TW201302837A - Curing agent composition for epoxy resin and thermosetting molding compound - Google Patents
Curing agent composition for epoxy resin and thermosetting molding compound Download PDFInfo
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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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
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- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
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- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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Abstract
Description
本發明係關於環氧樹脂用硬化劑組成物及熱硬化性成形材料。 The present invention relates to a hardener composition for an epoxy resin and a thermosetting forming material.
本發明係根據2011年4月11日在日本所提出申請的特願2011-087578號主張優先權，並將其內容爰引於本案中。 The present invention claims priority based on Japanese Patent Application No. 2011-087578, filed on Jan. 11, 2011, the content of which is incorporated herein.
電子材料領域中，有使用以含有酚樹脂的硬化劑組成物、環氧樹脂、及填充劑(填料)為主要成分的密封材(熱硬化性成形材料)。前述密封材係為保護半導體晶片免受諸如溫度、濕度、壓力等各種外部環境的影響而使用。 In the field of electronic materials, a sealing material (thermosetting molding material) containing a curing agent composition containing a phenol resin, an epoxy resin, and a filler (filler) as a main component is used. The foregoing sealing material is used to protect the semiconductor wafer from various external environments such as temperature, humidity, pressure, and the like.
現實下在密封材所使用的原料(例如：硬化劑組成物、環氧樹脂、填料等)中，有混入數百微米等級之微小金屬異物。 In reality, in the raw materials (for example, hardener composition, epoxy resin, filler, etc.) used for the sealing material, there are fine metal foreign matters of several hundred micrometers.
近年，隨電子零件的更進一步小型化、高機能化，正朝與IC晶片相連接的銲線間之窄寬化、銲線細線化演進。例如高機能的電子機器會將銲線間的間距距離細微化至50~100μm。 In recent years, with the further miniaturization and high performance of electronic components, the narrowing of the bonding wires and the thinning of the bonding wires are progressing toward the IC chips. For example, a high-performance electronic device will fine-tune the distance between the bonding wires to 50 to 100 μm.
當此種電子機器係使用前述密封材的情況，會造成電子機器的錯誤動作風險提高。針對此情形，便要求不要含有50μm以上大小之金屬異物的密封材用原料。又，渴求能通過更細篩孔過濾器且熔融黏度較低的硬化劑組成物。就 避免因銲線的細線化，而導致密封材成形時發生銲線斷裂、相鄰接銲線彼此間的接觸等觀點，亦是要求熔融黏度較低的硬化劑組成物。 When such an electronic device uses the aforementioned sealing material, the risk of malfunction of the electronic device is increased. In this case, a raw material for a sealing material containing no metal foreign matter having a size of 50 μm or more is required. Further, it is desired to pass through a finer mesh filter and to melt the composition of the hardener having a lower viscosity. on It is also a hardener composition which requires a low melt viscosity due to the fact that the wire is thinned and the wire is broken during the formation of the sealing material and the adjacent bonding wires are in contact with each other.
為獲得熔融黏度較低之硬化劑組成物的技術，已知有以下文獻所記載的技術。使用分子內的交聯基係具有伸烷型聚合體單元、與酚．甲醛聚合體單元，且藉由將二者的聚合度比設在特定範圍，而獲得低軟化點酚醛型酚樹脂的技術(專利文獻1)。 In order to obtain a composition of a hardener composition having a low melt viscosity, the techniques described in the following documents are known. The intramolecular crosslinking system has an alkylene type polymer unit and a phenol. A technique of obtaining a low-softening point novolac type phenol resin by setting a polymerization degree ratio of both of them to a specific range (Patent Document 1).
在保持硬化物耐熱性的情況下，降低熔融黏度之目的下，有採用樹脂中的雙核體含有率為10重量%以下，且四核體含有率為5~15重量%、三核體含有率為四核體含有率之2~19倍的酚醛型酚樹脂技術(專利文獻2)。 When the heat resistance of the cured product is maintained, the content of the dinuclear compound in the resin is 10% by weight or less, and the tetranuclear content is 5 to 15% by weight, and the trinuclear content is contained for the purpose of lowering the melt viscosity. A novolac type phenol resin technique having a tetranuclear content of 2 to 19 times (Patent Document 2).
[專利文獻1]國際公開第07/026553號手冊 [Patent Document 1] International Publication No. 07/026553
[專利文獻2]日本專利特開平6-100665號公報 [Patent Document 2] Japanese Patent Laid-Open No. Hei 6-100665
但是，硬化劑組成物係就秤量、操作等製造上的作業性較佳之觀點，通常係使用經加工為珠狀的成形品。 However, the hardener composition is usually a molded article processed into a bead shape from the viewpoint of satisfactory workability in manufacturing such as weighing and handling.
但是，當將專利文獻1所記載的低軟化點酚醛型酚樹脂使用為硬化劑時，會有抗黏性差、作業性不佳的問題。此現象係當將前述含有酚醛型酚樹脂的硬化劑組成物、環氧 樹脂、及填料等進行混合時，因為前述硬化劑組成物的強烈黏瘩，因而會導致該等混合物附著於混練機、成形機上，造成容易殘留髒汙，因而必需每次生產均施行清洗。又，亦會有熱硬化性成形材料的耐熱性降低之問題。 However, when the low-softening point novolac type phenol resin described in Patent Document 1 is used as a curing agent, there is a problem that the anti-stick property is poor and the workability is poor. This phenomenon is when the aforementioned hardener composition containing a novolac type phenol resin, epoxy When the resin, the filler, and the like are mixed, the hardener composition is strongly viscous, so that the mixture adheres to the kneader or the molding machine, and the residue is easily left. Therefore, it is necessary to perform cleaning every time. Further, there is a problem that the heat resistance of the thermosetting molding material is lowered.
專利文獻2所記載的酚醛型酚樹脂係不會有毛邊發生、且作業性良好。但是，硬化劑組成物的軟化點會提高，較難調製150℃下的熔融黏度低於100mPa．s(1P)之硬化劑組成物，頗難獲得填充劑(填料)含有率較高之密封材。 The novolac type phenol resin described in Patent Document 2 does not have burrs and has good workability. However, the softening point of the hardener composition will increase, and it is difficult to prepare the melt viscosity at 150 ° C below 100 mPa. The hardener composition of s (1P) is difficult to obtain a sealing material having a high filler (filler) content.
本發明係有鑑於上述實情而完成，課題在於提供：熔融黏度較低、且抗黏性良好的環氧樹脂用硬化劑組成物、以及耐熱性優異的熱硬化性成形材料。 The present invention has been made in view of the above circumstances, and it is an object of the invention to provide a curing agent composition for an epoxy resin having a low melt viscosity and excellent anti-adhesive property, and a thermosetting molding material excellent in heat resistance.
為解決上述課題，本發明係採用以下的構成。 In order to solve the above problems, the present invention adopts the following configuration.
本發明的環氧樹脂用硬化劑組成物，其特徵在於含有：質量平均分子量(Mw)為320~370，且分散度[質量平均分子量(以下簡稱「Mw」)/數量平均分子量(以下簡稱「Mn」)]為1.02~1.05的酚醛型酚樹脂。 The hardener composition for an epoxy resin according to the present invention is characterized by comprising a mass average molecular weight (Mw) of 320 to 370 and a degree of dispersion [mass average molecular weight (hereinafter referred to as "Mw") / number average molecular weight (hereinafter referred to as " Mn")] is a phenolic phenol resin of 1.02 to 1.05.
本發明的環氧樹脂用硬化劑組成物中，前述酚醛型酚樹脂較佳係在凝膠滲透色層分析儀(以下簡稱「GPC」)的色層分析圖中，尖峰面積比為雙核體：0.5~6面積%、三核體：72~82面積%、四核體以上：16~26面積%。 In the hardener composition for an epoxy resin according to the present invention, the novolac type phenol resin is preferably in a chromatogram of a gel permeation chromatography analyzer (hereinafter referred to as "GPC"), and the peak area ratio is a dinuclear body: 0.5~6 area%, trinuclear body: 72~82 area%, tetranuclear or more: 16~26 area%.
即，本發明係具有以下的態樣。 That is, the present invention has the following aspects.
<1>一種環氧樹脂用硬化劑組成物，其特徵在於含有Mw為320~370且分散度(Mw/Mn)為1.02~1.05之酚醛型酚樹 脂；<2>如前述<1>所記載的環氧樹脂用硬化劑組成物，其中前述酚醛型酚樹脂具有雙核體、三核體、及具有4或5以上核數的核體，前述酚醛型酚樹脂的GPC色層分析圖中，前述核體的尖峰面積佔總尖峰面積合計的比例係以下所示的值：雙核體的尖峰面積比為0.5~6面積%、三核體的尖峰面積比為72~82面積%、且具有4或5以上核數的核體之尖峰面積比為16~26面積%；<3>一種熱硬化性成形材料，特徵在於含有：前述<1>所記載的環氧樹脂用硬化劑組成物、與環氧樹脂；<4>如前述<3>所記載的熱硬化性成形材料，其係更進一步含有填充劑；<5>一種環氧樹脂用硬化劑組成物之製造方法，其特徵在於包括以下的步驟(i)及步驟(ii)；(i)在鹼性觸媒存在下，使酚類與醛類在反應溫度-5~20℃下進行反應的步驟；(ii)在依步驟(i)所獲得之反應液中，相對於前述步驟(i)的酚類1莫耳，添加5~15莫耳的酚類之後，再添加酸性觸媒使更進一步進行反應的步驟；<6>如前述<5>所記載的環氧樹脂用硬化劑組成物之製造方法，其中前述步驟(ii)中，添加酸性觸媒時的反應液溫度係-5~5℃；及<7>如前述<5>或<6>所記載的環氧樹脂用硬化 劑組成物之製造方法，其係在前述步驟(ii)中，經添加酸性觸媒後，加溫至20~80℃而使進行反應。 <1> A hardener composition for an epoxy resin, which comprises a phenolic phenolic tree having a Mw of 320 to 370 and a degree of dispersion (Mw/Mn) of 1.02 to 1.05. The hardener composition for epoxy resins according to the above-mentioned <1>, wherein the novolak-type phenol resin has a dinuclear body, a trinuclear body, and a core body having a core number of 4 or more, and the phenolic phenol. In the GPC color layer analysis chart of the phenol resin, the ratio of the peak area of the nucleus to the total peak area is the value shown below: the peak area ratio of the dinuclear body is 0.5 to 6 area%, and the peak area of the trinuclear body The peak area ratio of the core body having a ratio of 72 to 82% by area and having a number of cores of 4 or more is 16 to 26 area%; <3> A thermosetting forming material characterized by containing the above-mentioned <1> (4) The thermosetting molding material according to the above <3>, further comprising a filler; <5> a curing agent for an epoxy resin; The method for producing a composition, comprising the following steps (i) and (ii); (i) reacting a phenol with an aldehyde at a reaction temperature of -5 to 20 ° C in the presence of a basic catalyst (ii) in the reaction liquid obtained in the step (i), adding 5 to 15 moles relative to the phenolic 1 molar of the aforementioned step (i) The method of producing a hardener composition for an epoxy resin according to the above <5>, wherein the step (ii), The temperature of the reaction solution when the acid catalyst is added is -5 to 5 ° C; and <7> is the hardening of the epoxy resin as described in <5> or <6> above. In the method for producing a composition, in the step (ii), after adding an acidic catalyst, the reaction is carried out by heating to 20 to 80 °C.
