KR950004701B1 - Heat-latent curing catalyst - Google Patents

Heat-latent curing catalyst Download PDF

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KR950004701B1
KR950004701B1 KR1019940029626A KR19940029626A KR950004701B1 KR 950004701 B1 KR950004701 B1 KR 950004701B1 KR 1019940029626 A KR1019940029626 A KR 1019940029626A KR 19940029626 A KR19940029626 A KR 19940029626A KR 950004701 B1 KR950004701 B1 KR 950004701B1
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resin
parts
formula
meth
resins
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신지 나까노
히로하루 오오스기
사또시 우라노
마사미찌 후루까와
료오조오 다까가와
요시오 에구찌
다께시 엔도오
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닛뽄 페인트 가부시끼가이샤
사사끼 가즈오
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Priority to KR1019950005437A priority Critical patent/KR950013473B1/en
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Abstract

내용 없음.No content.

Description

열잠재성 경화촉매Heat latent curing catalyst

본 발명은 열잠재성(heat-latency) 즉, 통상 비활성적이지만 고온에서만 경화반응을 개시할 수 있는 신규한 계열의 경화촉매에 관한 것이다.The present invention relates to a novel series of curing catalysts that are heat-latency, ie usually inert but capable of initiating a curing reaction only at high temperatures.

본 발명은 또한 코팅제, 접착제, 인쇄잉크 및 기타 조성물의 제조에 유용한, 이러한 촉매를 함유하는 열경화성 수지조성물에 관한 것이다.The invention also relates to thermosetting resin compositions containing such catalysts, which are useful in the preparation of coatings, adhesives, printing inks and other compositions.

양성자 주개 방향족 술폰산염 촉매를 사용하는 열경화성(heat-curable) 코팅시스템에 있어서, 저장시에 발생하는 때이른 경화반응을 방지하기 위해 휘발성 아민으로 술폰산염 촉매를 차단시키는 것이 필수적이다.In heat-curable coating systems using proton donor aromatic sulfonate catalysts, it is essential to block the sulfonate catalyst with volatile amines to prevent premature curing reactions that occur during storage.

아민 차단된 술폰산염 촉매는 다음 스킴에 따라 양성자를 방출한다. 따라서 술폰산염이 비교적 낮은 온도에서 제기능을 나타내려면 아민 대 술폰산의 비가 감소되어야 한다. 이것은 자유 술폰산의 양을 증가시켜 전 시스템의 저장안정성을 감소시키게 된다.The amine blocked sulfonate catalyst releases protons according to the following scheme. Thus, for the sulfonate to function at relatively low temperatures, the ratio of amine to sulfonic acid must be reduced. This increases the amount of free sulfonic acid, which reduces the storage stability of the entire system.

[반응식1][Scheme 1]

[반응식 2]Scheme 2

반대로, 저장안정성을 높이기 위해 아민 대 술폰산 비율을 증가시키면 술폰산아민염의 양이 따라서 증가된다. 이것은 술폰산염 촉매가 완전히 작용하기 위해 바람직한 것보다 더 높은 경화온도를 필요로 한다. 따라서 아민 차단된 술폰산염 촉매를 이용하는 경화 가능 시스템의 경화성은 일반적으로 그의 저장안정성과 조화되지 않는다. 따라서 상기한 결점을 제거할 수 있는 양성자 주개 촉매가 절실히 필요하다.Conversely, increasing the amine to sulfonic acid ratio to increase storage stability thus increases the amount of sulfonic acid amine salts. This requires a higher curing temperature than is desirable for the sulfonate catalyst to fully function. Thus, the curability of curable systems using amine blocked sulfonate catalysts generally does not match their storage stability. Therefore, there is an urgent need for a proton donor catalyst capable of eliminating the above drawbacks.

한편에 있어서, 본 발명은 다음 일반식의 화합물을 제공한다.On the other hand, this invention provides the compound of the following general formula.

[화학식 1][Formula 1]

또는or

[화학식 2][Formula 2]

상기식에서 R1,R2,R3및 R6는 각각 H, 할로겐, 알킬, 알콕시, 니트로, 아미노, 알킬아미노, 시아노, 알콕시카르보닐 또는 카르바모일이고, R4와 R5는 각각 H, 알킬 또는 할로겐이고, R7, R8및 R9는 각각 알킬, 알케닐 또는 니트로, 시아노, 아미노, 할로겐, 알킬 또는 디알킬아미노로 치환될 수 있는 페닐이고, R10은 H 또는 알킬이다.Wherein R 1 , R 2 , R 3 and R 6 are each H, halogen, alkyl, alkoxy, nitro, amino, alkylamino, cyano, alkoxycarbonyl or carbamoyl, and R 4 and R 5 are each H , Alkyl or halogen, R 7 , R 8 and R 9 are each phenyl which may be substituted by alkyl, alkenyl or nitro, cyano, amino, halogen, alkyl or dialkylamino and R 10 is H or alkyl .

다른 면에서, 본 발명은 고온에서 조성물의 경화반응을 개시하기에 효과적인 양의 상기한 술폰산 벤질피리디늄 또는 술폰산벤질암모늄 화합물로 이루어지는 열경화성 수지조성물을 제공한다.In another aspect, the present invention provides a thermosetting resin composition composed of the aforementioned sulfonic acid benzylpyridinium or sulfonic acid benzyl ammonium compound in an amount effective to initiate the curing reaction of the composition at high temperature.

상기한 술폰산 벤질피리디늄 또는 술폰산벤질암모늄화합물은 다음 시스템중의 어떤 것에도 사용될 수 있다.The sulfonic acid benzylpyridinium or sulfonic acid benzyl ammonium compounds described above can be used in any of the following systems.

I. 필름-형성, 히드록시기 함유수지 및 멜라민수지를 함유한 시스템 ;I. Film-forming, hydroxy group-containing resins and melamine resins;

II. 알콕시실릴기 함유수지의 자기축합반응을 통해 경화가능한 시스템 ;II. A system curable through self-condensation of an alkoxysilyl group-containing resin;

III. 알콕시실릴기 함유수지와 히드록시기함유수지의 공축합반응을 통해 경화가능한 시스템.III. A system curable through the cocondensation reaction of an alkoxysilyl group-containing resin with a hydroxy group-containing resin.

1. 열잠재성 경화촉매1. Heat latent curing catalyst

일반식 I-aFormula I-a

[화학식 3][Formula 3]

의 술폰산벤질피리디늄 화합물은 일반식 IIThe sulfonic acid benzylpyridinium compound of formula II

[화학식 4][Formula 4]

(상기식에서, Y는 할로겐원자이다)(Wherein Y is a halogen atom)

의 대응 할로겐화 벤질을 일반식 I-aThe corresponding benzyl halide of general formula I-a

[화학식 5][Formula 5]

의 피리딘화합물과 반응시키고, 그런 후에 결과의 할로겐화 벤질피리디늄을 대응하는 알칼리금속 벤젠술포네이트와 반응시켜 치환반응으로 화합물 I-a를 생성함으로써 합성될 수 있다.Can be synthesized by reacting with a pyridine compound of and then reacting the resulting benzylpyridinium halide with the corresponding alkali metal benzenesulfonate to produce compound I-a by substitution.

