TW201540752A - Denatured polyhydric hydroxy resin, epoxy resin, epoxy resin composition and cured product thereof - Google Patents

Abstract

This invention provides a denatured polyhydric hydroxy resin, an epoxy resin, an epoxy resin composition and a cured product thereof. This invention provides a denatured polyhydric hydroxy resin that is a denatured polyhydric hydroxy resin obtained by the following steps: reacting a polyhydric hydroxy compound represented by the following general formula (1) and an aromatic denaturant including styrenes or a benzilization agent and substituting a substituent derivated from the aromatic denaturant, which is represented by formula (a), on benzene rings of the polyhydric hydroxyl compound, and a number average molecular weight Mn evaluated by gel permeation chromatography is 1000 to 5000 and a ratio Mw/Mn of a weight average molecular weight Mw and the number average molecular weight Mn is 2 or more.

Description

Modified polyhydroxy resin, epoxy resin, epoxy resin composition and cured product thereof

The present invention relates to an epoxy resin which provides a cured product which is excellent in high heat resistance and excellent in dielectric properties, moisture resistance, and workability, a modified polyvalent hydroxy resin suitable as a middle substance thereof, and an epoxy resin using these resins. The composition and the cured product thereof are suitably used, for example, as an insulating material for electric and electronic fields such as a circuit board material and a sealing material.

Epoxy resins are used industrially for a wide range of applications, but in recent years their performance has been increasing. For example, in the representative field of a resin composition using an epoxy resin as a main component, there is a semiconductor sealing material, but as the degree of integration of the semiconductor element is increased, the package size tends to be large, thin, and the mounting method is also It is desired to develop a material excellent in solder heat resistance by pushing it on the surface. Therefore, as a sealing material, in addition to low moisture absorption, the adhesion of interfaces of different materials such as lead frames and chips is strongly required. The adhesion is improved. In the same manner as in the circuit board material, in view of improvement in solder heat resistance, in addition to low moisture absorption, high heat resistance, and high adhesion In addition to the improvement in properties, it is desired to develop a material having excellent low dielectric properties from the viewpoint of reducing dielectric loss. In order to meet these requirements, various novel structures of epoxy resins and hardeners are being studied. Furthermore, from the viewpoint of environmental load reduction, there is a tendency to eliminate the halogen-based flame retardant, and an epoxy resin and a curing agent which are more excellent in flame retardancy are required.

Therefore, various epoxy resins and epoxy resin hardeners have been studied for the background. As an example of the epoxy resin curing agent, a naphthalene resin is known, and Patent Document 1 discloses that a naphthol aralkyl resin is applied to a semiconductor sealing material, and flame retardancy, low moisture absorption, low thermal expansion property, and the like are described. Excellent. Further, Patent Document 2 proposes a curing agent having a biphenyl structure, and is described as being effective for improving flame retardancy. However, both the naphthol aralkyl resin and the biphenyl aralkyl resin have the disadvantage of being inferior in hardenability, and the effect of improving flame retardancy is also insufficient.

On the other hand, regarding epoxy resins, those who meet these requirements are not known. For example, a well-known bisphenol type epoxy resin is liquid at normal temperature, is excellent in workability, or is easily mixed with a curing agent, an additive, etc., and is widely used, but has problems in heat resistance and moisture resistance. Moreover, as an improvement of heat resistance, an o-cresol novolac type epoxy resin is known, and flame retardance is not sufficient.

As a measure for improving flame retardancy without using a halogen-based flame retardant, a method of adding a phosphate-based flame retardant has been disclosed. However, in the method using a phosphate ester type flame retardant, moisture resistance is not sufficient. Further, in a high-temperature, high-humidity environment, there is a problem that hydrolysis of a phosphate ester causes a decrease in reliability as an insulating material.

Patent Document 2 and Patent Document 3 disclose an example in which an aralkyl type epoxy resin having a biphenyl structure is applied to a semiconductor sealing material, as a result of not including a phosphorus atom or a halogen atom and improving the flame retardancy. Patent Document 4 discloses an example of using an aralkyl type epoxy resin having a naphthalene structure. However, these epoxy resins are insufficient in performance in any of flame retardancy, moisture resistance, or heat resistance.

As an example of improving heat resistance, moisture resistance, and crack resistance, Patent Document 5 discloses a benzylated polyphenol and an epoxy resin thereof, but these examples do not pay attention to flame retardancy. Further, Patent Document 6 discloses a method for producing a styrene-modified novolak resin, but does not attract attention as an epoxy resin composition.

Further, as an example of an epoxy resin composition that improves moisture resistance and low stress, Patent Document 7 and Patent Document 8 disclose a styrene-modified phenol novolak resin and an epoxy resin using the epoxy resin. The resin composition, in these examples, does not have an example of a detailed study of the molecular weight distribution of the styrenated phenol novolak resin and the epoxy resin.

On the other hand, as an example of focusing on improvement of flame retardancy, Patent Document 9 discloses a styrene-modified phenol novolak resin and an epoxy resin composition using the epoxy resin. Here, focusing on the amount of styrene modification, a resin having a higher hydroxyl group equivalent or epoxy equivalent by increasing the amount of modification is used. In the cured product using such a resin, a high flame retardancy can be exhibited by relatively lowering the content of the epoxy group-derived aliphatic component. However, there is no example in which the molecular weight distribution of the polyvalent hydroxy resin and the epoxy resin is studied in detail. Further, in Patent Document 10, the polyhydroxy resin is a substance related to impurities of extremely low molecular weight. Sex studies were conducted but no studies related to high molecular weight bodies were performed.