本發明的雙核體、三核體、及具有4或5以上核數的核體之尖峰面積比、Mw、及Mn，係可依照以下的順序計算出。 The peak area ratio, Mw, and Mn of the dinuclear body, the trinuclear body, and the core body having 4 or more nuclei of the present invention can be calculated in the following order.
(1)雙核體、三核體、及具有4或5以上核數的核體之尖峰面積比計算方法：利用分取GPC分取出各個尖峰所對應的核體，再利用氣相色層分析質譜儀(以下簡稱「GC-MS」)測定其分層，並執行各尖峰所對應核體的鑑定。 (1) Calculation method of peak area ratio of dinuclear body, trinuclear body, and nuclear body having 4 or more core numbers: The core body corresponding to each peak is taken out by using GPC, and the gas chromatograph is used for mass spectrometry. The instrument (hereinafter referred to as "GC-MS") measures the stratification and performs identification of the nucleus corresponding to each peak.
[尖峰面積比(%)]=對象核體的尖峰面積/總尖峰面積 [spike area ratio (%)] = peak area of the target nucleus / total peak area
(2)Mw、Mn之計算方法：使由(1)所求得尖峰面積比與各核體分子量，對應於以下計算式，而計算出Mw、Mn。 (2) Calculation method of Mw and Mn: Mw and Mn were calculated by calculating the peak area ratio obtained by (1) and the molecular weight of each core, in accordance with the following calculation formula.
Mw={Σ(各核體分子量2×各核體尖峰面積%)}/{Σ(各核體分子量×各核體尖峰面積%)} Mw={Σ(molecular weight of each nucleus 2 ×% of each nucleus peak area)}/{Σ(molecular weight of each nucleus×% of peak area of each nucleus)}
Mn={Σ(各核體分子量×各核體尖峰面積%)}/(Σ各核體面積%) Mn={Σ(molecular weight of each core ×% of peak area of each nucleus)}/(% of each core area)
本發明中所謂「核體」係指具有在苯環上至少具1個羥基之構造單元(以下稱「酚單元」)的有機化合物。所以，本發明中所謂「雙核體」係指分子內具有2個酚單元的有機化合物。本發明中所謂「三核體」係指分子內具有3個酚單元的有機化合物；所謂「四核體」係指分子內具有4個酚單元的有機化合物。又，所謂「具有5以上核數的核體」係指分子內具有5個以上、較佳係5~15個酚單元的有機化合物。此處所謂「酚單元」中的「酚」係採用在苯環上具有至少1個 羥基的構造統稱，在苯環上亦可具有羥基以外的取代基，例如：低級烷基、低級環烷基、低級烷氧基、低級醯基、芳基、苯氧基等。 In the present invention, the "nuclear body" means an organic compound having a structural unit having at least one hydroxyl group on a benzene ring (hereinafter referred to as "phenol unit"). Therefore, the term "dual core" as used in the present invention means an organic compound having two phenol units in its molecule. In the present invention, the "trinuclear body" means an organic compound having three phenolic units in the molecule; and the "tetranuclear body" means an organic compound having four phenolic units in the molecule. In addition, the "nuclear body having a nuclear number of 5 or more" means an organic compound having 5 or more, preferably 5 to 15 phenolic units in the molecule. Here, the "phenol" in the "phenol unit" has at least one on the benzene ring. The structure of the hydroxyl group is generally referred to as a substituent other than a hydroxyl group on the benzene ring, for example, a lower alkyl group, a lower cycloalkyl group, a lower alkoxy group, a lower alkyl group, an aryl group, a phenoxy group or the like.
低級烷基可舉例如碳數1~9的直鏈或分支鏈烷基。低級環烷基係可舉例如碳數3~5的環烷基。低級烷氧基可舉例如碳數1~7的直鏈或分支鏈烷氧基。低級醯基可舉例如碳數2~6的直鏈或分支鏈醯基。芳基可舉例如碳數6~10的芳基，亦可被諸如碳數1~3的烷基、羥基等所取代。 The lower alkyl group may, for example, be a linear or branched alkyl group having 1 to 9 carbon atoms. The lower cycloalkyl group may, for example, be a cycloalkyl group having 3 to 5 carbon atoms. The lower alkoxy group may, for example, be a linear or branched alkoxy group having 1 to 7 carbon atoms. The lower sulfhydryl group may, for example, be a linear or branched fluorenyl group having 2 to 6 carbon atoms. The aryl group may, for example, be an aryl group having 6 to 10 carbon atoms, or may be substituted with an alkyl group having 1 to 3 carbon atoms, a hydroxyl group or the like.
本發明的酚醛型酚樹脂中，雙核體的較佳分子量係200~352、更佳係200。 In the novolac type phenol resin of the present invention, the preferred molecular weight of the dinuclear body is 200 to 352, more preferably 200.
三核體的較佳分子量係306~534、更佳係306。 The preferred molecular weight of the trinuclear body is 306 to 534, more preferably 306.
四核體的較佳分子量係412~716、更佳係412。 The preferred molecular weight of the tetranuclear body is 412 to 716, more preferably 412.
具有5以上核數的核體之較佳分子量係518~2718、更佳係518~1578。 The preferred molecular weight of the core having 5 or more core numbers is 518 to 2718, more preferably 518 to 1578.
本發明係提供熔融黏度低、且抗黏性良好的環氧樹脂用硬化劑組成物、及耐熱性優異的熱硬化性成形材料。 The present invention provides a hardener composition for an epoxy resin having low melt viscosity and good anti-sticking property, and a thermosetting molding material excellent in heat resistance.
第1圖係實施例1所獲得酚醛型酚樹脂(硬化劑組成物A)的GPC色層分析圖。 Fig. 1 is a GPC color layer analysis chart of the novolac type phenol resin (hardener composition A) obtained in Example 1.
本發明的環氧樹脂用硬化劑組成物係含有Mw為 320~370、且分散度(Mw/Mn)(以下簡稱「分散度」)為1.02~1.05的酚醛型酚樹脂。 The hardener composition for epoxy resin of the present invention contains Mw as The phenolic phenol resin having a degree of dispersion (Mw/Mn) (hereinafter referred to as "dispersion") of 1.02 to 1.05 is 320 to 370.
本發明的酚醛型酚樹脂之Mw係320~370、較佳係340~360。 The Mw of the novolac type phenol resin of the present invention is 320 to 370, preferably 340 to 360.
酚醛型酚樹脂的Mw若在上限值以下亦即370以下，軟化點便會降低，熔融黏度會降低，熱硬化性成形材料的流動性會提高而容易成形。 When the Mw of the novolac type phenol resin is 370 or less below the upper limit, the softening point is lowered, the melt viscosity is lowered, and the fluidity of the thermosetting molding material is improved to facilitate molding.
另一方面，酚醛型酚樹脂的Mw若在下限值以上亦即320以上，則軟化點會過度降低、抗黏性會變良好，能提升硬化劑組成物與環氧樹脂進行混練際的作業性。 On the other hand, when the Mw of the novolac type phenol resin is at least the lower limit value, that is, 320 or more, the softening point is excessively lowered, the anti-stick property is improved, and the workability of the hardener composition and the epoxy resin during mixing can be improved. .
酚醛型酚樹脂的分散度係1.02~1.05、較佳係1.03~1.05。 The dispersity of the novolac type phenol resin is 1.02 to 1.05, preferably 1.03 to 1.05.
即便將酚醛型酚樹脂的Mw設為下限值以上亦即320以上，但若分散度過大亦即大於1.05，仍無法獲得充分的抗黏性。另一方面，若將分散度設為上限值以下亦即1.05以下，便可獲得充分的抗黏性。理由可認為係因酚樹脂中的低分子量成分(雙核體)會變少所致。若低分子量成分(雙核體)變少，即GPC色層分析圖中，相對於總尖峰面積合計，若雙核體尖峰面積比在6面積%以下，便會抑制硬化後的熱硬化性成形材料產生毛邊，且亦會提高耐熱性。又，因為高分子量成分(具有4或5以上核數的核體)亦會減少，即GPC色層分析圖中，相對於總尖峰面積合計，具有4或5以上核數的核體之尖峰面積比在26面積%以下，便不易產生硬化不良，俾不易生成未硬化物。又，會提高熱硬化性成形材料的熱安定性。 When the Mw of the novolac type phenol resin is set to be equal to or higher than the lower limit value, that is, 320 or more, if the degree of dispersion is too large, that is, more than 1.05, sufficient anti-sticking property cannot be obtained. On the other hand, when the degree of dispersion is less than or equal to the upper limit, that is, 1.05 or less, sufficient anti-sticking property can be obtained. The reason is considered to be that the low molecular weight component (dual core) in the phenol resin is reduced. When the low molecular weight component (dinuclear body) is small, that is, in the GPC chromatogram analysis, if the ratio of the peak area of the dinuclear body is 6 area% or less in total, the thermosetting material after hardening is suppressed. Raw edges, and will also improve heat resistance. Further, since the high molecular weight component (nuclear body having a core number of 4 or more) is also reduced, that is, the peak area of the core body having a core number of 4 or more with respect to the total peak area in the GPC chromatogram analysis chart. When the ratio is 26% by area or less, it is less likely to cause hardening failure, and it is difficult to form an uncured material. Moreover, the thermal stability of the thermosetting forming material is improved.
本發明另一態樣，若將酚醛型酚樹脂的分散度設為下限值以上亦即1.02以上，便會某程度含有低分子量成分(雙核體)，即GPC色層分析圖中，相對於總尖峰面積合計，雙核體的尖峰面積比會成為0.5面積%以上，而降低熔融黏度。又，熱硬化性成形材料的流動性提高，俾容易成形。藉由亦某程度含有高分子量成分(具有4或5以上核數的核體)，即GPC色層分析圖中，相對於總尖峰面積合計，具有4或5以上核數的核體之尖峰面積比會成為16面積%以上，而提高耐熱性。 According to another aspect of the present invention, when the dispersity of the novolac type phenol resin is at least the lower limit value, that is, 1.02 or more, the low molecular weight component (dual core) is contained to some extent, that is, in the GPC chromatogram analysis, In total of the total peak area, the peak area ratio of the dinuclear body becomes 0.5 area% or more, and the melt viscosity is lowered. Moreover, the fluidity of the thermosetting molding material is improved, and the crucible is easily formed. By including a high molecular weight component (a nucleus having a nuclear number of 4 or more), that is, a peak area of a nucleus having a nuclear number of 4 or more with respect to the total peak area in a GPC chromatogram. The ratio is 16 area% or more, and the heat resistance is improved.
酚醛型酚樹脂係可使用1種以上由在酸性觸媒存在下，使酚類與醛類進行反應而獲得者。 The phenolic phenol resin can be obtained by reacting one or more kinds of phenols with an aldehyde in the presence of an acidic catalyst.