마찬가지로, 일반식 I-bSimilarly, general formula I-b

[화학식 6][Formula 6]

의 술폰산벤질암모늄 화합물은 할로겐화벤질(II)을 일반식(III-b)The sulfonate benzyl ammonium compound of benzyl halide is represented by general formula (III-b)

[화학식 7][Formula 7]

의 3차 아민과 반응시키고, 그런 후에 결과의 할로겐과 벤질암모늄을 대응하는 알칼리금속 벤젠술포네이트와반응시켜 합성할 수 있다.It can be synthesized by reacting with a tertiary amine of and then reacting the resulting halogen and benzyl ammonium with the corresponding alkali metal benzenesulfonate.

일반식 I-a 또는 I-b의 화합물은 고온에서 열절단되어Compounds of formula I-a or I-b are thermally cut at high temperature

일반식General formula

[화학식 8][Formula 8]

의 벤질 양이온을 생성시키는데, 그것은 차례로 H2O 또는 히드록시기와 반응하여 양성자를 생성한다. 그러나 이러한 화합물들은 그것들의 절단점 아래의 온도에서는 실질적으로 비활성적이다. 따라서, 이러한 유형의 열잠재성 촉매에 있어서는 열경화 가능한 수지조성물의 저장안정성이 그의 경화성과 조화되게 된다.Produces a benzyl cation, which in turn reacts with a H 2 O or hydroxy group to produce a proton. However, these compounds are substantially inert at temperatures below their break point. Therefore, in this type of thermal latent catalyst, the storage stability of the thermosetting resin composition is matched with its curability.

2. 열경화성 수지조성물2. Thermosetting resin composition

1. 멜라민 수지를 함유한 시스템1.System containing melamine resin

멜라민수지 함유 코팅조성물 또는 에나멜은 코팅공업에서 공지되어 있다. 이러한 조성물은 통상 멜라민수지와의 가교결합반응을 촉매하기 위해 p-톨루엔술폰산 같은 양성자주개가 함유되어 있다.Melamine resin-containing coating compositions or enamels are known in the coatings industry. Such compositions usually contain a proton donor such as p-toluenesulfonic acid to catalyze the crosslinking reaction with the melamine resin.

유리산을 조성물에 가하면 저장하는 동안에 전조성물을 겔화시키므로 촉매는 조성물의 경화온도에서 휘발성인 아민으로 그것의 산기능이 부분적으로 또는 전적으로 차단되어야 된다. 그러나 이러한 유형의 조성물의 경화가능성은 대개 그것의 저장안정성과 조화되지 않는다.Since the addition of free acid to the composition gels the precursor during storage, the catalyst must be partially or wholly blocked from its acid function with amines that are volatile at the curing temperature of the composition. However, the curability of this type of composition usually does not match its storage stability.

본 발명의 열잠재성 촉매를 사용하면 이러한 문제가 극복된다. 촉매는 실질직으로 임계온도에 이를때까지는 비활성적이다.The use of the heat latent catalyst of the present invention overcomes this problem. The catalyst is substantially inactive until the critical temperature is reached.

그러나 소정의 온도로 가열하면 촉매로부터 카르보늄 양이온이 유리되고, 카르보늄 양이온과 물 또는 조성물중에 함유된 히드록시기 함유 화합물과의 반응으로 양성자가 발생된다. 이것은 조성물의 경화가능성과 저장안정성이 조화되도록 한다.However, heating to a predetermined temperature releases the carbonium cation from the catalyst, and protons are generated by the reaction of the carbonium cation with water or a hydroxy group-containing compound contained in the composition. This ensures that the curability and storage stability of the composition match.

다양한 필름 헝성수지가 멜라민수지와 함께 코팅공업에서 사용된다. 그러한 예로는 폴리에스테르수지, 폴리락톤수지, 에폭시수지, 아크릴수지 등을 들 수 있다. 폴리에스테르수지는 폴리카르복실산 또는 그의 무수물을 다가 알코올과 축합반응시켜 제조된다. 폴리에스테르 사슬의 말단 및/또는 중간에 히드록시기를 가진 어떤 폴리에스테르수지도 멜라민수지와 가교결합될 수 있다.Various film-based resins are used in the coating industry together with melamine resins. Examples thereof include polyester resins, polylactone resins, epoxy resins, acrylic resins, and the like. Polyester resins are prepared by condensation of polycarboxylic acids or their anhydrides with polyhydric alcohols. Any polyester resin having a hydroxyl group at the end and / or middle of the polyester chain may be crosslinked with the melamine resin.

히드록시로 끝나는 폴리락톤 수지도 멜라민수지와 가교결합될 수 있다.Polylactone resins ending in hydroxy can also be crosslinked with melamine resins.

비스페놀 에폭시수지와 노볼락 에폭시수지같이 분자 말단과 중간에 각각 에폭시드기와 히드록시기가 있는 에폭시수지도 멜라민수지와 함께 사용할 수가 있다.Epoxy resins with epoxide and hydroxy groups at the end and middle of the molecule, such as bisphenol epoxy resin and novolak epoxy resin, can also be used with melamine resin.

다수의 히드록시기가 있는 아크릴수지는 2-히드록시에틸(메타) 아크릴레이트와 같은 히드록시기 함유 아크릴 단량체를 알킬(메타) 아크릴레이트, 예를들면 메틸(메타)아크릴레이트, 부틸(메타)아크릴레이트, 이소부틸(메타)아크릴레이트 및 2-에틸헥실(메타) 아크릴레이트 ; 스티렌 또는 그 유도체 ; (메타)아크릴로니트릴 ; 비닐아세테이트 등과 같은 하나 또는 그이상의 공단량체와 공중합하여 제조될 수 있다.Acrylic resins with a large number of hydroxy groups may contain hydroxy group-containing acrylic monomers, such as 2-hydroxyethyl (meth) acrylate, such as alkyl (meth) acrylates such as methyl (meth) acrylate, butyl (meth) acrylate, iso Butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate; Styrene or derivatives thereof; (Meth) acrylonitrile; It may be prepared by copolymerization with one or more comonomers such as vinyl acetate and the like.

