TW202142585A - Phenoxy resin, resin composition, cured product, laminate for electric/electronic circuits, and method for producing phenoxy resin - Google Patents

Abstract

The present invention provides: a phenoxy resin which exhibits excellent heat resistance, dielectric characteristics and folding resistance; a resin composition which contains this phenoxy resin and a curing agent; a cured product of this resin composition, said cured product exhibiting excellent heat resistance, dielectric characteristics and folding resistance; and a laminate for electric/electronic circuits. This phenoxy resin is represented by formula (1), and has a weight average molecular weight of from 10,000 to 200,000. In the formula, X represents a divalent group containing a dioxy group represented by formula (2) or formula (3); Y represents a hydrogen atom, an acyl group or a glycidyl group; and Z represents a hydrogen atom or an acyl group, with 5% by mole or more thereof being an acyl group.

Description

苯氧基樹脂、樹脂組成物、硬化物、電氣電子電路用積層板、及苯氧基樹脂的製造方法Phenoxy resin, resin composition, cured product, laminated board for electric and electronic circuits, and method for manufacturing phenoxy resin

本發明是有關於一種耐熱性、介電特性及耐折性優異的苯氧基樹脂。另外是有關於一種含有該苯氧基樹脂及硬化劑的樹脂組成物、及耐熱性、介電特性及耐折性優異的所述樹脂組成物的硬化物、以及包含該樹脂組成物的電氣電子電路用積層板。The present invention relates to a phenoxy resin with excellent heat resistance, dielectric properties and folding resistance. In addition, it relates to a resin composition containing the phenoxy resin and a curing agent, and a cured product of the resin composition having excellent heat resistance, dielectric properties, and folding resistance, and electrical and electronic components containing the resin composition Multilayer boards for circuits.

環氧樹脂由於耐熱性、接著性、耐藥品性、耐水性、機械強度及電特性等優異，因此在塗料、土木、接著、電氣材料用途等領域廣泛使用。而且，藉由利用各種方法進行高分子量化來賦予製膜性。該經高分子量化的環氧樹脂被稱為苯氧基樹脂。特別是雙酚A型的苯氧基樹脂主要是作為塗料用清漆的基礎樹脂、膜成形用的基礎樹脂而使用，或者出於如下目的而使用：添加至環氧樹脂清漆中來調整流動性或改良製成硬化物時的韌性、改良接著性。另外，骨架中具有磷原子或溴原子者用作環氧樹脂組成物或熱塑性樹脂中所調配的阻燃劑。Epoxy resins have excellent heat resistance, adhesiveness, chemical resistance, water resistance, mechanical strength, and electrical properties, so they are widely used in fields such as coatings, civil engineering, adhesives, and electrical material applications. In addition, film-forming properties are imparted by high molecular weight by various methods. This high molecular weight epoxy resin is called phenoxy resin. In particular, bisphenol A type phenoxy resins are mainly used as base resins for varnishes for paints and base resins for film formation, or are used for the following purposes: adding to epoxy resin varnishes to adjust fluidity or Improve the toughness and adhesiveness of hardened products. In addition, those having a phosphorus atom or a bromine atom in the skeleton are used as a flame retardant compounded in an epoxy resin composition or a thermoplastic resin.

對成為電氣電子電路用積層板等的電氣材料用途的苯氧基樹脂要求耐熱性、介電特性及耐折性。Phenoxy resins used as electrical materials such as laminates for electrical and electronic circuits are required to have heat resistance, dielectric properties, and folding resistance.

對於此種要求，提出了藉由擴展分子鏈來抑制微布朗運動（micro-Brownian motion）而提高耐熱性的方法。在專利文獻1中，揭示了使大體積雙酚化合物與二官能環氧樹脂反應而得的耐熱性優異的苯氧基樹脂。但是，在該方法中，雖然可對苯氧基樹脂賦予優異的耐熱性，但存在無法改善介電特性的問題。In response to this requirement, a method has been proposed to increase the heat resistance by suppressing micro-Brownian motion by extending the molecular chain. Patent Document 1 discloses a phenoxy resin having excellent heat resistance obtained by reacting a bulky bisphenol compound with a difunctional epoxy resin. However, in this method, although excellent heat resistance can be imparted to the phenoxy resin, there is a problem that the dielectric properties cannot be improved.

另一方面，提出了藉由使用乙醯基或苯甲醯基將苯氧基樹脂的側鏈中存在的羥基轉換成酯來提高介電特性的方法。在專利文獻2中，本發明者等人確認了使二官能環氧樹脂與二酯化合物反應而獲得的苯氧基樹脂具有優異的介電特性，但存在耐熱性差的問題。 [專利文獻]On the other hand, a method for improving the dielectric properties by converting the hydroxyl groups present in the side chain of the phenoxy resin into an ester using an acetyl group or a benzyl group has been proposed. In Patent Document 2, the inventors of the present invention confirmed that a phenoxy resin obtained by reacting a difunctional epoxy resin with a diester compound has excellent dielectric properties, but has a problem of poor heat resistance. [Patent Literature]

[專利文獻1]日本專利特開2008-231428號公報 [專利文獻2]日本專利特開2016-089165號公報[Patent Document 1] Japanese Patent Laid-Open No. 2008-231428 [Patent Document 2] Japanese Patent Laid-Open No. 2016-089165

本發明的課題在於提供一種耐熱性、介電特性及耐折性優異的苯氧基樹脂。另外，將含有苯氧基樹脂的樹脂組成物硬化，而提供一種耐熱性、介電特性及耐折性優異的硬化物。The subject of the present invention is to provide a phenoxy resin excellent in heat resistance, dielectric properties, and folding resistance. In addition, the resin composition containing the phenoxy resin is cured to provide a cured product excellent in heat resistance, dielectric properties, and bending resistance.

為了解決所述課題，本發明人對苯氧基樹脂進行了深入研究，結果發現具有特定結構的苯氧基樹脂的耐熱性、介電特性及耐折性優異，進而發現使含有所述苯氧基樹脂的樹脂組成物硬化而成的硬化物的耐熱性、介電特性及耐折性優異，從而完成了本發明。In order to solve the problem, the present inventors conducted intensive studies on phenoxy resins, and found that phenoxy resins having a specific structure are excellent in heat resistance, dielectric properties, and bending resistance. The cured product formed by curing the resin composition of the base resin is excellent in heat resistance, dielectric properties, and folding resistance, and completed the present invention.

即，本發明是由下述式（1）表示、重量平均分子量為10,000～200,000的苯氧基樹脂。 [化1]

式中，X獨立地為含有下述式（2）及式（3）所表示的二氧基的二價基，Y分別獨立地為氫原子、具有碳數1～20的烴基的醯基、或縮水甘油基，Z為具有碳數1～20的烴基的醯基或氫原子，且5莫耳%以上為所述醯基，n是重覆數的平均值，為15以上且500以下。That is, the present invention is a phenoxy resin represented by the following formula (1) and having a weight average molecular weight of 10,000 to 200,000. [化1]

In the formula, X is independently a divalent group containing a dioxy group represented by the following formula (2) and formula (3), and Y is each independently a hydrogen atom, an acyl group having a hydrocarbon group with 1 to 20 carbon atoms, Or a glycidyl group, Z is an acyl group or a hydrogen atom having a C1-C20 hydrocarbon group, 5 mol% or more is the acyl group, and n is the average of the number of repetitions, which is 15 or more and 500 or less.

[化2]

式（2）及式（3）中，R分別獨立地為選自由碳數1～12的烷基、碳數1～12的烷氧基、碳數6～12的芳基、碳數7～13的芳烷基、碳數6～12的芳氧基、碳數7～13的芳烷氧基、碳數2～12的烯基、及碳數2～12的炔基所組成的群組中的基，i為0～4的整數，j為0～6的整數。[化2]

In formula (2) and formula (3), R is each independently selected from alkyl groups having 1 to 12 carbons, alkoxy groups having 1 to 12 carbons, aryl groups having 6 to 12 carbons, and 7 to carbon atoms. The group consisting of 13 aralkyl, 6-12 aryloxy, 7-13 aralkoxy, 2-12 alkenyl, and 2-12 alkynyl In the base, i is an integer of 0-4, and j is an integer of 0-6.

另外，本發明是含有所述苯氧基樹脂及硬化劑的樹脂組成物。 相對於苯氧基樹脂的固體成分100質量份，所述樹脂組成物可含有以固體成分計為0.1質量份～100質量份的硬化劑。In addition, the present invention is a resin composition containing the phenoxy resin and a curing agent. With respect to 100 parts by mass of the solid content of the phenoxy resin, the resin composition may contain 0.1 parts by mass to 100 parts by mass of the curing agent in terms of solid content.

所述樹脂組成物含有所述的苯氧基樹脂、環氧樹脂及硬化劑，且苯氧基樹脂與環氧樹脂的固體成分的質量比可為99/1～1/99。 相對於苯氧基樹脂與環氧樹脂的固體成分的合計100質量份，該樹脂組成物可含有以固體成分計為0.1質量份～100質量份的硬化劑。The resin composition contains the phenoxy resin, epoxy resin, and hardener, and the mass ratio of the solid content of the phenoxy resin to the epoxy resin may be 99/1 to 1/99. The resin composition may contain 0.1 parts by mass to 100 parts by mass of the curing agent in terms of solid content with respect to 100 parts by mass of the total solid content of the phenoxy resin and the epoxy resin.

作為所述樹脂組成物中調配的硬化劑，有選自由丙烯酸酯樹脂、黑色素樹脂、脲樹脂、酚樹脂、酸酐化合物、胺系化合物、咪唑系化合物、醯胺系化合物、陽離子聚合起始劑、有機膦類、聚異氰酸酯化合物、封閉異氰酸酯化合物、及活性酯系硬化劑所組成的群組中的至少一種。As the hardener formulated in the resin composition, there are selected from acrylic resins, melanin resins, urea resins, phenol resins, acid anhydride compounds, amine compounds, imidazole compounds, amide compounds, cationic polymerization initiators, At least one of the group consisting of organic phosphines, polyisocyanate compounds, blocked isocyanate compounds, and active ester hardeners.

另外，本發明是將所述樹脂組成物硬化而成的硬化物。 此外，本發明是使用所述樹脂組成物而得的電氣電子電路用積層板。In addition, the present invention is a cured product obtained by curing the resin composition. In addition, the present invention is a laminate for electric and electronic circuits obtained by using the resin composition.

另外，本發明是所述苯氧基樹脂的製造方法，其特徵在於，使下述式（7）所表示的二官能環氧樹脂與下述式（8）所表示的化合物反應。 [化3]

式中，X¹ 獨立地為含有所述式（2）或式（3）所表示的二氧基的二價基，式（7）及式（8）的X¹ 中整體含有式（2）及式（3）所表示的二氧基。 Z¹ 為具有碳數1～20的烴基的醯基或氫原子，5莫耳%以上為所述醯基。此處，式（8）所表示的化合物可為選自Z¹ 的兩者為醯基的化合物、一者為醯基的化合物及兩者為氫原子的化合物的兩種以上的混合物。 m是重覆數的平均值，為0以上且6以下。In addition, the present invention is a method for producing the phenoxy resin, characterized by reacting a difunctional epoxy resin represented by the following formula (7) with a compound represented by the following formula (8). [化3]

In the formula, X ^{1 is} independently a divalent group containing the dioxy group represented by the formula (2) or formula (3), and X ¹ in the formula (7) and formula (8) contains the formula (2) as a whole And the dioxy group represented by formula (3). Z ¹ is an acyl group or a hydrogen atom having a hydrocarbon group having 1 to 20 carbons, and 5 mol% or more is the acyl group. Here, the compound represented by the formula (8) may be ^{a mixture of two or more compounds selected from Z 1} in which two are acyl groups, one is an acyl group, and both are hydrogen atoms. m is the average value of the number of repetitions, and is 0 or more and 6 or less.

本發明進而是所述苯氧基樹脂的製造方法，其特徵在於，使醯化劑的醯基相對於下述式（12）所表示的苯氧基樹脂的醇性羥基1莫耳，以0.05莫耳以上且2.0莫耳以下進行反應。 [化4]

式中，X² 獨立地為含有所述式（2）及式（3）所表示的二氧基的二價基，Y² 分別獨立地為氫原子或縮水甘油基。n是重覆數的平均值，為15以上且500以下。The present invention is further a method for producing the phenoxy resin, characterized in that the alcoholic hydroxyl group of the phenoxy resin represented by the following formula (12) is set to 0.05 The reaction is carried out at a mole or more and 2.0 mole or less. [化4]

In the formula, X ^{2 is} independently a divalent group containing the dioxy group represented by the formula (2) and formula (3), and Y ^{2 is} each independently a hydrogen atom or a glycidyl group. n is the average value of the number of repetitions, and is 15 or more and 500 or less.

根據本發明，可提供一種耐熱性、介電特性及耐折性優異的苯氧基樹脂。另外，藉由使用該苯氧基樹脂的樹脂組成物，可提供一種耐熱性、介電特性及耐折性優異的硬化物。According to the present invention, it is possible to provide a phenoxy resin excellent in heat resistance, dielectric properties, and folding resistance. In addition, by using the resin composition of the phenoxy resin, it is possible to provide a cured product excellent in heat resistance, dielectric properties, and folding resistance.

本發明的苯氧基樹脂是由所述式（1）表示的重量平均分子量（Mw）為10,000～200,000的苯氧基樹脂，並且具有所述式（2）所表示的苯骨架及式（3）所表示的萘骨架，並且進一步具有羥基中的氫原子的部分或全部經醯基（Z）取代的結構。 此處，若Mw小於10,000，則製膜性、機械特性（特別是耐折性）有可能降低，而不佳。若Mw大於200,000，則相容性有可能降低，而存在難以處理樹脂的情況，而不佳。Mw較佳為15,000～160,000，更佳為20,000～120,000，進而佳為20,000～120,000。再者，苯氧基樹脂的Mw可藉由實施例中記載的凝膠滲透層析法（（gel permeation chromatography，GPC）GPC法）進行測定。The phenoxy resin of the present invention is a phenoxy resin with a weight average molecular weight (Mw) represented by the formula (1) of 10,000 to 200,000, and has a benzene skeleton represented by the formula (2) and a formula (3) The naphthalene skeleton represented by ), and further has a structure in which part or all of the hydrogen atoms in the hydroxyl group are substituted with an acyl group (Z). Here, if Mw is less than 10,000, film-forming properties and mechanical properties (especially folding resistance) may decrease, which is not preferable. If the Mw is greater than 200,000, the compatibility may decrease, and it may be difficult to handle the resin, which is not good. Mw is preferably 15,000 to 160,000, more preferably 20,000 to 120,000, and still more preferably 20,000 to 120,000. In addition, the Mw of the phenoxy resin can be measured by the gel permeation chromatography (GPC (gel permeation chromatography, GPC) GPC method) described in the examples.

本發明的苯氧基樹脂藉由具有羥基中的氫原子經醯基取代的結構，成為低極性，而獲得介電特性優異的效果。另外，低吸濕性、溶劑溶解性變良好。The phenoxy resin of the present invention has a structure in which a hydrogen atom in a hydroxyl group is substituted with an acyl group, so that it has a low polarity and obtains an effect of excellent dielectric properties. In addition, low hygroscopicity and solvent solubility become good.

本發明的苯氧基樹脂可藉由本發明的製造方法有利地獲得。在本說明書中，有時將藉由本發明的製造方法獲得的苯氧基樹脂稱為「本發明的苯氧基樹脂」，有時將使本發明的樹脂組成物硬化而成的硬化物稱為「本發明的硬化物」、將本發明的苯氧基樹脂的製造方法稱為「本發明的製造方法」。The phenoxy resin of the present invention can be advantageously obtained by the production method of the present invention. In this specification, the phenoxy resin obtained by the production method of the present invention is sometimes referred to as the "phenoxy resin of the present invention", and the cured product obtained by curing the resin composition of the present invention is sometimes referred to as The "cured product of the present invention" and the manufacturing method of the phenoxy resin of the present invention are referred to as "the manufacturing method of the present invention".

所述式（1）中，X獨立地為含有所述式（2）及式（3）所表示的二氧基的二價基。式（2）及式（3）所表示的基在兩端具有氧原子，因此稱為二氧基。所述二價基是所述式（2）、式（3）或除該些以外的其他二價基中的任一種，作為整體，含有式（2）及式（3）所表示的二氧基。式（2）及式（3）所表示的二氧基的莫耳比（式2/式3）較佳為1/9～9/1，更佳為2/8～8/2，進而佳為3/7～7/3，特佳為4/6～6/4。另外，相對於X整體的莫耳數，式（2）及式（3）所表示的二氧基較佳為1莫耳%以上，更佳為10莫耳%以上，進而佳為30莫耳%以上，特佳為50莫耳%以上。若超出該範圍，則耐熱性或耐折性有可能惡化。作為所述二氧基以外的其他二價基，可列舉-O-Ar-O-所表示的二價基，作為Ar，可列舉自後述的可併用的二官能酚化合物除去兩個羥基而得的殘基等。In the formula (1), X is independently a divalent group containing the dioxy group represented by the formula (2) and the formula (3). The groups represented by formula (2) and formula (3) have oxygen atoms at both ends, and therefore are called dioxy groups. The divalent group is any one of the formula (2), formula (3) or other divalent groups other than these, and as a whole, contains the dioxygen represented by formula (2) and formula (3) base. The molar ratio of the dioxy group represented by formula (2) and formula (3) (formula 2/formula 3) is preferably 1/9-9/1, more preferably 2/8-8/2, and still more preferably It is 3/7～7/3, especially 4/6～6/4. In addition, the dioxy group represented by formula (2) and formula (3) is preferably 1 mol% or more, more preferably 10 mol% or more, and still more preferably 30 mol% with respect to the number of moles of X as a whole % Or more, particularly preferably 50 mol% or more. If it exceeds this range, heat resistance or folding resistance may deteriorate. Examples of divalent groups other than the above-mentioned dioxy groups include divalent groups represented by -O-Ar-O-, and examples of Ar include those obtained by removing two hydroxyl groups from a difunctional phenol compound that can be used in combination as described later. The residues and so on.

式（2）及式（3）中，R分別獨立地為自碳數1～12的烷基、碳數1～12的烷氧基、碳數6～12的芳基、碳數7～13的芳烷基、碳數6～12的芳氧基、碳數7～13的芳烷氧基、碳數2～12的烯基、或碳數2～12的炔基任意選擇的基。In formula (2) and formula (3), R is each independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, an aryl group having 6 to 12 carbons, and a carbon number of 7 to 13 Aralkyl group, aryloxy group having 6 to 12 carbons, aralkoxy group having 7 to 13 carbons, alkenyl group having 2 to 12 carbons, or alkynyl group having 2 to 12 carbons.

作為碳數1～12的烷基，可為直鏈狀、分支狀、環狀的任一種，例如可列舉：甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基、正戊基、異戊基、新戊基、第三戊基、環戊基、正己基、異己基、環己基、正庚基、環庚基、甲基環己基、正辛基、環辛基、正壬基、3,3,5-三甲基環己基、正癸基、環癸基、正十一烷基、正十二烷基、環十二烷基、苄基、甲基苄基、二甲基苄基、三甲基苄基、萘甲基、苯乙基、2-苯基異丙基等。The alkyl group having 1 to 12 carbon atoms may be linear, branched, or cyclic, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, and butyl Base, tertiary butyl, n-pentyl, isopentyl, neopentyl, tertiary pentyl, cyclopentyl, n-hexyl, isohexyl, cyclohexyl, n-heptyl, cycloheptyl, methylcyclohexyl, N-octyl, cyclooctyl, n-nonyl, 3,3,5-trimethylcyclohexyl, n-decyl, cyclodecyl, n-undecyl, n-dodecyl, cyclododecyl, Benzyl, methylbenzyl, dimethylbenzyl, trimethylbenzyl, naphthylmethyl, phenethyl, 2-phenylisopropyl, etc.