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2005-344081

[Patent Document 2] Japanese Patent Laid-Open No. Hei 11-140166

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2000-129092

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2004-59792

[Patent Document 5] Japanese Patent Laid-Open No. 8-120039

[Patent Document 6] Japanese Patent Laid-Open No. 48-52895

[Patent Document 7] Japanese Patent Laid-Open No. Hei 5-132544

[Patent Document 8] Japanese Patent Laid-Open No. Hei 5-140265

[Patent Document 9] Japanese Patent Laid-Open Publication No. 2010-235819

[Patent Document 10] WO2012/043213

An object of the present invention is to provide a modified polyhydric hydroxy resin which is excellent in heat resistance and mechanical properties in applications such as lamination, molding, casting, adhesion, and the like, and also excellent in dielectric properties, moisture resistance, workability, and the like. And an epoxy resin obtained by using the resin, and further provided to provide a cured product having excellent heat resistance and dielectric properties, and also excellent in moisture resistance, workability, and the like, and can be used for electrical. Epoxy resin composition of circuit board materials and sealing materials for electronic parts Further, it is provided to provide a cured product obtained by hardening the epoxy resin composition.

That is, the present invention is a modified polyhydric hydroxy resin which is obtained by reacting a polyvalent hydroxy compound represented by the following formula (1) with an aromatic modifier to obtain a source represented by the formula (a) a styrene-modified polyhydric hydroxy resin obtained by substituting a substituent of styrene on a benzene ring of a polyvalent hydroxy compound, and having a number average molecular weight Mn of 1,000 or more and 5,000 or less as measured by gel permeation chromatography, and a weight average molecular weight The ratio Mw/Mn of Mw to the number average molecular weight Mn is 2 or more.

(here, R ₁ , R ₂ , R ₃ and R ₄ represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms)

Further, the present invention is a modified polybasic hydroxy resin characterized in that the aromatic modifier is styrene.

Further, the present invention is a modified polyhydric hydroxy resin characterized by using a number average molecular weight Mn of 500 or more as measured by gel permeation chromatography. A polyvalent hydroxy compound is obtained as the polyvalent hydroxy compound of the above formula (1).

Further, the present invention is an epoxy resin obtained by reacting the modified polybasic hydroxy resin with epichlorohydrin.

Further, the present invention is an epoxy resin composition which comprises the modified polybasic hydroxy resin and/or the epoxy resin as an essential component in an epoxy resin composition comprising an epoxy resin and a hardener. Blended. Further, the present invention is an epoxy resin cured product obtained by curing the epoxy resin composition.

When the epoxy resin and the modified polyvalent hydroxy resin of the present invention are applied to an epoxy resin composition, a cured product excellent in heat resistance and dielectric properties and excellent in moisture resistance can be provided, which is suitable for use in a circuit. Substrate material, electrical. Uses such as sealing materials for electronic parts.

1 is a gel permeation Chromatography (GPC) chart of the polyvalent hydroxy compound A used in Example 1.

2 is a GPC chart of the polyvalent hydroxy compound B used in Example 2.

3 is a GPC chart of the polyvalent hydroxy compound C used in Comparative Example 1.

4 is a GPC chart of the polyhydric hydroxy resin synthesized in Example 1.

Fig. 5 is a GPC chart of the polyhydric hydroxy resin synthesized in Example 2.

Fig. 6 is a GPC chart of the polyhydric hydroxy resin synthesized in Comparative Example 1.

7 is a GPC chart of an epoxy resin synthesized in Example 3.

8 is a GPC chart of an epoxy resin synthesized in Example 4.

9 is a GPC chart of an epoxy resin synthesized in Comparative Example 2.

First, in the epoxy resin cured product, since the hydroxypropyl group formed by the reaction of the epoxy group and the hydroxyl group has a polarity, an increase in the dielectric constant or the like is likely to occur, but a compound having an aromatic ring or the like is obtained. In particular, when styrene is added to a polyvalent hydroxy compound to increase the hydroxyl equivalent, the content of the polar group derived from the epoxy group is lowered, and low dielectric properties can be exhibited. Further, the addition of the aromatic styrene-based olefin resin improves the aromaticity of the polyvalent hydroxy resin and also improves the moisture resistance.

On the other hand, in the method of improving physical properties by increasing the modification ratio of styrene, the crosslinking density is lowered due to a decrease in the number of functional groups, and the heat resistance (Tg) of the cured product tends to decrease. . Therefore, in the present invention, by controlling the molecular weight distribution of the polyvalent hydroxy compound of the raw material, the styrene modification ratio which does not impair the heat resistance or the dielectric property is found to be excellent in heat resistance and dielectric properties, and moisture resistance and A modified polyvalent hydroxy resin and an epoxy resin which are also excellent in handleability.

The polyvalent hydroxy compound used in the present invention is a polyvalent hydroxy compound represented by the formula (1), and is therefore also referred to as a polyvalent hydroxy compound (1). Further, since it is also one type of novolak resin, it is also called a phenol novolak resin.