前述酚類係只要屬於在酸性觸媒存在下，使與醛類進行反應而獲得的酚醛型酚樹脂便可，可舉例如：酚、鄰甲酚、間甲酚、對甲酚、2,3-二甲酚、3,5-二甲酚、間乙酚、間丙酚、間丁酚、對丁酚、鄰丁酚、間苯二酚、氫醌、兒茶酚、3-甲氧基酚、4-甲氧基酚、3-甲基兒茶酚、4-甲基兒茶酚、甲基氫醌、2-甲基間苯二酚、2,3-二甲基氫醌、2,5-二甲基間苯二酚、2-乙氧基酚、4-乙氧基酚、4-乙基間苯二酚、3-乙氧基-4-甲氧基酚、2-丙烯基酚、2-異丙基酚、3-異丙基酚、4-異丙基酚、3,4,5-三甲基酚、2-異丙氧基酚、4-丙氧基酚、2-烯丙基酚、3,4,5-三甲氧基酚、4-異丙基-3-甲基酚、五倍子酚、間苯三酚、1,2,4-苯三醇、5-異丙基-3-甲基酚、4-丁氧基酚、4-第三丁基兒茶酚、第三丁基氫醌、4-第三戊基酚、2-第三丁基-5-甲基酚、2-苯基酚、3-苯基酚、 4-苯基酚、3-苯氧基酚、4-苯氧基酚、4-己氧基酚、4-己醯基間苯二酚、3,5-二異丙基兒茶酚、4-己基間苯二酚、4-庚氧基酚、3,5-二第三丁酚、3,5-二第三丁基兒茶酚、2,5-二第三丁基氫醌、二第二丁酚、4-異丙苯基酚、壬酚、2-環戊基酚、4-環戊基酚、雙酚A、雙酚F等。 The phenolic type may be a phenolic phenol resin obtained by reacting with an aldehyde in the presence of an acidic catalyst, and examples thereof include phenol, o-cresol, m-cresol, p-cresol, and 2,3. -xylenol, 3,5-xylenol, m-cresol, m-cresol, m-butylphenol, p-butyrrol, o-butylphenol, resorcinol, hydroquinone, catechol, 3-methoxy Phenol, 4-methoxyphenol, 3-methylcatechol, 4-methylcatechol, methylhydroquinone, 2-methylresorcinol, 2,3-dimethylhydroquinone, 2 , 5-dimethylresorcinol, 2-ethoxyphenol, 4-ethoxyphenol, 4-ethylresorcinol, 3-ethoxy-4-methoxyphenol, 2-propene Phenol, 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, 3,4,5-trimethylphenol, 2-isopropoxyphenol, 4-propoxyphenol, 2-allyl phenol, 3,4,5-trimethoxy phenol, 4-isopropyl-3-methyl phenol, gallic phenol, phloroglucinol, 1,2,4-benzenetriol, 5- Isopropyl-3-methylphenol, 4-butoxyphenol, 4-tert-butylcatechol, tert-butylhydroquinone, 4-third amylphenol, 2-tert-butyl-5 -methylphenol, 2-phenylphenol, 3-phenylphenol, 4-phenylphenol, 3-phenoxyphenol, 4-phenoxyphenol, 4-hexyloxyphenol, 4-hexyl resorcinol, 3,5-diisopropylcatechol, 4 -hexylresorcinol, 4-heptyloxyphenol, 3,5-di-tert-butylphenol, 3,5-di-t-butylcatechol, 2,5-di-t-butylhydroquinone, two Second butanol, 4-cumylphenol, indophenol, 2-cyclopentylphenol, 4-cyclopentylphenol, bisphenol A, bisphenol F, and the like.
其中，較佳係酚、鄰甲酚、間甲酚、對甲酚、雙酚A、2,3-二甲酚、3,5-二甲酚、間丁酚、對丁酚、鄰丁酚、4-苯基酚、間苯二酚，更佳係酚。前述酚類係可單獨使用一種、亦可併用二種以上。 Among them, preferred are phenol, o-cresol, m-cresol, p-cresol, bisphenol A, 2,3-xylenol, 3,5-xylenol, m-butylphenol, p-butylphenol, o-butylphenol , 4-phenylphenol, resorcinol, more preferably phenol. These phenols may be used alone or in combination of two or more.
前述醛類係可舉例如：甲醛、三烷、糠醛、聚甲醛、苯甲醛、甲基半甲縮醛、乙基半甲縮醛、丙基半甲縮醛、水楊醛、丁基半甲縮醛、苯基半甲縮醛、乙醛、丙醛、苯乙醛、α-苯基丙醛、β-苯基丙醛、鄰羥基苯甲醛、間羥基苯甲醛、對羥基苯甲醛、鄰氯苯甲醛、鄰硝化苯甲醛、間硝化苯甲醛、對硝化苯甲醛、鄰甲基苯甲醛、間甲基苯甲醛、對甲基苯甲醛、對乙基苯甲醛、對正丁基苯甲醛等。 The aldehydes may be, for example, formaldehyde or three. Alkane, furfural, polyoxymethylene, benzaldehyde, methyl hemiacetal, ethyl hemiacetal, propyl hemiacetal, salicylaldehyde, butyl hemiacetal, phenyl hemiacetal, B Aldehyde, propionaldehyde, phenylacetaldehyde, α-phenylpropanal, β-phenylpropanal, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-chlorobenzaldehyde, ozonated benzaldehyde, metanitration Benzaldehyde, p-nitroaniline, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, p-n-butylbenzaldehyde, and the like.
其中，較佳係甲醛、聚甲醛、糠醛、苯甲醛、水楊醛，更佳係甲醛、聚甲醛。前述醛類係可單獨使用一種、亦可併用二種以上。 Among them, formaldehyde, polyoxymethylene, furfural, benzaldehyde, salicylaldehyde are preferred, and formaldehyde and polyoxymethylene are more preferred. These aldehydes may be used alone or in combination of two or more.
前述酸性觸媒係可舉例如：鹽酸、硫酸、磷酸、甲酸、醋酸、草酸、丁酸、乳酸、苯磺酸、對甲苯磺酸、硼酸；或者諸如氯化鋅或醋酸鋅等與金屬的鹽等等。前述酸性觸媒係可單獨使用一種、亦可併用二種以上。 The acidic catalyst may, for example, be hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, oxalic acid, butyric acid, lactic acid, benzenesulfonic acid, p-toluenesulfonic acid or boric acid; or a salt with a metal such as zinc chloride or zinc acetate. and many more. These acidic catalysts may be used alone or in combination of two or more.
將酚醛型酚樹脂的Mw與分散度控制於既定範圍亦即 Mw為320~370、且分散度為1.02~1.05的方法，係就較容易將Mw與分散度控制於既定範圍的觀點，較佳係調整酚醛型酚樹脂中所含雙核體、三核體、以及具有4或5以上核數之核體的含有比例之方法。 Controlling the Mw and dispersion of the novolac type phenol resin to a predetermined range, that is, A method in which the Mw is 320 to 370 and the degree of dispersion is 1.02 to 1.05 is that it is easier to control the Mw and the dispersion to a predetermined range, and it is preferred to adjust the dinuclear body, the trinuclear body, and the dinuclear body contained in the novolac type phenol resin. And a method of containing a ratio of a core body having a core number of 4 or more.
具有既定範圍Mw與分散度的酚醛型酚樹脂，係就容易獲得例如熱硬化性、成形性等優異硬化物特性的觀點，較佳係以單一多核體成分為主成分，且分散度較小者即較佳係在GPC總尖峰面積合計中，三核體的尖峰面積比佔有72~82面積%，且分散度為1.02~1.05的分散度較小者。 The novolac type phenol resin having a predetermined range Mw and a degree of dispersion is excellent in properties such as thermosetting properties and moldability, and is preferably a single polynuclear component as a main component and having a small dispersion. That is to say, in the total GPC total peak area, the peak area ratio of the trinuclear body is 72 to 82 area%, and the dispersion degree is 1.02 to 1.05.
再者，為降低熔融黏度，Mw最好更低。此種酚醛型酚樹脂最好係以三核體為主成分，且分散度較小者。 Furthermore, in order to lower the melt viscosity, Mw is preferably lower. The phenolic phenol resin is preferably a trinuclear component and has a small dispersion.
藉由以三核體為主成分，因為可輕易形成緻密的聚合物網狀結構，因而較容易獲得優異的熱硬化性。又，藉由設為分散度較小(分子量分佈呈單分散化)，便不易因低分子量成分(即雙核體)而生成的黏合，且會抑制因高分子量成分亦即具有4或5以上核數的核體所造成的熔融黏度增加，所以可輕易地獲得優異成形性。 By using a trinuclear body as a main component, since a dense polymer network structure can be easily formed, it is easy to obtain excellent thermosetting property. Further, when the degree of dispersion is small (the molecular weight distribution is monodispersed), adhesion due to a low molecular weight component (i.e., a dinuclear body) is less likely to occur, and a core having 4 or more cores due to a high molecular weight component is suppressed. The melt viscosity of the number of core bodies is increased, so that excellent formability can be easily obtained.
前述酚醛型酚樹脂中，更具體而言係在GPC色層分析圖中，相對於總尖峰面積合計，雙核體的尖峰面積比較佳為0.5~6面積%、更佳為0.5~5面積%。 In the above-mentioned novolac type phenol resin, more specifically, in the GPC chromatogram analysis, the peak area of the dinuclear body is preferably 0.5 to 6 area%, more preferably 0.5 to 5 area%, based on the total peak area.
相對於總尖峰面積合計，具有4或5以上核數的核體之尖峰面積比較佳係16~26面積%、更佳係18~24面積%。其中，相對於總尖峰面積合計，四核體的尖峰面積比較佳係12~26面積%、更佳係15~24面積%。當雙核體、與具有4或5 以上核數的核體設為適當的尖峰面積比，即雙核體、與具有4或5以上核數的核體之尖峰面積比係在上述所示數值範圍內之時，三核體的尖峰面積比係相對於總尖峰面積合計，較佳為72~82面積%、更佳為74~80面積%。 The peak area of the core body having a core number of 4 or more is preferably 16 to 26 area%, more preferably 18 to 24 area%, based on the total peak area. Among them, the peak area of the tetranuclear body is preferably 12 to 26 area%, and more preferably 15 to 24 area%, relative to the total peak area. When dual-nuclear, with 4 or 5 The nucleus of the above nucleus is set to an appropriate peak area ratio, that is, the peak area ratio of the dinuclear body and the nucleus having a nucleus having 4 or more nucleus numbers within the above numerical range, the peak area of the trinuclear body The ratio is preferably 72 to 82 area%, more preferably 74 to 80 area%, based on the total peak area.
若雙核體的尖峰面積比係低於較佳下限值亦即相對於總尖峰面積合計，低於0.5面積%，則熔融黏度會提高，成形加工性變差。另一方面，若雙核體的尖峰面積比超過較佳上限值亦即相對於總尖峰面積合計，超過6面積%，則抗黏性會變差，且在施行硬化時容易發生毛邊。相對於總尖峰面積合計，若雙核體的尖峰面積比為0.5~6面積%，則熔融黏度較低、成形加工性佳。且，抗黏性良好，在施行硬化時能抑制毛邊產生。 When the peak area ratio of the binuclear body is less than the preferred lower limit value, that is, the total area of the peak area is less than 0.5 area%, the melt viscosity is improved and the formability is deteriorated. On the other hand, if the peak area ratio of the binuclear body exceeds the preferable upper limit value, that is, the total area of the peak area is more than 6 area%, the anti-stick property is deteriorated, and burrs are likely to occur at the time of hardening. When the peak area ratio of the binuclear body is 0.5 to 6 area% in total, the melt viscosity is low and the formability is good. Moreover, the anti-adhesive property is good, and the generation of burrs can be suppressed when the curing is performed.
