KR20060059520A - Phosphous-modified epoxy compound mixed with novolac epoxy and tpe-modified epoxy - Google Patents

Phosphous-modified epoxy compound mixed with novolac epoxy and tpe-modified epoxy Download PDF

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KR20060059520A
KR20060059520A KR1020040098633A KR20040098633A KR20060059520A KR 20060059520 A KR20060059520 A KR 20060059520A KR 1020040098633 A KR1020040098633 A KR 1020040098633A KR 20040098633 A KR20040098633 A KR 20040098633A KR 20060059520 A KR20060059520 A KR 20060059520A
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epoxy resin
modified
modified epoxy
flame retardant
high heat
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KR1020040098633A
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Korean (ko)
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박종수
임충렬
최재호
최봉구
신태규
남동기
신주호
권정돈
도광호
이은용
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국도화학 주식회사
두산전자 주식회사
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Priority to KR1020040098633A priority Critical patent/KR20060059520A/en
Publication of KR20060059520A publication Critical patent/KR20060059520A/en

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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
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C08L63/04—Epoxynovolacs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C08L63/10—Epoxy resins modified by unsaturated compounds
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2363/04—Epoxynovolacs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2363/10—Epoxy resins modified by unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Abstract

본 발명은 에폭시 수지와 인계 난연제를 반응시켜 생성된 변성 인계 에폭시수지에 노볼락 에폭시 수지 및 티피이 변성 에폭시수지를 혼합한 신규의 논할로겐계 고내열 자외선 차폐형 난연성 에폭시 수지조성물을 제공한다. The present invention provides a novel non-halogen high heat resistant ultraviolet shielding flame retardant epoxy resin composition in which a novolak epoxy resin and a tippy modified epoxy resin are mixed with a modified phosphorus epoxy resin produced by reacting an epoxy resin with a phosphorus flame retardant.

본 발명에 의하면 논할로겐 난연시스템이면서도 난연효과가 우수할 뿐만 아니라 높은 내열도 및 자외선 흡광도에 의한 효과로 친환경적 고내열 다층 적층판에 적용할 수 있다.According to the present invention, the non-halogen flame retardant system is not only excellent in flame retardant effect but also can be applied to environment-friendly high heat-resistant multilayer laminate due to the effect of high heat resistance and ultraviolet absorbance.

논할로겐, 에폭시 수지, UV 차폐, 고내열 다층 적층판Non-halogen, epoxy resin, UV shielding, high heat resistant multilayer laminate

Description

고내열 자외선 차폐형 인변성 에폭시수지 및 이를 이용해 제조된 동박적층판{Phosphous-modified epoxy compound mixed with novolac epoxy and tpe-modified epoxy}Phosphous-modified epoxy compound mixed with novolac epoxy and tpe-modified epoxy}

본 발명은 난연성 에폭시수지에 관한 것으로, 더욱 상세하게는 공지의 에폭시 수지에 인 함유 화합물을 반응시켜 얻은 인-변성 에폭시수지에 노볼락 에폭시 수지 및 티피이(TPE) 변성 에폭시 수지를 혼합시켜서 얻은 고내열 자외선(UV) 차폐형 변성 인계 에폭시 수지 및 이를 이용해 제조된 고내열성의 다층 적층판에 관한 것이다.The present invention relates to a flame retardant epoxy resin, and more particularly to a high heat resistance obtained by mixing a novolak epoxy resin and a TPE modified epoxy resin with a phosphorus-modified epoxy resin obtained by reacting a phosphorus-containing compound with a known epoxy resin. The present invention relates to an ultraviolet (UV) shielding modified phosphorous epoxy resin and a high heat resistant multilayer laminate manufactured therefrom.

현재 전기기기, 수송기기, 건축재료 등의 각 산업분야에서는 열이나 불꽃이 타지 않는 난연성 플라스틱재료가 요구되고 있다. 난연효과를 나타내는 물질은 주로 주기율표상의 15족이나 17족 원소화합물로 알려져 있는데 예컨대 할로겐, 인, 안티몬 화합물 등이 가장 효과적인 난연제로 알려져 있다. 할로겐 화합물중에서도 염소와 브롬은 난연효과가 크며, 특히 브롬은 염소보다 난연효과가 더 우수한 것으로 알려져 있는데, 이와 같은 이유는 탄소와 브롬간의 결합강도(65kcal/mol)가 탄소와 염소간의 결합강도(81kcal/mol)보다 약하기 때문에 연소시 용이하게 분해되 며, 그 결과 난연효과를 나타내는 저 분자량의 브롬화합물을 생성하기 때문이다.At present, in each industrial field such as electrical equipment, transportation equipment, building materials, flame retardant plastic materials that do not burn heat or flame are required. Materials that exhibit a flame retardant effect are mainly known as group 15 or 17 elemental compounds on the periodic table. For example, halogen, phosphorus and antimony compounds are known as the most effective flame retardants. Among halogen compounds, chlorine and bromine are known to have a high flame retardant effect, and bromine is known to have a higher flame retardant effect than chlorine. For this reason, the bond strength between carbon and bromine (65 kcal / mol) has a bond strength between carbon and chlorine (81 kcal). / mol), so it is easily decomposed during combustion, resulting in a low molecular weight bromine compound exhibiting a flame retardant effect.

