroquinone, 3,5-di-tert- , 2,6-di-tert-butyl-p-cresol as a curing agent for unsaturated polyester resins, which is modified with dicyclopentadiene.

또한, 상기 중축합촉매는 인산, 포스폰산계 화합물, 포스핀산계 화합물, 포스핀옥사이드계 화합물, 아포스폰산계 화합물, 아포스핀산계 화합물, 포스핀계 화합물 중에서 1종 이상 선택되는 디사이클로펜타디엔으로 개질된 불포화폴리에스테르수지 조성물을 과제의 해결수단으로 한다.
The polycondensation catalyst may be modified with dicyclopentadiene selected from at least one of phosphoric acid, a phosphonic acid compound, a phosphinic acid compound, a phosphine oxide compound, an phosphonic acid compound, an aposphinic acid compound and a phosphine compound And the unsaturated polyester resin composition is a solution to the problem.

또한, 상기 분산제 및 상분리방지제는 1-Methoxy-2-propanol, n-Butyl acetate, 뷰틸셀로솔브, 에틸셀로솔브,이소프로판올, 이소부탄올, 로진, 로진의 유도체 중에서 1종 이상 선택되는 디사이클로펜타디엔으로 개질된 불포화폴리에스테르수지 조성물을 과제의 해결수단으로 한다.
The dispersant and the anti-decay agent may be at least one selected from the group consisting of 1-methoxy-2-propanol, n-butyl acetate, butyl cellosolve, ethyl cellosolve, isopropanol, isobutanol, rosin, An unsaturated polyester resin composition modified with a diene is a solution to the problem.

또한, 상기 발열억제제는 구리 나프텐에이트, 코발트 나프텐에이트, 아연 나프텐에이트, α -메틸 스티렌, 터피놀렌, 감마-터피넨, 디라우릴 티오디프로피오네이트, 4-t-부틸피로카테콜 중에서 1종 이상 선택되는 디사이클로펜타디엔으로 개질된 불포화폴리에스테르수지 조성물을 과제의 해결수단으로 한다.
The heat inhibitor may be at least one selected from the group consisting of copper naphthenate, cobalt naphthenate, zinc naphthenate, alpha -methylstyrene, terpinolene, gamma-terpinene, dilaurylthiodipropionate, 4- The unsaturated polyester resin composition modified with dicyclopentadiene is selected as a solution to the problem.

또한, 상기 디사이클로펜타디엔으로 개질된 불포화폴리에스테르수지 조성물의 30℃에서 초기 20분 증점거동구간이 10.0~15.0 poise이며, 45℃에서 말기 18시간 경과시 점도가 90만~100만 poise인 것을 과제의 해결수단으로 한다.
The unsaturated polyester resin composition modified with dicyclopentadiene had a viscosity of 10,000 to 15.0 poise at an initial 20 minutes at 30 DEG C and a viscosity of 90,000 to 1,000,000 poises at the end of 18 hours at 45 DEG C This is the solution to the problem.

또한, 상기 디사이클로펜타디엔으로 개질된 불포화폴리에스테르수지 조성물의 60°광택이 98~99이며, Q.U.V. 120시간 광택유지율(ΔE)이 9~10인 것을 과제의 해결수단으로 한다.
The unsaturated polyester resin composition modified with dicyclopentadiene has a 60 ° gloss of 98 to 99 and a QUV 120 hour gloss retention rate (ΔE) of 9 to 10.

또한, 본 발명은 반응기에 프로필렌글리콜(PG) 10~40중량부, 무수말레인산(MA) 10~40중량부를 투입하고 반응온도 170℃에서 반응개시 후, 205℃로 승온 유지하며 반응시키고 산가 10 이하에서 1차반응종료시키는 단계; 상기 1차반응물을 185℃ 이하로 냉각 후 반응물을 유지하면서 DCPD 0.1~20중량부를 1시간동안 Dropping하고 2시간동안 유지반응시키는 단계; 상기 유지반응물을 100℃ 이하로 냉각 후, 디프로필렌글리콜(DPG) 0.1~20중량부, 네오펜틸글리콜(NPG) 0.1~50중량부, 무수말레인산(MA) 10~40중량부, 중축합촉매 H3PO4 0.1~1중량부를 투입하고 170℃에서 반응개시 후, 205℃로 승온 유지하며 반응시키고 산가 24이하에서 반응종료시켜 불포화폴리에스데르 수지를 얻는 단계; 상기 불포화폴리에스데르 수지에 중합금지제 0.1~3중량부, 발열억제제 0.1~1중량부, 분산 및 상분리방지제 0.1~1중량부를 첨가하는 단계;를 포함하여 구성되는 디사이클로펜타디엔(DCPD ; Dicyclopentadiene)으로 개질된 불포화폴리에스테르수지 조성물을 제조하는 방법을 과제의 해결수단으로 한다.
In the present invention, 10 to 40 parts by weight of propylene glycol (PG) and 10 to 40 parts by weight of maleic anhydride (MA) are fed into a reactor, and after the reaction is started at a reaction temperature of 170 ° C, Terminating the first reaction in the reaction system; Cooling the primary reaction product to 185 ° C or lower, dropping DCPD (0.1 to 20 parts by weight) for 1 hour while maintaining the reaction product, and maintaining the reaction for 2 hours; (DPG), 0.1 to 20 parts by weight of neopentyl glycol (NPG), 10 to 40 parts by weight of maleic anhydride (MA), 10 to 40 parts by weight of a polycondensation catalyst H 3 PO 4 0.1 to 1 part by weight, and the reaction is initiated at 170 占 폚, followed by reaction with maintaining the temperature at 205 占 폚, and the reaction is terminated at an acid value of 24 or less to obtain an unsaturated polyester resin; Adding 0.1 to 3 parts by weight of a polymerization inhibitor, 0.1 to 1 part by weight of an exothermic inhibitor, and 0.1 to 1 part by weight of a dispersion and an anti-segregation agent to the unsaturated polyester resin, The present invention also provides a method for producing a modified unsaturated polyester resin composition.