멜라민 수지는 멜라민, 아세토구아나민 또는 벤조구아나민 같은 트리아진화합물을 포름알데히드와 반응시키고, 임의적으로 결과의 축합체의 메틸올기 일부 또는 전부를 메탄을 또는 부탄을 같은 저급 알칸올로 에스테르화하여 제조된다.Melamine resins are prepared by reacting a triazine compound such as melamine, acetoguanamine or benzoguanamine with formaldehyde and optionally esterifying some or all of the methylol groups of the resulting condensate with lower alkanols such as methane or butane do.

히드록시기 함유, 필름 형성수지와 멜라민수지로 이루어진 열경화성 수지조성물은 코팅공업에서 공지되어있다. 상기한 열잠재성 촉매를 사용하는 것을 제외하고는 본 발명의 조성물은 이러한 봉지의 조성물과 동일하다.Thermosetting resin compositions containing hydroxy groups, film forming resins and melamine resins are known in the coating industry. The composition of the present invention is identical to the composition of this encapsulation except for using the above-mentioned heat latent catalyst.

히드록시기-함유, 필름형성 수지 대 멜라민수지의 중량비는 고형분 기준으로 50 : 50 내지 95 : 5이다.본 발명의 조성물은 일반식 I -a 또는 I -b의 촉매를 수지 고형분의 0.01 내지 10중량%, 바람직하게는 0.05 내지 5중량%를 함유한다.The weight ratio of hydroxy group-containing, film-forming resin to melamine resin is from 50:50 to 95: 5 based on solids. The composition of the present invention comprises a catalyst of formula I-a or I-b 0.01 to 10% by weight of resin solids. And preferably 0.05 to 5% by weight.

촉매의 양이 부족하면 조성물의 경화성은 만족스럽지 못하다.If the amount of catalyst is insufficient, the curability of the composition is not satisfactory.

반대로 촉매를 과량으로 사용하면 어두운 외관과 방수성의 감소같이 경화된 조성물의 물성에 좋지 못한영 향을 끼친다.Conversely, excessive use of the catalyst adversely affects the physical properties of the cured composition, such as dark appearance and reduced water resistance.

조성물은 용도에 따라 안료, 충전제등과 같은 종래의 첨가제를 함유할 수 있다.The composition may contain conventional additives such as pigments, fillers and the like depending on the application.

II. 알콕시실릴기의 자기축합 또는 공축합 반응을 이용하는 시스템II. System using self-condensation or co-condensation reaction of alkoxysilyl group

일본 특허공보 제33512/88호에는 다수의 알콕시실릴기-함유 측쇄를 가진 비닐중합체, 폴리히드록시화합물 및 경화촉매를 함유한 경화가능한 수지조성물이 개시되어 있다. 조성물은 2개의 알콕시실릴기 사이의 자기축합반응 :Japanese Patent Publication No. 3312/88 discloses a curable resin composition containing a vinyl polymer having a large number of alkoxysilyl group-containing side chains, a polyhydroxy compound and a curing catalyst. The composition is self-condensing between two alkoxysilyl groups:

[반응식 3]Scheme 3

RoSi+-SiOR+H2O→-Si-O-Si-+2ROHRoSi + -SiOR + H 2 O → -Si-O-Si- + 2ROH

뿐만 아니라 알콕시실릴기와 히드록시기의 공축합 반응 :As well as the co-condensation reaction of the alkoxysilyl and hydroxy groups:

[반응식 4]Scheme 4

ROSi-+HO-C-→-Si-O-C-+ROHROSi- + HO-C- → -Si-O-C- + ROH

을 통해 경화한다고 믿어진다.It is believed to harden through.

상기한 반응을 촉매할 수 있는 것으로 다수의 촉매가 개시되어 있다.A number of catalysts have been disclosed that can catalyze the above reactions.

이러한 것들에는 부틸아민, 디부틸아민, t-부틸아민, 에틸렌디아민 등의 아민 ; 테트라이소프로필 티타네이트, 테트라부틸 티타네이트, 주석 옥테이트, 납옥테이트, 아연 옥테이트, 칼슘 옥테이트, 디부틸주석디아세테이트, 디부틸주석 디옥테이트, 디부틸주석 디라우레이트 등과 같은 유기금속화합물 ; 및 p-톨루엔술폰산, 트리클로로아세트산 등과 같은 산촉매가 포함된다. 이러한 촉매를 함유한 조성물은 실온에서 경화가능하다.These include amines, such as butylamine, dibutylamine, t-butylamine, and ethylenediamine; Organometallic compounds such as tetraisopropyl titanate, tetrabutyl titanate, tin octanate, lead octanate, zinc octanate, calcium octate, dibutyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate and the like; And acid catalysts such as p-toluenesulfonic acid, trichloroacetic acid and the like. Compositions containing such catalysts are curable at room temperature.

이러한 사실로부터 자명한 것처럼, 조성물은 경화촉매를 함유한 상태로 오래 저장할 수 없다. 장기간 저장할 필요가 있으면, 촉매와 수지성분을 별도로 저장하였다가 사용하기 직전에 두성분을 혼합하는 것이 필요하다.As is evident from this fact, the composition cannot be stored for a long time in a state containing a curing catalyst. If long term storage is required, it is necessary to store the catalyst and resin components separately and mix the two components immediately before use.

이것은 실제로 불편하고, 포트라이프(pot life)내에 사용해야 한다. 다른 접근법으로는 촉매량을 감소시키고 적당한 산 또는 아민으로 아민 또는 산 촉매를 차단하는 것이 포함된다. 불행하게도 그것들은 필름특성, 저장안정성등에 관하여 만족스럽지 못하다고 입증되었다.This is actually inconvenient and should be used in pot life. Other approaches include reducing the amount of catalyst and blocking the amine or acid catalyst with a suitable acid or amine. Unfortunately they have proved unsatisfactory with regard to film properties, storage stability, etc.

멜라민수지 함유 조성물과 마찬가지로, 상기한 시스템에 본 발명의 열잠재성 촉매를 사용하면 이러한 문제점이 극복된다. 다수의 알콕시 실릴기를 함유한 필름형성 수지의 예로는 다음의 것들이 포함된다.As with the melamine resin containing composition, the use of the heat latent catalyst of the present invention in the above system overcomes this problem. Examples of the film-forming resin containing a large number of alkoxy silyl groups include the followings.

(1) 알콕시실릴기 함유 아크릴 수지(1) Alkoxy silyl group containing acrylic resin

분자내에 에틸렌성 불포화기와 알콕시 실릴기 둘다를 가진 단량체는 단독으로 또는 아크릴 및/또는 기타공단량체와 함께 다수의 알콕시 실릴기를 함유한 단일 중합체 또는 공중합체를 형성한다.Monomers having both ethylenically unsaturated groups and alkoxy silyl groups in the molecule, alone or in combination with acrylics and / or other comonomers, form homopolymers or copolymers containing multiple alkoxy silyl groups.