에폭시수지의 난연효과 또한 브롬함유 난연제가 주로 이용되고 있으며 그 외에 인 함유 난연제 시스템, 할로겐(브롬) 및 인 함유 난연제 시스템이 널리 사용되고 있다. 예컨대 대한민국 특허공고 1995-6533호에는 중합체 기질과 반응하는 형태의 난연제 시스템으로 N-트리브로모페닐말레이미드가 개시되어 있다. Flame retardant effect of epoxy resin is also mainly used bromine-based flame retardant, phosphorus-containing flame retardant system, halogen (bromine) and phosphorus-containing flame retardant system is widely used. For example, Korean Patent Publication No. 1995-6533 discloses N-tribromophenylmaleimide as a flame retardant system in the form of reacting with a polymer substrate.

인 함유 난연제 시스템은 환경적인 측면에서 할로겐, 특히 브롬함유 난연제 시스템보다 선호된다. 예컨대 첨가형으로, 대한민국 특허 215639호는 적인계 난연제 시스템을 제공하고 있으며 반응형으로, 일본국 특허공개 평11-166035호는 9,10-Dihydro-oxa-10-phosphaphenanthrene-10-oxide을 중합체 수지에 반응시켜 난연효과를 얻는 시스템을 개시하고 있다.Phosphorus-containing flame retardant systems are preferred from the environmental point of view over halogen, in particular bromine-containing flame retardant systems. For example, as an additive, Korean Patent No. 215639 provides a flame retardant system and a reaction type, Japanese Patent Application Laid-Open No. 11-166035 discloses 9,10-Dihydro-oxa-10-phosphaphenanthrene-10-oxide in a polymer resin. A system for obtaining a flame retardant effect by reacting is disclosed.

본 발명에서는 논할로겐계 난연 에폭시수지로서, 공지의 인화합물인 9,10-Dihydro-oxa-10-phosphaphenanthrene-10-oxide을 에폭시수지에 반응시키는 난연시스템에서 더 나아가 일정량의 노볼락 에폭시 수지 및 티피이(TPE) 변성 에폭시 수지를 추가적으로 혼합시켜 제조된 에폭시수지 조성물을 이용하여 인쇄회로기판을 제조하였을 때 기판의 내열도 및 자외선차폐 효과를 향상시킨다는 사실이 개시된다. In the present invention, as a non-halogen flame-retardant epoxy resin, a certain amount of novolac epoxy resin and tippy are further added to a flame retardant system in which a known phosphorus compound 9,10-Dihydro-oxa-10-phosphaphenanthrene-10-oxide is reacted with an epoxy resin. It is disclosed that when a printed circuit board is manufactured by using an epoxy resin composition prepared by further mixing a modified (TPE) modified epoxy resin, the heat resistance and the UV shielding effect of the substrate are improved.

따라서 본 발명은 논 할로겐계 난연시스템의 제공을 목적으로 공지의 인 함유 화합물을 에폭시수지에 반응시켜서 얻은 인개질된 에폭시수지에 내열도 상승제로서의 노볼락 에폭시 수지를 도입하고 자외선 차폐를 위해서 TPE 변성 에폭시수지 조성물 및 이를 이용하여 제조한 친환경적인 고내열 다층적층판을 제공하는 것을 그 주목적으로 한다.Accordingly, the present invention introduces a novolak epoxy resin as a heat-resistance enhancer to a modified epoxy resin obtained by reacting a known phosphorus-containing compound with an epoxy resin for the purpose of providing a non-halogen flame retardant system, and modified TPE for ultraviolet shielding. An object of the present invention is to provide an epoxy resin composition and an environment-friendly high heat-resistant multilayer laminate prepared using the same.

상기의 목적은 신규의 고내열 자외선(UV) 차폐형 인변성 에폭시수지조성물을 제공하는 것에 의해 달성된다. 본 발명에 따른 최종적인 에폭시수지조성물은 논할로겐계 난연제시스템으로서 친환경적인 인새회로기판 제조용으로 사용될 수 있다. The above object is achieved by providing a novel high heat resistant ultraviolet (UV) shielding type modified modified epoxy resin composition. The final epoxy resin composition according to the present invention can be used for producing environmentally friendly insa printed circuit board as a non-halogen flame retardant system.