若具有4或5以上核數的核體之尖峰面積比係低於較佳下限值亦即相對於總尖峰面積合計，低於16面積%，則轉印成形時的轉矩會下降，較難獲得熱硬化性成形材料對模具的適度流動性。另一方面，若具有4或5以上核數的核體之尖峰面積比超過較佳上限值亦即相對於總尖峰面積合計，超過26面積%，則熔融黏度會提高、成形加工性會變差。相對於總尖峰面積比的合計，若具有4或5以上核數的核體之尖峰面積比為16~26面積%，則熔融黏度降低、成形加工性佳。且，轉印成形時的轉矩容易提高、可獲得熱硬化性成形材料對模具的適度流動性。 If the peak area ratio of the core body having 4 or more core numbers is lower than the lower limit value, that is, the total area of the peak area is less than 16 area%, the torque at the time of transfer molding is lowered. It is difficult to obtain moderate fluidity of the thermosetting forming material to the mold. On the other hand, if the peak area ratio of the core body having 4 or more core numbers exceeds the preferred upper limit value, that is, the total area of the peak area is more than 26 area%, the melt viscosity is increased and the formability is changed. difference. When the ratio of the peak area of the core having 4 or more cores is 16 to 26 area%, the melt viscosity is lowered and the moldability is good. Further, the torque at the time of transfer molding is easily increased, and moderate fluidity of the thermosetting molding material to the mold can be obtained.
若四核體的尖峰面積比低於較佳下限值亦即相對於總尖峰面積合計，低於12面積%，則熔融黏度偏高、熱硬化 性成形材料的流動性降低。另一方面，若四核體的尖峰面積比超過較佳上限值亦即相對於總尖峰面積合計，超過26面積%，則熔融黏度會降低、成形加工性差。相對於總尖峰面積比的合計，若四核體的尖峰面積比為12~26面積%，則熔融黏度低、熱硬化性成形材料的流動性呈良好。且，成形加工性亦呈良好。 If the peak area ratio of the tetranuclear body is lower than the lower limit value, that is, the total area of the peak area is less than 12 area%, the melt viscosity is high and the heat is hardened. The fluidity of the shaped material is lowered. On the other hand, when the peak area ratio of the tetranuclear body exceeds the preferred upper limit value, that is, the total area of the peak area is more than 26 area%, the melt viscosity is lowered and the moldability is poor. When the ratio of the peak area of the tetranuclear body is 12 to 26 area%, the melt viscosity is low and the fluidity of the thermosetting material is good. Moreover, the formability is also good.
若三核體的尖峰面積比達較佳下限值以上，亦即相對於總尖峰面積合計，在72面積%以上，便可圖熔融黏度降低化與抗黏性提升。另一方面，若三核體的尖峰面積比在較佳上限值以下亦即相對於總尖峰面積合計，在82面積%以下，則適度含有雙核體與具有4或5以上核數的核體，除熔融黏度與抗黏性之外，尚可提升熱硬化性成形材料的耐熱性。且，亦能提升諸如成形加工性、難燃性等其他的一般特性。 When the ratio of the peak area of the trinuclear body is more than the lower limit value, that is, the total area of the peak area is more than 72 area%, the viscosity reduction and the anti-adhesion property can be improved. On the other hand, if the peak area ratio of the trinuclear body is equal to or less than the upper limit of the preferred upper limit, that is, the total area of the peak area is 82% or less, the dinuclear body and the core body having a core number of 4 or more are appropriately contained. In addition to the melt viscosity and the anti-adhesive property, the heat resistance of the thermosetting forming material can be improved. Moreover, other general characteristics such as moldability and flame retardancy can be improved.
本發明的酚醛型酚樹脂可藉由特徵為包括以下的步驟(i)及步驟(ii)的環氧樹脂用硬化劑組成物之製造方法等，進行製造。 The novolak type phenol resin of the present invention can be produced by a method for producing a curing agent composition for an epoxy resin comprising the following steps (i) and (ii).
步驟(i)：在鹼性觸媒存在下，使酚類與醛類在反應溫度-5~20℃下進行反應的步驟。 Step (i): a step of reacting a phenol with an aldehyde at a reaction temperature of -5 to 20 ° C in the presence of a basic catalyst.
步驟(ii)：在由步驟(i)所獲得反應液中，相對於前述步驟(i)的酚類1莫耳添加5~15莫耳的酚類之後，再添加酸性觸媒，使更進一步進行反應的步驟。 Step (ii): after adding 5 to 15 moles of phenols to the phenol 1 molar of the above step (i) in the reaction liquid obtained in the step (i), adding an acid catalyst to further The step of carrying out the reaction.
步驟(i)：首先，使前述酚類與前述醛類，在鹼性觸媒存在下進 行反應。 Step (i): First, the phenol and the aldehyde are introduced in the presence of a basic catalyst Reaction.
酚類與醛類的混合比例係相對於酚類1莫耳，醛類較佳為1.5~2.5莫耳、更佳為1.8~2.2莫耳、特佳為2.0~2.2莫耳。若醛類的混合比例低於較佳下限值亦即低於1.5莫耳，則雙核體容易增加。另一方面，若超過較佳上限值亦即超過2.5莫耳，則具有4或5以上核數之核體的高分子量成分容易增加。相對於酚類1莫耳，若所混合醛類的量為1.5~2.5莫耳，便可抑制雙核體、以及具有4或5以上核數的核體增加。 The mixing ratio of the phenols to the aldehydes is preferably from 1.5 to 2.5 moles, more preferably from 1.8 to 2.2 moles, and particularly preferably from 2.0 to 2.2 moles, relative to the phenolic moles. If the mixing ratio of the aldehydes is less than the lower limit of the lower limit, that is, less than 1.5 moles, the dinuclear body is liable to increase. On the other hand, when it exceeds the preferable upper limit, that is, more than 2.5 mol, the high molecular weight component of the core body having a core number of 4 or more is likely to increase. With respect to the phenolic 1 molar, if the amount of the mixed aldehyde is 1.5 to 2.5 moles, the increase in the dinuclear body and the nucleus having a nuclear number of 4 or more can be suppressed.
相對於酚類1莫耳，鹼性觸媒的使用量較佳係0.7~1.3莫耳、更佳係0.9~1.1莫耳。若鹼性觸媒的使用量低於較佳下限值亦即低於0.7莫耳，則較容易殘留未反應成分。另一方面，若超過較佳上限值亦即超過1.3莫耳，則發熱溫度會提高、容易高分子量化。相對於酚類1莫耳，若鹼性觸媒的使用量為0.7~1.3莫耳，便不會殘留未反應成分，並可抑制高分子量化。且，能抑制反應時的發熱。 The amount of the alkaline catalyst used is preferably 0.7 to 1.3 moles, more preferably 0.9 to 1.1 moles, relative to the phenolic mole. If the amount of the alkaline catalyst used is less than the lower limit, that is, less than 0.7 mole, the unreacted component is more likely to remain. On the other hand, if it exceeds the preferable upper limit, that is, more than 1.3 mol, the heat generation temperature is increased and the polymer concentration is easy. When the amount of the basic catalyst used is 0.7 to 1.3 mol with respect to the phenolic 1 molar, no unreacted components remain, and the high molecular weight can be suppressed. Further, heat generation during the reaction can be suppressed.
鹼性觸媒係可舉例如：氫氧化鈉、氫氧化鋰等鹼金屬的氫氧化物；氫氧化鈣、氫氧化鋇等鹼土族金屬的氫氧化物；氫氧化銨；二乙胺、三乙胺、三乙醇胺、乙二胺、六亞甲基四胺等胺類等等。前述鹼性觸媒係可單獨使用一種、亦可併用二種以上。 Examples of the alkaline catalyst include hydroxides of alkali metals such as sodium hydroxide and lithium hydroxide; hydroxides of alkaline earth metals such as calcium hydroxide and barium hydroxide; ammonium hydroxide; diethylamine and triethylamine. Amines such as amines, triethanolamine, ethylenediamine, hexamethylenetetramine, and the like. These alkaline catalysts may be used alone or in combination of two or more.
反應溫度較佳係-5~20℃、更佳係0~5℃。 The reaction temperature is preferably -5 to 20 ° C, more preferably 0 to 5 ° C.
若反應溫度低於較佳下限值亦即低於-5℃，則反應的進行較慢。另一方面，若反應溫度超過較佳上限值亦即超過20℃，則容易高分子量化。若反應溫度為-5~20℃，便可 獲得適度的反應速度。且能抑制高分子量化。 If the reaction temperature is below the preferred lower limit, i.e., below -5 ° C, the reaction proceeds slowly. On the other hand, if the reaction temperature exceeds the preferred upper limit, that is, exceeds 20 ° C, the polymer concentration is easy. If the reaction temperature is -5 to 20 ° C, you can A moderate reaction rate is obtained. And can inhibit the high molecular weight.
反應時間較佳係3~25小時、更佳係5~22小時。若反應時間低於較佳下限值亦即低於3小時，則容易殘留未反應成分。另一方面，若反應時間超過較佳上限值亦即超過25小時，則生產性會降低。若反應時間為3~25小時，則不會殘留未反應成分，且生產性亦不會降低。 The reaction time is preferably 3 to 25 hours, more preferably 5 to 22 hours. If the reaction time is less than the preferred lower limit, that is, less than 3 hours, unreacted components tend to remain. On the other hand, if the reaction time exceeds the preferred upper limit, that is, exceeds 25 hours, the productivity is lowered. If the reaction time is 3 to 25 hours, no unreacted components remain and the productivity is not lowered.
步驟(ii)：接著，在依前述步驟(i)所獲得反應液中，相對於前述步驟(i)中所摻合的酚類1莫耳，添加5莫耳以上、較佳係5~15莫耳的酚類之後，再添加酸性觸媒而使進行反應。然後，去除未反應的酚類等，經施行水洗或濃縮等，最終可獲得酚醛型酚樹脂。 Step (ii): Next, in the reaction liquid obtained in the above step (i), 5 mol or more, preferably 5 to 15 is added with respect to the phenolic 1 molar blended in the above step (i). After the phenols of the moles, an acidic catalyst is added to carry out the reaction. Then, unreacted phenols and the like are removed, and water-washing or concentration is carried out to obtain a novolac type phenol resin.
相對於前述步驟(i)中所摻合酚類1莫耳，在前述反應液中所添加酚類的摻合量較佳係5~15莫耳、更佳係8~12莫耳。若在前述反應液中所添加酚類的摻合量低於較佳下限值亦即低於5莫耳，則分子量分佈容易變廣。另一方面，若酚類的摻合量超過較佳上限值亦即超過15莫耳，則未反應的酚類會增加，生產性會降低。相對於前述步驟(i)中所摻合的酚類1莫耳，若在前述步驟(i)所獲得反應液中添加的酚類摻合量為5~15莫耳，便可抑制高分子量化、且分子量分佈會變狹窄。又，會提升生產性。 The blending amount of the phenol added to the reaction liquid is preferably 5 to 15 moles, more preferably 8 to 12 moles, relative to the phenolic 1 mole blended in the above step (i). When the blending amount of the phenol added to the reaction liquid is less than the lower limit, that is, less than 5 mol, the molecular weight distribution tends to be broad. On the other hand, if the blending amount of the phenols exceeds the preferable upper limit value, that is, more than 15 moles, the unreacted phenols increase, and the productivity is lowered. Compared with the phenolic 1 molar blended in the above step (i), if the amount of the phenol added in the reaction liquid obtained in the above step (i) is 5 to 15 moles, the molecular weight can be suppressed. And the molecular weight distribution will become narrow. Also, it will increase productivity.