본 발명에 따른 디사이클로펜타디엔(DCPD ; Dicyclopentadiene)으로 개질된 불포화폴리에스테르수지 조성물은 초기 낮은 증점 거동을 보이면서도 말기 증점이 기존 불포화폴리에스테르보다 2~4배 향상되므로 SMC에 사용될 경우 초기 낮은 증점 거동으로 인해 유리섬유의 함침이 충분히 이루어지고 수지간의 계면접착이 향상되어 보강효과를 극대화할 수 있으며, 기계적 물성을 유지하면서도 내자외선성(내후성), 광택성이 향상되어 다양한 용도에 확대되어 사용될 수 있는 장점이 있다.
The unsaturated polyester resin composition modified with dicyclopentadiene (DCPD) according to the present invention exhibits an initial low viscosity behavior and has a 2- to 4-fold improvement in terminal viscosity than the conventional unsaturated polyester. Therefore, when used in an SMC, It is possible to maximize the reinforcement effect by improving the adhesion of the interfacial adhesion between the resins and to improve the ultraviolet resistance (weather resistance) and gloss while maintaining the mechanical properties, There is an advantage.

도 1은 본 발명의 증점성 개선 비교결과를 나타내는 도면
도 2는 본 발명의 Q.U.V. 120시간 광택유지율(ΔE)을 나타내는 비교사진BRIEF DESCRIPTION OF THE DRAWINGS FIG.
Figure 2 is a comparative photograph showing the QUV 120 hour gloss retention ([Delta] E)

본 발명은 프로필렌글리콜(PG) 10~40중량%, 네오펜틸글리콜(NPG) 0.1~50중량부, 디프로필렌글리콜(DPG) 0.1~20중량부, 무수말레인산(MA) 20~80중량부, 디사이클로펜타디엔(DCPD) 0.1~20중량부, 중합금지제 0.1~3중량부, 중축합촉매 0.1~1중량부, 분산제 및 상분리방지제 0.1~1중량부, 발열억제제 0.1~1중량부를 포함하여 구성되는 디사이클로펜타디엔(DCPD ; Dicyclopentadiene)으로 개질된 불포화폴리에스테르수지 조성물을 기술구성의 특징으로 한다.
(DPG), from 20 to 80 parts by weight of maleic anhydride (MA), from 10 to 40 parts by weight of propylene glycol (PG), from 0.1 to 50 parts by weight of neopentyl glycol (NPG), from 0.1 to 20 parts by weight of dipropylene glycol 0.1 to 20 parts by weight of cyclopentadiene (DCPD), 0.1 to 3 parts by weight of a polymerization inhibitor, 0.1 to 1 part by weight of a polycondensation catalyst, 0.1 to 1 part by weight of a dispersant and a phase separation inhibitor, and 0.1 to 1 part by weight of a heat- (Dicyclopentadiene) modified with an unsaturated polyester resin composition of the present invention.

또한, 상기 중합금지제는 하이드로퀴논, 메틸에테르하이드로퀴논, 2,5-다이부틸하이드로퀴논, 3,5-다이-3급-부틸-4-하이드록시톨루엔, 메틸-다이-3급-부틸페놀, 2,6-다이-3급-부틸-p-크레졸 중에서 1종 이상 선택되는 디사이클로펜타디엔으로 개질된 불포화폴리에스테르수지 조성물을 기술구성의 특징으로 한다.
The polymerization inhibitor may be at least one selected from the group consisting of hydroquinone, methyl ether hydroquinone, 2,5-dibutyl hydroquinone, 3,5-di-tert- , 2,6-di-tert-butyl-p-cresol, which is a dicyclopentadiene-modified unsaturated polyester resin composition.

또한, 상기 중축합촉매는 인산, 포스폰산계 화합물, 포스핀산계 화합물, 포스핀옥사이드계 화합물, 아포스폰산계 화합물, 아포스핀산계 화합물, 포스핀계 화합물 중에서 1종 이상 선택되는 디사이클로펜타디엔으로 개질된 불포화폴리에스테르수지 조성물을 기술구성의 특징으로 한다.
The polycondensation catalyst may be modified with dicyclopentadiene selected from at least one of phosphoric acid, a phosphonic acid compound, a phosphinic acid compound, a phosphine oxide compound, an phosphonic acid compound, an aposphinic acid compound and a phosphine compound The unsaturated polyester resin composition is characterized by its technical structure.

또한, 상기 분산제 및 상분리방지제는 1-Methoxy-2-propanol, n-Butyl acetate, 뷰틸셀로솔브, 에틸셀로솔브,이소프로판올, 이소부탄올, 로진, 로진의 유도체 중에서 1종 이상 선택되는 디사이클로펜타디엔으로 개질된 불포화폴리에스테르수지 조성물을 기술구성의 특징으로 한다.
The dispersant and the anti-decay agent may be at least one selected from the group consisting of 1-methoxy-2-propanol, n-butyl acetate, butyl cellosolve, ethyl cellosolve, isopropanol, isobutanol, rosin, The unsaturated polyester resin composition modified with a diene is characterized by its technical constitution.