구체적으로 본 발명의 신규의 고내열 자외선(UV) 차폐형 인변성 에폭시수지조성물은 페놀 노볼락 에폭시수지, 오르토 크레졸 노볼락 에폭시수지 또는 비피에이 노볼락 에폭시수지에 대해서 하기 화학식 (1)의 구조식을 갖는 화합물을 반응시켜서 인변성에폭시수지(A)를 얻고, 상기 인변성에폭시수지(A)에 페놀 노볼락 에폭시수지, 오르토 크레졸 노볼락 에폭시수지 및 비피에이 노볼락 에폭시수지로 이루어지는 군으로부터 선택된 1종 이상의 노볼락 에폭시수지화합물(B)와 티피이 변성 에폭시수지화합물(C)을 혼합시켜서 얻은 고내열 자외선 차폐형 인변성 에폭시수지조성물(D)로서, 상기 에폭시수지조성물(D)중의 인 함량이 0.5wt% ~ 3.5wt% 바람직하기로는 1.5wt% ~ 3.5wt%이고, 노볼락 에폭시수지화합물(B) 함량이 10wt% ~ 20wt%이고, 티피이 변성 에폭시수지화합물(C)이 5wt% ~ 9wt%인 것을 특징으로 한다.Specifically, the novel high heat resistant ultraviolet (UV) shielding-type modified epoxy resin composition of the present invention may be represented by the structural formula of the following formula (1) for phenol novolak epoxy resin, ortho cresol novolak epoxy resin or BP novolak epoxy resin. The phosphorus-containing epoxy resin (A) is obtained by reacting a compound having the same, and the phosphorous epoxy resin (A) is selected from the group consisting of phenol novolak epoxy resins, orthocresol novolak epoxy resins and BP novolak epoxy resins. A high heat resistant ultraviolet shielding-type modified epoxy resin composition (D) obtained by mixing the above novolac epoxy resin compound (B) and Tipi modified epoxy resin compound (C), wherein the phosphorus content in the epoxy resin composition (D) is 0.5wt. % ~ 3.5wt% Preferably it is 1.5wt%-3.5wt%, The novolak epoxy resin compound (B) content is 10wt%-20wt%, Tipi modified epoxy resin compound (C) It is characterized in that 5wt% ~ 9wt%.

(화학식 1) (Formula 1)

Figure 112004055931618-PAT00001
Figure 112004055931618-PAT00001

본 발명은 공지의 인화합물인 9,10-Dihydro-oxa-10-phosphaphenanthrene-10-oxide(이하 DOPO라고 약칭한다.)을 에폭시화 하여 제조된 인 개질된 에폭시수지에 경화물의 내열도를 상승시키기 위해 노볼락 에폭시수지를 혼합시키며, 자외선 흡습성 증가를 위해 티피이 변성 에폭시수지를 혼합하여 신규의 고내열 자외선(UV) 차폐형 인변성 에폭시수지조성물을 제공한다.The present invention is to increase the heat resistance of the cured product on the phosphorus-modified epoxy resin prepared by epoxidizing a known phosphorus compound 9,10-Dihydro-oxa-10-phosphaphenanthrene-10-oxide (hereinafter abbreviated as DOPO). In order to mix the novolak epoxy resin, and to increase the UV hygroscopicity, the TiPY modified epoxy resin is mixed to provide a novel high heat-resistant ultraviolet (UV) shielding type modified modified epoxy resin composition.

이하 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.

본 발명에서 사용하는 반응성 인 함유 화합물은 식 (1)로 표현되는 9,10-Dihydro-oxa-10-phosphaphenanthrene-10-oxide(DOPO)로서 환경적인 측면에서 브롬계 난연제의 대체물질로 자주 사용된다. DOPO는 에폭시기(基)에 대해서 반응하여 인 변성에폭시를 만든다. DOPO와 반응하는 에폭시수지(는 페놀 노볼락 에폭시수지, 오르토 크레졸 노볼락 에폭시수지 또는 비피에이 노볼락 에폭시수지로서 바람직하기로는 페놀 노볼락 에폭시수지이다.The reactive phosphorus-containing compound used in the present invention is 9,10-Dihydro-oxa-10-phosphaphenanthrene-10-oxide (DOPO) represented by Formula (1) and is often used as an alternative to bromine flame retardants from an environmental point of view. . DOPO reacts with epoxy groups to form phosphorus-modified epoxy. Epoxy resins reacting with DOPO (phenolic novolac epoxy resins, ortho cresol novolac epoxy resins or BP novolac epoxy resins are preferably phenol novolac epoxy resins).