作為碳數1～12的烷氧基，可為直鏈狀、分支狀、環狀的任一種，例如可列舉：甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、第二丁氧基、第三丁氧基、正戊氧基、異戊氧基、新戊氧基、第三戊氧基、環戊氧基、正己氧基、異己氧基、環己氧基、正庚氧基、環庚氧基、甲基環己氧基、正辛氧基、環辛氧基、正壬氧基、3,3,5-三甲基環己氧基、正癸氧基、環癸氧基、正十一烷氧基、正十二烷氧基、環十二烷氧基、苄氧基、甲基苄氧基、二甲基苄氧基、三甲基苄氧基、萘基甲氧基、苯乙氧基、2-苯基異丙氧基等，但並不限定於該些。The alkoxy group having 1 to 12 carbon atoms may be linear, branched, or cyclic. Examples include methoxy, ethoxy, n-propoxy, isopropoxy, and n-butyl. Oxy, second butoxy, tertiary butoxy, n-pentyloxy, isopentyloxy, neopentyloxy, tertiary pentyloxy, cyclopentyloxy, n-hexyloxy, isohexyloxy, ring Hexyloxy, n-heptyloxy, cycloheptyloxy, methylcyclohexyloxy, n-octyloxy, cyclooctyloxy, n-nonyloxy, 3,3,5-trimethylcyclohexyloxy, N-decyloxy, cyclodecyloxy, n-undecyloxy, n-dodecyloxy, cyclododecyloxy, benzyloxy, methylbenzyloxy, dimethylbenzyloxy, trimethyl Butyl benzyloxy, naphthylmethoxy, phenethoxy, 2-phenylisopropoxy, etc. are not limited to these.

作為碳數6～12的芳基，例如可列舉苯基、鄰甲苯基、間甲苯基、對甲苯基、乙基苯基、苯乙烯基、二甲苯基、正丙基苯基、異丙基苯基、均三甲苯基、乙炔基苯基、萘基、乙烯基萘基等，但並不限定於該些。Examples of aryl groups having 6 to 12 carbon atoms include phenyl, o-tolyl, m-tolyl, p-tolyl, ethylphenyl, styryl, xylyl, n-propylphenyl, and isopropyl. Phenyl, mesityl, ethynylphenyl, naphthyl, vinylnaphthyl, etc. are not limited to these.

作為碳數7～13的芳烷基，例如可列舉：苯基、鄰甲苯基、間甲苯基、對甲苯基、乙基苯基、苯乙烯基、二甲苯基、正丙基苯基、異丙基苯基、均三甲苯基、乙炔基苯基、萘基、乙烯基萘基等，但並不限定於該些。Examples of aralkyl groups having 7 to 13 carbon atoms include phenyl, o-tolyl, m-tolyl, p-tolyl, ethylphenyl, styryl, xylyl, n-propylphenyl, iso Propyl phenyl, mesityl, ethynyl phenyl, naphthyl, vinyl naphthyl, etc. are not limited to these.

作為碳數6～12的芳氧基，例如可列舉：苯氧基、鄰甲苯氧基、間甲苯氧基、對甲苯氧基、乙基苯氧基、苯乙烯氧基、二甲苯氧基、正丙基苯氧基、異丙基苯氧基、均三甲苯氧基、乙炔基苯氧基、萘氧基、乙烯基萘氧基等，但並不限定於該些。Examples of the aryloxy group having 6 to 12 carbon atoms include phenoxy group, o-tolyloxy group, m-tolyloxy group, p-tolyloxy group, ethylphenoxy group, styreneoxy group, xylyloxy group, N-propylphenoxy, isopropylphenoxy, mesityloxy, ethynylphenoxy, naphthyloxy, vinylnaphthyloxy, etc., but it is not limited to these.

作為碳數7～13的芳烷氧基，例如可列舉：苄基氧基、甲基苄基氧基、二甲基苄基氧基、三甲基苄基氧基、苯乙基氧基、1-苯基乙基氧基、2-苯基異丙基氧基、萘基甲基氧基等，但並不限定於該些。Examples of the aralkyloxy having 7 to 13 carbon atoms include benzyloxy, methylbenzyloxy, dimethylbenzyloxy, trimethylbenzyloxy, phenethyloxy, 1-phenylethyloxy, 2-phenylisopropyloxy, naphthylmethyloxy, etc. are not limited to these.

作為碳數2～12的烯基，例如可列舉：乙烯基、1-丙烯基、2-丙烯基、1-甲基乙烯基、1-丁烯基、2-丁烯基、3-丁烯基、1,3-丁二烯基、環己烯基、環己二烯基、肉桂基、萘基乙烯基等，但並不限定於該些。Examples of alkenyl groups having 2 to 12 carbon atoms include vinyl, 1-propenyl, 2-propenyl, 1-methylvinyl, 1-butenyl, 2-butenyl, and 3-butene. But not limited to these groups, 1,3-butadienyl, cyclohexenyl, cyclohexadienyl, cinnamyl, naphthylvinyl, etc.

作為碳數2～12的炔基，例如可列舉：乙炔基、1-丙炔基、2-丙炔基、1-丁炔基、2-丁炔基、3-丁炔基、1,3-丁二炔基、苯乙炔基、萘乙炔基等，但並不限定於該些。Examples of the alkynyl group having 2 to 12 carbon atoms include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1,3 -Butadiynyl, phenylethynyl, naphthaleneethynyl, etc., but not limited to these.

在以上列舉者中，作為R，較佳為氫原子、碳數1～4的烷基，進而特佳為氫原子、甲基。這是因為若取代基大，則耐熱性有可能降低。再者，R為氫原子是指i或j為0。 i為0～4的整數，j為0～6的整數，較佳為i為0～2的整數，j為0～2的整數。Among the above-listed, R is preferably a hydrogen atom and an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom and a methyl group. This is because if the substituent is large, the heat resistance may decrease. Furthermore, the fact that R is a hydrogen atom means that i or j is 0. i is an integer of 0-4, j is an integer of 0-6, preferably i is an integer of 0-2, and j is an integer of 0-2.

式（1）中，Y分別獨立地為氫原子、具有碳數1～20的烴基的醯基或縮水甘油基。在Y為氫原子的情況下，對末端賦予羥基，為醯基的情況下，對末端賦予酯基，為縮水甘油基的情況下，對末端賦予環氧基，因此可根據用途控制其比例。 作為碳數1～20的烴基，較佳為碳數1～12的烷基、碳數6～12的芳基、或碳數7～13的芳烷基，可列舉上述例示的基。該些中，更佳為具有碳數1～7的烴基的醯基，進而佳為乙醯基、丙醯基、丁醯基、苯甲醯基、甲基苯甲醯基，特佳為乙醯基、苯甲醯基。再者，乙醯基理解為為具有碳數1的烴基的醯基。In the formula (1), Y is each independently a hydrogen atom, an acyl group or a glycidyl group having a hydrocarbon group having 1 to 20 carbon atoms. When Y is a hydrogen atom, a hydroxyl group is provided to the terminal, and when it is an acyl group, an ester group is provided to the terminal, and when it is a glycidyl group, an epoxy group is provided to the terminal. Therefore, the ratio can be controlled according to the application. The hydrocarbon group having 1 to 20 carbons is preferably an alkyl group having 1 to 12 carbons, an aryl group having 6 to 12 carbons, or an aralkyl group having 7 to 13 carbons, and the groups exemplified above are exemplified. Among these, more preferred is an acyl group having a hydrocarbon group having 1 to 7 carbon atoms, further preferred is an acetyl group, a propionyl group, a butyryl group, a benzyl group, and a methylbenzyl group, and particularly preferably an acetyl group. , Benzoyl. In addition, an acetyl group is understood as an acyl group having a hydrocarbon group with a carbon number of 1.

式（1）中，Z為具有碳數1～20的烴基的醯基或氫原子。Z的5莫耳%以上為醯基，剩餘為氫原子。Z的10莫耳%以上、較佳為50莫耳%以上、更佳為70莫耳%以上為醯基。另外，上限較佳為100莫耳%，但實質上為95莫耳%即可。具有碳數1～20的烴基的醯基與所述Y中例示的醯基相同，較佳的醯基亦相同。 在Z全部（100莫耳%）為醯基的情況下，本發明的苯氧基樹脂不含二級羥基，可進一步改良介電特性、耐濕性。另一方面，例如在對相對於金屬的接著性進行微調整時，使Z的一部分作為氫原子而殘留，因此在不對以耐濕性為首的其他物性產生大的影響的範圍內，亦可在本發明的苯氧基樹脂中特意存在適量的二級羥基。In the formula (1), Z is an acyl group or a hydrogen atom having a hydrocarbon group having 1 to 20 carbon atoms. More than 5 mol% of Z is an acyl group, and the remainder is a hydrogen atom. 10 mol% or more of Z, preferably 50 mol% or more, and more preferably 70 mol% or more, are the base. In addition, the upper limit is preferably 100 mol%, but substantially 95 mol%. The acyl group having a hydrocarbon group having 1 to 20 carbons is the same as the acyl group exemplified in the above Y, and the preferred acyl group is also the same. When all of Z (100 mol%) is an acyl group, the phenoxy resin of the present invention does not contain a secondary hydroxyl group, which can further improve the dielectric properties and moisture resistance. On the other hand, for example, when fine-tuning the adhesion to metal, a part of Z remains as a hydrogen atom. Therefore, it can be used within a range that does not greatly affect other physical properties such as moisture resistance. The phenoxy resin of the present invention deliberately has an appropriate amount of secondary hydroxyl groups.

在式（1）中，n是重覆數並且是平均值。其值的範圍是15以上且500以下。就成形性及操作性的觀點而言，較佳為17以上且400以下，更佳為20以上且300以下。可根據藉由GPC法獲得的數量平均分子量（Mn）計算出n數。In formula (1), n is the number of repetitions and is the average value. The value range is 15 or more and 500 or less. From the viewpoint of formability and handleability, it is preferably 17 or more and 400 or less, and more preferably 20 or more and 300 or less. The n number can be calculated based on the number average molecular weight (Mn) obtained by the GPC method.

本發明的苯氧基樹脂的環氧當量並無特別限定，但較佳為2,000 g/eq.～50,000 g/eq.的範圍。若為該範圍，則本發明的苯氧基樹脂其本身參與硬化反應，而能夠併入交聯結構中。The epoxy equivalent of the phenoxy resin of the present invention is not particularly limited, but is preferably in the range of 2,000 g/eq. to 50,000 g/eq. If it is in this range, the phenoxy resin of the present invention itself participates in the hardening reaction and can be incorporated into the crosslinked structure.

本發明的苯氧基樹脂是二級羥基的部分或全部醯化而得者，可藉由各種方法獲得。作為較佳的製造方法，例如，有以下的製造方法。 （A）：使所述式（7）所表示的二官能環氧樹脂與所述式（8）所表示的二酯系化合物及/或二官能酚化合物反應的製造方法。以下，有時稱為製造方法（A）。 （B）：使所述式（12）所表示的苯氧基樹脂（為了與本發明的苯氧基樹脂區分，有時稱為苯氧基樹脂（a））與有機酸的酸酐、有機酸的鹵化物、有機酸的酯化物等酸成分（醯化劑）反應的製造方法。以下，有時稱為製造方法（B）。 藉由製造方法（A）及（B）獲得的苯氧基樹脂是本發明的苯氧基樹脂，並且由相同的式（1）表示。The phenoxy resin of the present invention is obtained by partial or complete acylation of secondary hydroxyl groups, and can be obtained by various methods. As a preferable manufacturing method, for example, there are the following manufacturing methods. (A): A manufacturing method of reacting the difunctional epoxy resin represented by the formula (7) with the diester compound and/or the bifunctional phenol compound represented by the formula (8). Hereinafter, it may be referred to as a manufacturing method (A). (B): The phenoxy resin represented by the formula (12) (in order to distinguish it from the phenoxy resin of the present invention, sometimes referred to as the phenoxy resin (a)) and the acid anhydride of organic acid, organic acid The production method of the reaction of acid components such as halides and organic acid esters (facilitating agents). Hereinafter, it may be referred to as manufacturing method (B). The phenoxy resin obtained by the production methods (A) and (B) is the phenoxy resin of the present invention, and is represented by the same formula (1).

製造方法（A）是使式（7）所表示的二官能環氧樹脂與式（8）所表示的化合物反應的方法。 所述式（7）中，G為縮水甘油基，m為重覆數，其平均值為0以上且6以下。 式（8）中，Z¹ 的5莫耳%以上為具有碳數1～20的烴基的醯基，剩餘為氫原子。此處，式（8）所表示的化合物可為選自Z¹ 的兩者為醯基的化合物、一者為醯基而另一者為氫原子的化合物、及兩者為氫原子的化合物的兩種以上的混合物。當Z¹ 的兩者是醯基時，為二酯，當兩者是氫原子時，為二酚類。將式（8）所表示的化合物稱為二酯系化合物。二酯系化合物可為Z¹ 的兩者為醯基的化合物、或主要成分（50%以上）為該化合物的化合物（混合物）。The production method (A) is a method of reacting the bifunctional epoxy resin represented by the formula (7) with the compound represented by the formula (8). In the formula (7), G is a glycidyl group, m is the number of repetitions, and the average value thereof is 0 or more and 6 or less. In formula (8), ^{5 mol% or more of Z 1} is an acyl group having a hydrocarbon group with 1 to 20 carbon atoms, and the remainder is a hydrogen atom. Here, the compound represented by the formula (8) may be a compound selected from Z ¹ in which two are acyl groups, one is an acyl group and the other is a hydrogen atom, and both are hydrogen atoms. A mixture of two or more. When ^{both of Z 1} are acyl groups, they are diesters, and when both of Z 1 are hydrogen atoms, they are diphenols. The compound represented by formula (8) is referred to as a diester compound. The diester compound may be a compound ^{in which both of Z 1} are acyl groups, or a compound (mixture) in which the main component (50% or more) is the compound.

選擇式（7）及式（8）中的X¹ 以賦予式（1）的X。因此，式（7）及式（8）中的X¹ 任意一個含有式（2）及/或式（3）所表示的二氧基，作為式（7）及式（8）的整體含有式（2）及式（3）所表示的二氧基。例如，式（7）或式（8）中一者的X¹ 包含式（2）所表示的二氧基，另一者包含式（3）所表示的二氧基，或者可僅式（7）或式（8）中一者的X¹ 包含式（2）及式（3）所表示的二氧基，另一者不包含二氧基，但是前者較佳。 本發明的苯氧基樹脂必須含有式（2）及式（3）所表示的二氧基，只要滿足該條件，式（2）及式（3）的二氧基可包含在作為原料的二官能環氧樹脂及/或式（8）所表示的化合物的任意一種中，並且其比例亦無限制。 另外，作為所述式（7）或式（8）中的X¹ ，在不包含式（2）及式（3）的化學結構的情況下，可將其他二價基引入X¹ 中。 ^{X 1} in equations (7) and (8) is selected to give X in equation (1). Therefore, ^{any one of X 1 in} formula (7) and formula (8) contains a dioxy group represented by formula (2) and/or formula (3), and contains formula (7) and formula (8) as a whole (2) and the dioxy group represented by the formula (3). ^{For example, X 1} in one of formula (7) or formula (8) includes a dioxy group represented by formula (2), and the other includes a dioxy group represented by formula (3), or only formula (7) ^{X 1} in one of) or formula (8) includes a dioxy group represented by formula (2) and formula (3), and the other does not include a dioxy group, but the former is preferred. The phenoxy resin of the present invention must contain the dioxy group represented by formula (2) and formula (3). As long as this condition is satisfied, the dioxy group of formula (2) and formula (3) can be included in the dioxy group as a raw material. In any one of the functional epoxy resin and/or the compound represented by formula (8), the ratio is not limited. ^{In addition, as X 1} in the formula (7) or formula (8), if the chemical structure of the formula (2) and the formula (3) is not included, other divalent groups may be introduced into X ¹ .

本發明的製造方法（A）中使用的二官能環氧樹脂為所述式（7）所表示的環氧樹脂，例如可列舉在鹼金屬化合物存在下使下述式（14）所表示的二官能酚化合物與表鹵醇反應而獲得的環氧樹脂等。 作為表鹵醇，例如可列舉表氯醇、表溴醇等。 作為鹼金屬化合物，例如可列舉：氫氧化鈉、氫氧化鋰、氫氧化鉀等鹼金屬氫氧化物；碳酸鈉、碳酸氫鈉、氯化鈉、氯化鋰、氯化鉀等鹼金屬鹽；甲醇鈉、乙醇鈉等鹼金屬醇鹽；乙酸鈉、硬脂酸鈉等有機酸的鹼金屬鹽；鹼金屬酚鹽、氫化鈉、氫化鋰等。The bifunctional epoxy resin used in the production method (A) of the present invention is the epoxy resin represented by the above formula (7), for example, the two represented by the following formula (14) can be exemplified in the presence of an alkali metal compound Epoxy resin obtained by reacting functional phenol compound with epihalohydrin, etc. As an epihalohydrin, epichlorohydrin, epibromohydrin, etc. are mentioned, for example. Examples of the alkali metal compound include alkali metal hydroxides such as sodium hydroxide, lithium hydroxide, and potassium hydroxide; alkali metal salts such as sodium carbonate, sodium bicarbonate, sodium chloride, lithium chloride, and potassium chloride; Alkali metal alkoxides such as sodium methoxide and sodium ethoxide; alkali metal salts of organic acids such as sodium acetate and sodium stearate; alkali metal phenates, sodium hydride, lithium hydride, etc.

在用於獲得原料環氧樹脂的二官能酚化合物與表鹵醇的反應中，使用相對於二官能酚化合物中的官能基為0.80倍莫耳～1.20倍莫耳、較佳為0.85倍莫耳～1.05倍莫耳的鹼金屬化合物。若少於此，殘存的水解性氯的量會增多，而不佳。作為鹼金屬化合物，在水溶液、醇溶液或固體的狀態下使用。In the reaction of the difunctional phenol compound used to obtain the raw material epoxy resin with epihalohydrin, the functional group in the difunctional phenol compound is used in a range of 0.80 times mol to 1.20 times mol, preferably 0.85 times mol ~1.05 times moles of alkali metal compounds. If it is less than this, the amount of remaining hydrolyzable chlorine will increase, which is not preferable. As an alkali metal compound, it is used in the state of an aqueous solution, an alcohol solution, or a solid.

在環氧化反應時，相對於二官能酚化合物使用過量的表鹵醇。通常，相對於二官能酚化合物中的官能基1莫耳，使用1.5倍莫耳～15倍莫耳的表鹵醇，較佳為2倍莫耳～10倍莫耳，更佳為5倍莫耳～8倍莫耳。若多於此，則生產效率降低，若少於此，則環氧樹脂的高分子量體的生成量增加，不適於苯氧基樹脂的原料。In the epoxidation reaction, an excess of epihalohydrin is used relative to the bifunctional phenol compound. Generally, 1.5 to 15 times mol of epihalohydrin is used relative to 1 mol of the functional group in the bifunctional phenol compound, preferably 2 times to 10 times mol, more preferably 5 times mol. Ear ~ 8 times mole. If it is more than this, the production efficiency is reduced, and if it is less than this, the amount of high molecular weight epoxy resin produced increases, which is not suitable for the raw material of phenoxy resin.

環氧化反應通常在120℃以下的溫度下進行。反應時，若溫度高，則所謂難水解性氯量增多，高純度化變得困難。較佳為100℃以下，進而佳為85℃以下的溫度。The epoxidation reaction is usually carried out at a temperature below 120°C. During the reaction, if the temperature is high, the amount of so-called hardly hydrolyzable chlorine increases, making it difficult to achieve high purity. Preferably it is 100 degrees C or less, More preferably, it is 85 degrees C or less temperature.

[化5]

式（14）中，X¹ 與所述式（7）或式（8）的X¹ 同樣。[化5]

Formula (14), X X ¹ and (7) or (8) of the same formula ^1.