First, the modified polyhydric hydroxy resin of the present invention (hereinafter referred to as StPN) Be explained. The StPN of the present invention is characterized in that the number average molecular weight Mn measured by gel permeation chromatography is 1000 or more and 5,000 or less, and the ratio Mw/Mn of the weight average molecular weight Mw to the number average molecular weight Mn is 2 or more. By using the polyvalent hydroxy compound represented by the formula (1) as a polyvalent hydroxy compound of the formula (1) when it is detected by gel permeation chromatography (GPC; RI), n is in the range of 1 to 100. Further, a polyvalent hydroxy compound having a number average molecular weight Mn of 500 or more measured by gel permeation chromatography is reacted with an aromatic modifier. When the number average molecular weight Mn is less than 1,000, the heat resistance at the time of forming a cured product tends to be inferior, and when it exceeds 5,000, the viscosity increases and the workability of the composition is inferior. On the other hand, when Mw/Mn is less than 2, the reactivity is inferior to the coating property of the composition when a sheet or the like is formed.

The range of the molecular weight distribution of the polyvalent hydroxy compound used in the present invention is such that n is in the range of 1 to 100, and more preferably in the range of 50 to 100. By using a high molecular weight component having n of 50 or more, the crosslinking density is increased, and heat resistance can be improved. Further, the number average molecular weight Mn of the polyvalent hydroxy compound (1) is preferably 500 or more and 5,000 or less, and more preferably 600 or more and 4,000 or less. When it is less than 500, heat resistance tends to be inferior, and if it exceeds 5,000, viscosity increases and workability is inferior.

The StPN of the present invention is obtained by subjecting a polyvalent hydroxy compound (1) represented by the formula (1) to an aromatic modifier. In this case, the ratio of the polyvalent hydroxy compound (1) to the aromatic modifier is considered to be a molar ratio with respect to the polyvalent hydroxy compound 1 in consideration of the balance between the dielectric properties and the curability of the obtained cured product. The use ratio of the aromatic modifier is preferably in the range of 0.1 mol to 1.5 mol, and more preferably in the range of 0.1 mol to 1.0 mol. When the amount is less than the above range, the properties of the polyvalent hydroxy compound which is a raw material are not improved, and when it is more than the above range, the functional group density tends to be too low and the hardenability tends to be lowered.

In the reaction, an aromatic modifier is added to an aromatic ring having an OH group in the polyvalent hydroxy compound (1), and the α-alkyl-substituted benzyl group represented by the formula (a) is substituted. . Further, the addition position of the aromatic modifier is the ortho and/or para position of the vacancy of the polyvalent hydroxy compound, and is mainly para.

Further, the StPN of the present invention preferably has a melt viscosity at 150 ° C of 0.50 Pa. s~10.0Pa. The range of s. In terms of workability, the melt viscosity is preferably 10.0 Pa. s below.

Further, the softening point is preferably in the range of 40 ° C to 150 ° C, preferably 50 ° C to 120 ° C. Here, the softening point means a softening point measured based on the ring and ball method of JIS-K-2207. When it is lower than the softening point, when it is blended in an epoxy resin, the heat resistance of the cured product is lowered, and when it is higher than the softening point, the fluidity at the time of molding is lowered.

The α-alkyl-substituted benzyl group represented by the formula (a) can be adjusted in an amount depending on the amount of the aromatic modifier, and is usually added in an amount of 0.1 to the benzene ring of the polyvalent hydroxy compound. 2.5. This refers to the average (number average) of the α-alkyl substituted benzyl groups substituted on one phenol ring. The amount of addition is preferably from 0.1 mol to 1.5 mol, and from 0.1 mol to 1.0 mol, relative to the benzene ring 1 mole of the polyvalent hydroxy compound. In addition, up to 4 α-alkyl substituted benzyl groups may be substituted on the phenol ring at both ends, and up to 3 α-alkanes may be substituted on the intermediate phenol ring. The benzyl group is substituted, so that in the case where n is 1, a maximum of 8 α-alkyl substituted benzyl groups may be substituted.

In the formula (a), R ₂ represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, preferably hydrogen or an alkyl group having 1 to 3 carbon atoms, more preferably hydrogen. The R ₂ is determined by styrene used as a reaction raw material.

Next, a method of manufacturing the StPN of the present invention will be described. A phenol novolak can be used for the polyvalent hydroxy compound (1) used for producing the StPN of the present invention.

The polyvalent hydroxy compound (1) is obtained by a reaction of a phenol with an aldehyde, and the phenol used is mainly phenol. The phenols may also contain minor amounts of other phenol components. For example, o-cresol, m-cresol, p-cresol, ethyl phenol, isopropyl phenol, tert-butyl phenol, allyl phenol, phenyl phenol, etc. are mentioned. These phenols may be used alone or in combination of two or more. In addition, if it is a small amount, it can be adjusted: 2,6-xylenol, 2,6-diethylphenol, hydroquinone, resorcinol, catechol, 1-naphthol, 2-naphthalene Other phenols such as phenol, 1,5-naphthalenediol, 1,6-naphthalenediol, 1,7-naphthalenediol, 2,6-naphthalenediol, 2,7-naphthalenediol or naphthols. In the case of formulating these phenols, it is preferably controlled to 30% by weight or less, preferably 20% by weight or less.