또한, 상기 발열억제제는 구리 나프텐에이트, 코발트 나프텐에이트, 아연 나프텐에이트, α -메틸 스티렌, 터피놀렌, 감마-터피넨, 디라우릴 티오디프로피오네이트, 4-t-부틸피로카테콜 중에서 1종 이상 선택되는 디사이클로펜타디엔으로 개질된 불포화폴리에스테르수지 조성물을 기술구성의 특징으로 한다.
The heat inhibitor may be at least one selected from the group consisting of copper naphthenate, cobalt naphthenate, zinc naphthenate, alpha -methylstyrene, terpinolene, gamma-terpinene, dilaurylthiodipropionate, 4- Wherein the unsaturated polyester resin composition is modified with dicyclopentadiene.

또한, 상기 디사이클로펜타디엔으로 개질된 불포화폴리에스테르수지 조성물의 30℃에서 초기 20분 증점거동구간이 10.0~15.0 poise이며, 45℃에서 말기 18시간 경과시 점도가 90만~100만 poise인 것을 기술구성의 특징으로 한다.
The unsaturated polyester resin composition modified with dicyclopentadiene had a viscosity of 10,000 to 15.0 poise at an initial 20 minutes at 30 DEG C and a viscosity of 90,000 to 1,000,000 poises at the end of 18 hours at 45 DEG C It is a feature of technology construction.

또한, 상기 디사이클로펜타디엔으로 개질된 불포화폴리에스테르수지 조성물의 60°광택이 98~99이며, Q.U.V. 120시간 광택유지율(ΔE)이 9~10인 것을 기술구성의 특징으로 한다.
The unsaturated polyester resin composition modified with dicyclopentadiene has a 60 ° gloss of 98 to 99 and a QUV 120 hour gloss retention (ΔE) of 9 to 10.

또한, 본 발명은 반응기에 프로필렌글리콜(PG) 10~40중량부, 무수말레인산(MA) 10~40중량부를 투입하고 반응온도 170℃에서 반응개시 후, 205℃로 승온 유지하며 반응시키고 산가 10 이하에서 1차반응종료시키는 단계; 상기 1차반응물을 185℃ 이하로 냉각 후 반응물을 유지하면서 DCPD 0.1~20중량부를 1시간동안 Dropping하고 2시간동안 유지반응시키는 단계; 상기 유지반응물을 100℃ 이하로 냉각 후, 디프로필렌글리콜(DPG) 0.1~20중량부, 네오펜틸글리콜(NPG) 0.1~50중량부, 무수말레인산(MA) 10~40중량부, 중축합촉매 H3PO4 0.1~1중량부를 투입하고 170℃에서 반응개시 후, 205℃로 승온 유지하며 반응시키고 산가 24이하에서 반응종료시켜 불포화폴리에스데르 수지를 얻는 단계; 상기 불포화폴리에스데르 수지에 중합금지제 0.1~3중량부, 발열억제제 0.1~1중량부, 분산 및 상분리방지제 0.1~1중량부를 첨가하는 단계를 포함하여 구성되는 디사이클로펜타디엔(DCPD ; Dicyclopentadiene)으로 개질된 불포화폴리에스테르수지 조성물을 제조하는 방법을 기술구성의 특징으로 한다.
In the present invention, 10 to 40 parts by weight of propylene glycol (PG) and 10 to 40 parts by weight of maleic anhydride (MA) are fed into a reactor, and after the reaction is started at a reaction temperature of 170 ° C, Terminating the first reaction in the reaction system; Cooling the primary reaction product to 185 ° C or lower, dropping DCPD (0.1 to 20 parts by weight) for 1 hour while maintaining the reaction product, and maintaining the reaction for 2 hours; (DPG), 0.1 to 20 parts by weight of neopentyl glycol (NPG), 10 to 40 parts by weight of maleic anhydride (MA), 10 to 40 parts by weight of a polycondensation catalyst H 3 PO 4 0.1 to 1 part by weight, and the reaction is initiated at 170 占 폚, followed by reaction with maintaining the temperature at 205 占 폚, and the reaction is terminated at an acid value of 24 or less to obtain an unsaturated polyester resin; Adding 0.1 to 3 parts by weight of a polymerization inhibitor, 0.1 to 1 part by weight of an exothermic inhibitor, and 0.1 to 1 part by weight of a dispersion and an anti-segregation agent to the unsaturated polyester resin, to prepare a dicyclopentadiene (DCPD) Is a feature of the technical construction of the method for producing the modified unsaturated polyester resin composition.

이하에서는 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 본 발명의 바람직한 실시예를 통하여 상세히 설명한다. 그러나 본 발명은 여러 가지 상이한 형태로 구현될 수 있으며, 여기에서 설명하는 실시예에 한정되지 않는다.
Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

먼저, 본 발명의 디사이클로펜타디엔(DCPD ; Dicyclopentadiene)으로 개질된 불포화폴리에스테르수지 조성물은 프로필렌글리콜(PG) 10~40중량부, 네오펜틸글리콜(NPG) 0.1~50중량부, 디프로필렌글리콜(DPG) 0.1~20중량부, 무수말레인산(MA) 20~80중량부, 디사이클로펜타디엔(DCPD) 0.1~20중량부를 중합금지제 0.1~3중량부, 중축합촉매 0.1~1중량부, 분산제 및 상분리방지제 0.1~1중량부, 발열억제제 0.1~1중량부를 첨가하여 중축합시켜 제조한다.
First, the unsaturated polyester resin composition modified with dicyclopentadiene (DCPD) of the present invention is prepared by mixing 10 to 40 parts by weight of propylene glycol (PG), 0.1 to 50 parts by weight of neopentyl glycol (NPG) 0.1 to 20 parts by weight of dicyclopentadiene (DCPD), 0.1 to 3 parts by weight of a polymerization inhibitor, 0.1 to 1 part by weight of a polycondensation catalyst, 0.1 to 1 part by weight of a phase separation inhibitor and 0.1 to 1 part by weight of an exothermic inhibitor.