에폭시수지와 반응하는 DOPO의 양은 고내열 자외선 차폐형 인변성 에폭시수지조성물(D) 중의 인 함량이 0.5wt% ~ 3.5wt% 바람직하기로는 1.5wt% ~ 3.5wt%(중량부 이하 같다)가 함유되게 하는 양이어야 한다. 만일 고내열 자외선 차폐형 인변성 에폭시수지조성물(D) 중 인함량이 0.5wt% 이하일 경우에는 바라는 난연효과가 얻어지지 않으며 3.5wt% 이상일 경우에는 난연효과는 뛰어날 지언정 점도가 상승하고 제품이 겔(gel)화될 가능성이 있다. 상업적으로 구득가능한 DOPO는 일본국 삼광화학주식회사의 HCA과 대한민국 아이디바이오(주)의 DPP 등이 있다.The amount of DOPO reacting with the epoxy resin contained 0.5 wt% to 3.5 wt% of phosphorus in the high heat resistant ultraviolet shielding-type modified epoxy resin composition (D), preferably 1.5 wt% to 3.5 wt% (the same as the weight part or less). Should be the amount to be made. If the phosphorus content is less than 0.5wt% in the high heat resistant UV shielding-type modified epoxy resin composition (D), the desired flame retardant effect is not obtained. If it is more than 3.5wt%, the flame retardant effect is excellent, but the viscosity increases and the product becomes a gel (gel). There is a possibility of becoming). Commercially available DOPOs include HCA of Samkwang Chemical Co., Ltd. and DPP of IDBIO of Korea.

에폭시수지와 DOPO와의 반응은 반응온도 140 ~ 190℃에서 인, 이미다졸 또는 3급아민 등을 촉매로하여 3 ~ 8시간 행한다.The reaction between the epoxy resin and DOPO is carried out for 3 to 8 hours using phosphorus, imidazole or tertiary amine as a catalyst at a reaction temperature of 140 to 190 ° C.

에폭시수지와 DOPO와의 반응으로 얻어지는 인변성 에폭시수지(A)는 페놀 노볼락 에폭시수지, 오르토 크레졸 노볼락 에폭시수지 및 비피에이 노볼락 에폭시수지로 이루어지는 군으로부터 선택된 1종 이상의 노볼락 에폭시수지화합물(B)와 일반적으로 식(2)로 표시되는 티피이 변성 에폭시수지화합물(C)과 혼합되어 최종적으로 본 발명에 따른 신규의 고내열 자외선 차폐형 인변성 에폭시수지조성물(D)이 얻어진다. 이때, 상기 티피이 변성 에폭시수지화합물(C)은 상기 에폭시수지조성물(D) 중에 5wt% ~ 9wt%이다. 만일 티피이 변성 에폭시수지화합물(C)함량이 5wt% 이하일 경우에는 자외선 차폐 효과가 미미하고 9wt% 이상일 경우에는 자외선 차폐성은 뛰어나나 다관능성 수지량이 다량 함유하게 되어 경화시간 및 공정컨트롤에 문제점이 생긴다. Phosphorus-modified epoxy resin (A) obtained by the reaction between epoxy resin and DOPO is at least one novolac epoxy resin compound selected from the group consisting of phenol novolac epoxy resins, ortho cresol novolac epoxy resins and BP novolac epoxy resins (B). ) And typi, generally represented by formula (2), are mixed with a modified epoxy resin compound (C) to finally obtain a novel high heat-resistant ultraviolet shielding-type modified epoxy resin composition (D) according to the present invention. At this time, the tippy modified epoxy resin compound (C) is 5wt% ~ 9wt% in the epoxy resin composition (D). If the TiP content of the modified epoxy resin compound (C) is less than 5wt%, the UV shielding effect is insignificant, and if it is more than 9wt%, the UV shielding is excellent, but the polyfunctional resin content is contained in a large amount, thereby causing problems in curing time and process control.

(화학식 2)(Formula 2)

Figure 112004055931618-PAT00002
Figure 112004055931618-PAT00002

티피이 변성 에폭시수지화합물(C)은 사관능성 에폭시수지로서 일반적으로는 상기 화학식(2)와 같이 표시하나 에폭시드기의 치환율은 3.4 내지 3.6 정도이어서 실질적으로는 1치환 내지 4치환 에폭시수지의 혼합물이라고 할 수 있다. 상업적으로 구득 가능한 티피이 변성 에폭시수지로서는 국도화학사의 KDT-4400 등이 있다.Tipi-modified epoxy resin compound (C) is a tetrafunctional epoxy resin, which is generally represented by the above formula (2), but the substitution rate of the epoxide group is about 3.4 to 3.6, which is substantially a mixture of 1 to 4 substituted epoxy resins. Can be. Commercially available Tipi modified epoxy resins include KDT-4400 manufactured by Kukdo Chemical.