As the aromatic modifier to be used in the reaction with the polyvalent hydroxy compound, a benzylating agent represented by the following formula (2) or a styrene is used, and a styrene is preferable. The styrene is styrene substituted with styrene or a hydrocarbon group having 1 to 6 carbon atoms. The styrene may contain a small amount of other reaction components, and other reaction components may be exemplified by α-methylstyrene, divinylbenzene, hydrazine, coumarone, An unsaturated bond-containing component such as benzothiophene, anthracene or vinylnaphthalene. In the case of formulating these components, it is preferably controlled to 30% by weight or less, preferably 20% by weight or less.

(wherein R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and Y is a halogen atom, an alkoxy group or a hydroxyl group)

The benzylating agent represented by the above formula (2), when Y is a halogen atom, may, for example, be benzyl chloride, benzyl bromide, benzyl iodide, o-methylbenzyl chloride or m-methyl group. Benzyl chloride, p-methylbenzyl chloride, p-ethylbenzyl chloride, p-isopropylbenzyl chloride, p-tert-butylbenzyl chloride, p-cyclohexylbenzyl chloride, p-phenylbenzyl chloride, α- Methylbenzyl chloride, α,α-dimethylbenzyl chloride, etc.; when Y is an alkoxy group, it is preferably an alkoxy group having 1 to 4 carbon atoms, and examples thereof include benzyl methyl ether and ortho-methyl group. Benzyl methyl ether, m-methylbenzyl methyl ether, p-methylbenzyl methyl ether, p-ethylbenzyl methyl ether, benzyl ether, benzyl isopropyl ether, benzyl n-propyl ether, benzyl isobutyl Ether, benzyl n-butyl ether, p-methylbenzyl methyl ether, etc.; in the case where Y is a hydroxyl group, benzyl alcohol, o-methylbenzyl alcohol, m-methylbenzyl alcohol, p-methylbenzyl Alcohol, p-ethylbenzyl alcohol, p-isopropylbenzyl alcohol, p-tert-butylbenzyl alcohol, p-cyclohexylbenzyl alcohol, p-phenylbenzyl alcohol, α-methylbenzyl alcohol, α, Α-dimethylbenzyl alcohol and the like.

The reaction of a polyvalent hydroxy compound with an aromatic modifier can be carried out in an acid catalyst The catalyst amount is used in the range of 10 ppm to 1000 ppm, preferably in the range of 100 ppm to 500 ppm. When the amount is more than the above range, the methylene crosslinkage of the polyvalent hydroxy compound is likely to be cracked, and the monophenol component produced by the cracking reaction is degraded in curability and heat resistance. On the other hand, when it is less than the above range, the reactivity is lowered, and a large amount of unreacted styrene monomer remains. In addition, the amount of catalyst here means the amount of catalyst with respect to the total weight of the polyhydric hydroxy compound and styrene used for reaction.

The reaction can be carried out in the presence of an acid catalyst. The acid catalyst can be appropriately selected from well-known inorganic acids and organic acids. Examples thereof include mineral acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, or organic acids such as formic acid, oxalic acid, trifluoroacetic acid, p-toluenesulfonic acid, dimethylsulfuric acid, and diethylsulfuric acid, or zinc chloride, aluminum chloride, and chlorine. A Lewis acid such as iron or boron trifluoride or an ion exchange resin, a solid acid such as activated clay, cerium oxide-alumina or zeolite, or the like.

Further, the reaction temperature in the reaction is carried out in the range of 40 ° C to 150 ° C. If it is less than the above range, the reactivity is lowered, and the reaction time becomes a long time. In addition, when it is more than the above range, a part of the methylene crosslinkage of the polyvalent hydroxy compound is easily cleaved, and the monophenol component which is produced by the cracking reaction is deteriorated in curability and heat resistance.

Further, the reaction is usually carried out for 1 hour to 20 hours. Further, in the reaction, an alcohol such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve or ethyl cellosolve may be used, or acetone, methyl ethyl ketone or methyl isobutylate may be used. Ketones such as ketones, ethers such as dimethyl ether, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, etc. An aromatic compound such as benzene, chlorobenzene or dichlorobenzene is used as a solvent.

The specific method for carrying out the reaction is usually a method in which all the raw materials are charged in batches, the reaction is carried out directly at a predetermined temperature, or a polyvalent hydroxy compound and a catalyst are charged, and while maintaining a predetermined temperature, the mixture is added dropwise. The styrene reacts while conducting. At this time, the dropping time is preferably 5 hours or shorter, and usually 1 hour to 10 hours. After the reaction, when a solvent is used, the catalyst component may be removed as needed, and then the solvent may be distilled off to obtain the resin of the present invention. When the solvent is not used, the target may be obtained by directly discharging it during heat.

Next, the epoxy resin of the present invention will be described.

The epoxy resin of the present invention (abbreviated as StPNE) can be obtained by epoxidizing StPN.

The StPNE of the present invention is produced by reacting the StPN with epichlorohydrin, which is advantageous.

The reaction for reacting the StPN with epichlorohydrin can be carried out in the same manner as the usual epoxidation reaction.