상기 무수 말레인산은 말레인산의 열탈수 또는 공기에 의한 벤젠의 촉매산화에 의해 얻어진 화합물로서 시판용 무수 말레인산, 바람직하게는 95% 이상의 순도 및 고 내열착색성을 갖는 등급을 지닌 것을 사용하는 것이 바람직하다.
The maleic anhydride is preferably a compound obtained by thermal dehydration of maleic acid or catalytic oxidation of benzene by air, having a commercial grade maleic anhydride, preferably a grade having a purity of 95% or more and a high heat resistance coloring property.

또한, 디사이클로펜타디엔(DCPD)은 고순도를 가질 필요는 없고, 시판용 제품이 사용될 수 있는데, 중축합시에 다량의 겔(열가교물)을 생성하지 않고 순도가 85% 이상인 성분으로 이루어진 DCPD를 사용하는 것이 바람직하다.
In addition, dicyclopentadiene (DCPD) does not need to have high purity, and commercially available products can be used. DCPD is made of a component having a purity of 85% or more without generating a large amount of gel (thermal crosslinking) .

상기 디사이클로펜타디엔(DCPD)은 무수말레인산(MA)의 카복시기와 부가반응에 의해 불포화폴리에스테르 수지를 개질시키게 되는데, 디사이클로펜타디엔(DCPD)의 첨가는 무수말레인산(MA) 첨가 전후 또는 동시에 첨가될 수 있으나, 바람직한 실시형태에 있어서는, 발열조절을 위하여 무수말레인산(MA) 첨가 후 첨가하는 것이 바람직하다.
The dicyclopentadiene (DCPD) modifies the unsaturated polyester resin by an addition reaction with a carboxy group of maleic anhydride (MA). The addition of dicyclopentadiene (DCPD) may be carried out before or after the addition of maleic anhydride In a preferred embodiment, it is preferable to add maleic anhydride (MA) after the addition of maleic anhydride (MA) in order to control exotherm.

또한, 상기 디사이클로펜타디엔(DCPD)과 무수말레인산(MA)의 카복시기와의 부가반응을 달성하기 위해서는 디사이클로펜타디엔(DCPD) 첨가비율 및 반응 생성물의 산가를 설정하는 것이 중요한데, 디사이클로펜타디엔(DCPD)을 원활하게 완료하기 위해서는 산가가 140∼300㎎KOH/g을 갖는 범위에서 반응시키는 것이 바람직하며, 무수말레인산(MA)의 카복시기에 대한 디사이클로펜타디엔(DCPD) 첨가비율은 전체에 대하여 무수말레인산(MA) 10~40중량부, 디사이클로펜타디엔(DCPD) 0.1~20중량부 첨가하는 것이 바람직하다.
In order to achieve the addition reaction of the dicyclopentadiene (DCPD) with the carboxy group of maleic anhydride (MA), it is important to set the addition rate of dicyclopentadiene (DCPD) and the acid value of the reaction product, and dicyclopentadiene (DCPD), the acid value is preferably in the range of 140 to 300 mgKOH / g, and the proportion of dicyclopentadiene (DCPD) added to the carboxy group of maleic anhydride (MA) 10 to 40 parts by weight of maleic anhydride (MA) and 0.1 to 20 parts by weight of dicyclopentadiene (DCPD) are preferably added.

상기 중합금지제는 하이드로퀴논, 메틸에테르하이드로퀴논, 2,5-다이부틸하이드로퀴논, 3,5-다이-3급-부틸-4-하이드록시톨루엔, 메틸-다이-3급-부틸페놀, 2,6-다이-3급-부틸-p-크레졸 중에서 1종 이상 선택하여 0.1~3중량부 사용하는 것이 바람직하다.
The polymerization inhibitor may be at least one selected from the group consisting of hydroquinone, methyl ether hydroquinone, 2,5-dibutyl hydroquinone, 3,5-di-tert- , And 6-di-tert-butyl-p-cresol is preferably used in an amount of 0.1 to 3 parts by weight.

상기 중축합촉매는 인산, 포스폰산계 화합물, 포스핀산계 화합물, 포스핀옥사이드계 화합물, 아포스폰산계 화합물, 아포스핀산계 화합물, 포스핀계 화합물 중에서 1종 이상 선택하여 0.1~1중량부 사용된다.
The polycondensation catalyst is used in an amount of 0.1 to 1 part by weight per 100 parts by weight of at least one selected from the group consisting of phosphoric acid, a phosphonic acid compound, a phosphinic acid compound, a phosphine oxide compound, an phosphonic acid compound, an apospinic acid compound and a phosphine compound.