酸性觸媒係具有當作酚類與醛類的反應等之觸媒、以及前述步驟(i)所使用鹼性觸媒的中和劑之作用。相對於前述步驟(i)中所摻合的鹼性觸媒1莫耳，酸性觸媒的使用量較 佳係1.0~1.5莫耳、更佳係1.2~1.3莫耳。若酸性觸媒的使用量低於較佳下限值亦即低於1.0莫耳，則鹼性觸媒便不會被充分中和。另一方面，若超過較佳上限值亦即超過1.5莫耳，則酸性觸媒會過剩殘留，導致洗淨次數增加，容易造成生產性降低。若酸性觸媒的使用量為1.0~1.5莫耳，則鹼性觸媒的中和可充分的進行。且，因為酸性觸媒的殘存量較少，依適當的洗淨次數便可除去，因而不會造成生產性降低。 The acid catalyst has a function as a catalyst for reaction such as phenols and aldehydes, and a neutralizing agent for the basic catalyst used in the above step (i). Compared with the alkaline catalyst 1 mole blended in the foregoing step (i), the amount of the acid catalyst used is higher. Good system 1.0~1.5 Mo, better 1.2~1.3 Moh. If the amount of the acidic catalyst used is less than the preferred lower limit, that is, less than 1.0 mole, the alkaline catalyst will not be sufficiently neutralized. On the other hand, when it exceeds the preferable upper limit, that is, more than 1.5 mol, the acidic catalyst may remain excessively, and the number of washings may increase, which tends to cause a decrease in productivity. When the amount of the acidic catalyst used is 1.0 to 1.5 mol, the neutralization of the alkaline catalyst can be sufficiently performed. Further, since the residual amount of the acidic catalyst is small, it can be removed in accordance with the appropriate number of times of washing, and thus the productivity is not lowered.
酸性觸媒係可使用與上述酸性觸媒為同樣物。酸性觸媒添加時的反應液溫度較佳係-5~5℃、更佳係0~5℃。若酸性觸媒添加時的反應液溫度低於較佳下限值亦即低於-5℃，則溫度控制困難、作業性差。另一方面，若反應液溫度超過較佳上限值亦即超過5℃，便容易高分子量化。若酸性觸媒添加時的反應液溫度為-5~5℃，則溫度控制容易、作業性佳。且，亦可抑制高分子量化。 The acid catalyst can be used in the same manner as the above acidic catalyst. The temperature of the reaction solution when the acid catalyst is added is preferably -5 to 5 ° C, more preferably 0 to 5 ° C. When the temperature of the reaction liquid at the time of addition of the acidic catalyst is lower than the lower limit of the lower limit, that is, lower than -5 ° C, temperature control is difficult and workability is poor. On the other hand, if the temperature of the reaction liquid exceeds the preferred upper limit, that is, exceeds 5 ° C, the polymer concentration is easy. When the temperature of the reaction liquid at the time of the addition of the acidic catalyst is -5 to 5 ° C, the temperature control is easy and the workability is good. Moreover, it is also possible to suppress the high molecular weight.
添加酸性觸媒後，較佳係施行加溫而使進行反應。此時的反應溫度較佳係20~80℃、更佳係40~60℃。若前述反應溫度低於較佳下限值亦即低於20℃，便容易殘留未反應成分。另一方面，若前述反應溫度超過較佳上限值亦即超過80℃，則會因前述步驟(i)的生成物彼此間之縮合而容易高分子量化。若反應溫度為20~80℃，便不會有未反應成分殘留，並可抑制因前述步驟(i)的生成物彼此間之縮合而造成高分子量化情形。 After the addition of the acidic catalyst, it is preferred to carry out the reaction by heating. The reaction temperature at this time is preferably 20 to 80 ° C, more preferably 40 to 60 ° C. If the reaction temperature is lower than the lower limit, that is, lower than 20 ° C, unreacted components tend to remain. On the other hand, when the reaction temperature exceeds the preferred upper limit, that is, exceeds 80 ° C, the products of the above step (i) are condensed to facilitate high molecular weight. When the reaction temperature is 20 to 80 ° C, no unreacted components remain, and the occurrence of high molecular weight due to condensation between the products of the above step (i) can be suppressed.
反應時間較佳係2~8小時、更佳係3~6小時。若反應時 間低於較佳下限值亦即低於2小時，便容易殘留未反應成分。另一方面，若反應時間超過較佳上限值亦即超過8小時，則生產性會降低。若反應時間為2~8小時，則不會殘留未反應成分，且生產性亦不會降低。 The reaction time is preferably 2 to 8 hours, more preferably 3 to 6 hours. If reaction If the amount is less than the lower limit of the lower limit, that is, less than 2 hours, the unreacted component tends to remain. On the other hand, if the reaction time exceeds the preferred upper limit, that is, exceeds 8 hours, the productivity is lowered. If the reaction time is 2 to 8 hours, no unreacted components remain, and productivity is not lowered.
本發明中各核體的尖峰面積比係當製造酚醛型酚樹脂時，藉由分別單獨、或適當組合實施包括前述製造方法的下述(1)~(3)方法，便可進行控制。 In the present invention, the peak area ratio of each core body can be controlled by performing the following methods (1) to (3) including the above-described production methods, either individually or in an appropriate combination, in the case of producing a novolac type phenol resin.
(1)使醛類相對於酚類的混合比例變化之方法。 (1) A method of changing the mixing ratio of an aldehyde to a phenol.
(2)酚類與醛類經使用鹼性觸媒進行反應後，再使用酸性觸媒進行反應的方法(相較於僅使用酸性觸媒的情況下，雙核體的尖峰面積比變小，三核體的尖峰面積比變大)。 (2) A method in which a phenol and an aldehyde are reacted using an alkaline catalyst, and then an acid catalyst is used for the reaction (the peak area ratio of the dinuclear is smaller than that in the case where only an acidic catalyst is used, The peak area ratio of the core becomes larger).
(3)將各核體依成為所需面積比的方式施行精製(使用溶劑並利用截留進行精製、利用再結晶進行精製、利用管柱色層分析儀進行分取)的方法。 (3) A method in which each of the nucleus bodies is purified in such a manner as to have a desired area ratio (purification by using a solvent, purification by resection, purification by recrystallization, and fractionation by a column chromatography analyzer).
本發明的酚醛型酚樹脂較佳係軟化點為68~70℃範圍。 The novolac type phenol resin of the present invention preferably has a softening point in the range of 68 to 70 °C.
若軟化點在較佳下限值以上亦即68℃以上，則在室溫中容易保持呈固態狀態。結果，抗黏性呈良好，可提升硬化劑組成物與環氧樹脂進行混練時的作業性。若軟化點在較佳上限值以下亦即70℃以下，則熔融黏度會降低、熱硬化性成形材料的流動性會提高而容易成形。 If the softening point is above the preferred lower limit value, that is, 68 ° C or more, it is easy to maintain a solid state at room temperature. As a result, the anti-stick property is good, and the workability when the hardener composition and the epoxy resin are kneaded can be improved. When the softening point is at most preferably less than the upper limit, that is, 70° C. or less, the melt viscosity is lowered, and the fluidity of the thermosetting molding material is improved to facilitate molding.
「軟化點」係表示使用METTLER TOLEDO公司製的METTLER軟化點測定裝置(FP900)，依2℃/分的昇溫速度，在30~150℃溫度範圍內進行測定的值。 The "softening point" is a value measured in a temperature range of 30 to 150 ° C at a temperature increase rate of 2 ° C / min using a METTLER softening point measuring device (FP900) manufactured by METTLER TOLEDO.
本發明的環氧樹脂用硬化劑組成物係可僅由上述酚醛 型酚樹脂構成，亦可含有上述酚醛型酚樹脂與其他成分。 The hardener composition for epoxy resin of the present invention may be composed only of the above phenolic aldehyde The phenol resin may be composed of a phenolic resin and other components.
其他成分係可舉例如：酚芳烷樹脂、萘酚芳烷樹脂、三苯甲烷型酚樹脂等。 Examples of the other components include a phenol aralkyl resin, a naphthol aralkyl resin, and a triphenylmethane phenol resin.
本發明環氧樹脂用硬化劑組成物的熔融黏度係可利用前述酚醛型酚樹脂中的雙核體、三核體、及具有4或5以上核數的核體之比例而進行控制。本發明的環氧樹脂用硬化劑組成物之熔融黏度較佳係70mPa．s以下、更佳係45~65mPa．s範圍。 The melt viscosity of the hardener composition for an epoxy resin of the present invention can be controlled by using a ratio of a dinuclear body, a trinuclear body, and a core body having a core number of 4 or more in the novolac type phenol resin. The melt viscosity of the hardener composition for epoxy resin of the present invention is preferably 70 mPa. s below, better 45~65mPa. s range.
若熔融黏度在較佳上限值以下亦即70mPa．s以下，則熱硬化性成形材料的流動性會提高，而容易成形。 If the melt viscosity is below the preferred upper limit, ie 70mPa. When s is below, the fluidity of the thermosetting molding material is improved, and molding is easy.
此處「熔融黏度」係表示使用黏度計(Brookfield公司製CAP2000黏度計)，依150℃溫度條件所測定的值。 Here, "melt viscosity" means a value measured by a temperature meter at 150 ° C using a viscometer (CAP2000 viscometer manufactured by Brookfield Co., Ltd.).
本發明的熱硬化性成形材料係含有前述本發明的環氧樹脂用硬化劑組成物、與環氧樹脂。 The thermosetting molding material of the present invention contains the above-described hardener composition for an epoxy resin of the present invention and an epoxy resin.
環氧樹脂係可舉例如：酚酚醛型、甲酚酚醛型、聯苯型等習知公知物。 Examples of the epoxy resin include conventionally known materials such as a phenol novolac type, a cresol novolac type, and a biphenyl type.
本發明的環氧樹脂用硬化劑組成物與環氧樹脂之混合比例，係環氧樹脂中的環氧基當量、與硬化劑組成物中的羥基當量，依當量比計，較佳係羥基/環氧基=0.8~1.2、更佳係0.9~1。若為上述混合比例，便可獲得耐熱性、難燃性等均優異的熱硬化性成形材料。 The mixing ratio of the hardener composition for an epoxy resin to the epoxy resin of the present invention is an epoxy equivalent in the epoxy resin and a hydroxyl equivalent in the hardener composition, and is preferably a hydroxyl group in terms of an equivalent ratio. The epoxy group is 0.8 to 1.2, more preferably 0.9 to 1. When the mixing ratio is the above, a thermosetting molding material excellent in heat resistance, flame retardancy, and the like can be obtained.
本發明的熱硬化性成形材料係除本發明的環氧樹脂用 硬化劑組成物、與環氧樹脂之外，尚可含有其他成分。 The thermosetting forming material of the present invention is used in addition to the epoxy resin of the present invention. The hardener composition and other components may be contained in addition to the epoxy resin.
其他成分係可舉例如：填充劑(填料)、硬化促進劑、脫模劑、表面處理劑、著色劑、可撓性賦予劑等。 Examples of the other components include a filler (filler), a curing accelerator, a release agent, a surface treatment agent, a colorant, and a flexibility imparting agent.
填充劑(填料)係可舉例如：結晶性二氧化矽粉、熔融性二氧化矽粉、石英玻璃粉、滑石、矽酸鈣粉、矽酸鋯粉、氧化鋁粉、碳酸鈣粉等，較佳係結晶性二氧化矽粉、熔融性二氧化矽粉。 Examples of the filler (filler) include crystalline cerium oxide powder, molten cerium oxide powder, quartz glass powder, talc, calcium silicate powder, zirconium silicate powder, alumina powder, calcium carbonate powder, and the like. Excellent crystalline cerium oxide powder and molten cerium oxide powder.