For example, a method in which the StPN is dissolved in excess epichlorohydrin is 20 to 150 ° C, preferably 30 ° C in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. The reaction was carried out in the range of 80 ° C for 1 hour to 10 hours. The alkali metal hydroxide is used in an amount of from 0.8 mol to 1.5 mol, preferably from 0.9 mol to 1.2 mol, relative to the hydroxyl group of StPN. Further, epichlorohydrin is excessively used with respect to the hydroxyl group 1 in StPN, but usually, the epichlorohydrin is 1.5 mol to 30 with respect to the hydroxyl group 1 in StPN. The range of moles is preferably in the range of 2 moles to 15 moles. After the completion of the reaction, the excess epichlorohydrin is distilled off, and the residue is dissolved in a solvent such as toluene or methyl isobutyl ketone, filtered, washed with water to remove the inorganic salt, and then the solvent is distilled off to obtain a target. Epoxy resin.

Further, the epoxy resin composition of the present invention contains at least three types of epoxy resins and hardeners.

1) A composition obtained by blending the StPNE as a part or all of an epoxy resin.

2) A composition obtained by blending the StPN as a part or the whole of a hardener.

3) A composition in which the StPNE and StPN are blended as a part or all of an epoxy resin and a hardener.

In the case of the compositions of the above 2) and 3), StPN is contained as an essential component. The amount of StPN is usually in the range of 2 parts by weight to 200 parts by weight, preferably in the range of 5 parts by weight to 80 parts by weight, based on 100 parts by weight of the epoxy resin. When the amount is less than the above range, the effect of improving the flame retardancy and the moisture resistance is small, and if it is more than the above range, there is a problem that the moldability and the strength of the cured product are lowered.

In the case where StPN is used as the total amount of the hardener, generally, the amount of StPN is formulated in consideration of the equivalent balance of the OH group of StPN and the epoxy group in the epoxy resin. The equivalent ratio of the epoxy resin and the curing agent is usually in the range of 0.2 to 5.0, preferably in the range of 0.5 to 2.0. Whether it is larger than the range or smaller than the range, not only the hardenability of the epoxy resin composition is lowered, but also the heat resistance and mechanics of the cured product. The strength and the like decrease.

As the curing agent, a curing agent other than StPN can be used in combination. The blending amount of the other curing agent is determined within a range of usually 2 parts by weight to 200 parts by weight, preferably 5 parts by weight to 80 parts by weight, based on 100 parts by weight of the epoxy resin and the amount of StPN. When the amount of StPN is less than the above range, the effect of improving low moisture absorption, adhesion, and flame retardancy is small, and if it is more than the above range, there is a problem that moldability and strength of the cured product are lowered. In this case, the equivalent ratio of the epoxy resin to the hardener (total) is also set to the above range.

As a curing agent other than StPN, it is generally known as a curing agent for an epoxy resin, and there are dicyandiamide, an acid anhydride, a polyhydric phenol, an aromatic, an aliphatic amine, and the like. Among these hardeners, in the field of requiring high electrical insulating properties such as a semiconductor sealing material, it is preferred to use a polyhydric phenol as a curing agent. In the case where the composition of StPN of the present invention is used as an essential component, the amount of StPN to be blended in the entire curing agent is preferably in the range of 50% to 100%, preferably in the range of 60% to 100%. Specific examples of the curing agent other than StPN are shown below.

Examples of the acid anhydride hardener include phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and methyl group. Methylene tetrahydrophthalic anhydride, dodecenyl succinic anhydride, nadic anhydride, trimellitic anhydride, and the like.

Examples of polyhydric phenols include bisphenol A, bisphenol F, bisphenol S, bismuth bisphenol, 4,4'-biphenol, 2,2'-biphenol, hydroquinone, resorcinol, naphthalene a dihydric phenol such as an alcohol, or tris-(4-hydroxyphenyl)methane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, phenol A ternary or higher phenol represented by a novolac, an o-cresol novolac, a naphthol novolak, a polyvinyl phenol or the like. Further, there are: phenols, naphthols, bisphenol A, bisphenol F, bisphenol S, bisphenol, 4,4'-biphenol, 2,2'-biphenol, hydroquinone, and Dihydric phenols such as benzenediol and naphthalenediol, and condensing agents such as formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, p-dichlorobenzyl, bischloromethylbiphenyl and dichloromethylnaphthalene Polyphenolic compounds and the like.

The amines are: 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylanthracene, m-phenylenediamine, p-benzene An aromatic amine such as dimethylamine, an aliphatic amine such as ethylenediamine, hexamethylenediamine, diethylenetriamine or triamethylenetetraamine.

One type of these curing agents or two or more types of these curing agents can be used in the composition.

The epoxy resin used in the composition is selected from those having two or more epoxy groups in one molecule. For example, bisphenol A, bisphenol F, 3,3', 5,5'-tetramethyl-bisphenol F, bisphenol S, bisphenol, 4,4'-biphenol, 2,2' Epoxy of dihydric phenols such as biphenol, 3,3',5,5'-tetramethyl-4,4'-dihydroxybiphenol, hydroquinone, resorcinol, naphthalenediol a ternary or higher phenolic ring such as tris-(4-hydroxyphenyl)methane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, phenol novolac, or cresol novolac An epoxide of a co-condensation resin of an oxide, a dicyclopentadiene and a phenol, an epoxide of a phenol aralkyl resin synthesized from a phenol and a p-dichlorobenzyl, and a phenol and a chlorin An epoxide of a biphenyl aralkyl type phenol resin synthesized from a phenyl group or the like, an epoxide of a naphthol aralkyl resin synthesized from naphthols and p-dichlorobenzyl or the like A glycidyl ether compound derived from a halogenated bisphenol such as bromobisphenol A or the like. These epoxy resins may be used alone or in combination of two or more.