若使所述式（14）所表示的二官能酚化合物與表鹵醇反應，則m通常大於0。為了使m為0，有藉由蒸餾、結晶等方式高度地精製利用公知的方法製造的環氧樹脂、或者將所述式（14）所表示的二官能酚化合物烯丙基化後，將烯烴部分氧化而進行環氧化的方法。When the bifunctional phenol compound represented by the formula (14) is reacted with epihalohydrin, m is usually greater than zero. In order to make m 0, there are methods such as distillation, crystallization, etc. to highly refine the epoxy resin produced by a known method, or the allylation of the bifunctional phenol compound represented by the formula (14), and then the olefin Partial oxidation and epoxidation method.

另外，本發明的製造方法（A）中使用的二酯系化合物例如藉由與有機酸的酸酐、有機酸的鹵化物、或有機酸的縮合反應將所述式（14）所表示的二官能酚化合物醯化而獲得。In addition, the diester compound used in the production method (A) of the present invention converts the bifunctional compound represented by the formula (14) by condensation reaction with an anhydride of an organic acid, a halide of an organic acid, or an organic acid. The phenol compound is obtained by acylation.

藉由將式（7）中的m為0的環氧樹脂作為原料，本發明的苯氧基樹脂不含有二級羥基，可進一步改良介電特性、耐濕性。另外，例如在對相對於金屬的接著性進行微調整時，使用適當的m數的環氧樹脂，因此在不對以耐濕性為首的其他物性產生大的影響的範圍內，亦可在本發明的苯氧基樹脂中特意存在適量的二級羥基。By using an epoxy resin in which m in formula (7) is 0 as a raw material, the phenoxy resin of the present invention does not contain a secondary hydroxyl group, and the dielectric properties and moisture resistance can be further improved. In addition, for example, when finely adjusting the adhesion to metal, an epoxy resin with an appropriate number of m is used. Therefore, the present invention may be used in the present invention within a range that does not greatly affect other physical properties such as moisture resistance. A moderate amount of secondary hydroxyl is deliberately present in the phenoxy resin.

在製造方法（A）中使用的二官能環氧樹脂或二酯系化合物中，相對於所述式（7）及式（8）中的X¹ 整體的莫耳數，較佳含有1莫耳%～100莫耳%的所述式（2）及式（3）所表示的化學結構。就充分表現起因於式（2）及式（3）所表示的化學結構的耐折性及介電特性的觀點而言，更佳為式（2）及式（3）所表示的化學結構為10莫耳%以上，進而佳為30莫耳%以上，特佳為50莫耳%以上。In the bifunctional epoxy resin or diester compound used in the production method (A), it is preferable to contain 1 mol ^{relative to the number of mols of X 1 in the above formula (7) and formula (8) as a whole} %-100 mol% of the chemical structure represented by the formula (2) and formula (3). From the viewpoint of fully expressing the folding resistance and dielectric properties resulting from the chemical structures represented by formulas (2) and (3), it is more preferable that the chemical structures represented by formulas (2) and (3) are 10 mol% or more, more preferably 30 mol% or more, particularly preferably 50 mol% or more.

關於所述二官能環氧樹脂與二酯系化合物的使用量，相對於環氧基1當量，酯基較佳為0.8當量～1.0當量。若為該當量比，則容易進行在分子末端具有環氧基的狀態下的高分子量化，因此較佳。另外，亦能夠將二酯系化合物的一部分取代為所述式（14）所表示的二官能酚化合物。藉此，如上所述，藉由在本發明的苯氧基樹脂中特意存在適量的二級羥基，可實現物性的微調整。 在製造方法（A）中，發生聚合反應與酯交換反應，Mw增加以生成苯氧基樹脂，並且苯氧基樹脂的部分羥基被酯化。Regarding the usage amount of the difunctional epoxy resin and the diester-based compound, the ester group is preferably 0.8 equivalent to 1.0 equivalent relative to 1 equivalent of the epoxy group. If it is this equivalent ratio, it is easy to perform high molecular weight in the state which has an epoxy group at a molecular terminal, and it is preferable. In addition, it is also possible to substitute a part of the diester-based compound with the bifunctional phenol compound represented by the above-mentioned formula (14). Thus, as described above, by deliberately presenting an appropriate amount of secondary hydroxyl groups in the phenoxy resin of the present invention, fine adjustment of physical properties can be achieved. In the manufacturing method (A), a polymerization reaction and a transesterification reaction occur, Mw increases to generate a phenoxy resin, and part of the hydroxyl groups of the phenoxy resin is esterified.

在製造方法（A）中，可使用觸媒，作為該觸媒，若為具有促進環氧基與酯基的反應般的觸媒能的化合物，則可為任意化合物。例如，可列舉：三級胺、環狀胺類、咪唑類、有機磷化合物、四級銨鹽等。另外，該些觸媒可單獨使用，亦可兩種以上組合使用。In the production method (A), a catalyst can be used, and as the catalyst, any compound may be used as long as it has a catalyst function that promotes the reaction between an epoxy group and an ester group. For example, tertiary amines, cyclic amines, imidazoles, organophosphorus compounds, quaternary ammonium salts, etc. can be cited. In addition, these catalysts can be used alone or in combination of two or more.

作為三級胺，例如可列舉：三乙胺、三-正丙胺、三-正丁胺、三乙醇胺、苄基二甲胺、2,4,6-三(二甲基胺基甲基)苯酚等，但並不限定於該些。Examples of tertiary amines include triethylamine, tri-n-propylamine, tri-n-butylamine, triethanolamine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol Etc., but not limited to these.

作為環狀胺類，例如可列舉：1,4-二氮雜雙環[2,2,2]辛烷（DABCO）、1,8-二氮雜雙環[5,4,0]十一烯-7（DBU）、1,5-二氮雜雙環[4,3,0]壬烯-5（DBN）、N-甲基嗎啉、吡啶、N,N-二甲基胺基吡啶（DMAP）等，但並不限定於該些。Examples of cyclic amines include: 1,4-diazabicyclo[2,2,2]octane (DABCO), 1,8-diazabicyclo[5,4,0]undecene- 7(DBU), 1,5-diazabicyclo[4,3,0]nonene-5 (DBN), N-methylmorpholine, pyridine, N,N-dimethylaminopyridine (DMAP) Etc., but not limited to these.

作為咪唑類，例如可列舉：2-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、1-苄基-2-甲基咪唑、1-苄基-2-苯基咪唑等，但並不限定於該些。Examples of imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methyl Butylimidazole, 1-benzyl-2-phenylimidazole, etc. are not limited to these.

作為有機磷化合物，例如可列舉：三-正丙基膦、三-正丁基膦、二苯基甲基膦、三苯基膦、三(對甲苯基)膦、三環己基膦、三(第三丁基)膦、三(對甲氧基苯基)膦、對甲基膦、1,2-雙(二甲基膦)乙烷、1,4-雙(二苯基膦)丁烷等膦類；四甲基溴化鏻、四甲基碘化鏻、四甲基氫氧化鏻、四丁基氫氧化鏻、三甲基環己基氯化鏻、三甲基環己基溴化鏻、三甲基苄基氯化鏻、三甲基苄基溴化鏻、四苯基溴化鏻、三苯基甲基溴化鏻、三苯基甲基碘化鏻、三苯基乙基氯化鏻、三苯基乙基溴化鏻、三苯基乙基碘化鏻、三苯基苄基氯化鏻、三苯基苄基溴化鏻等鏻鹽類等，但並不限定於該些。As the organophosphorus compound, for example, tri-n-propyl phosphine, tri-n-butyl phosphine, diphenyl methyl phosphine, triphenyl phosphine, tris (p-tolyl) phosphine, tricyclohexyl phosphine, tris( Tertiary butyl)phosphine, tris(p-methoxyphenyl)phosphine, p-methylphosphine, 1,2-bis(dimethylphosphine)ethane, 1,4-bis(diphenylphosphine)butane Phosphines; tetramethyl phosphonium bromide, tetramethyl phosphonium iodide, tetramethyl phosphonium hydroxide, tetrabutyl phosphonium hydroxide, trimethyl cyclohexyl phosphonium chloride, trimethyl cyclohexyl phosphonium bromide, Trimethylbenzylphosphonium chloride, trimethylbenzylphosphonium bromide, tetraphenylphosphonium bromide, triphenylmethylphosphonium bromide, triphenylmethylphosphonium iodide, triphenylethyl chloride Phosphonium salts such as phosphonium, triphenylethylphosphonium bromide, triphenylethylphosphonium iodide, triphenylbenzylphosphonium chloride, triphenylbenzylphosphonium bromide, etc., but not limited to these .

作為四級銨鹽，例如可列舉：四甲基氯化銨、四甲基溴化銨、四甲基氫氧化銨、三乙基甲基氯化銨、四乙基氯化銨、四乙基溴化銨、四乙基碘化銨、四丙基溴化銨、四丙基氫氧化銨、四丁基氯化銨、四丁基溴化銨、四丁基碘化銨、苄基三甲基氯化銨、苄基三甲基溴化銨、苄基三甲基氫氧化銨、苄基三丁基氯化銨、苯基三甲基氯化銨等，但並不限定於該些。Examples of quaternary ammonium salts include tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium hydroxide, triethylmethylammonium chloride, tetraethylammonium chloride, and tetraethyl Ammonium bromide, tetraethylammonium iodide, tetrapropylammonium bromide, tetrapropylammonium hydroxide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, benzyltrimethyl Benzyl ammonium chloride, benzyl trimethyl ammonium bromide, benzyl trimethyl ammonium hydroxide, benzyl tributyl ammonium chloride, phenyl trimethyl ammonium chloride, etc., but are not limited to these.

在以上列舉的觸媒中，較佳為4-(二甲基胺基)吡啶、1,4-二氮雜雙環[2,2,2]辛烷、1,8-二氮雜雙環[5,4,0]十一烯-7、1,5-二氮雜雙環[4,3,0]壬烯-5、2-乙基-4-甲基咪唑、三(對甲苯基)膦、三環己基膦、三(第三丁基)膦、三(對甲氧基苯基)膦、特佳為4-(二甲基胺基)吡啶、1,8-二氮雜雙環[5,4,0]十一烯-7、1,5-二氮雜雙環[4,3,0]壬烯-5、2-乙基-4-甲基咪唑。Among the above-listed catalysts, 4-(dimethylamino)pyridine, 1,4-diazabicyclo[2,2,2]octane, 1,8-diazabicyclo[5 ,4,0]Undecene-7,1,5-diazabicyclo[4,3,0]nonene-5,2-ethyl-4-methylimidazole, tris(p-tolyl)phosphine, Tricyclohexylphosphine, tris(tertiary butyl)phosphine, tris(p-methoxyphenyl)phosphine, particularly preferably 4-(dimethylamino)pyridine, 1,8-diazabicyclo[5, 4,0] Undecene-7, 1,5-diazabicyclo[4,3,0]nonene-5, 2-ethyl-4-methylimidazole.

儘管觸媒的使用量於反應固體成分中通常為0.001質量%～1質量%，但是在使用該些化合物作為觸媒的情況下，該些觸媒作為殘渣而殘留在所獲得的苯氧基樹脂中，從而有可能使印刷配線板的絕緣特性惡化、或縮短組成物的適用期，因此苯氧基樹脂中氮的含有量較佳為0.5質量%以下，更佳為0.3質量%以下。另外，苯氧基樹脂中磷的含有量較佳為0.5質量%以下，更佳為0.3質量%以下。Although the amount of the catalyst used is usually 0.001% by mass to 1% by mass in the solid content of the reaction, when these compounds are used as the catalyst, the catalyst remains as a residue in the obtained phenoxy resin In this case, the insulating properties of the printed wiring board may be deteriorated or the pot life of the composition may be shortened. Therefore, the nitrogen content in the phenoxy resin is preferably 0.5% by mass or less, more preferably 0.3% by mass or less. In addition, the content of phosphorus in the phenoxy resin is preferably 0.5% by mass or less, more preferably 0.3% by mass or less.

在製造方法（A）中，可使用反應用的溶媒，作為該溶媒，只要為溶解苯氧基樹脂的溶媒，則可為任意溶媒。例如可列舉：芳香族系溶媒、酮系溶媒、醯胺系溶媒、二醇醚系溶媒、酯系溶媒等。另外，該些溶媒可僅使用一種，亦可組合使用兩種以上。In the production method (A), a solvent for reaction can be used, and as the solvent, any solvent may be used as long as it dissolves the phenoxy resin. For example, aromatic solvents, ketone solvents, amide solvents, glycol ether solvents, ester solvents, etc. are mentioned. In addition, only one type of these solvents may be used, or two or more types may be used in combination.

作為芳香族系溶媒，例如可列舉：苯、甲苯、二甲苯等。As an aromatic solvent, benzene, toluene, xylene, etc. are mentioned, for example.

作為酮系溶媒，例如可列舉：丙酮、甲基乙基酮（methyl ethyl ketone，MEK）、甲基異丁基酮、2-庚酮、4-庚酮、2-辛酮、環己酮、乙醯丙酮、二噁烷、二異丁基酮、異佛爾酮、甲基環己酮、苯乙酮等。Examples of ketone-based solvents include acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, 2-heptanone, 4-heptanone, 2-octanone, cyclohexanone, Acetylacetone, dioxane, diisobutyl ketone, isophorone, methylcyclohexanone, acetophenone, etc.

作為醯胺系溶媒，例如可列舉：甲醯胺、N-甲基甲醯胺、N,N-二甲基甲醯胺（N,N-dimethyl formamide，DMF）、乙醯胺、N-甲基乙醯胺、N,N-二甲基乙醯胺、2-吡咯啶酮、N-甲基吡咯啶酮等。Examples of amide-based solvents include formamide, N-methyl formamide, N,N-dimethyl formamide (N,N-dimethyl formamide, DMF), acetamide, and N-methyl formamide. Acetamide, N,N-dimethylacetamide, 2-pyrrolidone, N-methylpyrrolidone, etc.

作為二醇醚系溶媒，例如可列舉：乙二醇單甲醚、乙二醇單***、乙二醇單正丁醚、乙二醇單烷基醚類；二乙二醇單甲醚、二乙二醇單***、二乙二醇單正丁醚、丙二醇單甲醚等乙二醇二烷基醚類；丙二醇單甲醚、丙二醇單***、丙二醇單正丁醚等丙二醇單烷基醚類；乙二醇二甲醚、乙二醇二***、乙二醇二丁醚等乙二醇二烷基醚類；二乙二醇二甲醚、二乙二醇二***、二乙二醇二丁醚、三乙二醇二甲醚、三乙二醇二***、三乙二醇二丁醚等聚乙二醇二烷基醚類；丙二醇二甲醚、丙二醇二***、丙二醇二丁醚等丙二醇二烷基醚類；二丙二醇二甲醚、二丙二醇二***、二丙二醇二丁醚、三丙二醇二甲醚、三丙二醇二***、三丙二醇二丁醚等聚丙二醇二烷基醚類；乙二醇單甲醚乙酸酯、乙二醇單***乙酸酯、乙二醇單丁醚乙酸酯等乙二醇單烷基醚乙酸酯類；二乙二醇單甲醚乙酸酯、二乙二醇單***乙酸酯、二乙二醇單丁醚乙酸酯、三乙二醇單甲醚乙酸酯、三乙二醇單***乙酸酯、三乙二醇單丁醚乙酸酯等聚乙二醇單烷基醚乙酸酯類；丙二醇單甲醚乙酸酯、丙二醇單***乙酸酯、丙二醇單丁醚乙酸酯等丙二醇單烷基醚乙酸酯類等。As the glycol ether solvent, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol monoalkyl ethers; diethylene glycol monomethyl ether, diethylene glycol monomethyl ether Ethylene glycol dialkyl ethers such as ethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, and propylene glycol monomethyl ether; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol mono-n-butyl ether ; Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether and other glycol dialkyl ethers; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol two Polyethylene glycol dialkyl ethers such as butyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, and triethylene glycol dibutyl ether; propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether, etc. Propylene glycol dialkyl ethers; dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol dibutyl ether and other polypropylene glycol dialkyl ethers; B Glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate and other ethylene glycol monoalkyl ether acetates; diethylene glycol monomethyl ether acetate, Diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, triethylene glycol monobutyl ether ethyl Polyethylene glycol monoalkyl ether acetates such as acid esters; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, etc.

作為酯系溶媒，例如可列舉：乙酸甲酯、乙酸乙酯、乙酸正丙酯、乙酸異丙酯、乙酸正丁酯、乙酸苄酯、丙酸乙酯、丁酸乙酯、丁酸丁酯、戊內酯、丁內酯等。Examples of ester solvents include methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, benzyl acetate, ethyl propionate, ethyl butyrate, and butyl butyrate. , Valerolactone, butyrolactone, etc.

另外，作為其他溶媒，例如可列舉：二甲基亞碸、環丁碸、γ-丁內酯、N-甲基-2-吡咯啶酮等。In addition, as other solvents, for example, dimethylsulfene, cyclobutene, γ-butyrolactone, N-methyl-2-pyrrolidone, and the like can be cited.

在製造方法（A）中，反應時的固體成分濃度較佳為35質量%～95質量%。另外，當在反應中途產生高黏性生成物時，亦可追加添加溶媒來使反應繼續。在反應結束後，溶媒亦可視需要除去，亦可進一步追加。In the production method (A), the solid content concentration during the reaction is preferably 35% by mass to 95% by mass. In addition, when a highly viscous product is produced in the middle of the reaction, a solvent may be additionally added to continue the reaction. After the completion of the reaction, the solvent may be removed as needed, and may be further added.

反應溫度在所使用的觸媒不會分解的程度的溫度範圍內進行。若反應溫度過高，則有可能觸媒分解而反應停止、或生成的苯氧基樹脂劣化。若反應溫度過低，則反應未充分進行而有可能無法成為目標分子量。因此，反應溫度較佳為50℃～230℃，更佳為120℃～200℃。另外，反應時間通常為1小時～12小時，較佳為3小時～10小時。於使用丙酮或甲基乙基酮般的低沸點溶媒的情況下，可藉由使用高壓釜在高壓下進行反應來確保反應溫度。另外，於需要除去反應熱的情況下，通常藉由利用反應熱的使用溶媒的蒸發/凝縮/回流法、間接冷卻法、或該些併用來進行。The reaction temperature is performed within the temperature range to the extent that the catalyst used does not decompose. If the reaction temperature is too high, the catalyst may decompose and the reaction may stop, or the phenoxy resin produced may deteriorate. If the reaction temperature is too low, the reaction may not proceed sufficiently and may not reach the target molecular weight. Therefore, the reaction temperature is preferably 50°C to 230°C, more preferably 120°C to 200°C. In addition, the reaction time is usually 1 hour to 12 hours, preferably 3 hours to 10 hours. In the case of using a low-boiling solvent such as acetone or methyl ethyl ketone, the reaction temperature can be ensured by using an autoclave to perform the reaction under high pressure. In addition, when the heat of reaction needs to be removed, it is usually performed by the evaporation/condensation/reflux method using a solvent using the heat of reaction, indirect cooling method, or a combination of these.

接著，對本發明的製造方法（B）進行說明。 製造方法（B）是使式（12）所表示的苯氧基樹脂與醯化劑以相對於苯氧基樹脂的醇性羥基1莫耳而醯基為0.05莫耳以上且2.0莫耳以下進行反應，而獲得重量平均分子量為10,000～200,000的由式（1）表示的苯氧基樹脂、即，本發明的苯氧基樹脂的方法。Next, the manufacturing method (B) of the present invention will be described. The production method (B) is to make the phenoxy resin represented by the formula (12) and the acylating agent 1 mol and the alcohol group of 0.05 mol or more and 2.0 mol or less with respect to the alcoholic hydroxyl group of the phenoxy resin. A method for obtaining the phenoxy resin represented by the formula (1) having a weight average molecular weight of 10,000 to 200,000, that is, the phenoxy resin of the present invention by reaction.