熱硬化性成形材料中的填充劑含有比例，較佳係75~95質量%、更佳係80~92質量%。若填充劑的含有比例在較佳下限值以上亦即75質量%以上，當硬化之際便可抑制發生熱膨脹。若填充劑含有比例在較佳上限值以下亦即95質量%以下，便可獲得充分的流動性、提升成形性。若使用本發明的硬化劑組成物，便可安定地摻合較習知更多量的填充劑，且熱硬化性成形材料的流動性亦優異。更，亦可提升對模具的填充性等。 The proportion of the filler in the thermosetting molding material is preferably from 75 to 95% by mass, more preferably from 80 to 92% by mass. When the content ratio of the filler is at least the lower limit value, that is, 75% by mass or more, thermal expansion can be suppressed when the curing is performed. When the filler content ratio is at most preferably less than the upper limit, that is, 95% by mass or less, sufficient fluidity and moldability can be obtained. When the hardener composition of the present invention is used, a relatively large amount of a filler can be stably blended, and the fluidity of the thermosetting mold material is also excellent. In addition, the filling property of the mold can be improved.
硬化促進劑係可舉例如：三苯膦、參-2,6-二甲氧基苯膦、三(對甲苯基)膦、亞磷酸三苯酯等磷化合物；2-甲基咪唑、2-苯基咪唑、2-月桂基咪唑、2-十七烷基咪唑、2-乙基-4-甲基咪唑等咪唑類；2-二甲胺基甲基酚、苄基二甲胺、α-甲基苄基甲胺等三級胺類；1,8-二氮雜雙環[5.4.0]月桂烯-7、1,8-二氮雜雙環[5.4.0]月桂烯-7的有機酸鹽類等。 Examples of the hardening accelerator include phosphorus compounds such as triphenylphosphine, stilbene-2,6-dimethoxyphenylphosphine, tris(p-tolyl)phosphine, and triphenyl phosphite; 2-methylimidazole, 2- Imidazoles such as phenylimidazole, 2-lauryl imidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole; 2-dimethylaminomethylphenol, benzyldimethylamine, α- a tertiary amine such as methylbenzylmethylamine; an organic acid of 1,8-diazabicyclo [5.4.0] myrcene-7, 1,8-diazabicyclo [5.4.0] myrcene-7 Salt and so on.
脫模劑係可例如棕櫚蠟等各種蠟類等等。 The release agent may be, for example, various waxes such as palm wax or the like.
表面處理劑係可例如公知的矽烷偶合劑等。著色劑係可例如碳黑等。可撓性賦予劑係可例如聚矽氧樹脂、丁二 烯-丙烯腈橡膠等。 The surface treatment agent may, for example, be a known decane coupling agent or the like. The colorant may be, for example, carbon black or the like. The flexibility imparting agent can be, for example, a polyoxyl resin or a dibutyl resin. Alkene-acrylonitrile rubber and the like.
本發明的熱硬化性成形材料係可依照以下的方法等進行製造。 The thermosetting molding material of the present invention can be produced by the following method or the like.
製造方法係將環氧樹脂用硬化劑組成物、以及從環氧樹脂、填充劑(填料)、硬化促進劑、脫模劑、表面處理劑、著色劑、及可撓性賦予劑所構成群組中選擇的其他成分，使用諸如輥式混練機、加壓捏合機、雙螺桿捏合機、及雙螺桿擠出機等混練機等等，依低於熱硬化性成形材料會硬化的溫度施行加熱熔融混合，經粉碎或顆粒化，便可製得能使用於成形品的熱硬化性成形材料。 The manufacturing method is a group consisting of a hardener composition for an epoxy resin, and an epoxy resin, a filler (filler), a hardening accelerator, a mold release agent, a surface treatment agent, a colorant, and a flexibility imparting agent. The other components selected in the above, using a kneading machine such as a roll kneader, a pressure kneader, a twin-screw kneader, and a twin-screw extruder, etc., are heated and melted at a temperature lower than that at which the thermosetting forming material hardens. By mixing, pulverization or granulation, a thermosetting molding material which can be used for a molded article can be obtained.
依此所獲得熱硬化性成形材料係可使用轉印成形、壓縮成形等各種成形方法，製造出所需的成形品。 In the thermosetting molding material obtained as described above, various molding methods such as transfer molding and compression molding can be used to produce a desired molded article.
熱硬化性成形材料的硬化較佳係將溫度控制於100~200℃實施。 The hardening of the thermosetting molding material is preferably carried out by controlling the temperature at 100 to 200 °C.
硬化操作一例係有如以下方法。先依前述較佳溫度亦即100~200℃施行30秒鐘以上且1小時以下的硬化後，更進一步依前述較佳溫度亦即100~200℃施行1~20小時之後硬化的方法。 An example of the hardening operation is as follows. First, after curing at a preferred temperature of 100 to 200 ° C for 30 seconds or more and 1 hour or less, the method of curing after 1 to 20 hours is further carried out at the preferred temperature, that is, 100 to 200 ° C.
本發明的環氧樹脂用硬化劑組成物係熔融黏度較低、且抗黏性良好。 The hardener composition for an epoxy resin of the present invention has a low melt viscosity and good anti-sticking property.
本發明的環氧樹脂用硬化劑組成物係含有既定具Mw與分散度的酚醛型酚樹脂。該酚醛型酚樹脂係屬於窄分散型亦即分散度1.02~1.05，因而含有主成分為三核體，且適度含有少量的低分子量成分(雙核體)與高分子量成分(具有 4或5以上核數的核體)。即，GPC的色層分析圖中，在總尖峰面積合計中，所佔有的雙核體之尖峰面積比為0.5~6面積%，三核體之尖峰面積比為72~82面積%，且具有4或5以上核數的核體之尖峰面積比為16~26面積%。藉此，含有前述酚醛型酚樹脂的硬化劑組成物便具有一定範圍較佳為68~70℃的軟化點，熔融黏度較低、且抗黏性亦呈良好。 The hardener composition for an epoxy resin of the present invention contains a phenolic phenol resin having a predetermined Mw and a degree of dispersion. The phenolic phenol resin is a narrow dispersion type, that is, a dispersion degree of 1.02 to 1.05, and thus contains a main component of a trinuclear body, and moderately contains a small amount of a low molecular weight component (dinucleon) and a high molecular weight component (having a nuclear body with 4 or more cores). That is, in the color layer analysis chart of GPC, in the total peak area total, the peak area ratio of the occupied dinuclear body is 0.5 to 6 area%, and the peak area ratio of the trinuclear body is 72 to 82 area%, and has 4 The ratio of the peak area of the core body with a nuclear number of 5 or more is 16 to 26 area%. Thereby, the hardener composition containing the above-mentioned novolac type phenol resin has a softening point in a range of preferably from 68 to 70 ° C, a low melt viscosity, and good anti-adhesiveness.
因為前述酚醛型酚樹脂係屬於窄分散型亦即分散度1.02~1.05，因而構造的均勻性高。所以，含有該酚醛型酚樹脂的熱硬化性成形材料可認為硬化反應較容易均勻進行。藉此，因為可獲得構造性呈安定的硬化物，因而熱收縮較小。 Since the aforementioned novolac type phenol resin belongs to a narrow dispersion type, that is, a dispersion degree of 1.02 to 1.05, the uniformity of the structure is high. Therefore, the thermosetting molding material containing the novolac type phenol resin is considered to be easier to carry out the curing reaction more easily. Thereby, since a hardened material having a stable structure is obtained, heat shrinkage is small.
相對於此，若使用單純為降低熔融黏度而大量含有低分子量成分(雙核體)、且為賦予耐熱性而大量含有高分子量成分亦即具有4或5以上核數的核體，即GPC色層分析圖中，相對於總尖峰面積合計，雙核體的尖峰面積比大於6面積%，且相對於總尖峰面積比的合計，具有4或5以上核數的核體之尖峰面積比大於26面積%之硬化劑組成物的熱硬化性成形材料，便容易產生毛送。又，因為硬化反應呈不均勻進行，因而熱收縮較大。 On the other hand, when a low molecular weight component (dinuclear body) is contained in a large amount to reduce the melt viscosity, and a high molecular weight component is contained in a large amount, that is, a core having 4 or more cores, that is, a GPC color layer is used. In the analysis chart, the peak area ratio of the dinuclear body is greater than 6 area% with respect to the total peak area, and the peak area ratio of the core body having 4 or more core numbers is greater than 26 area% with respect to the total ratio of the total peak area ratio. The thermosetting forming material of the hardener composition is liable to cause hair delivery. Further, since the hardening reaction proceeds unevenly, the heat shrinkage is large.
本發明含有環氧樹脂用硬化劑組成物的熱硬化性成形材料，係流動性高、容易成形。且，耐熱性(例如玻璃轉移溫度、5%熱分解溫度、成形收縮率等)呈良好。成形加工性(例如凝膠時間、毛邊產生等、以及難燃性等一般特性)亦呈良好。例如使用本發明的熱硬化性成形材料，利用轉印成 形而獲得的硬化物，不易產生毛邊、且亦不易發生模具污染。 The present invention contains a thermosetting molding material which is a hardener composition for an epoxy resin, and has high fluidity and is easily formed. Further, heat resistance (for example, glass transition temperature, 5% thermal decomposition temperature, mold shrinkage ratio, etc.) is good. Forming workability (for example, gel time, generation of burrs, etc., and general characteristics such as flame retardancy) is also good. For example, using the thermosetting forming material of the present invention, it is transferred into The hardened material obtained in the form is less likely to cause burrs and is less likely to cause mold contamination.
本發明之一態樣係當作Mw為320~370、且分散度為1.02~1.05之酚醛型酚樹脂的環氧樹脂用硬化劑使用。 One aspect of the present invention is used as a curing agent for an epoxy resin of a novolac type phenol resin having a Mw of 320 to 370 and a degree of dispersion of 1.02 to 1.05.
本發明另一態樣係當作前述酚醛型酚樹脂為含有雙核體、三核體、及具有4或5以上核數的核體，且在GPC色層分析圖中，於總尖峰面積合計中，所佔有之雙核體的尖峰面積比為0.5~6面積%、三核體的尖峰面積比為72~82面積%、具有4或5以上核數的核體之尖峰面積比為16~26面積%的酚醛型酚樹脂之環氧樹脂用硬化劑使用。 Another aspect of the present invention is that the novolac type phenol resin is a core body having a dinuclear body, a trinuclear body, and a core number of 4 or more, and is included in the total peak area in the GPC chromatogram analysis chart. The ratio of the peak area of the dinuclear body is 0.5 to 6 area%, the ratio of the peak area of the trinuclear body is 72 to 82 area%, and the ratio of the peak area of the core body having the number of cores of 4 or more is 16 to 26 area. The epoxy resin of the phenolic phenol resin is used as a hardener.
再者，本發明另一態樣的環氧樹脂之硬化方法，係將環氧樹脂、與含有Mw為320~370且分散度為1.02~1.05之酚醛型酚樹脂的環氧樹脂用硬化劑進行混合，視需要再將從填料、硬化促進劑、脫模劑、及表面處理劑所構成群組中選擇的其他成分，添加於前述混合物中。 Furthermore, in another aspect of the present invention, an epoxy resin is cured by using an epoxy resin and a hardener for an epoxy resin containing a novolac type phenol resin having a Mw of 320 to 370 and a dispersity of 1.02 to 1.05. The mixture is mixed, and other components selected from the group consisting of a filler, a hardening accelerator, a releasing agent, and a surface treating agent are added to the above mixture as needed.
再者，本發明另一態樣的熱硬化性成形材料之製造方法，係將環氧樹脂、與含有Mw為320~370且分散度為1.02~1.05之酚醛型酚樹脂的環氧樹脂用硬化劑進行混合，視需要再將從填料、硬化促進劑、脫模劑、及表面處理劑所構成群組中選擇的其他成分，添加於前述混合物中。 Further, in another method of producing a thermosetting molding material according to the present invention, an epoxy resin and an epoxy resin containing a novolac type phenol resin having a Mw of 320 to 370 and a dispersion degree of 1.02 to 1.05 are used for hardening. The agent is mixed, and if necessary, other components selected from the group consisting of a filler, a hardening accelerator, a releasing agent, and a surface treating agent are added to the above mixture.