그러한 단량체의 제1계열로는 일반식 :As the first series of such monomers, the general formula:

[화학식 9][Formula 9]

(상기식에서, R은 H 또는 CH3이고, R'와 R"는 각각 알킬이고, X는 정수, n은 0, 1 또는 2이다)의 아크릴산 또는 메타크릴산의 알콕시실릴알킬에스테르이다.Wherein R is H or CH 3 , R 'and R "are each alkyl, X is an integer, n is 0, 1 or 2) is an alkoxysilylalkyl ester of acrylic acid or methacrylic acid.

이러한 단량체의 구체예로는 γ-메타크릴로일옥시프로필트리메톡시실란, γ-메타크릴로일옥시프로필디메톡시실란, γ-메타크릴로일옥시프로필디메틸메톡시실란, γ-메타크릴로일옥시프로필트리에톡시실란, γ-메타크릴로일옥시프로필메틸디에톡시실란, γ-메타크릴로일옥시프로필디메틸에톡시실란, γ-메타크릴로일옥시 프로필트리프로폭시실란, γ-메타크릴로일옥시프로필메틸디프로폭시실란, γ-메타크릴로일옥시프로필디메 틸프로폭시실란, γ -메타크릴로일옥시프로필트리부톡시실란, γ-메타크릴로일옥시프로필메틸디부톡시실란 및 γ-메타크릴로일옥시프로필디메틸부톡시실란을 들 수 있다.Specific examples of such monomers include γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyldimethoxysilane, γ-methacryloyloxypropyldimethylmethoxysilane, and γ-methacrylo Yloxypropyltriethoxysilane, γ-methacryloyloxypropylmethyldiethoxysilane, γ-methacryloyloxypropyldimethylethoxysilane, γ-methacryloyloxy propyltripropoxysilane, γ-meta Cryloyloxypropylmethyldipropoxysilane, γ-methacryloyloxypropyl dimethylpropoxysilane, γ-methacryloyloxypropyltributoxysilane, γ-methacryloyloxypropylmethyldibutoxysilane And γ-methacryloyloxypropyldimethylbutoxysilane.

상기한 단량체의 제2계열은 (메타)아크릴산의 β-글리시딜프로필트리메톡시실란 또는 β-(3,4-에폭시시클로헥실)에틸트리메톡시실란과 같은 에폭시기 함유 알콕시실란 부가물이다.The second series of monomers described above are epoxy group-containing alkoxysilane adducts such as β-glycidylpropyltrimethoxysilane of (meth) acrylic acid or β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

알콕시실릴기 함유 단량체의 또다른 계열로는 히드록시에틸(메타)아크릴레이트, 히드록시프로필(메타)아크릴레이트 또는 4-히드록시부틸(메타)아크릴레이트 같은 히드록시알킬(메타)아크릴레이트의 γ-이소시아나토프로필트리메톡시실란, γ-이소시아나토프로필메틸메톡시실란, γ-이소시아나토프로필트리에톡시실란 또는 γ-이소시아나토프로필메틸디에톡시실란 같은 일반식 ;Another class of alkoxysilyl group-containing monomers is the γ of hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate or 4-hydroxybutyl (meth) acrylate. General formulas such as isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethylmethoxysilane, γ-isocyanatopropyltriethoxysilane, or γ-isocyanatopropylmethyldiethoxysilane;

[화학식 10][Formula 10]

OCN(CH2)xSr(R')n(OR")3-n OCN (CH 2 ) x Sr (R ') n (OR ") 3-n

의 이소시아나토알킬알콕시실란 부가물이다.Isocyanatoalkylalkoxysilane adduct of.

알콕시실릴기함유 단량체의 또다른 계열은 글리시딜(메타)아크릴레이트의 γ-아미노프로필트리메톡시실란, γ-아미노프로필트리에톡시실란, 3-(2-아미노에틸아미노)프로필메틸디메톡시실란, 3-(2-아미노에틸아미 노)프로필트리메톡시실란, γ-아미노프로필디메틸에톡시실란 또는 γ-아미노프로필메틸디에톡시실란같은 아미노알킬알콕시실란 부가물이 다.Another class of alkoxysilyl group-containing monomers are γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, 3- (2-aminoethylamino) propylmethyldimethoxy of glycidyl (meth) acrylate Aminoalkylalkoxysilane adducts such as silane, 3- (2-aminoethylamino) propyltrimethoxysilane, γ-aminopropyldimethylethoxysilane or γ-aminopropylmethyldiethoxysilane.

알콕시 실릴기함유 단량체와 공중합할 수 있는 아크릴 및/또는 기타 공단량체로는 알킬(메타)아크릴레이트, (메타)아크릴산, (메타)아크릴로니트릴, (메타)아크릴아미드, 스티렌, 염화비닐, 비닐아세테이트 등을들 수 있다.Acrylic and / or other comonomers that can be copolymerized with alkoxy silyl group-containing monomers include alkyl (meth) acrylates, (meth) acrylic acid, (meth) acrylonitrile, (meth) acrylamide, styrene, vinyl chloride, vinyl Acetates and the like.

2) 실리콘-개질된 에폭시 수지2) silicone-modified epoxy resin

글리시딜(메타)아크릴레이트 부가물을 제조하는데 사용되는 상기한 아미노알킬알콕시 실란은 에폭시 수지와 반응하여 다수의 알콕시실린기를 가진 개질된 에폭시수지를 생성할 수 있다.The aminoalkylalkoxy silanes described above used to prepare the glycidyl (meth) acrylate adducts can be reacted with epoxy resins to produce modified epoxy resins having a plurality of alkoxysilane groups.

3) 실리콘-개질된 폴리에스테르수지3) silicone-modified polyester resin

다수의 유리 카르복실기를 가진 폴리에스테르 수지는 상기한 에폭시기 함유알콕시실란으로 개질되어 실리콘 개질된 폴리에스테르 수지를 생성한다.Polyester resins having a large number of free carboxyl groups are modified with the epoxy group-containing alkoxysilanes described above to produce silicone modified polyester resins.

다수의 히드록시기가 있는 폴리에스테르는 상기 이소시아나토알킬알콕시실란과 반응하여 실리콘 개질된 폴리에스테르수지를 얻는다. 히드록시기 함유 수지의 대표적인 예로는 폴리에스테르수지, 폴리락톤수지, 에폭시수지 및 아크릴수지를 들 수 있다.Polyesters having a large number of hydroxy groups are reacted with the isocyanatoalkylalkoxysilane to obtain a silicone modified polyester resin. Representative examples of the hydroxy group-containing resin include polyester resins, polylactone resins, epoxy resins and acrylic resins.

폴리에스테르수지는 폴리카르복실산 또는 그의 무수물과 다가알코올을 축합반응시켜 제조된다. 폴리에스테르 사슬의 말단 및/또는 중간부에 히드록시기를 가진 어떤 폴리에스테르수지도 사용할 수 있다.Polyester resins are prepared by condensation of polycarboxylic acids or their anhydrides with polyhydric alcohols. Any polyester resin having a hydroxyl group at the terminal and / or middle portion of the polyester chain may be used.