상기 분산제 및 상분리방지제는 균일한 반응을 위해 필수 사용되며, 1-Methoxy-2-propanol, n-Butyl acetate, 뷰틸셀로솔브, 에틸셀로솔브,이소프로판올, 이소부탄올, 로진, 로진의 유도체 중에서 1종 이상 선택하여 0.1~1중량부 사용하는 것이 바람직한데, 0.1 중량부 미만으로 사용시에는 반응생성물의 층이 분리되는 문제가 발생하며, 1 중량부 초과시엔 더 이상의 개선 효과를 기대하기가 어렵다.
The dispersant and the anti-patterning agent are used for uniform reaction, and the dispersant and the phase separation inhibitor are preferably used in the reaction of 1-Methoxy-2-propanol, n-butyl acetate, butyl cellosolve, ethyl cellosolve, isopropanol, isobutanol, It is preferable to use 0.1 to 1 part by weight of the organopolysiloxane. If the amount is less than 0.1 part by weight, the reaction product layer may be separated. When the amount is more than 1 part by weight, it is difficult to expect further improvement.

상기 발열억제제는 조성물의 균일성을 향상시키고 SMC의 균일한 물성을 확보하기 위한 것으로, 적합한 것으로는 구리 나프텐에이트, 코발트 나프텐에이트, 아연 나프텐에이트, α -메틸 스티렌, 터피놀렌, 감마-터피넨, 디라우릴 티오디프로피오네이트, 4-t-부틸피로카테콜 중에서 1종 이상 선택하여 0.1~1중량부 사용하는 것이 바람직하다.
The exothermic inhibitor is used for improving the uniformity of the composition and securing the uniform physical properties of SMC. Suitable examples thereof include copper naphthenate, cobalt naphthenate, zinc naphthenate, alpha -methylstyrene, terpinolene, gamma- It is preferable to use 0.1 to 1 part by weight of at least one selected from terpinene, dilauryl thiodipropionate and 4-t-butyl pyrocatechol.

이상 설명한 디사이클로펜타디엔으로 개질된 불포화폴리에스테르수지 조성물은 30℃에서 초기 20분 증점거동구간이 10.0~15.0 poise이며, 45℃에서 말기 18시간 경과시 점도가 90만~100만 poise를 가지게 되고, 60°광택이 98~99이며, Q.U.V. 120시간 광택유지율(ΔE)이 9~10을 가지게 되어 SMC제조공정중의 작업성이 향상되고, 광택 및 내후성이 우수한 SMC를 제조할 수 있다.
The above unsaturated polyester resin composition modified with dicyclopentadiene has a viscosity of 10.0-15.0 poise at the initial 20 minutes at 30 ° C and a viscosity of 90,000-1 million poise at the end of 18 hours at 45 ° C , A 60 ° gloss of 98 to 99 and a gloss retention (ΔE) of QUV of 120 hours is 9 to 10, which improves workability in the SMC manufacturing process and can produce an SMC with excellent gloss and weatherability.

교반기, 환류냉각기, 불활성 가스 도입관, 온도계등 2리터 4구플라스크의 반응기의 청결상태, 밸브의 상태, 콘덴서의 냉각수 및 반응기의 질소라인 등을 확인하였다.
The cleanliness of the reactor, the state of the valve, the cooling water of the condenser and the nitrogen line of the reactor were checked in a 2-liter four-necked flask such as a stirrer, a reflux condenser, an inert gas introducing tube and a thermometer.

반응기에 프로필렌글리콜(PG) 30중량부, 무수말레인산(MA) 30중량부를 투입하고 반응온도 170℃에서 반응개시 후, 205℃로 승온 유지하며 반응시키고 산가 10 이하에서 1차반응종료시켰다.
30 parts by weight of propylene glycol (PG) and 30 parts by weight of maleic anhydride (MA) were charged into the reactor, and the reaction was initiated at a reaction temperature of 170 占 폚, followed by heating to 205 占 폚.

1차반응물을 185℃ 이하로 냉각 후 반응물을 유지하면서 DCPD 15중량부를 1시간동안 Dropping하고 2시간동안 유지반응시킨 후, 100℃ 이하로 냉각 후, 디프로필렌글리콜(DPG) 10중량부, 네오펜틸글리콜(NPG) 30중량부, 무수말레인산(MA) 30중량부, 중축합촉매 H3PO4 0.7중량부를 투입하고 170℃에서 반응개시 후, 205℃로 승온 유지하며 반응시키고 산가 24이하에서 반응종료시켜 불포화폴리에스데르 수지를 얻은 후, 여기에 하이드로퀴논 중합금제제 2중량부, 발열억제제 5% Cu-Naph 0.5중량부, 상분리방지제 BYK-W972 0.5중량부를 첨가하여 SMC용 수지조성물을 제조하였다.
After cooling the primary reaction product to 185 ° C or lower, 15 parts by weight of DCPD was dropped for 1 hour while maintaining the reaction product, and maintained for 2 hours. After cooling to 100 ° C or less, 10 parts by weight of dipropylene glycol (DPG) 30 parts by weight of glycol (NPG), 30 parts by weight of maleic anhydride (MA), a polycondensation catalyst H 3 PO 4 After the reaction was initiated at 170 ° C, the reaction was carried out while maintaining the temperature at 205 ° C, and the reaction was terminated at an acid value of 24 or less to obtain an unsaturated polyester resin. To the unsaturated polyester resin, 2 parts by weight of hydroquinone- 0.5% by weight of Cu-Naph and 0.5% by weight of BYC-W972 as a phase separation inhibitor were added to prepare a resin composition for SMC.

실시예 1에서 제조된 디사이클로펜타디엔(DCPD ; Dicyclopentadiene)으로 개질된 불포화폴리에스테르수지 조성물의 증점성을 기존 SMC용 불포화폴리에스테르와 비교하여 [도 1]에 나타내었다.
The viscosity of the unsaturated polyester resin composition modified with dicyclopentadiene (DCPD) prepared in Example 1 was compared with that of the conventional unsaturated polyester for SMC [Fig. 1].