In the case of the compositions of the above 1) and 3), StPNE is included as an essential component. In the epoxy resin composition, in addition to StPNE, other types of epoxy resins may be blended as the epoxy resin component. As the epoxy resin in this case, a general epoxy resin having two or more epoxy groups in the molecule can be used, and for example, the epoxy compound. Further, in the case of using the composition of StPNE of the present invention as an essential component, the amount of StPNE in the entire epoxy resin is preferably in the range of 50% to 100%, preferably in the range of 60% to 100%.

In the epoxy resin composition of the present invention, polyester, polyamine, polyimine, polyether, polyurethane, petroleum resin, enamel resin, ruthenium may also be appropriately formulated. An oligomer or a polymer compound such as a benzofuran resin or a phenoxy resin is used as another modifier. The amount of the other modifier to be added is usually in the range of 2 parts by weight to 30 parts by weight based on 100 parts by weight of the epoxy resin.

Further, the epoxy resin composition of the present invention may be formulated with an additive such as an inorganic filler, a pigment, a flame retardant, a shake imparting agent, a coupling agent, and a fluidity improver. Examples of the inorganic filler include spherical or crushed cerium oxide powder such as cerium oxide or cerium oxide, alumina powder, glass powder, or mica, talc, calcium carbonate, alumina, hydrated alumina, and the like. A preferred blending amount in the case of use in a semiconductor sealing material is 70% by weight or more, and particularly preferably 80% by weight or more.

The pigments include organic or inorganic extender pigments, flaky pigments, and the like. Examples of the shake imparting agent include an anthraquinone, a castor oil, an aliphatic amide wax, an oxidized polyethylene wax, and an organic bentonite.

Further, in the epoxy resin composition of the present invention, a curing accelerator may be used as needed. For example, there are amines, imidazoles, organic phosphines, Lewis acids, etc., specifically: 1,8-diazabicyclo(5,4,0)undecene-7, triethylenediamine, Tertiary amines such as benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol, 2-methylimidazole, 2-phenylimidazole, 2-ethyl- Imidazoles such as 4-methylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine , organic phosphines such as phenylphosphine, tetraphenylphosphonium. Tetraphenylborate, tetraphenylphosphonium. Ethyltriphenylborate, tetrabutylphosphonium. Tetrabutyl hydride such as tetrabutyl borate. Tetrasubstituted borate, 2-ethyl-4-methylimidazole. Tetraphenylborate, N-methylmorpholine. A tetraphenylboron salt such as tetraphenylborate. The hardening accelerator is usually added in an amount of from 0.2 part by weight to 5 parts by weight per 100 parts by weight of the epoxy resin.

Further, if necessary, a resin composition of the present invention may be used: a release agent such as carnauba wax or OP wax, a coupling agent such as γ-glycidoxypropyltrimethoxydecane, a coloring agent such as carbon black, and a trioxide. A flame retardant such as ruthenium, a low stress agent such as eucalyptus oil, or a lubricant such as calcium stearate.

The epoxy resin composition of the present invention can be impregnated into a fibrous material such as a glass cloth, an aromatic polyamide non-woven fabric, a liquid crystal polymer or the like, and then removed in a varnish state obtained by dissolving an organic solvent, and then removed. Solvent to form a prepreg. In addition, depending on the case, it can be applied to copper foil, stainless steel foil, polyimide film, and poly A laminate is formed on a sheet such as an ester film.

When the epoxy resin composition of the present invention is heat-cured, an epoxy resin cured product can be formed, and the cured product is excellent in curability, flame retardancy, low hygroscopicity, low elasticity, and the like. The cured product can be obtained by subjecting an epoxy resin composition to molding by a method such as casting, compression molding, or transfer molding. The temperature at this time is usually in the range of 120 ° C to 220 ° C.

[Examples]

Hereinafter, the present invention will be further specifically described by way of examples.

(Synthesis of StPN)

Example 1

In a 1 L four-necked flask, a polyvalent hydroxy compound A (BRG-558, manufactured by Showa Denko, having a softening point of 95 ° C, a melt viscosity of 0.8 Pa·s, a Mn of 670, Mw/Mn =) was added as a component of a polyvalent hydroxy compound. 2.20) 105 g of 0.099 g (500 ppm) of p-toluenesulfonic acid as an acid catalyst, and the temperature was raised to 150 °C. Then, while stirring at 150 ° C, 93.6 g (0.9 mol) of styrene was added dropwise for 3 hours to carry out a reaction. Further, after reacting at 150 ° C for 1 hour, 197 g of a styrene-modified polybasic hydroxy resin was obtained. Its hydroxyl equivalent is 197g / eq., the softening point is 99 ° C, the melt viscosity at 150 ° C is 1.5Pa. s, molecular weight is Mn = 1030, Mw / Mn = 2.32. The resin is referred to as StPN-A. The GPC chart of StPN-A is shown in Fig. 4. Further, a GPC chart of the polyvalent hydroxy compound A used herein is shown in Fig. 1 .