또한 상기 노볼락 에폭시수지화합물(B)은 상기 에폭시수지조성물(D) 중에 10wt% ~ 20wt%이어야 하는데, 그 함량이 10% 이하일 경우는 기대한 만큼 내열도 향상을 볼 수 없고, 20% 이상일 경우 점도가 과도하게 증가되며 프리프레그 제작시 수지면이 깨끗하지 못하고 유리섬유와의 접착력에 문제가 생기기 때문이다. In addition, the novolac epoxy resin compound (B) should be 10wt% ~ 20wt% in the epoxy resin composition (D), when the content is less than 10% can not see the improvement in heat resistance as expected, if more than 20% This is because the viscosity is excessively increased and the surface of the prepreg is not clean and there is a problem in adhesion to the glass fiber.

본 발명의 에폭시수지조성물(D)은 경화제에 의해 경화된다. 본 발명에서 사용될 수 있는 경화제는 일반적으로 알려진 공지의 물질을 포함한다. 예컨대 산무수물, 폴리아미드, 아민, 페놀노볼락, 크레졸노볼락 등이 있으며 이 중 디시안디아미드, 디아미노디페닐메탄, 디아미노디페닐술폰 등이 주로 사용된다. 또한 본 발명의 에폭시수지조성물(D)은 경화제와 함께 용도에 따라 당업계에 알려진 첨가제를 포함 할 수 있는 바 충진재, 안료, 착색제, 난연보조제 등이 있다.The epoxy resin composition (D) of the present invention is cured by a curing agent. Curing agents that can be used in the present invention include generally known materials. Examples include acid anhydrides, polyamides, amines, phenol novolacs, cresol novolacs, and dicyandiamide, diaminodiphenylmethane and diaminodiphenylsulfone. In addition, the epoxy resin composition (D) of the present invention may include additives known in the art depending on the use, together with a curing agent, fillers, pigments, colorants, flame retardant aids and the like.

본 발명의 에폭시수지조성물(D)의 주요 용도는 인쇄회로기판 제조용 동박적층판(CCL:Copper Clad Laminates)이다. 에폭시수지조성물(D) 35 ~ 60wt%와 유리 섬유 40 ~ 65wt%를 함유하는 동박적층판 제조용 프리프레그를 하나 이상의 라미네이트로 하고, 상기 라미네이트의 외부에 위치한 동박 외부층을 가열 가압에 의해 일체화시켜 인쇄회로기판제조용 동박적층판을 제조한다.The main use of the epoxy resin composition (D) of the present invention is a copper clad laminate (CCL: Copper Clad Laminates) for manufacturing a printed circuit board. Prepreg for preparing copper foil laminated plates containing 35 to 60 wt% of epoxy resin composition (D) and 40 to 65 wt% of glass fiber is formed of at least one laminate, and the outer layer of copper foil located outside of the laminate is integrated by heating and press Copper foil laminated board for board | substrate manufacture is manufactured.

이하 본 발명의 실시예를 설명한다.Hereinafter, embodiments of the present invention will be described.

(실시예 1)(Example 1)

페놀노볼락 에폭시수지인 YDPN-638(국도화학주식회사 제품, EEW:180g/eq) 800g에 HCA(일본국 삼광화학주식회사 제품) 200g을 촉매 ETPPI(Ethyl Triphenyl Phosphonium Iodide)를 사용하여 반응온도 160℃에서 6시간 벌크중합하여 인변성 에폭시수지를 제조하였다. 이 인변성 에폭시수지에 오르토 크제졸 노볼락 에폭시수지인 YDCN-500-4P(국도화학사 제품, EEW:204g/eq) 200g와 티피이변성 에폭시주지 KDT-4400(국도화학사 제품, EEW:225g/eq)을 110g 혼합하여 인과 후첨된 노볼락에폭시수지 및 티피이 변성에폭시수지의 함량이 전체 생성물 대비 각각 2.1wt%, 15wt% 및 8wt%인 신규의 논할로겐계 고내열 자외선 차폐형 인변성 에폭시수지조성물(EEW: 290g/eq)을 제조하였다.800g of phenol novolac epoxy resin (YDPN-638, manufactured by Kukdo Chemical Co., Ltd., EEW: 180g / eq), 200g of HCA (made by Samkwang Chemical Co., Ltd.) at the reaction temperature of 160 ° C using ETPPI (Ethyl Triphenyl Phosphonium Iodide) Bulk polymerization was performed for 6 hours to prepare a modified epoxy resin. 200 g of YDCN-500-4P (product of Kukdo Chemical Co., Ltd., EEW: 204g / eq) which is an ortho-zezol novolak epoxy resin, and TPI bimodal epoxy resin KDT-4400 (product of Kukdo Chemical Co., Ltd., EEW: 225g / eq) The new non-halogen, high heat resistant UV-shielding-type modified resin resin composition (EEW) containing 2.1 wt%, 15 wt% and 8 wt% of phosphorus and post novolac epoxy resins and Tippy modified epoxy resins, respectively, by mixing 110 g of : 290 g / eq) was prepared.