히드록시기가 말단에 있는 폴리락톤 수지도 사용할 수 있다. 비스페놀 에폭시수지와 노볼락 에폭시수지와같은, 분자의 말단과 중간부에 각각 에폭시드와 히드록시기를 가지는 에폭시 수지도 사용할 수 있다.Polylactone resins with hydroxy groups at the end may also be used. Epoxy resins having epoxide and hydroxy groups at the terminal and middle of the molecule, such as bisphenol epoxy resin and novolak epoxy resin, may also be used.

다수의 히드록시기를 가진 아크릴수지는 2-히드록시에틸(메타)아크릴레디트 같은 히드록시기 함유 아크릴 단량체를 알킬(메타)아크릴레이트, 예를들면, 메틸(메타)아크릴레이트, 부틸(메타)아크릴레이트, 이소부틸(메타)아크릴레이트 및 2-에틸헥실(메타)아크릴레이트, 스티렌 또는 그 유도체 ; (메타)아크릴로니트릴비닐아세테이트 등과 같은 하나 또는 그이상의 공단량체와 공중합하여 제조할 수 있다.Acrylic resins having a large number of hydroxy groups include hydroxy group-containing acrylic monomers such as 2-hydroxyethyl (meth) acrylate, alkyl (meth) acrylates such as methyl (meth) acrylate, butyl (meth) acrylate, Isobutyl (meth) acrylate and 2-ethylhexyl (meth) acrylate, styrene or derivatives thereof; It may be prepared by copolymerization with one or more comonomers such as (meth) acrylonitrilevinylacetate and the like.

알콕시실릴기의 자기축합 반응을 이용하는 시스템은 상기한 실리콘함유 수지와 수지 고형분의 0.01 내지10중량%, 바람직하게는 0.05 내지 5중량%의 화합물 I-a 또는 I-b를 함유한다. 알콕시실릴기와 히드록시의 공축합을 이용하는 시스템에는 상기한 실리콘함유수지, 몰비로 알콕시실릴기에 대한 히드록시기가 0.1 내지 10인 양의 히드록시기 함유수지 및 수지고형분의 0.01 내지 10중량%, 바람직하게는 0.05 내지 5중량%의 화합물 I-a 또는 I-b가 들어있다.The system utilizing the self-condensation reaction of the alkoxysilyl group contains 0.01 to 10% by weight, preferably 0.05 to 5% by weight of the compound I-a or I-b of the above-mentioned silicone-containing resin and the resin solids. In the system using the co-condensation of alkoxysilyl group and hydroxy, the silicone-containing resin, the hydroxyl group-containing resin in an amount of 0.1 to 10 with respect to the alkoxysilyl group in molar ratio and 0.01 to 10% by weight of the resin solid content, preferably 0.05 to 5% by weight of compound Ia or Ib.

화합물 I-a 또는 I-b의 양이 부족하면 조성물의 경화성이 만족스럽지 못하다. 반대로, 화합물 I-a 또는 I-b를 과량 사용하면 어두운 외관과 방수성의 감소같이 경화된 조성물의 물성에 불리한 영향을 미친다.If the amount of compound I-a or I-b is insufficient, the curability of the composition is not satisfactory. Conversely, excessive use of compounds I-a or I-b adversely affects the properties of the cured composition, such as a decrease in dark appearance and water resistance.

조성물에는 그 용도에 따라 충전제, 안료등과 같은 종래의 첨가제가 함유될 수 있다.The composition may contain conventional additives such as fillers, pigments and the like, depending on the use thereof.

결과의 조성물은 실온에서는 증가된 저장안정성을 가지지만 화합물 I -a 또는 I -b의 절단점 위의 온도에서는 경화 가능하다. 경화시간은 경화온도에 따라 다양하지만 통상 한시간 이내이다.The resulting composition has increased storage stability at room temperature but is curable at temperatures above the cut point of compound I-a or I-b. The curing time varies depending on the curing temperature but is usually within one hour.

다음의 실시예들은 본 발명을 제한하지는 않고서 더욱 잘 나타내기 위해서이다. 여기서 모든 부와 퍼센트는 달리 표시하지 않으면 중량부와 중량%를 나타낸다.The following examples are intended to better illustrate the present invention without restricting it. All parts and percentages herein refer to parts by weight and percentages unless otherwise indicated.

[실시예]EXAMPLE

I. 촉매의 합성I. Synthesis of Catalyst

실시예 I-1Example I-1

α, α -디메틸벤질-P-도데실벤젠술포네이트α, α-dimethylbenzyl-P-dodecylbenzenesulfonate

4-메톡시벤질클로라이드 4.698g (0.03mol)과 4-시아노피리딘 10.22g (0.09mol)을 메탄올 90ml 중에서 40℃로 3일동안 반응시켰다.4.698 g (0.03 mol) of 4-methoxybenzylchloride and 10.22 g (0.09 mol) of 4-cyanopyridine were reacted at 40 ° C. in 90 ml of methanol for 3 days.

반응 후 용매를 진공하에서 증발시키고 에테르를 잔류물에 가하여 에테르층중의 미반응물질을 추출하였다. 잔류물을 메탄올 30ml에 용해시키고 p-도데실벤젠술폰산나트륨 10.44g (0.03mol)을 용액에 가했다.After the reaction, the solvent was evaporated in vacuo and ether was added to the residue to extract the unreacted material in the ether layer. The residue was dissolved in 30 ml of methanol and 10.44 g (0.03 mol) of p-dodecylbenzenesulfonate was added to the solution.

그런후에 반응혼합물을 여과하여 생성된 염화나트륨 결정을 제거하고 여액을 증발시켜 표제화합물을 얻었다.The reaction mixture was then filtered to remove the sodium chloride crystals produced and the filtrate was evaporated to afford the title compound.

NMR : 0.6-1.5ppm(m, 25H, 도데실), 3.8ppm(s, 3H, MeO), 5.8ppm(s, 2H, CH2), 7.2-7.4ppm (m, 6H, Ph), 7.5ppm(d, 2H, Ph), 8.7ppm(d, 2H, Py), 9.4ppm(d, 2H, Py)NMR: 0.6-1.5 ppm (m, 25H, dodecyl), 3.8 ppm (s, 3H, MeO), 5.8 ppm (s, 2H, CH 2 ), 7.2-7.4 ppm (m, 6H, Ph), 7.5 ppm (d, 2H, Ph), 8.7 ppm (d, 2H, Py), 9.4 ppm (d, 2H, Py)

[실시예 I -2 내지 I -38][Examples I-2 to I-38]

실시예 I -1과 마찬가지로, 다음 표에 열거한 일반식 I -a의 여러 화합물을 합성하였다.As in Example I-1, various compounds of Formula I-a listed in the following table were synthesized.