Example 2

In a 1 L four-necked flask, polyhydric hydroxy group as a component of a polyvalent hydroxy compound was added. Base compound B (PS-6362, manufactured by Qunrong Chemical Industry, softening point 105 ° C, melt viscosity 5.0 Pa.s, Mn 840, Mw / Mn = 3.14) 105 g, p-toluenesulfonic acid 0.099 g as an acid catalyst (500 ppm), the temperature was raised to 150 °C. Then, while stirring at 150 ° C, 93.6 g (0.9 mol) of styrene was added dropwise for 3 hours to carry out a reaction. Further, after reacting at 150 ° C for 1 hour, 195 g of a styrene-modified polybasic hydroxy resin was obtained. Its hydroxyl equivalent is 195g / eq., the softening point is 108 ° C, the melt viscosity at 150 ° C is 7.0Pa. s, molecular weight is Mn = 1280, Mw / Mn = 3.83. The resin is referred to as StPN-B. The GPC chart of StPN-B is shown in Fig. 5. Further, a GPC chart of the polyvalent hydroxy compound B used herein is shown in Fig. 2 .

Comparative example 1

In a 1 L four-necked flask, a polyvalent hydroxy compound C (BRG-555, manufactured by Showa Denko, having a softening point of 68 ° C, a melt viscosity of 0.1 Pa.s, a Mn of 450, Mw/Mn =) was added as a component of a polyvalent hydroxy compound. 1.45) 105 g of 0.099 g (500 ppm) of p-toluenesulfonic acid as an acid catalyst, and the temperature was raised to 150 °C. Then, while stirring at 150 ° C, 93.6 g (0.9 mol) of styrene was added dropwise for 3 hours to carry out a reaction. Further, after reacting at 150 ° C for 1 hour, 197 g of a styrene-modified polybasic hydroxy resin was obtained. The hydroxyl equivalent is 199 g/eq., the softening point is 74 ° C, and the melt viscosity at 150 ° C is 0.16 Pa. s, molecular weight is Mn = 760, Mw / Mn = 1.54. The resin is referred to as StPN-C. The GPC chart of StPN-C is shown in Fig. 6. Further, a GPC chart of the polyvalent hydroxy compound C used herein is shown in Fig. 3 .

(synthesis of epoxy resin)

Example 3

To a four-neck separable flask, 150 g of StPN-A obtained in Example 1, 314 g of epichlorohydrin, and 47 g of diethylene glycol dimethyl ether were added and stirred and dissolved. After uniformly dissolving, it was kept at 65 ° C under a reduced pressure of 130 mmHg, and 58 g of a 48% aqueous sodium hydroxide solution was added dropwise over 4 hours, and the water distilled under reflux in the dropwise addition was separated from epichlorohydrin in a separation tank. The chlorohydrin is returned to the reaction vessel and the water is removed to the outside of the system for reaction. After completion of the reaction, the salt formed by filtration was removed, and after washing with water, epichlorohydrin was distilled off to obtain 173 g (StPNE-A) epoxy resin. The obtained resin had an epoxy equivalent of 281 g/eq., a softening point of 86 ° C, and a melt viscosity of 1.1 Pa at 150 ° C. s, molecular weight is Mn = 1180, Mw / Mn = 2.85. The GPC chart of StPNE-A is shown in Fig. 7.

Example 4

150 g of StPN-B obtained in Example 2, 320 g of epichlorohydrin, and 48 g of diethylene glycol dimethyl ether were added to a four-neck separable flask, and stirred and dissolved. After uniformly dissolving, it was kept at 65 ° C under a reduced pressure of 130 mmHg, and 59 g of a 48% aqueous sodium hydroxide solution was added dropwise over 4 hours, and the water distilled under reflux in the dropwise addition was separated from epichlorohydrin in a separation tank. Epichlorohydrin is returned to the reaction vessel and the water is removed to the outside of the system for reaction. After completion of the reaction, the salt formed by filtration was removed, and after washing with water, epichlorohydrin was distilled off to obtain 164 g (StPNE-B) epoxy resin. The obtained resin had an epoxy equivalent of 288 g/eq., a softening point of 96 ° C, and a melt viscosity of 5.2 Pa at 150 ° C. s, molecular weight is Mn=1420, Mw/Mn=6.18. The GPC chart of StPNE-B is shown in Fig. 8.

Comparative example 2

Into a four-neck separable flask, 150 g of StPN-C obtained in Comparative Example 1, 314 g of epichlorohydrin, and 47 g of diethylene glycol dimethyl ether were added and stirred and dissolved. After uniformly dissolving, it was kept at 65 ° C under a reduced pressure of 130 mmHg, and 58 g of a 48% aqueous sodium hydroxide solution was added dropwise over 4 hours, and the water distilled under reflux in the dropwise addition was separated from epichlorohydrin in a separation tank. Epichlorohydrin is returned to the reaction vessel and the water is removed to the outside of the system for reaction. After completion of the reaction, the salt formed by filtration was removed, and after washing with water, epichlorohydrin was distilled off to obtain 173 g (StPNE-C) of an epoxy resin. The obtained resin had an epoxy equivalent of 271 g/eq., a softening point of 61 ° C, and a melt viscosity at 150 ° C of 0.15 Pa. s, molecular weight is Mn = 610, Mw / Mn = 1.91. The GPC chart of StPNE-C is shown in Fig. 9.