(실시예 2)(Example 2)

비피에이(BPA) 노볼락 에폭시수지인 KBPN-120(국도화학주식회사 제품, EEW:220g/eq) 800g에 HCA(일본국 삼광화학주식회사 제품) 200g을 촉매 ETPPI(Ethyl Triphenyl Phosphonium Iodide)를 사용하여 반응온도 160℃에서 6시간 벌크중합하여 인변성 에폭시수지를 제조하였다. 이 인변성 에폭시수지에 YDCN-500-4P(국도화학사 제품) 200g와 KDT-4400(국도화학사 제품)을 110g 혼합하여 인과 후첨된 노볼락에폭시수지 및 티피이 변성에폭시수지의 함량이 전체 생성물 대비 각각 2.1wt%, 15wt% 및 8wt%인 신규의 논할로겐계 고내열 자외선 차폐형 인변성 에폭시수지조성물(EEW: 340g/eq)을 제조하였다.Reaction of 800 g of KBPN-120 (product of Kukdo Chemical Co., Ltd., EEW: 220g / eq), BPA novolak epoxy resin, 200g of HCA (product of Samkwang Chemical Co., Ltd.) using catalyst ETPPI (Ethyl Triphenyl Phosphonium Iodide) A bulk-modified epoxy resin was prepared by bulk polymerization at temperature 160 ° C for 6 hours. 200 g of YDCN-500-4P (product of Kukdo Chemical Co., Ltd.) and 110 g of KDT-4400 (product of Kukdo Chemical Co., Ltd.) were mixed with phosphorus modified epoxy resin, and the content of phosphorus and novolac epoxy resin and TPI modified epoxy resin were 2.1. A novel non-halogen high heat resistant UV shielding-type modified epoxy resin composition (EEW: 340 g / eq) was prepared, which was wt%, 15 wt% and 8 wt%.

(실시예 3)(Example 3)

오르토 크레졸 노볼락 에폭시수지인 YDCN-500-4P(국도화학주식회사 제품, EEW:204g/eq) 800g에 HCA(일본국 삼광화학주식회사 제품) 200g을 촉매 ETPPI(Ethyl Triphenyl Phosphonium Iodide)를 사용하여 반응온도 160℃에서 6시간 벌크중합하여 인변성 에폭시수지를 제조하였다. 이 인변성 에폭시수지에 YDCN-500-10P(국도화학사 제품) 200g와 KDT-4400(국도화학사 제품)을 110g 혼합하여 인과 후첨된 노볼락에폭시수지 및 티피이 변성에폭시수지의 함량이 전체 생성물 대비 각각 2.1wt%, 15wt% 및 8wt%인 신규의 논할로겐계 고내열 자외선 차폐형 인변성 에폭시수지조성물(EEW: 310g/eq)을 제조하였다.800g of ortho cresol novolac epoxy resin, YDCN-500-4P (product of Kukdo Chemical Co., Ltd., EEW: 204g / eq), 200g of HCA (product of Samkwang Chemical Co., Ltd.) was used as catalyst ETPPI (Ethyl Triphenyl Phosphonium Iodide) A bulk-modified epoxy resin was prepared by bulk polymerization at 160 ° C. for 6 hours. 200 g of YDCN-500-10P (product of Kukdo Chemical Co., Ltd.) and 110 g of KDT-4400 (product of Kukdo Chemical Co., Ltd.) were mixed with phosphorus modified epoxy resin, and the content of phosphorus and novolac epoxy resin and TPI modified epoxy resin were 2.1. A new non-halogen, high heat resistant UV shielding-type modified epoxy resin composition (EEW: 310 g / eq) was prepared, which was wt%, 15 wt% and 8 wt%.