以下，針對本發明利用實施例進行更具體說明，惟本發明並不僅侷限於該等。 Hereinafter, the present invention will be more specifically described by way of examples, but the invention is not limited thereto.
本實施例中，針對硬化劑組成物的Mw、分散度、軟化點及熔融黏度之測定，以及抗黏性的評價，分別依照以下方法實施。 In the present embodiment, the measurement of the Mw, the dispersibility, the softening point, the melt viscosity, and the evaluation of the anti-stick property of the hardener composition were carried out in accordance with the following methods.
針對熱硬化性成形材料的流動性(螺旋流動)、玻璃轉移溫度、5%熱分解溫度、成形收縮率及凝膠時間的測定，以及毛邊產生及難燃性評價，分別依照以下方法實施。 The flowability (spiral flow) of the thermosetting molding material, the glass transition temperature, the 5% thermal decomposition temperature, the molding shrinkage ratio, and the gel time, and the generation of burrs and the evaluation of the flame retardancy were carried out in accordance with the following methods.
使用下述GPC測定裝置與管柱等，從針對各例的酚醛型酚樹脂所測得之GPC色層分析圖，求取各核體的尖峰面積比(面積%)。 The peak area ratio (area%) of each nucleus was determined from the GPC chromatogram analysis of the phenolic phenol resin for each example using the following GPC measuring apparatus, column, or the like.
GPC測定裝置：Tosoh製HCL8220GPC。 GPC measuring device: HCL8220GPC manufactured by Tosoh.
管柱：TSKgel G3000HXL+G2000HXL+G2000H。 Column: TSKgel G3000HXL+G2000HXL+G2000H.
移動相：四氫呋喃。 Mobile phase: tetrahydrofuran.
檢測器：RI檢測器。 Detector: RI detector.
藉由使根據利用GC-MS所測得酚單元數的對應分子量亦即各核體的分子量，對應於依前述所求得各核體的尖峰面積比，而計算出Mw。 Mw is calculated by calculating the peak area ratio of each nucleus according to the corresponding molecular weight of the number of phenol units measured by GC-MS, that is, the molecular weight of each nucleus.
藉由使根據利用GC-MS所測得酚單元數的對應分子量亦即各核體的分子量，對應於依前述所求得各核體的尖峰面積比，而計算出Mn。再從該Mn、與前述所求得Mw，計算出分散度。 Mn is calculated by determining the peak area ratio of each nucleus according to the corresponding molecular weight of the number of phenol units measured by GC-MS, that is, the molecular weight of each nucleus. From the Mn and the Mw obtained as described above, the degree of dispersion was calculated.
硬化劑組成物的軟化點(℃)測定係使用METTLER TOLEDO公司製的METTLER軟化點測定裝置(FP900)，依2℃/分的昇溫速度，於50~150℃溫度中施行測定。 The softening point (° C.) of the hardener composition was measured by using a METTLER softening point measuring apparatus (FP900) manufactured by METTLER TOLEDO Co., Ltd. at a temperature rising rate of 2° C./min. at a temperature of 50 to 150° C.
硬化劑組成物的熔融黏度(mPa．s)係使用黏度計(Brookfield公司製CAP2000黏度計)，依150℃的溫度條件施行測定。 The melt viscosity (mPa.s) of the hardener composition was measured by a temperature meter at 150 ° C using a viscometer (CAP2000 viscometer manufactured by Brookfield Co., Ltd.).
硬化劑組成物的抗黏性係將經粉碎至粒徑2mm以下的硬化劑組成物，於調整為25℃、相對濕度40%之中放置2小時後，針對前述硬化劑組成物的取用性，依照以下的評價基準施行評價。 The anti-adhesive property of the hardener composition is pulverized to a hardener composition having a particle diameter of 2 mm or less, and is allowed to stand for 2 hours after being adjusted to 25 ° C and a relative humidity of 40%, and the availability of the hardener composition. The evaluation was carried out in accordance with the following evaluation criteria.
○：硬化劑組成物彼此間並無黏疊、取用容易。 ○: The hardener compositions do not stick to each other and are easy to use.
×：硬化劑組成物彼此間出現黏疊、不易取用。 ×: The hardener compositions stick to each other and are difficult to access.
熱硬化性成形材料的流動性(螺旋流動)係利用根據JIS K 6910的方法進行測定。 The fluidity (spiral flow) of the thermosetting molding material was measured by a method in accordance with JIS K 6910.
該流動性係以硬化前的熱硬化性成形材料，從熔融起至硬化為止所流動的流動長度(吋)為指標。所以，該流動長度越長便表示流動性越高、越容易成形。 This fluidity is an index of the flow length (吋) flowing from the melting to the hardening before the curing. Therefore, the longer the flow length, the higher the fluidity and the easier it is to form.
另外，表2中的「Over」係表示熱硬化性成形材料過度流動，導致無法進行前述流動長度的測定。 In addition, "Over" in Table 2 indicates that the thermosetting molding material excessively flows, and the measurement of the flow length cannot be performed.
經硬化後的熱硬化性成形材料之玻璃轉移溫度係依照以下的方法進行測定。將硬化前的熱硬化性成形材料施行轉印成形(175℃-120秒鐘)，而製作試驗片(寬2mm×長30mm×厚1mm)。接著，將該試驗片依180℃-5小時施行後硬化。然後，使用黏彈性光譜儀(精工儀器製DMS110)，依10℃/分的昇溫速度，在前述試驗片的30~300℃溫度範圍內施行測定。 The glass transition temperature of the hardened thermosetting molding material was measured by the following method. The thermosetting molding material before curing was subjected to transfer molding (175 ° C - 120 seconds) to prepare a test piece (width 2 mm × length 30 mm × thickness 1 mm). Next, the test piece was post-hardened at 180 ° C for 5 hours. Then, using a viscoelastic spectrometer (DMS110 manufactured by Seiko Instruments), the measurement was carried out at a temperature rise rate of 10 ° C / min in the temperature range of 30 to 300 ° C of the test piece.
該玻璃轉移溫度(℃)越高，表示耐熱性越優異。 The higher the glass transition temperature (°C), the more excellent the heat resistance.
經硬化後的熱硬化性成形材料之5%熱分解溫度，係使用熱重-卡量計雙重分析儀裝置(精工儀器製TG/DTA 6300)，依10℃/分的昇溫速度在30~500℃溫度範圍內施行測定便可求得。 The 5% thermal decomposition temperature of the hardened thermosetting molding material is a thermogravimetric-card gauge dual analyzer device (TG/DTA 6300 manufactured by Seiko Instruments Co., Ltd.) at a temperature increase rate of 30 to 500 at 10 ° C / min. The measurement can be obtained by measuring in the °C temperature range.
該5%熱分解溫度(℃)越高，表示熱安定性越高、耐熱性越優異。 The higher the 5% thermal decomposition temperature (°C), the higher the thermal stability and the more excellent the heat resistance.
經硬化後的熱硬化性成形材料之成形收縮率，係根據JIS K 6911的方法進行測定。 The mold shrinkage ratio of the hardenable thermosetting molding material was measured in accordance with the method of JIS K 6911.
該成形收縮率(%)越低，表示熱收縮越小，越能抑制成形物翹曲的發生，成形時的尺寸安定性越優異。 The lower the mold shrinkage ratio (%), the smaller the heat shrinkage is, and the more the warpage of the molded product is suppressed, and the dimensional stability at the time of molding is excellent.
硬化前的熱硬化性成形材料之凝膠時間，係根據JIS K 6910.5.14.2的方法進行測定。 The gel time of the thermosetting forming material before curing is measured in accordance with the method of JIS K 6910.5.14.2.
針對經硬化後的熱硬化性成形材料之毛邊發生，使用依據毛邊特性EMMI規格的模具，依照以下方法施行測定。依照成形溫度175℃、成形壓力70kg/cm2的條件，將硬化前的熱硬化性成形材料施行成形。此時，測定從狹縫厚10μm、30μm、52μm的狹縫中所流出之熱硬化性成形材料的長度，並設為毛邊的長度。 For the occurrence of burrs of the hardened thermosetting molding material, the measurement was carried out in accordance with the following method using a mold according to the burr characteristic EMMI standard. The thermosetting molding material before curing was molded in accordance with the conditions of a molding temperature of 175 ° C and a molding pressure of 70 kg/cm 2 . At this time, the length of the thermosetting molding material flowing out from the slit having a slit thickness of 10 μm, 30 μm, and 52 μm was measured, and the length of the burr was set.
經硬化後的熱硬化性成形材料之難燃性，係依照以下方法進行測定。將硬化前的熱硬化性成形材料施行轉印成形(175℃-120秒鐘)，而製作難燃性評價用試驗片(寬13mm×長125mm×厚3.2mm)。接著，將該試驗片依180℃-5小時施行後硬化。然後，對上述試驗片施行UL94所規定的20mm火焰垂直燃燒試驗，並根據UL94 V-0規格的判定基準施行評價。 The flame retardancy of the hardened thermosetting molding material was measured by the following method. The thermosetting molding material before curing was subjected to transfer molding (175 ° C - 120 seconds) to prepare a test piece for evaluation of flame retardancy (width 13 mm × length 125 mm × thickness 3.2 mm). Next, the test piece was post-hardened at 180 ° C for 5 hours. Then, the test piece was subjected to a 20 mm flame vertical burning test prescribed by UL94, and evaluated according to the criterion of the UL94 V-0 standard.
在具備有溫度計、攪拌裝置及冷卻管的四口分離式燒瓶中，裝填入：酚94g(1.0mol)、與30質量%氫氧化鋰水溶液79.8g(氫氧化鋰1.0mol)。其次，於5℃以下，歷時20小時滴下37質量%福馬林162g(甲醛2.0mol)。 In a four-part separable flask equipped with a thermometer, a stirring device, and a cooling tube, 94 g (1.0 mol) of phenol and 79.8 g (1.0 mol of lithium hydroxide) of a 30% by mass aqueous lithium hydroxide solution were charged. Next, 372 g (formaldehyde 2.0 mol) of 37% by mass of formalin was dropped over 5 hours at 5 ° C or lower.
接著，添加大量過剩的酚941g(10mol)，並於5℃以下，歷時5小時滴下10質量%鹽酸水溶液438g(鹽酸1.2mol)。待滴下結束後，加溫至50℃而使進行4小時反應。 Then, a large amount of excess phenol 941 g (10 mol) was added, and 438 g (1.2 mol of hydrochloric acid) of 10% by mass aqueous hydrochloric acid solution was added dropwise at 5 ° C for 5 hours. After the completion of the dropwise addition, the mixture was heated to 50 ° C to carry out a reaction for 4 hours.
然後，藉由過濾除去中和鹽，並餾除未反應的酚等， 再施行濃縮，便獲得軟化點69℃的酚醛型酚樹脂(硬化劑組成物A)。 Then, the neutralized salt is removed by filtration, and unreacted phenol or the like is distilled off, Further, concentration was carried out to obtain a novolac type phenol resin (hardener composition A) having a softening point of 69 °C.
第1圖所示係實施例1所獲得酚醛型酚樹脂(硬化劑組成物A)的GPC色層分析圖(使用RI檢測器的情況)。 Fig. 1 is a GPC chromatogram of the novolac type phenol resin (hardener composition A) obtained in Example 1 (in the case of using an RI detector).