SMC제조공정에서 초기증점의 경우 증점이 덜 되는 것이 작업성 및 보강재 함침 등 물성 면에서 유리하므로 상기 [도 1]에서 보는 바와 같이, 본 발명의 디사이클로펜타디엔(DCPD ; Dicyclopentadiene)으로 개질된 불포화폴리에스테르수지 조성물은 초기증점에서 기존 수지보다 낮은 거동을 보이므로 작업성 및 물성이 우수하게 됨을 알 수 있으며, 말기증점의 경우 기존 수지에 비해 3배 이상 증점되므로 SMC재료로서 우수함을 알 수 있다.
In the SMC manufacturing process, as shown in FIG. 1, it is preferable to use a dicyclopentadiene (DCPD) modified (dicyclopentadiene) The unsaturated polyester resin composition exhibits lower workability than the conventional resin at the initial donation point, and thus shows excellent workability and physical properties. In the terminal donation point, it is excellent as an SMC material .

실시예 1에서 제조된 디사이클로펜타디엔(DCPD ; Dicyclopentadiene)으로 개질된 불포화폴리에스테르수지 조성물에 열경화제를 투입 경화시켜 광택 및 내후성테스트를 실시하였다.
The unsaturated polyester resin composition modified with dicyclopentadiene (DCPD) prepared in Example 1 was applied and cured with a thermosetting agent to perform gloss and weatherability test.

광택(GLOSS 60')은 BYK사 광택기를 사용하여, 60`광택을 측정하였으며, 광택유지율은 미국 Q-PANEL 사 제품인 Q.U.V -se기기를 사용하여, 120시간 광택유지율(△E)을 평가하여 [도 2]에 나타내었다. △E는 변색의 정도를 나타내는 결과로서 수치가 높을수록 내후성/내자외선성이 떨어짐을 나타낸다.
Gloss (GLOSS 60 ') was measured by using a BYK polisher and the gloss of 60` was measured. The gloss retention was evaluated using a QUV-se apparatus manufactured by Q-PANEL, Inc., USA, Fig. 2]. ? E is a result indicating the degree of discoloration, and the higher the numerical value, the lower the weatherability / ultraviolet ray resistance.

[도 2]에 나타난 바와 같이 본 발명의 디사이클로펜타디엔(DCPD ; Dicyclopentadiene)으로 개질된 불포화폴리에스테르수지 조성물 경화체는 기존 TPA, THPA 수지에 비해 광택도가 우수하며, △E수치도 기존 TPA, THPA 수지에 비해 낮아 내후성/내자외선성이 우수함을 알 수 있다.
As shown in FIG. 2, the unsaturated polyester resin composition cured product modified with dicyclopentadiene (DCPD) of the present invention has an excellent gloss compared to conventional TPA and THPA resins, THPA resin. Thus, it can be seen that the weather resistance / ultraviolet ray resistance is excellent.

이상의 설명은 본 발명의 기술사상을 예시적으로 설명한 것에 불과한 것으로서, 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자라면 본 발명의 본질적인 특성에서 벗어나지 않는 범위에서 다양한 수정 및 변형이 가능할 것이다. 따라서, 본 발명에 개시된 실시예들은 본 발명의 기술 사상을 한정하기 위한 것이 아니라 설명하기 위한 것이고, 이러한 실시예에 의하여 본 발명의 기술 사상의 범위가 한정되는 것은 아니다. 본 발명의 보호 범위는 아래의 청구범위에 의하여 해석되어야 하며, 그와 동등한 범위 내에 있는 모든 기술 사상은 본 발명의 권리범위에 포함되는 것으로 해석되어야 할 것이다.The foregoing description is merely illustrative of the technical idea of the present invention and various changes and modifications may be made by those skilled in the art without departing from the essential characteristics of the present invention. Therefore, the embodiments disclosed in the present invention are intended to illustrate rather than limit the scope of the present invention, and the scope of the technical idea of the present invention is not limited by these embodiments. The scope of protection of the present invention should be construed according to the following claims, and all technical ideas falling within the scope of the same shall be construed as falling within the scope of the present invention.

Claims (12)