(비교예 1)(Comparative Example 1)

페놀 노볼락 에폭시수지인 YDPN-638(국도화학주식회사 제품, EEW:180g/eq) 800g에 HCA(일본국 삼광화학주식회사 제품) 200g을 촉매 SHS(Sodium Hydrosulfide)를 사용하여 반응온도 160℃에서 6시간 벌크중합하여 인변성 에폭시수지(EEW: 280g/eq)를 제조하였다. 800 g of phenol novolac epoxy resin (YDPN-638, manufactured by Kukdo Chemical Co., Ltd., EEW: 180g / eq), 200g of HCA (manufactured by Samkwang Chemical Co., Ltd.) in Japan, was used for 6 hours at the reaction temperature of 160 ° C. Bulk polymerization was carried out to prepare a modified epoxy resin (EEW: 280 g / eq).

(비교예 2)(Comparative Example 2)

비교예1의 인변성 에폭시수지 1000g에 YDCN-500-10P(국도화학사 제품, EEW:204g/eq) 200g를 혼합하여 인과 노볼락의 함량이 전체 생성물 대비 각각 2.3wt% 와 17wt%인 에폭시수지조성물(EEW: 316g/eq)을 제조하였다.Epoxy resin composition containing 2.3wt% and 17wt% of phosphorus and novolac, respectively, by mixing 200g of YDCN-500-10P (Kukdo Chemical, EEW: 204g / eq) with 1000g of the modified epoxy resin of Comparative Example 1 (EEW: 316 g / eq) was prepared.

(비교예 3)(Comparative Example 3)

비교예1의 인변성 에폭시수지 1000g에 KDT-4400(국도화학사 제품, EEW:225g/eq)을 110g 혼합하여 인과 티피이(TPE)변성 에폭시수지의 함량이 전체 생성물 대비 각각 2.5wt% 와 11wt%인 에폭시수지조성물(EEW: 303g/eq)을 제조하였다.110 g of KDT-4400 (EEW: 225g / eq, Kukdo Chemical Co., Ltd.) was mixed with 1000g of the modified epoxy resin of Comparative Example 1, and the content of phosphorus and TPE modified epoxy resins was 2.5wt% and 11wt%, respectively. An epoxy resin composition (EEW: 303 g / eq) was prepared.

* 에폭시수지의 경화 및 프리프레그의 제작* Hardening of epoxy resin and production of prepreg

위 실시예 및 비교예에서 제조한 에폭시수지의 난연성을 시험하기 위해 경화제로 디시안디아미드(디시안디아미드 사용량(g) = 12.6/에폭시당량 * 100)를 사용하고 경화촉진제로 2-Methyl Imidazole(디시안 디아미드에 대해 3.3phr)을 사용하여 경화반응을 시켰다. 프리프레그(prepreg)는 175℃에서 5분간 진행하여 반경화상 태로 한 후 8겹의 시편을 190℃에서 25kgf/cm2 압력으로 15분간 프레싱 한 후 다시 120분간 40kgf/cm2 압력을 가하여 프레싱했다. 이후 30분간 냉매로 냉각시켰다. 내열도 실험은 시차열분석기(DSC)를 이용하였고, 자외선 차폐 효과는 Spectrophtometer(TU-1800)로 이용하였다. 표 1은 그 결과를 나타낸 것이다.In order to test the flame retardancy of the epoxy resins prepared in Examples and Comparative Examples, dicyandiamide (dicyandiamide amount (g) = 12.6 / epoxy equivalent * 100) was used as a curing agent, and 2-Methyl Imidazole (dicish) was used as a curing accelerator. The curing reaction was carried out using 3.3 phr) for andamide. Prepreg (prepreg) was pressed proceeds from 175 ℃ 5 bungan added to radial image state 120 minutes 40kgf / cm 2 pressure and then re-pressed for 15 minutes the specimen of 8-fold to 25kgf / cm 2 pressure in a 190 ℃ after. After cooling for 30 minutes with a refrigerant. The heat resistance test was performed by differential thermal analyzer (DSC), and the UV shielding effect was used by Spectrophtometer (TU-1800). Table 1 shows the results.

Figure 112004055931618-PAT00003
Figure 112004055931618-PAT00003

비교예 4는 브롬화 에폭시수지인 YDB-424A80(국도화학 주식회사 제품, 브롬함량 21%)에 KDT-4400(국도화학 주식회사 제품)을 혼합한 것으로서 디시안디아미드로 경화하여 실시예와 동일하게 난연테스트를 시행한 결과이다.Comparative Example 4 is a mixture of KDT-4400 (product of Kukdo Chemical Co., Ltd.) with YDB-424A80 (product of Kukdo Chemical Co., Ltd., bromine content 21%), which is a brominated epoxy resin, and cured with dicyandiamide to perform flame retardant test in the same manner as in Example. This is the result.