第1圖中，在總尖峰面積中所佔有的尖峰面積(I)之比例(面積%)，係對應於酚醛型酚樹脂中的雙核體之含有比例。 In Fig. 1, the ratio (area%) of the peak area (I) occupied by the total peak area corresponds to the content ratio of the dinuclear body in the novolac type phenol resin.
總尖峰面積中所佔有的尖峰面積(II)之比例(面積%)，係對應於酚醛型酚樹脂中的三核體含有比例。 The ratio (area%) of the peak area (II) occupied by the total peak area corresponds to the trinuclear content ratio in the novolac type phenol resin.
總尖峰面積中所佔有的尖峰面積(III)之比例(面積%)，係對應於酚醛型酚樹脂中之具有4或5以上核數的核體含有比例。 The ratio (area%) of the peak area (III) occupied by the total peak area corresponds to the ratio of the core body having a core number of 4 or more in the novolac type phenol resin.
除將實施例1所使用的37質量%福馬林摻合量，變更為170.3g(甲醛2.1mol)之外，其餘均與實施例1同樣的操作，獲得軟化點70℃的酚醛型酚樹脂(硬化劑組成物B)。 A novolac type phenol resin having a softening point of 70 ° C was obtained in the same manner as in Example 1 except that the blending amount of 37% by mass of formalin used in Example 1 was changed to 170.3 g (formaldehyde: 2.1 mol). Hardener composition B).
除將實施例1所使用的37質量%福馬林摻合量，變更為154g(甲醛1.9mol)之外，其餘均與實施例1同樣的操作，獲得軟化點65℃的酚醛型酚樹脂(硬化劑組成物C)。 A phenolic phenol resin having a softening point of 65 ° C was obtained by the same operation as in Example 1 except that the blending amount of 37% by mass of formalin used in Example 1 was changed to 154 g (1.9 mol of formaldehyde). Agent composition C).
在具備有溫度計、攪拌裝置及冷卻管的四口分離式燒瓶中，裝填入酚188.2g(2.0mol)、37質量%福馬林108.6g(甲醛1.34mol)、以及85質量%磷酸水溶液56.5g，並於60℃中進行5小時反應。反應物經水洗並餾除未反應的酚，獲得軟化 點43℃的酚醛型酚樹脂(硬化劑組成物D)。 In a four-part separable flask equipped with a thermometer, a stirring device, and a cooling tube, 188.2 g (2.0 mol) of phenol, 108.6 g of fumarin (1.34 mol of formaldehyde), and 56.5 g of an aqueous solution of 85% by mass of phosphoric acid were charged. And reacted at 60 ° C for 5 hours. The reaction is washed with water and the unreacted phenol is distilled off to obtain softening. A novolac type phenol resin (hardener composition D) at 43 ° C.
從實施例1所獲得硬化劑組成物A中，利用管柱色層分析儀分取各核體。具體而言，將甲苯與醋酸乙酯的混合溶液使用為展開溶劑，並以矽膠(矽膠60、關東化學管柱色層分析儀用)為吸附劑，且填充於管柱中。然後，在前述管柱中，一邊使前述展開溶劑流動，一邊分取目標物。獲得GPC色層分析圖中，三核體尖峰面積比為94面積%的軟化點55℃之酚醛型酚樹脂(硬化劑組成物E)。 From the hardener composition A obtained in Example 1, each core body was fractionated by a column chromatography analyzer. Specifically, a mixed solution of toluene and ethyl acetate was used as a developing solvent, and an anthracene (silicone 60, Kanto chemical column chromatography analyzer) was used as an adsorbent, and was filled in a column. Then, in the column, the target material is dispensed while flowing the developing solvent. In the GPC chromatogram, a novolac type phenol resin (hardener composition E) having a trinuclear peak area ratio of 94 area% and a softening point of 55 ° C was obtained.
獲得軟化點70℃之通用酚樹脂(群榮化學工業股份有限公司製商品名GSF-70)(硬化劑組成物F)。 A general-purpose phenol resin (trade name: GSF-70, manufactured by Kyoei Chemical Industry Co., Ltd.) (hardener composition F) having a softening point of 70 ° C was obtained.
各例所獲得硬化劑組成物的GPC色層分析圖之尖峰面積比、及Mw、分散度、軟化點及熔融黏度的測定值、以及抗黏性的評價結果，分別如表1所示。 The peak area ratio of the GPC chromatogram of the hardener composition obtained in each example, and the measured values of Mw, dispersity, softening point, and melt viscosity, and the evaluation results of the anti-viscosity are shown in Table 1, respectively.
由表1的結果可確認到實施例1、2的硬化劑組成物A、B，係熔融黏度較低、且抗黏性良好。 From the results of Table 1, it was confirmed that the hardener compositions A and B of Examples 1 and 2 have low melt viscosity and good anti-sticking properties.
雖Mw在320~370範圍內，但分散度偏離1.02~1.05範圍外的比較例1之硬化劑組成物C，相較於實施例1、2之下，因為含有較多的雙核體，因而呈現軟化點下降、抗黏性差的結果。 Although the Mw is in the range of 320 to 370, the hardener composition C of Comparative Example 1 whose dispersion is deviated from the range of 1.02 to 1.05 is lower than that of Examples 1 and 2 because it contains more dinuclear bodies. The result of a decrease in softening point and poor anti-adhesion.
Mw小於既定範圍、分散度大於既定範圍、亦即Mw小於320、分散度大於1.05的比較例2之硬化劑組成物D，因為含有非常多的低分子量成分(雙核體)，因而雖熔融黏度偏低，但軟化點亦會降低，呈現抗黏性差的結果。 The hardener composition D of Comparative Example 2, in which the Mw is smaller than the predetermined range and the dispersion is larger than the predetermined range, that is, the Mw is less than 320 and the dispersion is more than 1.05, the melt viscosity is biased because it contains a very large amount of low molecular weight components (dual core). Low, but the softening point is also reduced, resulting in poor anti-adhesive results.
Mw小於既定範圍、分散度亦小於既定範圍亦即Mw小於320、分散度亦小於1.02的比較例3之硬化劑組成物E，雖含有非常多的三核體，但卻熔融黏度偏低、軟化點亦降低，呈現抗黏性差的結果。 The hardener composition E of Comparative Example 3, in which the Mw is smaller than the predetermined range and the dispersion is smaller than the predetermined range, that is, the Mw is less than 320 and the dispersion is less than 1.02, although it contains a very large number of trinuclear bodies, the melt viscosity is low and softened. The dots are also lowered, resulting in poor anti-adhesive results.
Mw大於既定範圍、分散度亦大於既定範圍亦即Mw大於370、分散度大於1.05的比較例4之硬化劑組成物F，係屬於一般所使用的通用等級。硬化劑組成物F係因為含有非常多的高分子量成分(具有4或5以上核數的核體)，因而熔融黏度偏高。且，因為亦含有較多的低分子量成分(雙核體)，因而呈現抗黏性差的結果。 The hardener composition F of Comparative Example 4 in which the Mw is larger than the predetermined range and the dispersion is also larger than the predetermined range, that is, the Mw is more than 370 and the dispersion is more than 1.05, is a general grade generally used. Since the hardener composition F contains a very large amount of a high molecular weight component (a core body having a core number of 4 or more), the melt viscosity is high. Further, since it also contains a large amount of low molecular weight components (dual cores), it exhibits poor adhesion resistance.
分散度控制於1.02~1.0範圍內，但若Mw大於既定範圍亦即大於370，則可確認到雖軟化點提高、抗黏性提升，但熔融黏度會提高。 The degree of dispersion is controlled in the range of 1.02 to 1.0. However, if Mw is larger than the predetermined range, that is, greater than 370, it is confirmed that although the softening point is increased and the anti-sticking property is improved, the melt viscosity is improved.
依照表2所示組成，將各原料予以混合而調製熱硬化性成形材料。 According to the composition shown in Table 2, each raw material was mixed to prepare a thermosetting molding material.
環氧樹脂與硬化劑組成物係依環氧樹脂中的環氧基當量、與硬化劑組成物中的羥基當量之當量比成為1的方式進行摻合。 The epoxy resin and the hardener composition are blended so that the equivalent ratio of the epoxy equivalent in the epoxy resin to the hydroxyl equivalent in the hardener composition becomes 1.
所使用的原料係如下所示。 The raw materials used are as follows.
環氧樹脂：環氧當量196、熔點106℃的聯苯型環氧樹脂、三菱化學股份有限公司製商品名「YX-4000H」。 Epoxy resin: a biphenyl type epoxy resin having an epoxy equivalent of 196 and a melting point of 106 ° C, and a trade name "YX-4000H" manufactured by Mitsubishi Chemical Corporation.
球狀二氧化矽：填充劑、龍森製商品名「MSR-2212」。 Spherical cerium oxide: a filler, the product name "MSR-2212" manufactured by Ronson.
三苯膦：硬化促進劑、試劑。 Triphenylphosphine: a hardening accelerator and a reagent.
棕櫚蠟：脫模劑、Nihon Wax製。 Palm wax: release agent, made by Nihon Wax.
針對各例所獲得熱硬化性成形材料的流動性(螺旋流動)、玻璃轉移溫度、5%熱分解溫度、成形收縮率、凝膠時間、及毛邊長度的測定值，以及難燃性的評價結果，分別如表2所示。 The measured values of fluidity (spiral flow), glass transition temperature, 5% thermal decomposition temperature, mold shrinkage ratio, gel time, and burr length of the thermosetting molding material obtained in each example, and evaluation results of flame retardancy , as shown in Table 2.
由表2的結果可確認到實施例3、4的熱硬化性成形材料，係流動性優異、容易成形，且耐熱性亦即玻璃轉移溫度、5%熱分解溫度、成形收縮率良好。成形加工性亦即凝膠時間、毛送產生與難燃性等一般特性亦良好。 From the results of Table 2, the thermosetting molding materials of Examples 3 and 4 were found to have excellent fluidity and easy molding, and the heat resistance, that is, the glass transition temperature, the 5% thermal decomposition temperature, and the mold shrinkage ratio were good. Forming workability, that is, general characteristics such as gel time, hair generation, and flame retardancy are also good.
比較例6的熱硬化性成形材料係因為流動性過高，且因為硬化劑組成物D的Mw過低，因而呈現硬化變慢、容易發生毛邊的結果。且，呈現耐熱性與難燃性均偏低的結果。 The thermosetting forming material of Comparative Example 6 was caused by excessively high fluidity and because the Mw of the hardener composition D was too low, so that the hardening became slow and burrs were likely to occur. Moreover, the results of low heat resistance and flame retardancy are exhibited.
比較例8的熱硬化性成形材料係相較於實施例3、4的熱硬化性成形材料之下，呈現流動性差，且耐熱性、成形加工性及難燃性均差的結果。 The thermosetting molding material of Comparative Example 8 exhibited poor fluidity and poor heat resistance, moldability, and flame retardancy as compared with the thermosetting molding materials of Examples 3 and 4.
可提供熔融黏度低、且抗黏性良好的環氧樹脂用硬化劑組成物、及耐熱性優異的熱硬化性成形材料。 A hardener composition for an epoxy resin having a low melt viscosity and excellent anti-adhesive properties, and a thermosetting molding material excellent in heat resistance can be provided.
第1圖係實施例1所獲得酚醛型酚樹脂(硬化劑組成物A)的GPC色層分析圖。 Fig. 1 is a GPC color layer analysis chart of the novolac type phenol resin (hardener composition A) obtained in Example 1.
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