프로필렌글리콜(PG) 10~40중량%, 네오펜틸글리콜(NPG) 0.1~50중량부, 디프로필렌글리콜(DPG) 0.1~20중량부, 무수말레인산(MA) 20~80중량부, 디사이클로펜타디엔(DCPD) 0.1~20중량부, 중합금지제 0.1~3중량부, 중축합촉매 0.1~1중량부, 분산제 및 상분리방지제 0.1~1중량부, 발열억제제 0.1~1중량부를 포함하여 구성되는 것을 특징으로 하는 디사이클로펜타디엔(DCPD ; Dicyclopentadiene)으로 개질된 불포화폴리에스테르수지 조성물
(DPG), 20 to 80 parts by weight of maleic anhydride (MA), 10 to 40 parts by weight of dicyclopentadiene (PG), 10 to 40% by weight of propylene glycol (PG), 0.1 to 50 parts by weight of neopentyl glycol 0.1 to 1 part by weight of a polycondensation catalyst, 0.1 to 1 part by weight of a dispersant and a phase separation inhibitor, and 0.1 to 1 part by weight of an exothermic inhibitor. (Dicyclopentadiene) modified with an unsaturated polyester resin composition
제1항에 있어서,
상기 중합금지제는 하이드로퀴논, 메틸에테르하이드로퀴논, 2,5-다이부틸하이드로퀴논, 3,5-다이-3급-부틸-4-하이드록시톨루엔, 메틸-다이-3급-부틸페놀, 2,6-다이-3급-부틸-p-크레졸 중에서 1종 이상 선택되는 것을 특징으로 하는 디사이클로펜타디엔(DCPD ; Dicyclopentadiene)으로 개질된 불포화폴리에스테르수지 조성물
The method according to claim 1,
The polymerization inhibitor may be at least one selected from the group consisting of hydroquinone, methyl ether hydroquinone, 2,5-dibutyl hydroquinone, 3,5-di-tert- , And 6-di-t-butyl-p-cresol (dicyclopentadiene) modified unsaturated polyester resin composition
제1항에 있어서,
상기 중축합촉매는 인산, 포스폰산계 화합물, 포스핀산계 화합물, 포스핀옥사이드계 화합물, 아포스폰산계 화합물, 아포스핀산계 화합물, 포스핀계 화합물 중에서 1종 이상 선택되는 것을 특징으로 하는 디사이클로펜타디엔(DCPD ; Dicyclopentadiene)으로 개질된 불포화폴리에스테르수지 조성물
The method according to claim 1,
Wherein the polycondensation catalyst is at least one selected from the group consisting of phosphoric acid, a phosphonic acid-based compound, a phosphinic acid-based compound, a phosphine oxide-based compound, an phosphonate-based compound, (DCPD; Dicyclopentadiene) modified unsaturated polyester resin composition
제1항에 있어서,
상기 분산 및 상분리방지제는 1-Methoxy-2-propanol, n-Butyl acetate, 뷰틸셀로솔브, 에틸셀로솔브,이소프로판올, 이소부탄올, 로진, 로진의 유도체 중에서 1종 이상 선택되는 것을 특징으로 하는 디사이클로펜타디엔(DCPD ; Dicyclopentadiene)으로 개질된 불포화폴리에스테르수지 조성물
The method according to claim 1,
Wherein the dispersion and the phase separation agent are selected from one or more of derivatives of 1-methoxy-2-propanol, n-butyl acetate, butyl cellosolve, ethyl cellosolve, isopropanol, isobutanol, rosin and rosin. Unsaturated polyester resin compositions modified with cyclopentadiene (DCPD)
제1항에 있어서,
상기 발열억제제는 구리 나프텐에이트, 코발트 나프텐에이트, 아연 나프텐에이트, α -메틸 스티렌, 터피놀렌, 감마-터피넨, 디라우릴 티오디프로피오네이트, 4-t-부틸피로카테콜 중에서 1종 이상 선택되는 것을 특징으로 하는 디사이클로펜타디엔(DCPD ; Dicyclopentadiene)으로 개질된 불포화폴리에스테르수지 조성물
The method according to claim 1,
Wherein the heat inhibitor is selected from the group consisting of copper naphthenate, cobalt naphthenate, zinc naphthenate,? -Methylstyrene, terpinolene, gamma-terpinene, dilauryl thiodipropionate and 4-t- (Dicyclopentadiene) modified unsaturated polyester resin composition (DCPD)
제1항 내지 제5항중 어느 한 항에 있어서,
상기 디사이클로펜타디엔으로 개질된 불포화폴리에스테르수지 조성물의 30℃에서 초기 20분 증점거동구간이 10.0~15.0 poise이며, 45℃에서 말기 18시간 경과시 점도가 90만~100만 poise인 것을 특징으로 하는 디사이클로펜타디엔(DCPD ; Dicyclopentadiene)으로 개질된 불포화폴리에스테르수지 조성물
6. The method according to any one of claims 1 to 5,
The unsaturated polyester resin composition modified with dicyclopentadiene has a viscosity of 10.0-15.0 poise at 30 ° C for the initial 20 minutes and a viscosity of 90,000-1,000,000 poise at the end of 18 hours at 45 ° C (Dicyclopentadiene) modified unsaturated polyester resin composition
제1항 내지 제5항중 어느 한 항에 있어서,
상기 디사이클로펜타디엔으로 개질된 불포화폴리에스테르수지 조성물의 60°광택이 98~99이며, Q.U.V. 120시간 광택유지율(ΔE)이 9~10인 것을 특징으로 하는 디사이클로펜타디엔(DCPD ; Dicyclopentadiene)으로 개질된 불포화폴리에스테르수지 조성물
6. The method according to any one of claims 1 to 5,
Wherein the unsaturated polyester resin composition modified with dicyclopentadiene has a degree of gloss of 60 to 98 and a gloss retention rate (DELTA E) of 120 to 9 hours of QUV is 9 to 10. The dicyclopentadiene (DCPD) The modified unsaturated polyester resin composition
반응기에 프로필렌글리콜(PG) 10~40중량부, 무수말레인산(MA) 10~40중량부를 투입하고 반응온도 170℃에서 반응개시 후, 205℃로 승온 유지하며 반응시키고 산가 10 이하에서 1차반응종료시키는 단계;
상기 1차반응물을 185℃ 이하로 냉각 후 반응물을 유지하면서 DCPD 0.1~20중량부를 1시간동안 Dropping하고 2시간동안 유지반응시키는 단계;