作為原料的苯氧基樹脂（a）在式（12）的X² 中必須含有由所述式（2）及式（3）表示的二氧基。 該苯氧基樹脂（a）可藉由先前已知的方法獲得。例如，可列舉使二官能酚化合物類與表鹵醇在鹼金屬化合物存在下反應來製造的方法（以下，稱為「一段法」），其中所述二官能酚化合物類將具有由所述式（2）表示的結構的二官能酚化合物（有時稱為二官能酚化合物（a））及具有由所述式（3）表示的結構的二官能酚化合物（有時稱為二官能酚化合物（b））作為必須成分；或使二官能環氧樹脂類及二官能酚化合物類中的至少一種具有由所述式（2）及式（3）表示的結構的二官能環氧樹脂類與二官能酚化合物類在觸媒存在下反應來製造的方法（以下，稱為二段法）。苯氧基樹脂（a）可藉由任意製造方法來獲得，通常，與一段法相比，二段法更容易獲得苯氧基樹脂，因此較佳使用二段法。The phenoxy resin (a) as a raw material must contain the dioxy group represented by the formula (2) and the formula (3) ^{in X 2 of the formula (12).} The phenoxy resin (a) can be obtained by a previously known method. For example, a method of producing a bifunctional phenol compound and epihalohydrin in the presence of an alkali metal compound (hereinafter referred to as the "one-stage method") can be cited, wherein the bifunctional phenol compound will have the formula (2) The bifunctional phenol compound (sometimes referred to as difunctional phenol compound (a)) of the structure represented by the formula (3) and the difunctional phenol compound (sometimes referred to as difunctional phenol compound (B)) as an essential component; or difunctional epoxy resins having at least one of the bifunctional epoxy resins and difunctional phenol compounds having the structure represented by the formula (2) and formula (3) and A method in which bifunctional phenol compounds are produced by reacting in the presence of a catalyst (hereinafter, referred to as a two-stage method). The phenoxy resin (a) can be obtained by any manufacturing method. Generally, the two-stage method is easier to obtain the phenoxy resin than the one-stage method, so the two-stage method is preferably used.

關於苯氧基樹脂（a）的重量平均分子量或環氧當量，於一段法中，可藉由適當調整表鹵醇與二官能酚化合物類的投入莫耳比來製造處於目標範圍者，於二段法中，可藉由適當調整二官能環氧樹脂類與二官能酚化合物類的投入莫耳比來製造處於目標範圍者。Regarding the weight average molecular weight or epoxy equivalent of the phenoxy resin (a), in the one-stage method, the molar ratio of the epihalohydrin and the bifunctional phenol compound can be adjusted appropriately to produce the one in the target range. In the stage method, the molar ratio of the bifunctional epoxy resins and the bifunctional phenol compounds can be adjusted appropriately to produce those in the target range.

作為一段法及二段法的製造中所使用的二官能酚化合物，將二官能酚化合物（a）及二官能酚化合物（b）作為必須成分。 作為二官能酚化合物（a），例如可列舉鄰苯二酚、間苯二酚、對苯二酚。另外，該些亦可經烷基、芳基等無不良影響的取代基取代。 作為二官能酚化合物（b），例如可列舉1,4-二羥基萘、1,5-二羥基萘、1,6-二羥基萘、2,6-二羥基萘、2,7-二羥基萘等。另外，該些亦可經烷基、芳基等無不良影響的取代基取代。As the bifunctional phenol compound used in the production of the one-stage method and the two-stage method, the bifunctional phenol compound (a) and the bifunctional phenol compound (b) are essential components. Examples of the bifunctional phenol compound (a) include catechol, resorcinol, and hydroquinone. In addition, these may be substituted with substituents that have no adverse effects, such as alkyl groups and aryl groups. Examples of the bifunctional phenol compound (b) include 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, and 2,7-dihydroxynaphthalene. Naphthalene and so on. In addition, these may be substituted with substituents that have no adverse effects, such as alkyl groups and aryl groups.

另外，只要不損害本發明的目的，亦可併用除該些之外的二官能酚化合物。作為可併用的二官能酚化合物，例如可列舉：雙酚A、雙酚F、雙酚S、雙酚B、雙酚E、雙酚C、雙酚苯乙酮、雙酚芴、二羥基聯苯醚、二羥基聯苯硫醚等雙酚類；4,4'-聯苯酚、2,4'-聯苯酚等聯苯酚類；1,1-聯-2-萘酚等。 另外，該些二官能酚化合物亦可併用多種。In addition, as long as the purpose of the present invention is not impaired, difunctional phenol compounds other than these may be used in combination. Examples of bifunctional phenol compounds that can be used in combination include: bisphenol A, bisphenol F, bisphenol S, bisphenol B, bisphenol E, bisphenol C, bisphenol acetophenone, bisphenol fluorene, and dihydroxy biphenyl Bisphenols such as phenyl ether and dihydroxybiphenyl sulfide; biphenols such as 4,4'-biphenol and 2,4'-biphenol; 1,1-bin-2-naphthol, etc. Moreover, these bifunctional phenol compounds can also use multiple types together.

首先，對一段法進行說明。 於一段法的情況下，相對於二官能酚化合物類1莫耳，使表鹵醇0.985莫耳～1.015莫耳、較佳為0.99莫耳～1.012莫耳、更佳為0.995莫耳～1.01莫耳於鹼金屬化合物的存在下、在非反應性溶媒中進行反應，從而消耗表鹵醇，並且以重量平均分子量為10,000以上的方式進行縮合反應，藉此可獲得苯氧基樹脂（a）。再者，反應結束後，需要藉由過濾分離或水洗來去除副產生的鹽。作為鹼金屬化合物，可例示與製造用於本發明的製造方法（A）的由所述式（7）表示的二官能環氧樹脂時使用的鹼金屬化合物相同者。First, the one-paragraph method will be explained. In the case of the one-stage method, the epihalohydrin is 0.985 mol to 1.015 mol, preferably 0.99 mol to 1.012 mol, and more preferably 0.995 mol to 1.01 mol relative to 1 mol of the bifunctional phenol compound. In the presence of an alkali metal compound, the reaction is carried out in a non-reactive solvent to consume epihalohydrin, and the condensation reaction is carried out so that the weight average molecular weight is 10,000 or more, whereby the phenoxy resin (a) can be obtained. Furthermore, after the reaction is completed, it is necessary to remove the by-produced salt by filtration or washing with water. As the alkali metal compound, the same alkali metal compound used in the production of the bifunctional epoxy resin represented by the formula (7) used in the production method (A) of the present invention can be exemplified.

作為原料使用的二官能酚化合物（a）與二官能酚化合物（b）的莫耳比較佳為1/9～9/1，更佳為2/8～8/2，進而佳為3/7～7/3，特佳為4/6～6/4。另外，二官能酚化合物（a）及二官能酚化合物（b）的合計莫耳數在全部二官能酚化合物類中較佳為1莫耳%以上，更佳為20莫耳%以上，進而佳為50莫耳%以上，特佳為75莫耳%以上。若超出該範圍，則製成發明的苯氧基樹脂時耐熱性、耐折性有可能惡化。The molar ratio of the difunctional phenol compound (a) and the difunctional phenol compound (b) used as the raw material is preferably 1/9-9/1, more preferably 2/8-8/2, and still more preferably 3/7 ～7/3, particularly preferably 4/6～6/4. In addition, the total number of moles of the bifunctional phenol compound (a) and the bifunctional phenol compound (b) is preferably 1 mole% or more, more preferably 20 mole% or more, and still more preferably It is more than 50 mol%, particularly preferably more than 75 mol%. If it exceeds this range, heat resistance and folding resistance may deteriorate when the phenoxy resin of the invention is used.

該反應可在常壓下或減壓下進行。反應溫度通常在常壓下反應的情況下，較佳為20℃～200℃，更佳為30℃～170℃，進而佳為40℃～150℃，特佳為50℃～100℃。在減壓下反應的情況下，較佳為20℃～100℃，更佳為30℃～90℃，進而佳為35℃～80℃。若反應溫度在此範圍內，則不易引起副反應，而容易使反應進行。反應壓力通常為常壓。另外，在需要除去反應熱的情況下，通常藉由利用反應熱的使用溶媒的蒸發/凝縮/回流法、間接冷卻法、或該些的併用來進行。The reaction can be carried out under normal pressure or under reduced pressure. The reaction temperature is usually in the case of the reaction under normal pressure, preferably 20°C to 200°C, more preferably 30°C to 170°C, still more preferably 40°C to 150°C, particularly preferably 50°C to 100°C. In the case of the reaction under reduced pressure, it is preferably 20°C to 100°C, more preferably 30°C to 90°C, and still more preferably 35°C to 80°C. If the reaction temperature is within this range, side reactions are less likely to occur, and the reaction is likely to proceed. The reaction pressure is usually atmospheric pressure. In addition, when the heat of reaction needs to be removed, it is usually carried out by an evaporation/condensation/reflux method using a solvent, an indirect cooling method, or a combination of these using the heat of reaction.

作為反應性溶媒，除了使用本發明的製造方法（A）中例示的反應用溶媒之外，亦可使用乙醇、異丙醇、丁醇等醇類。可僅使用一種，亦可將兩種以上組合使用。As the reactive solvent, in addition to the reaction solvent exemplified in the production method (A) of the present invention, alcohols such as ethanol, isopropanol, and butanol may also be used. Only one type may be used, or two or more types may be used in combination.

接著，對二段法進行說明。 就作為二段法的原料環氧樹脂的二官能環氧樹脂而言，使用與本發明的製造方法（A）中所使用的由所述式（7）表示的二官能環氧樹脂相同的樹脂。Next, the two-stage method will be described. For the difunctional epoxy resin as the raw material epoxy resin of the two-stage method, the same resin as the difunctional epoxy resin represented by the formula (7) used in the production method (A) of the present invention is used .

就二段法的作為原料的二官能環氧樹脂而言，較佳為所述式（7）所表示的二官能環氧樹脂，但只要不損害本發明的目的，可併用除此之外的二官能環氧樹脂。作為可併用的二官能環氧樹脂，例如可列舉雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、雙酚苯乙酮型環氧樹脂、二苯硫醚型環氧樹脂、二苯醚型環氧樹脂等雙酚型環氧樹脂；聯苯酚型環氧樹脂、二苯基二環戊二烯型環氧樹脂、烷二醇型環氧樹脂、脂肪族環狀環氧樹脂等。該些環氧樹脂可經烷基、芳基等無不良影響的取代基取代。該些環氧樹脂亦可併用多種。As for the difunctional epoxy resin as the raw material of the two-stage method, the difunctional epoxy resin represented by the above formula (7) is preferred, but as long as the object of the present invention is not impaired, other than that can be used in combination Difunctional epoxy resin. Examples of bifunctional epoxy resins that can be used in combination include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol acetophenone type epoxy resin, and diphenyl sulfide. Bisphenol type epoxy resin such as ether type epoxy resin and diphenyl ether type epoxy resin; biphenol type epoxy resin, diphenyldicyclopentadiene type epoxy resin, alkylene glycol type epoxy resin, fat Group cyclic epoxy resin and so on. These epoxy resins can be substituted with substituents that have no adverse effects such as alkyl and aryl groups. These epoxy resins can also use multiple types together.

在二段法的情況下，可使用觸媒，若為具有促進環氧基與酚性羥基的反應般的觸媒能的化合物，則可為任意化合物。例如可列舉與本發明的製造方法（A）所例示的觸媒相同的觸媒。另外，亦可使用在製造所述式（7）所表示的二官能環氧樹脂時使用的鹼金屬化合物。該些觸媒可單獨使用，亦可組合使用兩種以上。另外，使用量亦與本發明的製造方法（A）所例示的使用量相同。In the case of the two-stage method, a catalyst may be used, and any compound may be used as long as it has a catalyst function that promotes the reaction between an epoxy group and a phenolic hydroxyl group. For example, the same catalyst as the catalyst exemplified in the manufacturing method (A) of the present invention can be cited. Moreover, the alkali metal compound used when manufacturing the bifunctional epoxy resin represented by said formula (7) can also be used. These catalysts can be used alone, or two or more of them can be used in combination. In addition, the usage amount is also the same as the usage amount exemplified in the production method (A) of the present invention.

在二段法的情況下，可使用溶媒，作為該溶媒，若為溶解苯氧基樹脂且對反應沒有不利影響的溶媒，則可為任意溶媒。例如，可例示與本發明的製造方法（A）中例示的溶媒相同的溶媒。該些溶媒可僅使用一種，亦可將兩種以上組合使用。In the case of the two-stage method, a solvent can be used. As the solvent, any solvent may be used as long as it dissolves the phenoxy resin and does not adversely affect the reaction. For example, the same solvent as the solvent exemplified in the production method (A) of the present invention can be exemplified. Only one type of these solvents may be used, or two or more types may be used in combination.

所使用的溶媒的量可根據反應條件適當選擇，例如，在二段法的情況下，固體成分濃度較佳為35質量%～95質量%。另外，於在反應過程中產生高黏性生成物的情況下，可在反應中途添加溶劑而使反應繼續。反應結束後，溶媒可視需要藉由蒸餾等除去，亦可進一步追加。The amount of the solvent used can be appropriately selected according to the reaction conditions. For example, in the case of the two-stage method, the solid content concentration is preferably 35% by mass to 95% by mass. In addition, when a highly viscous product is produced during the reaction, a solvent may be added in the middle of the reaction to continue the reaction. After the reaction, the solvent may be removed by distillation or the like as needed, and it may be further added.

反應溫度在所使用的觸媒不會分解的程度的溫度範圍內進行。若反應溫度過高，則有觸媒分解而反應停止、或生成的苯氧基樹脂劣化的可能性。若反應溫度過低，則反應並未充分進行而有無法成為目標分子量的可能性。因此，反應溫度較佳為50℃～230℃，更佳為100℃～210℃，進而佳為120℃～200℃。另外，反應時間通常為1小時～12小時，較佳為3小時～10小時。於使用丙酮或甲基乙基酮般的低沸點溶媒的情況下，可藉由使用高壓釜在高壓下進行反應來確保反應溫度。另外，於需要除去反應熱的情況下，通常藉由利用反應熱的使用溶媒的蒸發/凝縮/回流法、間接冷卻法、或該些併用來進行。The reaction temperature is performed within the temperature range to the extent that the catalyst used does not decompose. If the reaction temperature is too high, the catalyst decomposes and the reaction stops, or the phenoxy resin produced may deteriorate. If the reaction temperature is too low, the reaction may not proceed sufficiently and may not reach the target molecular weight. Therefore, the reaction temperature is preferably 50°C to 230°C, more preferably 100°C to 210°C, and still more preferably 120°C to 200°C. In addition, the reaction time is usually 1 hour to 12 hours, preferably 3 hours to 10 hours. In the case of using a low-boiling solvent such as acetone or methyl ethyl ketone, the reaction temperature can be ensured by using an autoclave to perform the reaction under high pressure. In addition, when the heat of reaction needs to be removed, it is usually performed by the evaporation/condensation/reflux method using a solvent using the heat of reaction, indirect cooling method, or a combination of these.

本發明的苯氧基樹脂是藉由將如此獲得的由所述式（12）表示的苯氧基樹脂（a）中的羥基醯化而獲得。醯化不僅可藉由直接酯化，而且可使用酯交換等方法。The phenoxy resin of the present invention is obtained by acylating the hydroxyl group in the phenoxy resin (a) represented by the formula (12) thus obtained. Not only can the acylation be directly esterified, but also methods such as transesterification can be used.

作為所述醯化中使用的酸成分，例如可使用：乙酸、丙酸、丁酸、異丁酸、戊酸、辛酸（octanoic acid）、辛酸（Caprylic acid）、月桂酸、硬脂酸、油酸、苯甲酸、第三丁基苯甲酸、六氫苯甲酸、苯氧基乙酸、丙烯酸、甲基丙烯酸等有機酸；有機酸的酸酐；有機酸的鹵化物；有機酸的酯化物等。該些醯化劑中，較佳為下述式（13）所表示的酸酐。As the acid component used in the acylation, for example, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, octanoic acid, caprylic acid, lauric acid, stearic acid, oil can be used. Acid, benzoic acid, tertiary butyl benzoic acid, hexahydrobenzoic acid, phenoxyacetic acid, acrylic acid, methacrylic acid and other organic acids; anhydrides of organic acids; halides of organic acids; esters of organic acids, etc. Among these acylating agents, an acid anhydride represented by the following formula (13) is preferred.

[化6]

式中，Z² 為具有碳數1～20的烴基的醯基。[化6]

In the formula, Z ² is an acyl group having a hydrocarbon group having 1 to 20 carbon atoms.

作為有機酸的酸酐，例如可列舉：乙酸酐、苯甲酸酐、苯氧乙酸酐等。 作為有機酸的酯化物，例如可列舉：乙酸甲酯、乙酸乙酯、乙酸丁酯、苯甲酸甲酯、苯甲酸乙酯等。作為有機酸的鹵化物，例如可列舉：乙醯氯、苯甲醯氯、苯氧乙醯氯等。As an acid anhydride of an organic acid, acetic anhydride, benzoic anhydride, phenoxyacetic anhydride, etc. are mentioned, for example. Examples of ester products of organic acids include methyl acetate, ethyl acetate, butyl acetate, methyl benzoate, ethyl benzoate, and the like. As the halide of an organic acid, for example, acetyl chloride, benzyl chloride, phenoxy acetyl chloride, etc. may be mentioned.

作為用於酯化的化合物，較佳為乙醯氯、苯甲醯氯、苯氧乙醯氯等有機酸的鹵化物、乙酸酐、苯甲酸酐、苯氧乙酸酐等酸鹵化物或有機酸的酸酐，就不需要酯化後的水洗，且避免在電材料應用中混入不希望的鹵素的意義而言，更佳為乙酸酐、苯甲酸酐等酸酐。As the compound used for esterification, halides of organic acids such as acetyl chloride, benzyl chloride, and phenoxyacetyl chloride, acid halides such as acetic anhydride, benzoic anhydride, and phenoxyacetic anhydride, or organic acids are preferred. The acid anhydride is more preferably acetic anhydride, benzoic anhydride, etc., in the sense that it does not require water washing after esterification and avoids mixing of undesirable halogens in the application of electrical materials.

苯氧基樹脂（a）所具有的羥基的酯化中使用的所述有機酸、有機酸的酸酐、有機酸的鹵化物、有機酸的酯化物等酸成分與苯氧基樹脂（a）反應時的投入比例可為與目標酯化比率相同的投入比例，在反應性低的情況下，可相對於羥基過量地投入所述酸成分，使其反應至目標酯化率後，除去未反應的酸成分。 此處，關於相對於作為原料的苯氧基樹脂（a）的醯化劑的使用量，相對於苯氧基樹脂（a）的醇性羥基1莫耳，醯化劑的醯基為0.05莫耳以上且2.0莫耳以下，較佳為0.1莫耳～1.0莫耳，更佳為0.2莫耳～0.8莫耳。而且，在醯化劑是式（13）所表示的酸酐的情況下，可理解為相對於1莫耳醯化劑，具有2莫耳醯基。The organic acid used in the esterification of the hydroxyl group of the phenoxy resin (a), the acid anhydride of the organic acid, the halide of the organic acid, the esterification of the organic acid, and other acid components react with the phenoxy resin (a) The input ratio at the time can be the same as the target esterification ratio. In the case of low reactivity, the acid component can be excessively added to the hydroxyl group to react to the target esterification ratio before removing unreacted Acid ingredients. Here, regarding the usage amount of the acylating agent relative to the phenoxy resin (a) as a raw material, the alcoholic hydroxyl group of the phenoxy resin (a) is 1 mol, and the acylating agent has an acylating agent of 0.05 mol. Ears or more and 2.0 mols or less, preferably 0.1 mol to 1.0 mol, more preferably 0.2 mol to 0.8 mol. In addition, when the acylating agent is an acid anhydride represented by formula (13), it can be understood that it has 2 molaryl groups with respect to one mol acylating agent.