일반식 I -a :Formula I -a:

[화학식 11][Formula 11]

[표 1]TABLE 1

[실시예 I -39]Example I-39

N-(4-메톡시벤질)-N, N-디메틸아닐리늄 p-도데실벤젠술포네이트N- (4-methoxybenzyl) -N, N-dimethylanilinium p-dodecylbenzenesulfonate

4-메톡시벤질 클로라이드 4.698g(0.03mol)과 N, N-디메틸아닐린 3.638g( 0.03mol)을 메탄올 40ml중에서 40℃로 3일동안 반응시켰다.4.698 g (0.03 mol) of 4-methoxybenzyl chloride and 3.638 g (0.03 mol) of N and N-dimethylaniline were reacted at 40 ° C. in 40 ml of methanol for 3 days.

반응 후, 용매를 진공하에서 증발시키고 에테르를 잔류물에 가하여 에테르중의 미반응물질을 추출하였다.잔류물을 메탄올 30ml에 용해시키고 p-도데실벤젠술폰산나트륨 10.44g(0.03mol)을 거기에 가했다.After the reaction, the solvent was evaporated in vacuo and ether was added to the residue to extract the unreacted material in ether. The residue was dissolved in 30 ml of methanol and 10.44 g (0.03 mol) of p-dodecylbenzenesulfonate was added thereto. .

반응혼합물을 여과하여 염화나트륨결정을 제거하고 여액을 증발시켜 표제화합물을 얻었다.The reaction mixture was filtered to remove sodium chloride crystals and the filtrate was evaporated to afford the title compound.

NMR : 0.6-1.5ppm(m, 25H, 도데실), 3.6ppm(s, 6H, Me) , 3.8ppm(s, 3H, MeO), 5.8ppm(s, 2H, CH2), 7.0ppm(d, 2H, Ph), 7.2ppm(m, 11H, Ph)NMR: 0.6-1.5 ppm (m, 25H, dodecyl), 3.6 ppm (s, 6H, Me), 3.8 ppm (s, 3H, MeO), 5.8 ppm (s, 2H, CH 2 ), 7.0 ppm (d , 2H, Ph), 7.2 ppm (m, 11H, Ph)

[실시예 I-40 내지 I-71][Examples I-40 to I-71]

실시예 I-39와 마찬가지로 다음표에 열거된 일반식 I-b의 여러화합물을 합성하였다.As in Example I-39, various compounds of the general formula I-b listed in the following table were synthesized.

일반식 I-bFormula I-b

[화학식 12][Formula 12]

[표 2]TABLE 2

II. 비이클 수지의 제조II. Preparation of Vehicle Resin

폴리에스테르수지Polyester resin

실시예 II-1Example II-1

히이터, 교반기, 환류응축기, 수분리기, 분별증류관 및 온도계가 구비된 반응용기에 헥사히드로프탈산 36부, 트리메틸올프로판 42부, 네오펜틸글리콜 50부, 1,6-헥산디올 56부를 채워 넣었다. 혼합물을 교반하면서 210℃로 가열하였다. 그런 후에 혼합물을 축합반응부산물로 생성되는 물을 증류 제거하면서 일정한 속도로 2시간에 걸쳐 230℃로 가열하였다.A reaction vessel equipped with a heater, agitator, reflux condenser, water separator, fractional distillation tube, and thermometer was charged with 36 parts of hexahydrophthalic acid, 42 parts of trimethylolpropane, 50 parts of neopentyl glycol, and 56 parts of 1,6-hexanediol. The mixture was heated to 210 ° C. with stirring. The mixture was then heated to 230 ° C. over 2 hours at a constant rate while distilling off the water produced as the condensation reaction byproduct.

산가가 1.0이 될 때까지 230℃에서 반응을 계속하고 냉각시켜 반응을 중단시켰다. 이소프탈산 153부를 가한 후 반응혼합물을 190℃로 다시 가열하고, 그 후에 생성된 물을 증류 제거하면서 190℃에서 210℃까지 3시간에 걸쳐 일정한 속도로 가열하였다. 이 온도에 달했을때 크실렌 3부를 가하곤 산가가 5.0이 될 때까지 반응을 계속하였다. 냉각시킨 후 반응혼합물을 크실렌 190부로 회석시켜 폴리에스테르 용액 A를 얻었다.The reaction was continued by cooling at 230 ° C. until the acid number reached 1.0 and stopped. After adding 153 parts of isophthalic acid, the reaction mixture was heated again to 190 ° C., and then heated at a constant rate from 190 ° C. to 210 ° C. over 3 hours while distilling off the produced water. When this temperature was reached, 3 parts of xylene was added and the reaction continued until the acid value reached 5.0. After cooling, the reaction mixture was distilled off with 190 parts of xylene to obtain a polyester solution A.

아크릴수지Acrylic resin

실시예 II-2Example II-2

교반기, 온도계, 환류응축기, 질소가스도입튜브와 적하깔때기가 구비된 반응용기에 솔베소(SOLVESSO)100 90부를 넣고 질소가스를 도입하면서 160℃로 가열하였다. 아래의 단량체혼합물을 일정한 속도로 용기에 적 가하였다.90 parts of SOLVESSO 100 were put into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen gas introduction tube and a dropping funnel, and heated to 160 ° C. while introducing nitrogen gas. The monomer mixture below was added to the vessel at a constant rate.

2-히드록시에틸 메타크릴레이트 23.20부23.20 parts of 2-hydroxyethyl methacrylate

메틸메타크릴레이트 40.15부Methyl methacrylate 40.15 parts

n-부틸아크릴레이트 35.65부35 parts of n-butyl acrylate

메타크릴산 1.00부Methacrylic acid 1.00 part

t-부틸퍼옥시-2-에틸헥사노에이트 10.00부t-butylperoxy-2-ethylhexanoate 10.00 parts

가하고나서 한시간 후 크실렌 10부와 t-부틸퍼옥시-2-에틸헥사노에이트 1부의 혼합물을 30분에 걸쳐일정한 속도로 적가하였다. 반응을 2시간동안 계속하여 완료되도록 하고 냉각시켜 중단하여 아크릴수지 A를 얻었다.One hour after addition, a mixture of 10 parts of xylene and 1 part of t-butylperoxy-2-ethylhexanoate was added dropwise at a constant rate over 30 minutes. The reaction was continued for 2 hours, cooled and stopped to obtain acrylic resin A.