상기 유지반응물을 100℃ 이하로 냉각 후, 디프로필렌글리콜(DPG) 0.1~20중량부, 네오펜틸글리콜(NPG) 0.1~50중량부, 무수말레인산(MA) 10~40중량부, 중축합촉매 H3PO4 0.1~1중량부를 투입하고 170℃에서 반응개시 후, 205℃로 승온 유지하며 반응시키고 산가 24이하에서 반응종료시켜 불포화폴리에스데르 수지를 얻는 단계;
상기 불포화폴리에스데르 수지에 중합금지제 0.1~3중량부, 발열억제제 0.1~1중량부, 분산 및 상분리방지제 0.1~1중량부를 첨가하는 단계;를 포함하여 구성되는 것을 특징으로 하는 디사이클로펜타디엔(DCPD ; Dicyclopentadiene)으로 개질된 불포화폴리에스테르수지 조성물을 제조하는 방법
10 to 40 parts by weight of propylene glycol (PG) and 10 to 40 parts by weight of maleic anhydride (MA) were fed into the reactor, and the reaction was initiated at a reaction temperature of 170 ° C, followed by heating at 205 ° C. ;
Cooling the primary reaction product to 185 ° C or lower, dropping DCPD (0.1 to 20 parts by weight) for 1 hour while maintaining the reaction product, and maintaining the reaction for 2 hours;
(DPG), 0.1 to 20 parts by weight of neopentyl glycol (NPG), 10 to 40 parts by weight of maleic anhydride (MA), 10 to 40 parts by weight of a polycondensation catalyst H 3 PO 4 0.1 to 1 part by weight, and the reaction is initiated at 170 占 폚, followed by reaction with maintaining the temperature at 205 占 폚, and the reaction is terminated at an acid value of 24 or less to obtain an unsaturated polyester resin;
Adding 0.1 to 3 parts by weight of a polymerization inhibitor, 0.1 to 1 part by weight of an exothermic inhibitor, and 0.1 to 1 part by weight of a dispersion and a phase separation inhibitor to the unsaturated polyester resin, (DCPD; Dicyclopentadiene) modified unsaturated polyester resin composition
제8항에 있어서,
상기 중합금지제는 하이드로퀴논, 메틸에테르하이드로퀴논, 2,5-다이부틸하이드로퀴논, 3,5-다이-3급-부틸-4-하이드록시톨루엔, 메틸-다이-3급-부틸페놀, 2,6-다이-3급-부틸-p-크레졸 중에서 1종 이상 선택되는 것을 특징으로 하는 디사이클로펜타디엔(DCPD ; Dicyclopentadiene)으로 개질된 불포화폴리에스테르수지 조성물을 제조하는 방법
9. The method of claim 8,
The polymerization inhibitor may be at least one selected from the group consisting of hydroquinone, methyl ether hydroquinone, 2,5-dibutyl hydroquinone, 3,5-di-tert- , 6-di-tert-butyl-p-cresol (DCPD: Dicyclopentadiene) modified unsaturated polyester resin composition
제8항에 있어서,
상기 중축합촉매는 인산, 포스폰산계 화합물, 포스핀산계 화합물, 포스핀옥사이드계 화합물, 아포스폰산계 화합물, 아포스핀산계 화합물, 포스핀계 화합물 중에서 1종 이상 선택되는 것을 특징으로 하는 디사이클로펜타디엔(DCPD ; Dicyclopentadiene)으로 개질된 불포화폴리에스테르수지 조성물을 제조하는 방법
9. The method of claim 8,
Wherein the polycondensation catalyst is at least one selected from the group consisting of phosphoric acid, a phosphonic acid-based compound, a phosphinic acid-based compound, a phosphine oxide-based compound, an phosphonate-based compound, (DCPD; Dicyclopentadiene) modified unsaturated polyester resin composition
제8항에 있어서,
상기 분산 및 상분리방지제는 1-Methoxy-2-propanol, n-Butyl acetate, 뷰틸셀로솔브, 에틸셀로솔브,이소프로판올, 이소부탄올, 로진, 로진의 유도체 중에서 1종 이상 선택되는 것을 특징으로 하는 디사이클로펜타디엔(DCPD ; Dicyclopentadiene)으로 개질된 불포화폴리에스테르수지 조성물을 제조하는 방법
9. The method of claim 8,
Wherein the dispersion and the phase separation agent are selected from one or more of derivatives of 1-methoxy-2-propanol, n-butyl acetate, butyl cellosolve, ethyl cellosolve, isopropanol, isobutanol, rosin and rosin. Method for producing an unsaturated polyester resin composition modified with cyclopentadiene (DCPD; Dicyclopentadiene)
제8항에 있어서,
상기 발열억제제는 구리 나프텐에이트, 코발트 나프텐에이트, 아연 나프텐에이트, α -메틸 스티렌, 터피놀렌, 감마-터피넨, 디라우릴 티오디프로피오네이트, 4-t-부틸피로카테콜 중에서 1종 이상 선택되는 것을 특징으로 하는 디사이클로펜타디엔(DCPD ; Dicyclopentadiene)으로 개질된 불포화폴리에스테르수지 조성물을 제조하는 방법9. The method of claim 8,
Wherein the heat inhibitor is selected from the group consisting of copper naphthenate, cobalt naphthenate, zinc naphthenate,? -Methylstyrene, terpinolene, gamma-terpinene, dilauryl thiodipropionate and 4-t- (DCPD: Dicyclopentadiene) modified unsaturated polyester resin composition is characterized in that at least one selected from the group consisting of dicyclopentadiene
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KR20160038503A (en) * 2014-09-30 2016-04-07 강남제비스코 주식회사 The manufacturing method of unsaturated polyester resin composition using dicyclopentadiene capable of manufacturing BMC for excellent headlamp, and the composition

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CN104893518A (en) * 2015-05-28 2015-09-09 展辰涂料集团股份有限公司 Medium density fiberboard undercoat

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