在藉由酸成分直接進行酯化的情況下，例如可使用對甲苯磺酸、磷酸等酸觸媒、鈦酸四異丙酯、鈦酸四丁酯、二丁基氧化錫、二辛基氧化錫、氯化鋅等金屬觸媒等各種酯化觸媒進行脫水的同時來進行。通常，在氮氣氛下，較佳為在100℃～250℃下進行，更佳為130℃～230℃。In the case of direct esterification with acid components, for example, acid catalysts such as p-toluenesulfonic acid and phosphoric acid, tetraisopropyl titanate, tetrabutyl titanate, dibutyltin oxide, and dioctyl oxide can be used. Various esterification catalysts such as metal catalysts such as tin and zinc chloride are dehydrated at the same time. Generally, it is performed under a nitrogen atmosphere, preferably at 100°C to 250°C, more preferably 130°C to 230°C.

在酯化中使用酸鹵化物或酸酐的情況下，為了除去產生的酸，可利用在使用鹼性化合物中和後過濾鹽的方法、在使用鹼性化合物中和後進行水洗的方法、不進行中和而進行水洗的方法、藉由蒸餾或吸附等除去的方法中的任一種方法，亦可併用。在除去沸點較反應溶媒低的酸的情況下，較佳為蒸餾除去。In the case of using acid halide or acid anhydride in the esterification, in order to remove the generated acid, a method of filtering the salt after neutralization with a basic compound or a method of washing with water after neutralization with a basic compound can be used. Either the method of neutralizing and washing with water, the method of removing by distillation, adsorption, etc., can also be used together. In the case of removing an acid having a lower boiling point than the reaction solvent, it is preferably removed by distillation.

在藉由酯交換將苯氧基樹脂（a）酯化的情況下，理想的是通常在氮氣氛下，使用例如二丁基氧化錫或二辛基氧化錫、錫氧烷觸媒、鈦酸四異丙酯、鈦酸四丁酯、乙酸鉛、乙酸鋅、三氧化銻等有機金屬觸媒；鹽酸、硫酸、磷酸、磺酸等酸觸媒；氫氧化鋰、氫氧化鈉等鹼性觸媒等公知的酯化觸媒進行脫醇的同時來進行。In the case of esterifying the phenoxy resin (a) by transesterification, it is desirable to use, for example, dibutyltin oxide or dioctyltin oxide, stannoxane catalyst, titanic acid, usually under a nitrogen atmosphere Organic metal catalysts such as tetraisopropyl ester, tetrabutyl titanate, lead acetate, zinc acetate, and antimony trioxide; acid catalysts such as hydrochloric acid, sulfuric acid, phosphoric acid, and sulfonic acid; alkaline catalysts such as lithium hydroxide and sodium hydroxide A well-known esterification catalyst such as a catalyst is carried out while dealcoholizing.

在本發明的製造方法（B）中，可使用反應用的溶媒，作為該溶媒，若為溶解苯氧基樹脂的溶媒，則可為任意溶媒。例如，可列舉本發明的製造方法（A）中例示的溶媒等。該些溶媒可與苯氧基樹脂（a）的製備中使用的溶媒相同，亦可不同。另外，可僅使用一種，亦可將兩種以上組合使用。In the production method (B) of the present invention, a solvent for reaction can be used, and as the solvent, any solvent may be used as long as it dissolves the phenoxy resin. For example, the solvent etc. illustrated in the manufacturing method (A) of this invention are mentioned. These solvents may be the same as or different from the solvent used in the preparation of the phenoxy resin (a). In addition, only one type may be used, or two or more types may be used in combination.

本發明的樹脂組成物為至少含有本發明的苯氧基樹脂及硬化劑的樹脂組成物。另外，在本發明的樹脂組成物中，可視需要適當調配環氧樹脂、無機填料、偶合劑、抗氧化劑等各種添加劑。本發明的樹脂組成物提供充分滿足各種用途所要求的各項物性的硬化物。The resin composition of the present invention is a resin composition containing at least the phenoxy resin of the present invention and a curing agent. In addition, in the resin composition of the present invention, various additives such as epoxy resins, inorganic fillers, coupling agents, and antioxidants can be appropriately blended as necessary. The resin composition of the present invention provides a cured product that sufficiently satisfies various physical properties required for various applications.

可在本發明的苯氧基樹脂中調配硬化劑來製成樹脂組成物。在本發明中所謂硬化劑表示有助於苯氧基樹脂與交聯反應及/或鏈長延長反應的物質。再者，在本發明中，即便是通常稱為「硬化促進劑」者，只要是有助於苯氧基樹脂與交聯反應及/或鏈長延長反應的物質，則視為硬化劑。A hardener can be blended in the phenoxy resin of the present invention to form a resin composition. In the present invention, the hardener means a substance that contributes to the crosslinking reaction and/or chain length extension reaction of the phenoxy resin. In addition, in the present invention, even those generally referred to as "hardening accelerators" are regarded as hardeners as long as they contribute to the crosslinking reaction and/or chain length extension reaction of the phenoxy resin.

相對於本發明的苯氧基樹脂的固體成分100質量份，本發明的樹脂組成物中的硬化劑的含量較佳為以固體成分計為0.1質量份～100質量份。另外，更佳為80質量份以下，進而佳為60質量份以下。The content of the hardener in the resin composition of the present invention is preferably 0.1 to 100 parts by mass in terms of solid content relative to 100 parts by mass of the solid content of the phenoxy resin of the present invention. In addition, it is more preferably 80 parts by mass or less, and still more preferably 60 parts by mass or less.

在本發明的樹脂組成物中，在含有後述的環氧樹脂的情況下，本發明的苯氧基樹脂與環氧樹脂的固體成分的重量比為99/1～1/99。在本發明中，「固體成分」是指除去溶媒後的成分，不僅包含固體的苯氧基樹脂或環氧樹脂，亦包含半固體或黏稠的液狀物。另外，「樹脂成分」是指本發明的苯氧基樹脂與後述的環氧樹脂的合計。In the resin composition of the present invention, when the epoxy resin described later is contained, the weight ratio of the solid content of the phenoxy resin of the present invention to the epoxy resin is 99/1 to 1/99. In the present invention, "solid content" refers to a component after removing the solvent, and includes not only solid phenoxy resin or epoxy resin, but also semi-solid or viscous liquid. In addition, "resin component" means the total of the phenoxy resin of this invention and the epoxy resin mentioned later.

作為本發明的樹脂組成物中使用的硬化劑，並無特別限制，可使用通常作為環氧樹脂硬化劑已知的全部硬化劑。就提高耐熱性的觀點而言，作為較佳者，可列舉：酚系硬化劑、醯胺系硬化劑、咪唑類及活性酯系硬化劑等。該些硬化劑可單獨使用，亦可併用兩種以上。The hardener used in the resin composition of the present invention is not particularly limited, and all hardeners generally known as epoxy resin hardeners can be used. From the viewpoint of improving heat resistance, preferred ones include phenolic curing agents, amide curing agents, imidazoles, active ester curing agents, and the like. These hardeners may be used alone, or two or more of them may be used in combination.

作為酚系硬化劑，例如可列舉：雙酚A、雙酚F、4,4'-二羥基二苯基甲烷、4,4'-二羥基二苯醚、1,4-雙(4-羥基苯氧基)苯、1,3-雙(4-羥基苯氧基)苯、4,4'-二羥基二苯硫醚、4,4'-二羥基二苯基酮、4,4'-二羥基二苯基碸、4,4'-二羥基聯苯、2,2'-二羥基聯苯、10-(2,5-二羥基苯基)-10H-9-氧雜-10-磷雜菲-10-氧化物、苯酚酚醛清漆、雙酚A酚醛清漆、鄰甲酚酚醛清漆、間甲酚酚醛清漆、對甲酚酚醛清漆、二甲酚酚醛清漆、聚對羥基苯乙烯、對苯二酚、間苯二酚、鄰苯二酚、第三丁基鄰苯二酚、第三丁基對苯二酚、氟代乙醇胺（fluoroglycinol）、五倍子酚（pyrogallol）、第三丁基五倍子酚、烯丙基化五倍子酚、聚烯丙基化五倍子酚、1,2,4-苯三醇、2,3,4-三羥基二苯甲酮、1,2-二羥基萘、1,3-二羥基萘、1,4-二羥基萘、1,5-二羥基萘、1,6-二羥基萘、1,7-二羥基萘、1,8-二羥基萘、2,3-二羥基萘、2,4-二羥基萘、2,5-二羥基萘、2,6-二羥基萘、2,7-二羥基萘、2,8-二羥基萘、所述二羥基萘的烯丙基化物或聚烯丙基化物、烯丙基化雙酚A、烯丙基化雙酚F、烯丙基化苯酚酚醛清漆、烯丙基化五倍子酚等。Examples of phenolic hardeners include bisphenol A, bisphenol F, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl ether, 1,4-bis(4-hydroxy Phenoxy)benzene, 1,3-bis(4-hydroxyphenoxy)benzene, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'- Dihydroxydiphenyl sulfide, 4,4'-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphorus Phenanthrene-10-oxide, phenol novolak, bisphenol A novolak, o-cresol novolak, m-cresol novolak, p-cresol novolak, xylenol novolak, polyp-hydroxystyrene, p-benzene Diphenol, resorcinol, catechol, tertiary butyl catechol, tertiary butyl hydroquinone, fluoroglycinol, pyrogallol, tertiary butyl catechol , Allylated gallic phenol, polyallylated gallic phenol, 1,2,4-benzenetriol, 2,3,4-trihydroxybenzophenone, 1,2-dihydroxynaphthalene, 1,3 -Dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene Hydroxynaphthalene, 2,4-dihydroxynaphthalene, 2,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,8-dihydroxynaphthalene, the alkene of the dihydroxynaphthalene Propyl compound or polyallyl compound, allylated bisphenol A, allylated bisphenol F, allylated phenol novolak, allylated gallic phenol, etc.

作為醯胺系硬化劑，例如可列舉：二氰二胺及其衍生物、聚醯胺樹脂等。Examples of the amide-based curing agent include dicyandiamine and its derivatives, and polyamide resins.

作為咪唑類，例如可列舉：2-苯基咪唑、2-乙基-4(5)-甲基咪唑、2-苯基-4-甲基咪唑、1-苄基-2-甲基咪唑、1-苄基-2-苯基咪唑、1-氰基乙基-2-十一烷基咪唑、1-氰基-2-苯基咪唑、1-氰基乙基-2-十一烷基咪唑偏苯三甲酸酯、1-氰基乙基-2-苯基咪唑偏苯三甲酸酯、2,4-二胺基-6-[2'-甲基咪唑基-(1')]-乙基-均三嗪、2,4-二胺基-6-[2'-乙基-4'-甲基咪唑基-(1')]-乙基-均三嗪、2,4-二胺基-6-[2'-甲基咪唑基-(1')]-乙基-均三嗪異三聚氫酸加成物、2-苯基咪唑異三聚氫酸加成物、2-苯基-4,5-二羥甲基咪唑、2-苯基-4-甲基-5-羥甲基咪唑、及環氧樹脂與所述咪唑類的加成物等。再者，由於咪唑類具有觸媒能，因此一般亦被分類為後述的硬化促進劑，在本發明中，被分類為硬化劑。Examples of imidazoles include 2-phenylimidazole, 2-ethyl-4(5)-methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-undecyl Imidazole trimellitate, 1-cyanoethyl-2-phenylimidazole trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]- Ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-bis Amino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isotrimer acid adduct, 2-phenylimidazole isotrimer acid adduct, 2 -Phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and adducts of epoxy resin and the imidazoles, etc. Furthermore, imidazoles are generally classified as hardening accelerators described later because they have catalytic properties, and in the present invention, they are classified as hardening agents.

作為活性酯系硬化劑，例如較佳為酚酯類、硫代酚酯類、N-羥胺酯類或雜環羥基化合物的酯類等在一個分子中具有兩個以上反應活性高的酯基的化合物，其中，更佳為使羧酸化合物與具有酚性羥基的芳香族化合物反應而得的酚酯類。作為羧酸化合物，具體而言可列舉苯甲酸、乙酸、琥珀酸、馬來酸、衣康酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸、均苯四甲酸等。作為具有酚性羥基的芳香族化合物，可列舉：鄰苯二酚、1,5-二羥基萘、1,6-二羥基萘、2,6-二羥基萘、二羥基二苯甲酮、三羥基二苯甲酮、四羥基二苯甲酮、均苯三酚、苯三醇、二環戊二烯基二苯酚、苯酚酚醛清漆等。As the active ester curing agent, for example, phenolic esters, thiophenolic esters, N-hydroxylamine esters, or esters of heterocyclic hydroxy compounds, etc. having two or more highly reactive ester groups in one molecule are preferred. Among them, the compound is more preferably a phenol ester obtained by reacting a carboxylic acid compound with an aromatic compound having a phenolic hydroxyl group. Specific examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of aromatic compounds having a phenolic hydroxyl group include: catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, three Hydroxybenzophenone, tetrahydroxybenzophenone, pyrogallol, benzenetriol, dicyclopentadienyl diphenol, phenol novolac, etc.

作為可用於本發明的樹脂組成物的其他硬化劑，例如可列舉：胺系硬化劑、酸酐系硬化劑、三級胺、有機膦類、鏻鹽、四苯基硼鹽、有機酸二醯肼、鹵化硼胺錯合物、聚硫醇系硬化劑、異氰酸酯系硬化劑、封閉異氰酸酯系硬化劑等。該些其他硬化劑可僅使用一種，亦可以任意組合及比率混合使用兩種以上。Examples of other hardeners that can be used in the resin composition of the present invention include amine hardeners, acid anhydride hardeners, tertiary amines, organic phosphines, phosphonium salts, tetraphenyl boron salts, and organic acid dihydrazide , Boron halide amine complexes, polythiol-based hardeners, isocyanate-based hardeners, blocked isocyanate-based hardeners, etc. Only one kind of these other hardeners may be used, or two or more kinds may be mixed and used in any combination and ratio.

本發明的樹脂組成物可含有環氧樹脂。藉由使用環氧樹脂，可彌補不足的物性、或提高各種物性。作為環氧樹脂，較佳為分子內具有兩個以上環氧基的環氧樹脂，更佳為具有三個以上環氧基的環氧樹脂。例如可列舉：聚縮水甘油醚化合物、聚縮水甘油胺化合物、聚縮水甘油酯化合物、脂環式環氧化合物、其他改質環氧樹脂等。該些環氧樹脂可單獨使用，亦可併用兩種以上同一系的環氧樹脂，另外，亦可將不同系的環氧樹脂組合使用。The resin composition of the present invention may contain an epoxy resin. By using epoxy resin, insufficient physical properties can be made up or various physical properties can be improved. As the epoxy resin, an epoxy resin having two or more epoxy groups in the molecule is preferable, and an epoxy resin having three or more epoxy groups is more preferable. For example, a polyglycidyl ether compound, a polyglycidyl amine compound, a polyglycidyl ester compound, an alicyclic epoxy compound, other modified epoxy resins, etc. are mentioned. These epoxy resins can be used alone, or two or more epoxy resins of the same series can be used in combination, and epoxy resins of different series can also be used in combination.

作為聚縮水甘油醚化合物，例如可使用雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、雙酚AF型環氧樹脂、雙酚Z型環氧樹脂、雙酚芴型環氧樹脂、二苯硫醚型環氧樹脂、二苯醚型環氧樹脂、萘型環氧樹脂、對苯二酚型環氧樹脂、間苯二酚型環氧樹脂、苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、烷基酚醛清漆型環氧樹脂、苯乙烯化苯酚酚醛清漆型環氧樹脂、雙酚酚醛清漆型環氧樹脂、萘酚酚醛清漆型環氧樹脂、苯酚芳烷基型環氧樹脂、β-萘酚芳烷基型環氧樹脂、萘二酚芳烷基型環氧樹脂、α-萘酚芳烷基型環氧樹脂、聯苯芳烷基苯酚型環氧樹脂、聯苯型環氧樹脂、三苯基甲烷型環氧樹脂、二環戊二烯型環氧樹脂、烷二醇型環氧樹脂、脂肪族環狀環氧樹脂等各種環氧樹脂。As the polyglycidyl ether compound, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, bisphenol Z type epoxy resin, Bisphenol fluorene type epoxy resin, diphenyl sulfide type epoxy resin, diphenyl ether type epoxy resin, naphthalene type epoxy resin, hydroquinone type epoxy resin, resorcinol type epoxy resin, phenol Novolak type epoxy resin, cresol novolak type epoxy resin, alkyl novolak type epoxy resin, styrenated phenol novolak type epoxy resin, bisphenol novolak type epoxy resin, naphthol novolak type Epoxy resin, phenol aralkyl epoxy resin, β-naphthol aralkyl epoxy resin, naphthalene diphenol aralkyl epoxy resin, α-naphthol aralkyl epoxy resin, biphenyl Aralkylphenol type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, dicyclopentadiene type epoxy resin, alkylene glycol type epoxy resin, aliphatic cyclic epoxy resin And other various epoxy resins.

作為聚縮水甘油胺化合物，例如可列舉：二胺基二苯基甲烷型環氧樹脂、間二甲苯二胺型環氧樹脂、1,3-雙胺基甲基環己烷型環氧樹脂、異氰脲酸酯型環氧樹脂、苯胺型環氧樹脂、乙內醯脲型環氧樹脂、胺基苯酚型環氧樹脂等。As the polyglycidylamine compound, for example, diaminodiphenylmethane type epoxy resin, meta-xylene diamine type epoxy resin, 1,3-bisaminomethylcyclohexane type epoxy resin, Isocyanurate type epoxy resin, aniline type epoxy resin, hydantoin type epoxy resin, aminophenol type epoxy resin, etc.

作為聚縮水甘油酯化合物，例如可列舉：二聚物酸型環氧樹脂、六氫鄰苯二甲酸型環氧樹脂、偏苯三甲酸型環氧樹脂等。As a polyglycidyl ester compound, a dimer acid type epoxy resin, a hexahydrophthalic acid type epoxy resin, a trimellitic acid type epoxy resin, etc. are mentioned, for example.

作為脂環式環氧化合物，可列舉：賽羅西德（Celloxide）2021（大賽璐（Daicel）化學工業股份有限公司製造）等脂肪族環狀環氧樹脂等。As an alicyclic epoxy compound, aliphatic cyclic epoxy resins, such as Celloxide 2021 (made by Daicel Chemical Industry Co., Ltd.), etc. are mentioned.

作為其他改質環氧樹脂，例如可列舉：胺基甲酸酯改質環氧樹脂、含噁唑啶酮環的環氧樹脂、環氧改質聚丁二烯橡膠衍生物、羧基末端丁二烯腈橡膠（CTBN）改質環氧樹脂、聚乙烯基芳烴聚氧化物（例如，二乙烯基苯二氧化物、三乙烯基萘三氧化物等）、苯氧基樹脂等。As other modified epoxy resins, for example, urethane modified epoxy resins, oxazolidone ring-containing epoxy resins, epoxy modified polybutadiene rubber derivatives, carboxyl-terminated butadiene Acrylonitrile rubber (CTBN) modified epoxy resin, polyvinyl aromatic hydrocarbon polyoxide (for example, divinylbenzene dioxide, trivinylnaphthalene trioxide, etc.), phenoxy resin, etc.

當在本發明的樹脂組成物中使用本發明的苯氧基樹脂及環氧樹脂時，在作為固體成分的苯氧基樹脂及環氧樹脂的全部成分中，環氧樹脂的調配量較佳為1質量%～99質量%，更佳為5質量%～97質量%，進而佳為10質量%～95質量%，進而佳為10質量%～90質量%。藉由環氧樹脂在所述調配量內，當製成包含本發明的樹脂組成物的硬化物時，可提高耐熱性及機械強度。When the phenoxy resin and epoxy resin of the present invention are used in the resin composition of the present invention, among all the components of the phenoxy resin and epoxy resin as solid components, the blending amount of the epoxy resin is preferably 1% by mass to 99% by mass, more preferably 5% by mass to 97% by mass, still more preferably 10% by mass to 95% by mass, and still more preferably 10% by mass to 90% by mass. With the epoxy resin in the above-mentioned compounding amount, when it is made into a cured product containing the resin composition of the present invention, heat resistance and mechanical strength can be improved.