실리콘수지Silicone resin

[실시예 II-3]Example II-3

실시예 II-2에서 사용한 반응용기에 크실렌 45부를 넣고 질소가스를 도입하면서 130℃로 가열하였다. γ-메타크릴로일옥시프로필트리메톡시실란 50부와 t-부틸퍼옥시-2-에틸헥사노에이트 4부의 혼합물을 3시간에 걸쳐 일정한 속도로 용기에 적가하였다.45 parts of xylene was put into the reaction vessel used in Example II-2 and heated to 130 ° C. while introducing nitrogen gas. A mixture of 50 parts of γ-methacryloyloxypropyltrimethoxysilane and 4 parts of t-butylperoxy-2-ethylhexanoate was added dropwise to the vessel at a constant rate over 3 hours.

가하고나서 30분 후에 혼합물을 90℃로 냉각하고 부틸퍼옥시-2-에틸헥사노에이트 1부와 크실렌 5부의 혼합물을 거기에 가했다. 2시간동안 더 반응을 계속하여 완결시키고 냉각하여 중단하여 실리콘수지 A를 얻었다.30 minutes after the addition, the mixture was cooled to 90 DEG C and a mixture of 1 part of butylperoxy-2-ethylhexanoate and 5 parts of xylene was added thereto. The reaction was continued for further 2 hours, cooled and stopped to obtain silicone resin A.

[실시예 II-4]Example II-4

실시예 II-3과 마찬가지로, γ-메타크릴로일옥시프로필메틸디메톡시실란 50부와 t-부틸퍼옥시-2-에틸헥사노에이트 4부의 혼합물을 중합하여 실리큰수지 B를 얻었다.In the same manner as in Example II-3, a mixture of 50 parts of γ-methacryloyloxypropylmethyldimethoxysilane and 4 parts of t-butylperoxy-2-ethylhexanoate was polymerized to obtain a silical resin B.

[실시예 II-5]Example II-5

실시예 II-3과 마찬가지로, γ-메타크릴로일옥시프로필디메틸메톡시실란 50부와 t-부틸퍼옥시-2-에틸헥사노에이트 4부의 혼합물을 중합하여 실리콘수지 C를 얻었다.In the same manner as in Example II-3, a mixture of 50 parts of γ-methacryloyloxypropyldimethylmethoxysilane and 4 parts of t-butylperoxy-2-ethylhexanoate was polymerized to obtain silicone resin C.

[실시예 II-6]Example II-6

실시예 II-3과 마찬가지로, γ-메타크릴로일옥시프로필트리에톡시실란 50부와 t-우틸퍼옥시-2-에틸헥사노에이트 4부의 혼합물을 중합하여 실리콘수지 D를 얻었다.In the same manner as in Example II-3, a mixture of 50 parts of γ-methacryloyloxypropyltriethoxysilane and 4 parts of t-utylperoxy-2-ethylhexanoate was polymerized to obtain a silicone resin D.

[실시예 II-7]Example II-7

실시예 II-3과 마찬가지로, γ-메타크릴로일옥시프로필트리에톡시실란 25부, 메틸메타크릴레이트 25부및 t-부틸퍼옥시-2-에틸헥사노에이트 4부의 혼합물을 중합하여 실리콘수지 E를 얻었다.As in Example II-3, a mixture of 25 parts of γ-methacryloyloxypropyltriethoxysilane, 25 parts of methyl methacrylate and 4 parts of t-butylperoxy-2-ethylhexanoate was polymerized to obtain a silicone resin. E was obtained.

[실시예 II-8]Example II-8

교반기, 온도계 및 환류응축기가 구비된 반응용지에 실시예 I-1에서 얻은 폴리에스테르수지 A 100부를넣고 100℃로 가열하였다. 디부틸주석 디라우레이트 0.2부를 가한 후 KBK-9007(Shin-Etsu Chemical Co., Ltd에서 판매하는, 화학적으로는 γ-이소시아나토프로필트리메톡시실란임.) 10부를 일정한 속도로30분에 걸쳐 적가하고, 1시간 더 반응을 계속하여 완결시켰다. 냉각시킨 후 실리콘수지 F를 얻었다. 1720cm-1에서의 NCO기의 흡수가 수지의 IR 스펙트럼에서 환전히 사라졌다.100 parts of the polyester resin A obtained in Example I-1 were added to a reaction paper equipped with a stirrer, a thermometer, and a reflux condenser, and heated to 100 ° C. After adding 0.2 parts of dibutyltin dilaurate, 10 parts of KBK-9007 (Shi-Etsu Chemical Co., Ltd., which is chemically gamma -isocyanatopropyltrimethoxysilane) were added at a constant rate for 30 minutes. The reaction mixture was added dropwise over and the reaction continued for 1 hour. After cooling, a silicone resin F was obtained. Absorption of NCO groups at 1720 cm −1 disappeared from the IR spectrum of the resin.

[실시예 II-9]Example II-9

교반기, 온도계 및 환류응축기가 구비된 반응용기에 비스페놀 A 디글리시딜에테르 100부를 넣고 150℃로가열하였다. 그런 후에 γ-아미노프로필트리메톡시실란 100부를 1시간에 걸쳐 일정한 속도로 적가하고 1시간 더 반응하도록 하였다. 냉각후 실리콘수지 G를 얻었다.100 parts of bisphenol A diglycidyl ether was added to a reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser, and heated at 150 ° C. Thereafter, 100 parts of γ-aminopropyltrimethoxysilane were added dropwise at a constant rate over 1 hour and allowed to react for another 1 hour. After cooling, a silicone resin G was obtained.

III. 멜라민 수지 함유 시스템III. Melamine Resin Containing System

[실시예 III-1]Example III-1

PLACCEL 308 70부, CYMEL 303 30부(Mitsui Toatsu Chemicals, Inc.에서 판매하는 멜라민수지) 및1-(4-메틸벤질)-4-시아노-피리디늄 p-도데실벤젠 술포네이트 2부를 완전히 혼합하였다. 혼합물을 주석판에 쏟고 140℃에서 소부하였다. 혼합물의 경화성과 저안정성은 표 III-1에 나타내었다.Completely mix 70 parts PLACCEL 308, 30 parts CYMEL 303 (melamine resin sold by Mitsui Toatsu Chemicals, Inc.) and 2 parts 1- (4-methylbenzyl) -4-cyano-pyridinium p-dodecylbenzene sulfonate It was. The mixture was poured onto a tin plate and baked at 140 ° C. Curability and low stability of the mixtures are shown in Table III-1.

[실시예 III-2 내지 III-16][Examples III-2 to III-16]

실시예 III-1과 마찬가지로 다음의 조성물을 경화성과 저장안정성에 대해 테스트하였다. 결과는 III-1에 나타내었다.The following compositions were tested for curability and storage stability as in Example III-1. The results are shown in III-1.

촉매 :catalyst :

[화학식 13][Formula 13]

[표 3]TABLE 3

1) Mitsui-Toatsu Chemicals, Inc.에서 판매하는 멜라민1) Melamine sold by Mitsui-Toatsu Chemicals, Inc.