표에서 나타난 바와 같이 본 발명에 따른 에폭시수지조성물로 제조한 경화물은 할로겐 화합물을 포함하지 않으면서도 브롬계 난연시스템에 의한 그것과 동등한 난연성을 보이고 있으며 기존의 브롬계 에폭시수지보다 높은 유리전이온도(Tg)를 보이고 있으며 동일한 UV 차폐 효과를 보이고 있다. 내열성은 노볼락 에폭시 함량 및 TPE 변성 에폭시 함량이 증가할수록 증가하는 경향을 보인다. As shown in the table, the cured product prepared from the epoxy resin composition according to the present invention shows a flame retardancy equivalent to that of the brominated flame retardant system without containing a halogen compound and has a higher glass transition temperature than that of the conventional bromine epoxy resin. Tg) and the same UV shielding effect. Heat resistance tends to increase as the novolak epoxy content and the TPE modified epoxy content increase.

본 발명에 따른 에폭시수지는 논 할로겐계 난연성 에폭시수지로서 우수한 난연특성과 함께 전기적 및 열적특성도 양호하며 자외선 흡광성도 우수하여 다층 인쇄회로기판 제작에 사용될 수 있다.The epoxy resin according to the present invention is a non-halogen flame-retardant epoxy resin with excellent flame retardant properties, good electrical and thermal properties, and excellent UV absorbance, which can be used for manufacturing a multilayer printed circuit board.

Claims (3)

페놀 노볼락 에폭시수지, 오르토 크레졸 노볼락 에폭시수지 또는 비피에이 노볼락 에폭시수지에 대해서 하기 화학식 (1)의 구조식을 갖는 화합물을 반응시켜서 인변성에폭시수지(A)를 얻고,A phenol novolac epoxy resin, ortho cresol novolac epoxy resin, or BP novolac epoxy resin was reacted with a compound having the structural formula (1) to obtain a modified epoxy resin (A), 상기 인변성에폭시수지(A)에 페놀 노볼락 에폭시수지, 오르토 크레졸 노볼락 에폭시수지 및 비피에이 노볼락 에폭시수지로 이루어지는 군으로부터 선택된 1종 이상의 노볼락 에폭시수지화합물(B)와 티피이 변성 에폭시수지화합물(C)을 혼합시켜서 얻은 고내열 자외선 차폐형 인변성 에폭시수지조성물(D)로서, At least one novolak epoxy resin compound (B) selected from the group consisting of a phenol novolak epoxy resin, an ortho cresol novolak epoxy resin and a BP novolak epoxy resin in the modified phosphorous epoxy resin (A) and a TPI modified epoxy resin As a high heat-resistant ultraviolet shielding type modified epoxy resin composition (D) obtained by mixing (C), 상기 에폭시수지조성물(D)중의 인 함량이 0.5wt% ~ 3.5wt% 바람직하기로는 1.5wt% ~ 3.5wt%이고, 노볼락 에폭시수지화합물(B) 함량이 10wt% ~ 20wt%이고, 티피이 변성 에폭시수지화합물(C)이 5wt% ~ 9wt%인 것을 특징으로 하는 고내열 자외선 차폐형 인변성 에폭시수지조성물.Phosphorus content in the epoxy resin composition (D) is 0.5wt% ~ 3.5wt%, preferably 1.5wt% ~ 3.5wt%, novolak epoxy resin compound (B) content is 10wt% ~ 20wt%, Tippy modified epoxy High heat resistant ultraviolet shielding-type modified epoxy resin composition, characterized in that the resin compound (C) is 5wt% ~ 9wt%. (화학식 1) (Formula 1)
Figure 112004055931618-PAT00004
Figure 112004055931618-PAT00004
 제 1항 기재의 에폭시수지조성물(D) 35 ~ 60wt%와 유리 섬유 40 ~ 65wt%를 함유하는 동박적층판 제조용 프리프레그.A prepreg for producing a copper clad laminate containing 35 to 60 wt% of the epoxy resin composition (D) according to claim 1 and 40 to 65 wt% of glass fibers. 제 2항 기재의 프리프레그로 된 하나 이상의 라미네이트와 상기 라미네이트의 외부에 위치한 동박 외부층을 가열 가압에 의해 일체화시킨 인쇄회로기판제조용 동박적층판.A copper foil laminated plate for manufacturing a printed circuit board in which one or more laminates of the prepreg according to claim 2 and an outer layer of copper foil located outside of the laminate are integrated by heat and pressure.
KR1020040098633A 2004-11-29 2004-11-29 Phosphous-modified epoxy compound mixed with novolac epoxy and tpe-modified epoxy KR20060059520A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100771331B1 (en) * 2006-05-16 2007-10-29 삼성전기주식회사 Epoxy resin composition and printed circuit board using the same

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100771331B1 (en) * 2006-05-16 2007-10-29 삼성전기주식회사 Epoxy resin composition and printed circuit board using the same

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