為了在形成塗膜時的處理時適度地調整樹脂組成物的黏度，本發明的樹脂組成物可調配溶劑或反應性稀釋劑。在本發明的樹脂組成物中，使用溶劑或反應性稀釋劑以確保在樹脂組成物成形中的處理性、作業性，並且其使用量並無特別限制。再者，在本發明中，「溶劑」一詞與所述的「溶媒」一詞根據其使用形態區別使用，但可分別獨立地使用同種者，亦可使用異種者。In order to appropriately adjust the viscosity of the resin composition at the time of processing when forming a coating film, the resin composition of the present invention can be formulated with a solvent or a reactive diluent. In the resin composition of the present invention, a solvent or a reactive diluent is used to ensure handleability and workability in the molding of the resin composition, and the amount used is not particularly limited. Furthermore, in the present invention, the term "solvent" and the term "solvent" described above are used differently according to the form of use, but the same species may be used independently, or different species may be used.

作為本發明的樹脂組成物可包含的溶劑，例如可列舉：丙酮、甲基乙基酮（MEK）、甲基異丁基酮、環己酮等酮類；乙酸乙酯等酯類；乙二醇單甲醚等醚類；N,N-二甲基甲醯胺、N,N-二甲基乙醯胺等醯胺類；甲醇、乙醇等醇類；己烷、環己烷等烷烴類；甲苯、二甲苯等芳香族類。以上所列舉的溶劑可僅使用一種，亦可將兩種以上以任意的組合及比率混合使用。Examples of solvents that can be included in the resin composition of the present invention include ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, and cyclohexanone; esters such as ethyl acetate; Alcohol monomethyl ether and other ethers; N,N-dimethylformamide, N,N-dimethylacetamide and other amines; methanol, ethanol and other alcohols; hexane, cyclohexane and other alkanes ; Aromatics such as toluene and xylene. Only one type of the solvents listed above may be used, or two or more types may be mixed and used in any combination and ratio.

作為反應性稀釋劑，例如可列舉：烯丙基縮水甘油醚等單官能縮水甘油醚類、丙二醇二縮水甘油醚等二官能縮水甘油醚類、三羥甲基丙烷聚縮水甘油醚等多官能縮水甘油醚類、縮水甘油酯類、縮水甘油胺類。Examples of reactive diluents include monofunctional glycidyl ethers such as allyl glycidyl ether, difunctional glycidyl ethers such as propylene glycol diglycidyl ether, and polyfunctional glycidyl ethers such as trimethylolpropane polyglycidyl ether. Glyceryl ethers, glycidyl esters, and glycidylamines.

該些溶劑或反應性稀釋劑中，作為不揮發成分較佳為在90質量%以下使用，其適當的種類或使用量根據用途適當選擇。例如，在印刷配線板用途中，較佳為甲基乙基酮、丙酮、1-甲氧基-2-丙醇等沸點為160℃以下的極性溶媒，其使用量較佳為以不揮發成分計為40質量%～80質量%。另外，在接著膜用途中，例如較佳使用酮類、乙酸酯類、卡必醇類、芳香族烴類、二甲基甲醯胺、二甲基乙醯胺、N-甲基吡咯啶酮等，其使用量較佳為以不揮發成分計為30質量%～60質量%。Among these solvents or reactive diluents, it is preferable to use 90% by mass or less as a non-volatile component, and the appropriate kind or usage amount is appropriately selected according to the application. For example, in the use of printed wiring boards, polar solvents such as methyl ethyl ketone, acetone, 1-methoxy-2-propanol and the like having a boiling point of 160° C. or less are preferred, and the amount used is preferably a non-volatile component. It is calculated as 40% by mass to 80% by mass. In addition, for film bonding applications, for example, ketones, acetates, carbitols, aromatic hydrocarbons, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone are preferably used. The amount used is preferably 30% by mass to 60% by mass in terms of non-volatile components.

本發明的樹脂組成物可視需要使用硬化促進劑（其中，「硬化劑」中所含的硬化促進劑除外）。作為硬化促進劑，例如可列舉：咪唑類、三級胺類、膦類等磷化合物、金屬化合物、路易斯酸（Lewis acid）、胺錯鹽等。該些硬化促進劑可單獨使用，亦可併用兩種以上。The resin composition of the present invention may optionally use a hardening accelerator (except for the hardening accelerator contained in the "hardening agent"). Examples of hardening accelerators include phosphorus compounds such as imidazoles, tertiary amines, and phosphines, metal compounds, Lewis acid, and amine complex salts. These hardening accelerators may be used alone, or two or more of them may be used in combination.

硬化促進劑的調配量只要根據使用目的適宜選擇即可，相對於樹脂組成物中的環氧樹脂成分100質量份，視需要使用0.01質量份～15質量份，較佳為0.01質量份～10質量份，更佳為0.05質量份～8質量份，進而佳為0.1質量份～5質量份。藉由使用硬化促進劑，可降低硬化溫度、或縮短硬化時間。The blending amount of the hardening accelerator may be appropriately selected according to the purpose of use. Relative to 100 parts by mass of the epoxy resin component in the resin composition, 0.01 parts by mass to 15 parts by mass, preferably 0.01 parts by mass to 10 parts by mass are used as needed. Parts, more preferably 0.05 parts by mass to 8 parts by mass, and still more preferably 0.1 parts by mass to 5 parts by mass. By using a hardening accelerator, the hardening temperature can be lowered or the hardening time can be shortened.

在本發明的樹脂組成物中，出於提高所得的硬化物的阻燃性的目的，可於不降低可靠性的範圍內使用公知的各種阻燃劑。作為可使用的阻燃劑，例如可列舉：鹵素系阻燃劑、磷系阻燃劑、氮系阻燃劑、矽酮系阻燃劑、無機系阻燃劑、有機金屬鹽系阻燃劑等。就環境的觀點而言，較佳為不含鹵素的阻燃劑、特佳為磷系阻燃劑。該些阻燃劑可單獨使用，亦可將同一系列的阻燃劑併用兩種以上，另外，亦可將不同系列的阻燃劑組合使用。In the resin composition of the present invention, for the purpose of improving the flame retardancy of the obtained cured product, various known flame retardants can be used within a range that does not reduce the reliability. Usable flame retardants include, for example, halogen flame retardants, phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, inorganic flame retardants, and organic metal salt flame retardants. Wait. From an environmental point of view, halogen-free flame retardants are preferred, and phosphorus-based flame retardants are particularly preferred. These flame retardants can be used alone, or two or more of the same series of flame retardants can be used in combination, and in addition, different series of flame retardants can also be used in combination.

於本發明的樹脂組成物中，出於進一步提高其功能性的目的，可包含除以上列出的成分之外的成分（在本發明中有時稱為「其他成分」）。作為所述其他成分，可列舉：填充材、熱塑性樹脂、熱硬化性樹脂、光硬化性樹脂、紫外線抑制劑、抗氧化劑、偶合劑、增塑劑、助熔劑、觸變性賦予劑、平滑劑、著色劑、顏料、分散劑、乳化劑、低彈性化劑、脫模劑、消泡劑、離子捕集劑等。In the resin composition of the present invention, for the purpose of further improving its functionality, components other than the above-listed components (sometimes referred to as "other components" in the present invention) may be included. Examples of the other components include fillers, thermoplastic resins, thermosetting resins, photocurable resins, ultraviolet inhibitors, antioxidants, coupling agents, plasticizers, fluxes, thixotropy imparting agents, smoothing agents, Colorants, pigments, dispersants, emulsifiers, low-elasticity agents, mold release agents, defoamers, ion trapping agents, etc.

作為填充材，例如可列舉：熔融二氧化矽、結晶二氧化矽、氧化鋁、氮化矽、氮化硼、氮化鋁、氫氧化鋁、氫氧化鈣、氫氧化鎂、水鋁石（boehmite）、滑石、雲母、黏土、碳酸鈣、碳酸鎂、碳酸鋇，氧化鋅、氧化鈦、氧化鎂、矽酸鎂、矽酸鈣、矽酸鋯、硫酸鋇、碳等無機填充劑，或碳纖維、玻璃纖維、氧化鋁纖維、二氧化矽氧化鋁纖維、碳化矽纖維、聚酯纖維、纖維素纖維、聚芳醯胺纖維、陶瓷纖維等纖維狀填充劑，或微粒子橡膠等。As the filler, for example, fused silica, crystalline silica, alumina, silicon nitride, boron nitride, aluminum nitride, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, diaspore (boehmite ), talc, mica, clay, calcium carbonate, magnesium carbonate, barium carbonate, zinc oxide, titanium oxide, magnesium oxide, magnesium silicate, calcium silicate, zirconium silicate, barium sulfate, carbon and other inorganic fillers, or carbon fiber, Fibrous fillers such as glass fiber, alumina fiber, silica alumina fiber, silicon carbide fiber, polyester fiber, cellulose fiber, polyaramid fiber, ceramic fiber, etc., or fine particle rubber.

本發明的樹脂組成物亦可併用本發明的苯氧基樹脂以往的熱塑性樹脂。作為熱塑性樹脂，例如可列舉：本發明以外的苯氧基樹脂、聚胺基甲酸酯樹脂、聚酯樹脂、聚乙烯樹脂、聚丙烯樹脂、聚苯乙烯樹脂、丙烯腈丁二烯苯乙烯（Acrylonitrile Butadiene Styrene，ABS）樹脂、丙烯腈苯乙烯（Acrylonitrile Styrene，AS）樹脂、氯乙烯樹脂、聚乙酸乙烯基酯樹脂、聚甲基丙烯酸甲酯樹脂、聚碳酸酯樹脂、聚縮醛樹脂、環狀聚烯烴樹脂、聚醯胺樹脂、熱塑性聚醯亞胺樹脂、聚醯胺醯亞胺樹脂、聚四氟乙烯樹脂、聚醚醯亞胺樹脂、聚苯醚樹脂、改質聚苯醚樹脂、聚醚碸樹脂、聚碸樹脂、聚醚醚酮樹脂、聚苯硫醚樹脂、聚乙烯基縮甲醛樹脂等。就相容性的方面而言，較佳為本發明以外的苯氧基樹脂，就低介電特性的方面而言，較佳為聚苯醚樹脂或改質聚苯醚樹脂。The resin composition of the present invention may also use the conventional thermoplastic resin of the phenoxy resin of the present invention in combination. Examples of thermoplastic resins include phenoxy resins, polyurethane resins, polyester resins, polyethylene resins, polypropylene resins, polystyrene resins, acrylonitrile butadiene styrene ( Acrylonitrile Butadiene Styrene (ABS) resin, Acrylonitrile Styrene (AS) resin, vinyl chloride resin, polyvinyl acetate resin, polymethyl methacrylate resin, polycarbonate resin, polyacetal resin, ring Shape polyolefin resin, polyamide resin, thermoplastic polyimide resin, polyimide resin, polytetrafluoroethylene resin, polyetherimide resin, polyphenylene ether resin, modified polyphenylene ether resin, Polyether resin, polyether resin, polyether ether ketone resin, polyphenylene sulfide resin, polyvinyl formal resin, etc. In terms of compatibility, phenoxy resins other than those of the present invention are preferred, and in terms of low dielectric properties, polyphenylene ether resins or modified polyphenylene ether resins are preferred.

作為其他成分，可列舉：喹吖啶酮系、偶氮系、酞菁系等有機顏料，或氧化鈦、金屬箔狀顏料、防鏽顏料等無機顏料，或受阻胺系、苯並***系、二苯甲酮系等紫外線吸收劑，或受阻酚系、磷系、硫系、醯肼系等抗氧化劑，或硬脂酸、棕櫚酸、硬脂酸鋅、硬脂酸鈣等脫模劑，流平劑，流變控制劑，顏料分散劑，防凹陷劑，消泡劑等添加劑等。相對於樹脂組成物中的總固體成分，該些其他成分的調配量較佳為0.01質量%～20質量%的範圍。Examples of other components include: organic pigments such as quinacridone, azo, and phthalocyanine, or inorganic pigments such as titanium oxide, metal foil-like pigments, and anti-rust pigments, or hindered amine, benzotriazole, etc. , Benzophenone series and other ultraviolet absorbers, or hindered phenol series, phosphorus series, sulfur series, hydrazine series and other antioxidants, or stearic acid, palmitic acid, zinc stearate, calcium stearate and other mold release agents , Leveling agent, rheology control agent, pigment dispersant, anti-sagging agent, defoamer and other additives. The blending amount of these other components is preferably in the range of 0.01% by mass to 20% by mass relative to the total solid content in the resin composition.

本發明的樹脂組成物可藉由將所述各成分均勻地混合而獲得。調配有苯氧基樹脂、硬化劑、進而視需要的各種成分的樹脂組成物可利用與先前已知的方法相同的方法而容易地製成硬化物。該硬化物在低吸濕性、介電特性、耐熱性、密接性等方面具有優異的平衡，表現出良好的硬化物性。此處所謂「硬化」是指藉由熱及/或光等有意地使樹脂組成物硬化，且其硬化程度根據所需的物性、用途來控制即可。進行的程度可為完全硬化，亦可為半硬化的狀態，並無特別限制，但環氧基與硬化劑的硬化反應的反應率通常為5%～95%。The resin composition of the present invention can be obtained by uniformly mixing the respective components. A resin composition prepared with a phenoxy resin, a curing agent, and various components as necessary can be easily made into a cured product by the same method as the previously known method. The cured product has an excellent balance of low moisture absorption, dielectric properties, heat resistance, adhesion, etc., and exhibits good cured physical properties. The term "curing" here means that the resin composition is intentionally cured by heat and/or light, and the degree of curing can be controlled according to the required physical properties and applications. The degree of progress may be a fully hardened state or a semi-hardened state, and is not particularly limited, but the reaction rate of the hardening reaction between the epoxy group and the hardening agent is usually 5% to 95%.

本發明的樹脂組成物可藉由與公知的環氧樹脂組成物相同的方法進行硬化而獲得硬化物。作為用以獲得硬化物的方法，可採用與公知的環氧樹脂組成物相同的方法，並且可適當地使用注塑、注入、灌注（potting）、浸漬、滴塗（drip coating）、轉移成形、壓縮成形等、或者以樹脂片、帶樹脂的銅箔、預浸體等形態進行積層並加熱加壓硬化而製成積層板等方法。此時的硬化溫度通常為80℃～300℃的範圍，硬化時間通常硬化時間為10分鐘～360分鐘左右。該加熱較佳為藉由在80℃～180℃下實施10分鐘～90分鐘的一次加熱、與在120℃～200℃下實施60分鐘～150分鐘的二次加熱的二段處理來進行，另外，在玻璃化轉移溫度（Tg）超過二次加熱的溫度的調配體系中，較佳為進而在150℃～280℃下進行60分鐘～120分鐘的三次加熱。藉由進行此種二次加熱、三次加熱，可減低硬化不良。於製作樹脂片、帶樹脂的銅箔、預浸體等樹脂半硬化物時，通常藉由加熱等以保持形狀的程度進行樹脂組成物的硬化反應。於樹脂組成物含有溶媒的情況下，通常藉由加熱、減壓、風乾等方法除去大部分溶媒，亦可在樹脂半硬化物中殘留5質量%以下的溶媒。The resin composition of the present invention can be cured by the same method as a known epoxy resin composition to obtain a cured product. As a method for obtaining a hardened product, the same method as that of a known epoxy resin composition can be used, and injection molding, injection, potting, dipping, drip coating, transfer molding, and compression can be used as appropriate. Molding or the like, or laminating in the form of a resin sheet, a resin-coated copper foil, a prepreg, etc., and heat and pressure hardening to form a laminated board. The curing temperature at this time is usually in the range of 80°C to 300°C, and the curing time is usually about 10 minutes to 360 minutes. The heating is preferably performed by a two-stage treatment of primary heating at 80°C to 180°C for 10 minutes to 90 minutes and secondary heating at 120°C to 200°C for 60 minutes to 150 minutes. In a formulation system in which the glass transition temperature (Tg) exceeds the temperature of the secondary heating, it is preferable to further perform three heating at 150°C to 280°C for 60 minutes to 120 minutes. By performing such secondary heating and tertiary heating, poor hardening can be reduced. In the production of semi-cured resins such as resin sheets, resin-coated copper foils, and prepregs, the curing reaction of the resin composition is usually carried out by heating or the like so as to maintain the shape. When the resin composition contains a solvent, most of the solvent is usually removed by heating, decompression, air drying, etc., and 5 mass% or less of the solvent may remain in the semi-cured resin.

對使用本發明的樹脂組成物獲得的預浸體進行說明。作為片狀基材，可使用玻璃等無機纖維、或聚酯等、多胺、聚丙烯酸、聚醯亞胺、凱夫拉（kevlar）、纖維素等有機質纖維的織布或不織布，但並不限定於該些。作為由本發明的樹脂組成物及基材製造預浸體的方法，並無特別限定，例如可在將所述基材浸漬並含浸在用溶劑對所述樹脂組成物進行了黏度調整的樹脂清漆後，進行加熱乾燥而使樹脂成分半硬化（B階段化）而獲得，並且例如可在100℃～200℃下加熱乾燥1分鐘～40分鐘。此處，預浸體中的樹脂量較佳設為樹脂成分的30質量%～80質量%。The prepreg obtained using the resin composition of the present invention will be described. As the sheet-like substrate, a woven or non-woven fabric of inorganic fibers such as glass or polyester, polyamine, polyacrylic acid, polyimide, kevlar, cellulose, and other organic fibers can be used, but it is not limited For that. The method for producing a prepreg from the resin composition and the base material of the present invention is not particularly limited. For example, the base material may be impregnated and impregnated with a resin varnish in which the resin composition is adjusted in viscosity with a solvent. It is obtained by performing heat drying to semi-harden the resin component (B-staged), and it can be heated and dried at 100°C to 200°C for 1 minute to 40 minutes, for example. Here, the amount of resin in the prepreg is preferably set to 30% by mass to 80% by mass of the resin component.

對使用預浸體或絕緣接著片來製造積層板的方法進行說明。在使用預浸體形成積層板的情況下，將一片或多片預浸體積層，在單側或兩側配置金屬箔以構成積層物，並對該積層物加熱、加壓來進行積層一體化。此處，作為金屬箔，可使用銅、鋁、黃銅、鎳等的單獨、合金、複合的金屬箔。作為對積層物加熱加壓的條件，只要在樹脂組成物硬化的條件下適當地調整來進行加熱加壓即可，但是當加壓的壓力量太低時，存在氣泡殘留在所獲得的積層板的內部，從而電特性降低的情況，因此理想的是在滿足成型性的條件下進行加壓。例如，可將溫度設定為160℃～220℃、將壓力設定為49.0 N/cm² ～490.3 N/cm² （5 kgf/cm² ～50 kgf/cm² ）、將加熱時間設定為40分鐘～240分鐘。The method of manufacturing a laminated board using a prepreg or an insulating adhesive sheet is demonstrated. In the case of using a prepreg to form a laminate, one or more prepreg bulk layers are placed on one side or both sides of the metal foil to form a laminate, and the laminate is heated and pressurized to integrate the laminate . Here, as the metal foil, individual, alloy, or composite metal foils such as copper, aluminum, brass, and nickel can be used. As the conditions for heating and pressing the laminate, as long as the resin composition is hardened, the heating and pressing can be adjusted appropriately. However, when the amount of pressurized pressure is too low, air bubbles remain in the obtained laminate. In the case of the inside, and thus the electrical characteristics are reduced, it is desirable to pressurize under the condition that satisfies the moldability. For example, you can set the temperature to 160°C to 220°C, the pressure to 49.0 N/cm ² to 490.3 N/cm ² (5 kgf/cm ² to 50 kgf/cm ² ), and the heating time to 40 minutes to 240 minutes.