[표 4]TABLE 4

1) MEK 마찰시험후의 필름 외관(100회 왕복)1) Film appearance after MEK friction test (100 round trips)

㉧ : 변화없음 ○ : 약간변화 △ : 회게됨 × : 용해됨㉧: No change ○: Slight change △: Grayed ×: Melted

2) 닫힌계에서 40℃로 2주동안 저장한후의 점도 증가2) Increased viscosity after 2 weeks storage at 40 ℃ in closed system

㉧ : 증가되지 않음 ○ : 약간 증가 △ : 증가 × : 겔화㉧: not increased ○: slightly increased △: increased ×: gelation

실시예 III-17 내지 III-21Examples III-17 to III-21

실시예 III-1과 마찬가지로 다음의 조성물을 경화가능성과 저장안정성에 대해 시험하였다. 결과는 표III-2에 나타내 었다.As in Example III-1, the following compositions were tested for curability and storage stability. The results are shown in Table III-2.

달리 표시하지 않으면 다음식의 촉매 :Unless otherwise indicated, catalysts of the following formula:

[화학식 14][Formula 14]

[표 5]TABLE 5

[표 6]TABLE 6

1) MEK 마찰시험 후의 필름 외관(100회 왕복)1) Film appearance after MEK friction test (100 round trips)

◎ : 변화없음; ○: 약간변화; △ : 희게됨 : ×: 용해됨◎: no change; ○: slight change; △: whitened: ×: dissolved

2) 닫힌계에서 40℃로 2주동안 저장한 후의 점도 증가2) Increased viscosity after 2 weeks storage at 40 ℃ in closed system

◎ : 변화 없음; ○ : 약간증가; △ : 증가; × : 겔화◎: no change; ○: slightly increased; Δ: increase; ×: gelation

IV. 알콕시실릴기 자기축합 또는 공축합 시드템IV. Alkoxysilyl group self-condensation or co-condensation systems

실시예 IV-1Example IV-1

아크릴수지 A 100부, 실리콘 수지 A 30.9부, 메탄올 5분 및 1-벤질-4-시아노피리디늄 p-도데실벤젠술포네이트 2.62부를 완전히 혼합하였다. 혼합물을 주석판에 쏟고 2시간동안 두었다가 140℃에서 30분동안 소부하였다. 혼합물의 경화가능성과 저장안정성은 표 IV-1에 나타내었다.100 parts of acrylic resin A, 30.9 parts of silicone resin A, 5 minutes of methanol and 2.62 parts of 1-benzyl-4-cyanopyridinium p-dodecylbenzenesulfonate were thoroughly mixed. The mixture was poured onto a tin plate and left for 2 hours before baking at 140 ° C. for 30 minutes. Curability and storage stability of the mixtures are shown in Table IV-1.

실시예 IV-2 내지 IV-20Examples IV-2 to IV-20

실시예 IV-1과 마찬가지로 다음 조성물을 경화가능과 저장안정성에 대해 시험하였다. 결과는 표 IV-1에 나타내었다.As in Example IV-1, the following compositions were tested for curability and storage stability. The results are shown in Table IV-1.

개시제 :Initiator:

[화학식 15][Formula 15]

[표 7]TABLE 7

[표 8]TABLE 8

1) MEK 마찰시험 후의 필름 외관(100회 왕복)1) Film appearance after MEK friction test (100 round trips)

◎ : 변화없음; ○: 약간변화;◎: no change; ○: slight change;

△ : 희게됨 : ×: 용해됨△: whitened: ×: dissolved

2) 닫힌계에서 40℃로 2주동안 저장한 후의 점도 증가2) Increased viscosity after 2 weeks storage at 40 ℃ in closed system

◎ : 변화 없음; ○ : 약간증가;◎: no change; ○: slightly increased;

△ : 증가; × : 겔화Δ: increase; ×: gelation

실시예 IV-21 내지 IV-34Examples IV-21 through IV-34

실시예 IV-1과 마찬가지로, 다음의 조성물을 경화가능성과 저장안정성예 대해 시험하였다. 결과는 표IV-2에 나타내었다.As in Example IV-1, the following compositions were tested for curability and storage stability examples. The results are shown in Table IV-2.

달리 표시하지 않으면 다음식의 촉매 :Unless otherwise indicated, catalysts of the following formula:

[화학식 16][Formula 16]

[표 9]TABLE 9

[표 10]TABLE 10

1) MEK 마찰시험후의 필름 외관(100회 왕복)1) Film appearance after MEK friction test (100 round trips)

◎ : 변화없음; ○: 약간변화;◎: no change; ○: slight change;

△ : 희게됨 : ×: 용해됨△: whitened: ×: dissolved

2) 닫힌계에서 40℃로 2주동안 저장한 후의 점도 증가2) Increased viscosity after 2 weeks storage at 40 ℃ in closed system

◎ : 변화 없음; ○ : 약간 증가;◎: no change; ○: slightly increased;

△ : 증가; × : 겔화Δ: increase; ×: gelation

Claims (1)

일반식 :General formula: 의 화합물(상기식에서, R1, R2, R3및 R6는 각각 수소, 할로겐, 알킬, 알콕시, 니트로, 아미노, 알킬아미노, 시아노, 알콕시카르보닐 또는 카바모일이고 ; R4와 R5는 각각 수소, 알킬 또는 할로겐이고; R10은 수소 또는 알킬이고 ; 이하의 화합물을 제외한다 : N-(p-니트로벤질) 피리디늄 벤젠술포네이트, N-(1-p-니트로페닐에틸) 피리디늄 벤젠술포네이트, N-(벤질) 피리디늄 벤젠술포네이트, N-(1-페닐에틸) 피리디늄 벤젠술포네이트, N- (p-메톡시벤질) 피리디늄 벤젠술포네이트 및 N-(벤질) 피리디늄 p-톨루엔술포네이트)Wherein R 1 , R 2 , R 3 and R 6 are each hydrogen, halogen, alkyl, alkoxy, nitro, amino, alkylamino, cyano, alkoxycarbonyl or carbamoyl; R 4 and R 5 Are each hydrogen, alkyl or halogen, R 10 is hydrogen or alkyl, except for the following compounds: N- (p-nitrobenzyl) pyridinium benzenesulfonate, N- (1-p-nitrophenylethyl) pyri Dinium benzenesulfonate, N- (benzyl) pyridinium benzenesulfonate, N- (1-phenylethyl) pyridinium benzenesulfonate, N- (p-methoxybenzyl) pyridinium benzenesulfonate and N- (benzyl) Pyridinium p-toluenesulfonate)
KR1019940029626A 1989-03-03 1994-11-11 Heat-latent curing catalyst KR950004701B1 (en)

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