1) Gel permeation chromatography (GPC) determination

The TSKgel G4000HXL, TSKgel G3000HXL, and TSKgel G2000HXL manufactured by Tosoh Corporation were used in series, and the column temperature was set to 40 °C. Further, tetrahydrofuran was used in the eluent to set a flow rate of 1 ml/min, and the detector was an RI (differential refractometer) detector. 0.1 g of the sample was dissolved in 10 ml of tetrahydrofuran (THF). The number average molecular weight (Mn) was determined from a standard curve obtained from standard polystyrene.

2) Softening point

The measurement was carried out by a ring and ball method using an automatic softening point device (manufactured by Mingfeng Co., Ltd., ASP-M4SP) in accordance with JIS-K-2207.

3) Melt viscosity

Captain (CAP) 2000H made by BROOKFIELD A rotary viscometer was measured at 150 °C.

4) Determination of hydroxyl equivalent

Using a potentiometric titration apparatus, 1,4-dioxane was used as a solvent, and acetonitrile was carried out with 1.5 mol/L of ethyl hydrazine chloride, and excess ethyl hydrazine chloride was decomposed with water, and 0.5 mol/L of potassium hydroxide was used. Titration.

5) Determination of epoxy equivalent

A potentiometric titration apparatus was used, and methyl ethyl ketone was used as a solvent, and a tetraethylammonium bromide acetic acid solution was added thereto, and the mixture was measured by a potentiometric titration apparatus using a 0.1 mol/L perchloric acid-acetic acid solution.

6) Glass transfer point (Tg)

It is represented by the following temperature, that is, when measured by a differential scanning calorimeter (EXSTAR 6000 DSC6200 manufactured by SII NanoTechnology Co., Ltd.) at a temperature rising condition of 10 ° C/min. The temperature of the differential scanning calorimeter (DSC) extrapolated value.

7) Dielectric constant, dielectric loss tangent

The dielectric constant (manufactured by AGILENT Technologies) was used to evaluate the dielectric constant and the dielectric loss tangent at a frequency of 1 GHz by a volumetric method.

8) Water absorption rate

The condition of 25 ° C and a relative humidity of 50% was taken as a standard state, and the weight change rate after moisture absorption for 100 hours under conditions of 85 ° C and a relative humidity of 85% was used.

Example 5, Example 6 and Comparative Example 3

An o-cresol novolac type epoxy resin (OCNE; an epoxy equivalent of 200 and a softening point of 65 ° C) was used as the epoxy resin component, and StPN-A obtained in Example 1 and StPN- obtained in Example 2 were used. B. StPN-C obtained in Comparative Example 1 was used as a hardener component, and 2-ethyl-4-methylimidazole (2E4MZ; manufactured by Shikoku Chemicals Co., Ltd.) was used as a curing catalyst, and mixed in the formulation shown in Table 1. An epoxy resin composition is obtained. The epoxy resin composition was molded at 130 ° C for 15 minutes, and molded at 190 ° C for 80 minutes to obtain a cured test piece, which was then subjected to various physical property measurements. The blending table and physical property evaluation results are shown in Table 1.

Example 7, Example 8 and Comparative Example 4

Using StPNE-A obtained in Example 3, StPNE-B obtained in Example 4, and StPNE-C obtained in Comparative Example 2 as an epoxy resin component, a phenol novolak resin (BRG-557, manufactured by Showa Denko, was used. The softening point was 80 ° C. As a hardener component, 2-ethyl-4-methylimidazole (2E4MZ, manufactured by Shikoku Chemicals Co., Ltd.) was used as a hardening catalyst, and the mixture shown in Table 2 was mixed to obtain an epoxy resin. Composition. The epoxy resin composition was molded at 130 ° C for 15 minutes and at 190 ° C for 80 minutes to obtain a cured test piece, which was then subjected to various physical property measurements. The blending table and the physical property evaluation results are shown in Table 2.

Claims (8)

A modified polyhydric hydroxy resin obtained by reacting a polyvalent hydroxy compound represented by the following formula (1) with an aromatic modifier containing a styrene or a benzylating agent, The modified polyhydric hydroxy resin obtained by substituting a substituent derived from an aromatic modifier on a benzene ring of a polyvalent hydroxy compound, and having a number average molecular weight Mn of 1,000 or more as measured by gel permeation chromatography is 5,000 or more Hereinafter, the ratio Mw/Mn of the weight average molecular weight Mw to the number average molecular weight Mn is 2 or more, Here, R ₁ , R ₂ , R ₃ and R ₄ represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and n represents a number of 1 to 100. The modified polyhydric hydroxy resin according to claim 1, wherein the aromatic modifier is styrene. The modified polyhydric hydroxy resin according to claim 1 or 2, wherein the polyvalent hydroxy compound having a number average molecular weight Mn of 500 or more as measured by gel permeation chromatography is used as the general formula (1) Obtained from a polyhydroxy compound. An epoxy resin composition characterized in that it is a part or all of a hardener in an epoxy resin composition comprising an epoxy resin and a hardener, as in the first to third items of the patent application scope Any of the modified polybasic hydroxy resins described above is an essential component. An epoxy resin cured product obtained by hardening an epoxy resin composition as described in claim 4 of the patent application. An epoxy resin obtained by reacting a modified polyhydric hydroxy resin according to any one of claims 1 to 3 with epichlorohydrin. An epoxy resin composition characterized in that an epoxy resin composition comprising an epoxy resin and a hardener is used as an essential component in an epoxy resin composition according to claim 6 . An epoxy resin cured product obtained by hardening an epoxy resin composition as described in claim 7 of the patent application.