此外，可將以此種方式獲得的單層的積層板作為內層材，來製造多層板。在此種情況下，首先藉由加成法或減成法等對積層板實施電路形成，並用酸溶液處理所形成的電路表面來實施黑化處理，從而獲得內層材。藉由預浸體或絕緣接著片在該內層材的單面或兩側的電路形成面上形成絕緣層，並且在絕緣層的表面形成導體層，從而形成多層板。In addition, a single-layer laminated board obtained in this way can be used as an inner layer material to produce a multilayer board. In this case, first, circuit formation is performed on the laminate by an additive method or a subtractive method, and the surface of the formed circuit is treated with an acid solution to perform a blackening treatment to obtain an inner layer material. An insulating layer is formed on one or both sides of the circuit forming surface of the inner layer material by a prepreg or an insulating adhesive sheet, and a conductor layer is formed on the surface of the insulating layer, thereby forming a multilayer board.

當利用絕緣接著片形成絕緣層時，將絕緣接著片配置在多片內層材的電路形成面上來形成積層物。或者，將絕緣接著片配置在內層材的電路形成面與金屬箔之間來形成積層物。然後對該積層物加熱加壓而一體成型，藉此將絕緣接著片的硬化物形成為絕緣層，同時形成內層材的多層化。或者，將絕緣接著片的硬化物作為絕緣層形成內層材與作為導體層的金屬箔。此處，作為金屬箔，可使用與用作內層材的積層板中使用的金屬箔相同的金屬箔。 另外，可在與內層材的成型相同的條件下進行加熱加壓成形。當將樹脂組成物塗佈到積層板上而形成絕緣層時，針對內層材的最外層的電路形成面樹脂，較佳為將所述樹脂組成物塗佈成5 μm～100 μm厚度，然後在100℃～200℃下加熱乾燥1分鐘～90分鐘以形成片狀。通常藉由被稱為鑄造法的方法形成。乾燥後的厚度理想的是形成為5 μm～80 μm。在以此種方式形成的多層積層板的表面上可進一步藉由加成法或減成法形成通孔或形成電路來形成印刷配線板。 另外，進而將該印刷配線板作為內層材並重覆所述作法，可進一步形成多層的積層板。When the insulating layer is formed by the insulating adhesive sheet, the insulating adhesive sheet is arranged on the circuit forming surface of a plurality of inner layer materials to form a laminate. Alternatively, the insulating adhesive sheet is arranged between the circuit formation surface of the inner layer material and the metal foil to form a laminate. Then, the laminate is heated and pressurized and integrally molded, whereby the cured product of the insulating adhesive sheet is formed as an insulating layer, and at the same time, a multilayered inner layer material is formed. Alternatively, the hardened product of the insulating adhesive sheet is used as an insulating layer to form an inner layer material and a metal foil as a conductor layer. Here, as the metal foil, the same metal foil as the metal foil used in the laminated sheet used as the inner layer material can be used. In addition, heating and pressure forming can be performed under the same conditions as the forming of the inner layer material. When the resin composition is applied to the laminate to form an insulating layer, it is preferable to apply the resin composition to a thickness of 5 μm to 100 μm for the circuit forming surface resin of the outermost layer of the inner layer material, and then Heat and dry at 100°C to 200°C for 1 minute to 90 minutes to form a sheet. It is usually formed by a method called casting method. The thickness after drying is desirably 5 μm to 80 μm. A printed wiring board can be formed by forming via holes or forming circuits on the surface of the multilayer laminate formed in this manner. In addition, by using the printed wiring board as an inner layer material and repeating the above-mentioned method, a multilayer laminate board can be further formed.

另外，當藉由預浸體形成絕緣層時，在內層材的電路形成面上配置將一片或多片預浸體積層而成者，進而在其外側配置金屬箔以形成積層物。然後，藉由對該積層物加熱加壓來一體成形，將預浸體的硬化物形成為絕緣層，同時將其外側的金屬箔形成為導體層。 此處，作為金屬箔，亦可使用與用作內層材的積層板中使用的金屬箔相同的金屬箔。另外，可在與內層材的成型相同的條件下進行加熱加壓成形。進而可藉由加成法或減成法在以此種方式成形的多層積層板的表面上形成通孔或形成電路，而將印刷配線板成型。 另外，進而將該印刷配線板作為內層材並重覆所述作法，可進一步形成多層的多層板。In addition, when the insulating layer is formed by the prepreg, one or more prepreg bulk layers are arranged on the circuit forming surface of the inner layer material, and a metal foil is arranged on the outer side to form a laminate. Then, the laminate is integrally molded by heating and pressing to form the hardened product of the prepreg as an insulating layer, and at the same time, the metal foil on the outer side thereof is formed as a conductor layer. Here, as the metal foil, the same metal foil as the metal foil used in the laminated sheet used as the inner layer material can also be used. In addition, heating and pressure forming can be performed under the same conditions as the forming of the inner layer material. Furthermore, the printed wiring board can be molded by forming a through hole or forming a circuit on the surface of the multilayer laminate formed in this manner by an additive method or a subtractive method. In addition, by using the printed wiring board as an inner layer material and repeating the above-mentioned method, a multi-layer multilayer board can be further formed.

由本發明的樹脂組成物獲得的硬化物、電氣電子電路用積層板具有優異的阻燃性及耐熱性。 [實施例]The cured product obtained from the resin composition of the present invention and the laminated board for electric and electronic circuits have excellent flame retardancy and heat resistance. [Example]

以下，將基於實施例及比較例更具體地說明本發明，但本發明並不限定於此。除非另有說明，否則份表示質量份，%表示質量%。分析方法、測定方法如下所示。另外，各種當量的單位均為g/eq.。Hereinafter, the present invention will be explained more specifically based on examples and comparative examples, but the present invention is not limited to these. Unless otherwise specified, parts means parts by mass, and% means mass%. The analysis method and measurement method are as follows. In addition, the units of various equivalents are g/eq.

（1）重量平均分子量（Mw）及數量平均分子量（Mn）： 藉由GPC測定求出。具體而言，使用於主體HLC8320GPC（東曹（Tosoh）股份有限公司製造）上串聯地包括管柱（TSKgel SuperH-H、SuperH2000、SuperHM-H、SuperHM-H，以上為東曹股份有限公司製造）者，並將管柱溫度設為40℃。另外，溶離液使用DMF（含20 mM溴化鋰品），流速設為0.3 mL/分，檢測器使用示差折射率檢測器。使用20 μL將以固體成分計為0.1 g的測定試樣溶解在10 mL的DMF中，並利用0.45 μm的微型過濾器過濾而成的試樣。根據由標準聚環氧乙烷（東曹股份有限公司製造、SE-2、SE-5、SE-8、SE-15、SE-30、SE-70、SE-150）求出的校準曲線來進行換算，求出Mw。再者，資料處理使用了東曹股份有限公司製造的GPC8020型號II版本6.00。(1) Weight average molecular weight (Mw) and number average molecular weight (Mn): Determined by GPC measurement. Specifically, it is used on the main body HLC8320GPC (manufactured by Tosoh Co., Ltd.) including columns (TSKgel SuperH-H, SuperH2000, SuperHM-H, SuperHM-H, the above are manufactured by Tosoh Co., Ltd.) , And set the column temperature to 40°C. In addition, DMF (containing 20 mM lithium bromide) was used as the eluent, the flow rate was set to 0.3 mL/min, and the differential refractive index detector was used as the detector. A sample obtained by dissolving 0.1 g of a measurement sample in terms of solid content in 10 mL of DMF and filtering it with a 0.45 μm micro filter was used in 20 μL. Based on the calibration curve obtained from standard polyethylene oxide (manufactured by Tosoh Co., Ltd., SE-2, SE-5, SE-8, SE-15, SE-30, SE-70, SE-150) Perform conversion to find Mw. In addition, the data processing used GPC8020 model II version 6.00 manufactured by Tosoh Corporation.

（2）環氧當量： 依據日本工業標準（Japanese industrial standard，JIS）K 7236標準進行測定。具體而言，使用電位差滴定裝置，使用環己酮作為溶媒，加入溴化四乙基銨乙酸溶液，並使用0.1 mol/L過氯酸-乙酸溶液。再者，關於溶媒稀釋品（樹脂清漆），是由不揮發成分算出作為固體成分換算值的數值。(2) Epoxy equivalent: The measurement is carried out in accordance with the Japanese industrial standard (JIS) K 7236 standard. Specifically, a potentiometric titration device is used, cyclohexanone is used as a solvent, a tetraethylammonium bromide acetic acid solution is added, and a 0.1 mol/L perchloric acid-acetic acid solution is used. In addition, the solvent-diluted product (resin varnish) is a value calculated from the non-volatile content as a solid content conversion value.

（3）不揮發成分： 依據JIS K 7235標準進行測定。乾燥溫度為200℃，乾燥時間為60分鐘。(3) Non-volatile ingredients: Measured in accordance with JIS K 7235 standard. The drying temperature is 200°C, and the drying time is 60 minutes.

（4）玻璃轉移溫度（Tg）： 依據印刷電路協會（Institute of printed circuits，IPC）-TM-650 2.4.25.c標準進行測定。具體而言，使用示差掃描熱量測定裝置EXSTAR6000 DSC6200（SII奈米科技（SII nanotechnology）股份有限公司製造），在10℃/分的升溫條件下，在20℃～280℃範圍內，對厚度為4 mm、直徑為3 mm的試樣進行了兩個循環測定，以所獲得的第二掃描測定圖中的中間點玻璃轉移溫度（Tmg）表示。(4) Glass transition temperature (Tg): Measured according to the Institute of printed circuits (IPC)-TM-650 2.4.25.c standard. Specifically, using a differential scanning calorimetry device EXSTAR6000 DSC6200 (manufactured by SII nanotechnology Co., Ltd.), under a temperature increase of 10°C/min, in the range of 20°C to 280°C, the thickness is 4 The sample with a diameter of 3 mm and a diameter of 3 mm was measured in two cycles, which is represented by the glass transition temperature (Tmg) at the middle point in the second scan measurement chart obtained.

（5）介電特性： 藉由空腔諧振器攝動法在1 GHz下測定時的介電損耗正切來評價。具體而言，使用PNA網路分析儀N5230A（安捷倫科技（Agilent Technology）股份有限公司製造）及空腔諧振器CP431（關東電子應用開發股份有限公司製造），在室溫23℃、濕度50%RH的測定環境下，使用寬1.5 mm×長80 mm×厚150 μm的試驗片進行測定。(5) Dielectric characteristics: It is evaluated by the dielectric loss tangent when the cavity resonator perturbation method is measured at 1 GHz. Specifically, PNA network analyzer N5230A (manufactured by Agilent Technology Co., Ltd.) and cavity resonator CP431 (manufactured by Kanto Electronics Application Development Co., Ltd.) are used at room temperature of 23°C and humidity of 50%RH In the measurement environment, use a test piece with a width of 1.5 mm × a length of 80 mm × a thickness of 150 μm for measurement.

（6）耐折性： 在耐折疲勞試驗中，藉由膜斷裂前的彎曲次數進行評價。具體而言，使用寬15 mm×長100 mm×厚100 μm的試驗片，利用MIT耐折疲勞試驗機D型（東洋精機股份有公司製造），在載荷0.5 kgf、速度90 cpm、角度45度、R=0.38 mm的條件下進行了試驗。(6) Folding resistance: In the flexural fatigue test, the evaluation is based on the number of bendings before the film breaks. Specifically, a test piece with a width of 15 mm × a length of 100 mm × a thickness of 100 μm was used, and the MIT flexural fatigue testing machine Type D (manufactured by Toyo Seiki Co., Ltd.) was used at a load of 0.5 kgf, a speed of 90 cpm, and an angle of 45 degrees. The test was conducted under the condition of R=0.38 mm.

實施例、比較例中使用的代號如以下所述。The codes used in Examples and Comparative Examples are as follows.

[二官能環氧樹脂] A1：對苯二酚型環氧樹脂（日鐵化學（Chemical）&材料（Material）股份有限公司製造、ZX-1027、環氧當量131、m≒0.18） A2：間苯二酚型環氧樹脂（西格瑪瑞奧奇（Sigma Aldrich）公司製造、環氧當量127、m≒0.14） A3：2,5-二-第三丁基對苯二酚型環氧樹脂（日鐵化學&材料股份有限公司製造、艾伯特（Epotohto）YDC-1213、環氧當量175、m≒0.05） A4：萘型環氧樹脂（迪愛生（DIC）股份有限公司製造、艾比克隆（EPICLON）HP4032D、環氧當量142、m≒0.07） A5：雙酚A型液狀環氧樹脂（日鐵化學&材料股份有限公司製造、艾伯特（Epotohto）YD-128、環氧當量186） 此處，m具有與所述式（7）中的m相同的含義。[Difunctional epoxy resin] A1: Hydroquinone epoxy resin (manufactured by Nippon Steel Chemical & Material Co., Ltd., ZX-1027, epoxy equivalent 131, m≒0.18) A2: Resorcinol type epoxy resin (manufactured by Sigma Aldrich, epoxy equivalent 127, m≒0.14) A3: 2,5-Di-tertiary butyl hydroquinone epoxy resin (manufactured by Nittetsu Chemical & Materials Co., Ltd., Epotohto YDC-1213, epoxy equivalent 175, m≒0.05) A4: Naphthalene epoxy resin (manufactured by DIC Co., Ltd., EPICLON HP4032D, epoxy equivalent 142, m≒0.07) A5: Bisphenol A liquid epoxy resin (manufactured by Nittetsu Chemical & Materials Co., Ltd., Epotohto YD-128, epoxy equivalent 186) Here, m has the same meaning as m in the above-mentioned formula (7).

[二酯系化合物] B1：2,6-二乙醯氧基萘（東京化成工業股份有限公司製造、活性當量=122） B2：1,4-二乙醯氧基萘（富士膠片和光純藥股份有限公司製造、活性當量=122） B3：2,2-雙(4-乙醯氧基苯基)丙烷（東京化成工業股份有限公司製造、活性當量=156）[Diester Compounds] B1: 2,6-Diacetyloxynaphthalene (manufactured by Tokyo Chemical Industry Co., Ltd., active equivalent = 122) B2: 1,4-Diacetyloxynaphthalene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., active equivalent = 122) B3: 2,2-bis(4-acetoxyphenyl)propane (manufactured by Tokyo Chemical Industry Co., Ltd., active equivalent = 156)

[二官能酚化合物] C1：2,6-萘二酚（東京化成工業股份有限公司製造、羥基當量80）[Difunctional phenol compound] C1: 2,6-Naphthalenediol (manufactured by Tokyo Chemical Industry Co., Ltd., hydroxyl equivalent 80)

[觸媒] D1：N,N'-二甲胺基吡啶（東京化成工業股份有限公司製造） D2：2-乙基-4-甲基咪唑（四國化成工業股份有限公司製造、固唑（Curezol）2E4MZ）[catalyst] D1: N,N'-Dimethylaminopyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) D2: 2-Ethyl-4-methylimidazole (manufactured by Shikoku Chemical Industry Co., Ltd., Curezol 2E4MZ)

[溶媒、溶劑] S1：環己酮 S2：甲基乙基酮（MEK）[Solvent, solvent] S1: Cyclohexanone S2: Methyl ethyl ketone (MEK)

[酸酐] E1：乙酸酐（富士膠片和光純藥股份有限公司製造） E2：苯甲酸酐（東京化成工業股份有限公司製造）[Acid anhydride] E1: Acetic anhydride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) E2: Benzoic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.)

[硬化劑] H1：苯酚酚醛清漆樹脂（艾克（Aica）工業股份有限公司製造、新澳（SHONOL）BRG-5575、羥基當量105）[hardener] H1: Phenol novolac resin (manufactured by Aica Industrial Co., Ltd., SHONOL BRG-5575, hydroxyl equivalent 105)

實施例1 於包括攪拌裝置、溫度計、氮氣導入裝置、冷卻管及滴加裝置的玻璃製反應容器中，在室溫下，投入100份A1、89份B1、及47份作為反應溶媒的S1，使氮氣流動並在攪拌的同時升溫至130℃，添加0.2份作為觸媒的D1後，升溫至145℃，在該溫度下進行7小時反應。將47份S1、189份S2用作稀釋溶劑進行稀釋混合，獲得不揮發成分為40%的苯氧基樹脂清漆（R1）。Example 1 Put 100 parts of A1, 89 parts of B1, and 47 parts of S1 as a reaction solvent into a glass reaction vessel including a stirring device, a thermometer, a nitrogen introduction device, a cooling tube, and a dripping device at room temperature, and let nitrogen flow The temperature was raised to 130°C while stirring, and after adding 0.2 part of D1 as a catalyst, the temperature was raised to 145°C, and the reaction was performed at this temperature for 7 hours. 47 parts of S1 and 189 parts of S2 were used as a dilution solvent to dilute and mix to obtain a phenoxy resin varnish (R1) with a non-volatile content of 40%.

實施例2～實施例8、比較例1～3 按照表1～表2所示的各原料的投入量（份）進行與實施例1相同的操作而獲得苯氧基樹脂清漆。再者，表中的莫耳比表示二官能環氧樹脂相對於二酯系化合物及二官能酚化合物的莫耳比，清漆表示苯氧基樹脂清漆。Example 2 to Example 8, Comparative Examples 1 to 3 According to the input amount (part) of each raw material shown in Table 1-Table 2, the same operation as Example 1 was performed, and the phenoxy resin varnish was obtained. In addition, the molar ratio in the table represents the molar ratio of the difunctional epoxy resin to the diester compound and the bifunctional phenol compound, and the varnish represents the phenoxy resin varnish.

[表1] 實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 A1 100 100 100 100 A2 100   A3 100   B1 89 92 66 89 44 B2 89   C1           29 D1 0.2 0.2 0.2 0.2   D2 0.2 0.2 莫耳比 1.05 1.05 1.05 1.05 1.05 1.05 反應時間（Hr） 7 7 7 7 7 9 反應溫度（℃） 145 145 145 145 145 145 （反應溶媒）    S1 47 47 48 42 47 43 （稀釋溶媒）    S1                 S2 47 189 47 189 48 192 42 166 47 189 43 174 清漆 R1 R2 R3 R4 R5 R6 [Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 A1 100 100 100 100 A2 100 A3 100 B1 89 92 66 89 44 B2 89 C1 29 D1 0.2 0.2 0.2 0.2 D2 0.2 0.2 Molby 1.05 1.05 1.05 1.05 1.05 1.05 Response time (Hr) 7 7 7 7 7 9 Reaction temperature (℃) 145 145 145 145 145 145 (Reaction solvent) S1 47 47 48 42 47 43 (Dilution solvent) S1 S2 47 189 47 189 48 192 42 166 47 189 43 174 Varnish R1 R2 R3 R4 R5 R6

[表2] 實施例7 實施例8 實施例9 比較例1 比較例2 比較例3 A1 100 100 100 100   100 A4         100   B1 98 85 74   82   B3     19 113     C1           58 D1 0.2 0.2 0.2 0.2 0.2 0.2 莫耳比 0.95 1.10 1.05 1.05 1.05 1.05 反應時間（Hr） 9 7 7 7 7 10 反應溫度（℃） 145 145 145 145 145 145 （反應溶媒）    S1 50 46 50 53 45 39 （稀釋溶媒）    S1                 S2 49 198 47 184 50 173 53 213 46 182 40 158 清漆 R7 R8 R9 RH1 RH2 RH3 [Table 2] Example 7 Example 8 Example 9 Comparative example 1 Comparative example 2 Comparative example 3 A1 100 100 100 100 100 A4 100 B1 98 85 74 82 B3 19 113 C1 58 D1 0.2 0.2 0.2 0.2 0.2 0.2 Molby 0.95 1.10 1.05 1.05 1.05 1.05 Response time (Hr) 9 7 7 7 7 10 Reaction temperature (℃) 145 145 145 145 145 145 (Reaction solvent) S1 50 46 50 53 45 39 (Dilution solvent) S1 S2 49 198 47 184 50 173 53 213 46 182 40 158 Varnish R7 R8 R9 RH1 RH2 RH3

實施例10 調配比較例3中獲得的苯氧基樹脂清漆（RH3）100份（以固體成分計為40份）、600份S1，升溫至100℃後，加入5份E1，進行4小時反應。將獲得的樹脂清漆加入甲醇中，過濾析出的不溶解成分後，將濾液用真空乾燥器在150℃、0.4 kPa（3 torr）的條件下乾燥1小時，獲得苯氧基樹脂。對獲得的苯氧基樹脂加入21份S1、42份S2，使其均勻溶解，獲得不揮發成分40%的苯氧基樹脂清漆（R10）。Example 10 100 parts of the phenoxy resin varnish (RH3) obtained in Comparative Example 3 (40 parts in terms of solid content) and 600 parts of S1 were prepared, and after the temperature was raised to 100°C, 5 parts of E1 were added, and the reaction was carried out for 4 hours. The obtained resin varnish was added to methanol, the precipitated insoluble components were filtered, and the filtrate was dried with a vacuum dryer at 150° C. and 0.4 kPa (3 torr) for 1 hour to obtain a phenoxy resin. 21 parts of S1 and 42 parts of S2 were added to the obtained phenoxy resin to dissolve uniformly to obtain a phenoxy resin varnish (R10) with 40% non-volatile content.

實施例11 除了使E1為23份、稀釋溶媒的S1為25份及S2為49份以外，進行與實施例10相同的操作，獲得苯氧基樹脂清漆（R11）。Example 11 Except that E1 was 23 parts, S1 of the dilution solvent was 25 parts, and S2 was 49 parts, the same operation as Example 10 was performed, and the phenoxy resin varnish (R11) was obtained.

實施例12 除了代替E1而使E2為51份、使作為稀釋溶媒的S1為31份及使S2為62份以外，進行與實施例10同樣的操作，獲得苯氧基樹脂清漆（R12）。Example 12 Except that instead of E1, E2 was 51 parts, S1 as a dilution solvent was 31 parts, and S2 was 62 parts, the same operation as Example 10 was performed, and the phenoxy resin varnish (R12) was obtained.

將實施例1～實施例12及比較例1～比較例3中獲得的樹脂清漆R1～樹脂清漆R12及樹脂清漆RH1～樹脂清漆RH3以乾燥後的膜厚為100 μm及150 μm的方式塗佈在鐵板上，使用乾燥機在150℃下乾燥1小時，獲得樹脂膜。 利用苯氧基樹脂清漆測定環氧當量及Mw，利用樹脂膜測定Tg、介電特性、及耐折性。其結果如表3所示。再者，表中的「式（2）含有率」表示式（1）中的全部X中的式（2）的結構的含有率（莫耳%），「式（3）含有率」表示式（1）中的全部X中的式（3）結構的含有率（莫耳%），「醯化率」表示全部Z中的醯基的含有率（莫耳%）。使用樹脂清漆RH1～樹脂清漆RH3的例子是比較例。The resin varnish R1 to resin varnish R12 and the resin varnish RH1 to resin varnish RH3 obtained in Example 1 to Example 12 and Comparative Example 1 to Comparative Example 3 were coated in such a way that the film thicknesses after drying were 100 μm and 150 μm The iron plate was dried at 150°C for 1 hour using a dryer to obtain a resin film. Use phenoxy resin varnish to measure epoxy equivalent and Mw, and use resin film to measure Tg, dielectric properties, and folding resistance. The results are shown in Table 3. In addition, the "content rate of formula (2)" in the table represents the content rate (mol%) of the structure of formula (2) in all Xs in formula (1), and the "content rate of formula (3)" represents the formula (1) The content rate (mole %) of the structure of formula (3) in all Xs in (1), and the "alternation rate" means the content rate (mole %) of the radicals in all Z. Examples using resin varnish RH1 to resin varnish RH3 are comparative examples.

[表3] 清漆 環氧當量 Mw 式（2）含有率 式（3）含有率 醯化率 Tg（℃） 介電特性 耐折性 （次） R1 9000 29000 51 49 89 120 0.01 49 R2 8700 30000 51 49 89 125 0.01 55 R3 9200 28000 51 49 91 121 0.01 57 R4 8200 31000 51 49 99 123 0.01 65 R5 8000 24000 51 49 89 123 0.01 44 R6 7000 26000 51 49 44 133 0.02 47 R7 8600 26000 49 51 89 133 0.02 47 R8 5000 14000 52 48 89 122 0.01 35 R9 8800 31000 51 41 89 125 0.02 40 R10 8300 28000 51 49 20 122 0.01 62 R11 10000 28000 51 49 100 118 0.01 67 R12 11300 28000 51 49 100 120 0.01 54 RH1 10000 28000 51 0 89 101 0.01 52 RH2 7800 30000 0 100 99 113 0.01 20 RH3 8000 31000 51 49 0 123 0.04 60 [table 3] Varnish Epoxy equivalent Mw Formula (2) Concentration rate Formula (3) Concentration rate Fusion rate Tg (℃) Dielectric properties Folding resistance (times) R1 9000 29000 51 49 89 120 0.01 49 R2 8700 30000 51 49 89 125 0.01 55 R3 9200 28000 51 49 91 121 0.01 57 R4 8200 31000 51 49 99 123 0.01 65 R5 8000 24000 51 49 89 123 0.01 44 R6 7000 26000 51 49 44 133 0.02 47 R7 8600 26000 49 51 89 133 0.02 47 R8 5000 14000 52 48 89 122 0.01 35 R9 8800 31000 51 41 89 125 0.02 40 R10 8300 28000 51 49 20 122 0.01 62 R11 10000 28000 51 49 100 118 0.01 67 R12 11300 28000 51 49 100 120 0.01 54 RH1 10000 28000 51 0 89 101 0.01 52 RH2 7800 30000 0 100 99 113 0.01 20 RH3 8000 31000 51 49 0 123 0.04 60

實施例13～實施例15、比較例4～比較例5 調配30份（以固體成分計為12份）實施例1、實施例2、實施例4及比較例1～比較例3中獲得的苯氧基樹脂清漆（R1、R2、R4、RH1～RH3）、2份作為環氧樹脂的A5、且利用50%MEK溶液調配2.5份的作為硬化劑的H1、以及利用20%MEK溶液調配0.6份的作為硬化促進劑的C2，獲得樹脂組成物。再將該些以使乾燥後的膜厚為100 μm及150 μm的方式塗佈在鐵板上，利用乾燥機在150℃下乾燥1小時，獲得膜狀的硬化物。分別測定了Tg、介電特性、及耐折性。其結果如表4所示。Example 13 to Example 15, Comparative Example 4 to Comparative Example 5 30 parts (12 parts in terms of solid content) of the phenoxy resin varnish (R1, R2, R4, RH1 to RH3) obtained in Example 1, Example 2, Example 4, and Comparative Example 1 to Comparative Example 3 were formulated , 2 parts of A5 as an epoxy resin, 2.5 parts of H1 as a hardener using a 50% MEK solution, and 0.6 parts of C2 as a hardening accelerator using a 20% MEK solution to obtain a resin composition. These were applied to an iron plate so that the film thickness after drying was 100 μm and 150 μm, and dried at 150° C. for 1 hour with a dryer to obtain a film-like cured product. The Tg, dielectric properties, and flexural resistance were measured separately. The results are shown in Table 4.

[表4] 實施例13 實施例14 實施例15 比較例4 比較例5 比較例6 清漆 R1 R2 R4 RH1 RH2 RH3 Tg（℃） 131 133 130 109 125 138 介電特性 0.01 0.01 0.01 0.01 0.01 0.04 耐折性（次） 35 39 46 35 5 40 [Table 4] Example 13 Example 14 Example 15 Comparative example 4 Comparative example 5 Comparative example 6 Varnish R1 R2 R4 RH1 RH2 RH3 Tg (℃) 131 133 130 109 125 138 Dielectric properties 0.01 0.01 0.01 0.01 0.01 0.04 Folding resistance (times) 35 39 46 35 5 40

由表3可知，實施例1～實施例12所表示的本發明的苯氧基樹脂的耐熱性、介電特性、及耐折性優異。另外，由表4可知，包含本發明的樹脂組成物的硬化物的耐熱性、介電特性、及耐折性亦優異。 [產業上之可利用性]From Table 3, it can be seen that the phenoxy resins of the present invention shown in Examples 1 to 12 are excellent in heat resistance, dielectric properties, and folding resistance. In addition, as can be seen from Table 4, the cured product including the resin composition of the present invention is also excellent in heat resistance, dielectric properties, and folding resistance. [Industrial availability]

本發明的苯氧基樹脂及樹脂組成物可適用於接著劑、塗料、土木用建築材料、電氣電子零件的絕緣材料等各種領域，特別是作為電氣電子領域中的絕緣注模、積層材料、密封材料等是有用的。本發明的苯氧基樹脂及含有該苯氧基樹脂的樹脂組成物可適宜用於多層印刷配線基板、電容器等電氣電子電路用積層板、膜狀接著劑、液狀接著劑等接著劑、半導體密封材料、填底膠材料、三維大型積體電路（three-dimensional large-scale integration，3D-LSI）用晶片間填充（Inter Chip Fill）材料、絕緣片、預浸體、放熱基板等。The phenoxy resin and resin composition of the present invention can be applied to various fields such as adhesives, paints, civil construction materials, and insulating materials for electrical and electronic parts, especially as insulating injection molding, laminated materials, and sealing materials in the electrical and electronic fields. Materials etc. are useful. The phenoxy resin of the present invention and the resin composition containing the phenoxy resin can be suitably used for multilayer printed wiring boards, laminates for electrical and electronic circuits such as capacitors, adhesives such as film adhesives, liquid adhesives, and semiconductors. Sealing materials, primer materials, inter Chip Fill materials for three-dimensional large-scale integration (3D-LSI), insulating sheets, prepregs, heat-radiating substrates, etc.

無none

無。none.

Claims (10)

一種苯氧基樹脂，由下述式（1）表示，且重量平均分子量為10,000～200,000，

式中，X獨立地為含有下述式（2）及式（3）所表示的二氧基的二價基，Y分別獨立地為氫原子、具有碳數1～20的烴基的醯基、或縮水甘油基，Z為具有碳數1～20的烴基的醯基或氫原子，且5莫耳%以上為所述醯基，n是重覆數的平均值，為15以上且500以下，

式（2）及式（3）中，R分別獨立地為選自由碳數1～12的烷基、碳數1～12的烷氧基、碳數6～12的芳基、碳數7～13的芳烷基、碳數6～12的芳氧基、碳數7～13的芳烷氧基、碳數2～12的烯基、及碳數2～12的炔基所組成的群組中的基，i為0～4的整數，j為0～6的整數。A phenoxy resin represented by the following formula (1) with a weight average molecular weight of 10,000 to 200,000,

In the formula, X is independently a divalent group containing a dioxy group represented by the following formula (2) and formula (3), and Y is each independently a hydrogen atom, an acyl group having a hydrocarbon group with 1 to 20 carbon atoms, Or a glycidyl group, Z is an acyl group or a hydrogen atom having a hydrocarbon group with 1 to 20 carbons, and 5 mol% or more is the acyl group, n is the average of the number of repetitions, which is 15 or more and 500 or less,

In formula (2) and formula (3), R is each independently selected from alkyl groups having 1 to 12 carbons, alkoxy groups having 1 to 12 carbons, aryl groups having 6 to 12 carbons, and 7 to carbon atoms. The group consisting of 13 aralkyl, 6-12 aryloxy, 7-13 aralkoxy, 2-12 alkenyl, and 2-12 alkynyl In the base, i is an integer of 0-4, and j is an integer of 0-6. 一種樹脂組成物，包含如請求項1所述的苯氧基樹脂、及硬化劑。A resin composition comprising the phenoxy resin described in claim 1 and a hardener. 如請求項2所述的樹脂組成物，其中，相對於苯氧基樹脂的固體成分100質量份，含有以固體成分計為0.1質量份～100質量份的硬化劑。The resin composition according to claim 2, wherein the curing agent is contained in a solid content of 0.1 to 100 parts by mass relative to 100 parts by mass of the solid content of the phenoxy resin. 如請求項2所述的樹脂組成物，其含有如請求項1所述的苯氧基樹脂、環氧樹脂及硬化劑，且苯氧基樹脂與環氧樹脂的固體成分的質量比為99/1～1/99。The resin composition according to claim 2, which contains the phenoxy resin, epoxy resin, and hardener according to claim 1, and the mass ratio of the solid content of the phenoxy resin to the epoxy resin is 99/ 1～1/99. 如請求項4所述的樹脂組成物，其中，相對於苯氧基樹脂與環氧樹脂的固體成分的合計100質量份，含有以固體成分計為0.1質量份～100質量份的硬化劑。The resin composition according to claim 4, wherein the curing agent is contained in a solid content of 0.1 to 100 parts by mass relative to 100 parts by mass of the total solid content of the phenoxy resin and the epoxy resin. 如請求項2所述的樹脂組成物，其中硬化劑為選自由丙烯酸酯樹脂、黑色素樹脂、脲樹脂、酚樹脂、酸酐化合物、胺系化合物、咪唑系化合物、醯胺系化合物、陽離子聚合起始劑、有機膦類、聚異氰酸酯化合物、封閉異氰酸酯化合物、及活性酯系硬化劑所組成的群組中的至少一種。The resin composition according to claim 2, wherein the hardener is selected from the group consisting of acrylate resins, melanin resins, urea resins, phenol resins, acid anhydride compounds, amine compounds, imidazole compounds, amide compounds, and cationic polymerization initiators. At least one of the group consisting of an agent, an organic phosphine, a polyisocyanate compound, a blocked isocyanate compound, and an active ester curing agent. 一種硬化物，將如請求項2至請求項6中任一項所述的樹脂組成物硬化而成。A hardened product obtained by hardening the resin composition according to any one of Claims 2 to 6. 一種電氣電子電路用積層板，使用如請求項2至請求項6中任一項所述的樹脂組成物而得。A laminated board for electrical and electronic circuits, which is obtained by using the resin composition described in any one of Claims 2 to 6. 一種苯氧基樹脂的製造方法，其特徵在於，使下述式（7）所表示的二官能環氧樹脂與下述式（8）所表示的化合物反應，獲得重量平均分子量為10,000～200,000的下述式（1）所表示的苯氧基樹脂，

式中，X¹ 獨立地為含有下述式（2）或式（3）所表示的二氧基的二價基，式（7）及式（8）的X¹ 中整體含有式（2）及式（3）所表示的二氧基， Z¹ 為具有碳數1～20的烴基的醯基或氫原子，5莫耳%以上為所述醯基，此處，式（8）所表示的化合物可為選自Z¹ 的兩者為醯基的化合物、一者為醯基的化合物及兩者為氫原子的化合物中的兩種以上的混合物， m是重覆數的平均值，為0以上且6以下，

式中，R分別獨立地為選自由碳數1～12的烷基、碳數1～12的烷氧基、碳數6～12的芳基、碳數7～13的芳烷基、碳數6～12的芳氧基、碳數7～13的芳烷氧基、碳數2～12的烯基、及碳數2～12的炔基所組成的群組中的基，i為0～4的整數，j為0～6的整數，

式中，X獨立地為含有所述式（2）及式（3）所表示的二氧基的二價基，Y分別獨立地為氫原子、具有碳數1～20的烴基的醯基、或縮水甘油基，Z為具有碳數1～20的烴基的醯基或氫原子，且5莫耳%以上為所述醯基，n是重覆數的平均值，為15以上且500以下。A method for producing a phenoxy resin, characterized by reacting a difunctional epoxy resin represented by the following formula (7) with a compound represented by the following formula (8) to obtain a weight average molecular weight of 10,000 to 200,000 The phenoxy resin represented by the following formula (1),

In the formula, X ^{1 is} independently a divalent group containing a dioxy group represented by the following formula (2) or formula (3), and X ¹ of formula (7) and formula (8) contains formula (2) as a whole And the dioxy group represented by the formula (3), Z ¹ is an acyl group or a hydrogen atom having a hydrocarbon group with 1 to 20 carbon atoms, and 5 mol% or more is the acyl group. Here, the formula (8) represents The compound of can be ^{a mixture of two or more compounds selected from Z 1} in which two are acyl groups, one is an acyl group, and both are hydrogen atoms. m is the average of the number of repetitions, which is 0 or more and 6 or less,

In the formula, R is each independently selected from an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, an aryl group having 6 to 12 carbons, an aralkyl group having 7 to 13 carbons, and In the group consisting of 6-12 aryloxy, 7-13 aralkoxy, 2-12 alkenyl, and 2-12 alkynyl, i is 0- An integer of 4, j is an integer of 0-6,

In the formula, X is independently a divalent group containing the dioxy group represented by the formula (2) and formula (3), and Y is each independently a hydrogen atom, an acyl group having a hydrocarbon group with 1 to 20 carbon atoms, Or a glycidyl group, Z is an acyl group or a hydrogen atom having a C1-C20 hydrocarbon group, 5 mol% or more is the acyl group, and n is the average of the number of repetitions, which is 15 or more and 500 or less. 一種苯氧基樹脂的製造方法，其特徵在於，使醯化劑的醯基相對於下述式（12）所表示的苯氧基樹脂的醇性羥基1莫耳，以0.05莫耳以上且2.0莫耳以下進行反應，獲得重量平均分子量為10,000～200,000的下述式（1）所表示的苯氧基樹脂，

式中，X² 獨立地為含有下述式（2）及式（3）所表示的二氧基的二價基，Y² 分別獨立地為氫原子或縮水甘油基，n是重覆數的平均值，為15以上且500以下，

式中，R分別獨立地為選自由碳數1～12的烷基、碳數1～12的烷氧基、碳數6～12的芳基、碳數7～13的芳烷基、碳數6～12的芳氧基、碳數7～13的芳烷氧基、碳數2～12的烯基、及碳數2～12的炔基所組成的群組中的基，i為0～4的整數，j為0～6的整數，

式中，X、n分別與式（12）的X² 、n為相同含義，Y分別獨立地為氫原子、具有碳數1～20的烴基的醯基、或縮水甘油基，Z為具有碳數1～20的烴基的醯基或氫原子，且5莫耳%以上為所述醯基。A method for producing a phenoxy resin, characterized in that the alcoholic hydroxyl group of a phenoxy resin represented by the following formula (12) is adjusted to 0.05 mol or more and 2.0 mol with respect to the alcoholic hydroxyl group of the phenoxy resin represented by the following formula (12). The reaction is carried out below mol to obtain a phenoxy resin represented by the following formula (1) with a weight average molecular weight of 10,000 to 200,000,

In the formula, X ^{2 is} independently a divalent group containing a dioxy group represented by the following formula (2) and formula (3), Y ^{2 is} independently a hydrogen atom or a glycidyl group, and n is the number of repetitions The average value is 15 or more and 500 or less,

In the formula, R is each independently selected from an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, an aryl group having 6 to 12 carbons, an aralkyl group having 7 to 13 carbons, and In the group consisting of 6-12 aryloxy, 7-13 aralkoxy, 2-12 alkenyl, and 2-12 alkynyl, i is 0- An integer of 4, j is an integer of 0-6,

In the formula, X and n have the ^{same meanings as X 2} and n in the formula (12), Y is each independently a hydrogen atom, an acyl group having a hydrocarbon group with 1 to 20 carbons, or a glycidyl group, and Z is a carbon The number of the acyl group or the hydrogen atom of the hydrocarbon group of 1 to 20, and 5 mol% or more is the acyl group.