JP6956647B2 - Epoxy resin, its manufacturing method, resin composition, and cured product - Google Patents

Description

The present invention relates to an epoxy resin that provides a cured product having excellent low dielectric properties, high heat resistance, high adhesiveness, etc., a method for producing this epoxy resin, an epoxy resin composition containing this epoxy resin as an essential component, and this epoxy resin. It relates to a cured product, a prepreg, and a laminated board obtained from the composition.

Epoxy resins are widely used in paints, civil engineering adhesives, castings, electrical and electronic materials, film materials, etc. because they are excellent in adhesiveness, flexibility, heat resistance, chemical resistance, insulation, and curing reactivity. In particular, epoxy resins are widely used in printed wiring board applications, which are one of the electrical and electronic materials, because they exhibit high heat resistance and good electrical characteristics.

The characteristics such as low dielectric constant, low dielectric loss tangent and high adhesive strength are largely derived from the structure of the epoxy resin, which is the matrix resin of the printed wiring board.

With the dramatic increase in the amount of information in recent years, there is a constant demand for higher functionality in portable devices, which are one of the uses of printed wiring boards, and infrastructure devices such as base stations that connect them. In portable devices, the number of layers and fine wiring are increasing for the purpose of miniaturization, and a material with a lower dielectric constant is required to make the substrate thinner, and the fine wiring reduces the adhesive surface, which is higher. Adhesive materials are required. Substrates for base stations are required to have a lower dielectric loss tangent material in order to suppress signal attenuation due to high frequencies.

Regarding the high heat resistance of the epoxy resin, Patent Document 1 discloses an epoxy resin composition for a laminated board using triglycidyl isocyanurate. Further, Patent Document 2 discloses a dicyclopentadiene type epoxy resin, which shows that it has a low dielectric constant. However, these epoxy resin compositions do not simultaneously satisfy the requirements for high heat resistance and low dielectric properties associated with high-density mounting of laminated plates in recent years.

Regarding the high adhesive strength of the epoxy resin, Patent Document 3 discloses a glycidyloxy compound of tris- (3,5-dimethyl-4-hydroxybenzyl) isocyanurate. However, with the recent increase in functionality, further improvement in dielectric properties and heat resistance is required.

Japanese Unexamined Patent Publication No. 9-183831 Japanese Unexamined Patent Publication No. 11-181052 International Publication No. 2002/48235

The problem to be solved by the present invention is that the cured product has excellent low dielectric properties as well as excellent heat resistance, adhesiveness, etc., and is useful for applications such as lamination, molding, casting, and adhesion. It is an object of the present invention to provide an epoxy resin, an epoxy resin composition, and a cured product thereof.

As a result of diligent studies on isocyanurate-type epoxy resins in order to solve the above problems, the present inventor has low dielectric properties and heat resistance of a cured product obtained from an epoxy resin made from isocyanurate having a specific substituent as a raw material. The present invention has been completed by finding excellent properties and adhesiveness.

（但し、Ｘ^１は下記式（２）で表され、Ｘ^２及びＸ^３は独立にグリシジル基又は下記式（２）を表す）

（但し、Ｒ^１及びＲ^２は独立に炭素数１から８の炭化水素基を表し、Ｒ^３、Ｒ^４、及びＲ^５のうち一つがグリシジルオキシ基を表し、その他の二つがそれぞれ水素原子又は炭素数１から８の炭化水素基を表す。） That is, the present invention is an epoxy resin represented by the following general formula (1).

(However, X ¹ is represented by the following formula (2), and X ² and X ³ independently represent a glycidyl group or the following formula (2)).

(However, R ¹ and R ² independently represent hydrocarbon groups having 1 to 8 carbon atoms, one of R ³ , R ⁴ , and R ⁵ represents a glycidyloxy group, and the other two represent hydrogen atoms or hydrogen atoms, respectively. Represents a hydrocarbon group having 1 to 8 carbon atoms.)

The epoxy equivalent of the epoxy resin is 140 g / eq. As mentioned above, 700 g / eq. The range is preferably as follows.

（但し、Ｙ^１は下記式（４）で表され、Ｙ^２及びＹ^３は独立に水素原子又は下記式（４）で表す。）

（但し、Ｒ^１１及びＲ^１２は独立に炭素数１から８の炭化水素基を表し、Ｒ^１３、Ｒ^１４、及びＲ^１５のうち一つが水酸基を表し、その他の二つがそれぞれ水素原子又は炭素数１から８の炭化水素基を表す。） Further, the present invention is a method for producing an epoxy resin, which comprises reacting epichlorohydrin with a hydroxy compound represented by the following general formula (3).

(However, Y ¹ is represented by the following formula (4), and Y ² and Y ³ are independently represented by a hydrogen atom or the following formula (4).)

(However, R ¹¹ and R ¹² independently represent hydrocarbon groups having 1 to 8 carbon atoms, one of R ¹³ , R ¹⁴ and R ¹⁵ represents a hydroxyl group, and the other two represent hydrogen atoms or carbon atoms, respectively. Represents 1 to 8 hydrocarbon groups.)

Further, the present invention is an epoxy resin composition comprising the epoxy resin and a curing agent, wherein the epoxy resin is blended as an essential component.

It is preferable that the active hydrogen group of the curing agent is 0.2 to 1.5 mol with respect to 1 mol of the epoxy group of all the epoxy resins in the epoxy resin composition.

Further, the present invention is a cured product obtained by curing the epoxy resin composition. Further, the present invention is a sealing material, a prepreg, or a laminated board, characterized in that the epoxy resin composition is used.

The epoxy resin of the present invention and the epoxy resin composition thereof exhibit excellent heat resistance and adhesiveness in the cured product thereof. Further, it has excellent dielectric properties, and exhibits good properties in laminated boards and electronic circuit boards that require low dielectric constant and low dielectric loss tangent.

6 is a GPC chart of the epoxy resin obtained in Example 1. It is a chart of FT-IR of the epoxy resin obtained in Example 1. 6 is an NMR chart of the epoxy resin obtained in Example 1.

Hereinafter, embodiments of the present invention will be described in detail.
The epoxy resin of the present invention is represented by the above general formula (1). The method for producing the epoxy resin of the present invention is not limited, but a method of reacting a hydroxy compound represented by the above general formula (3) with epiclohydrin is suitable.
In the general formula (3), Y ¹ represents a group represented by the formula (4) (referred to as a hydroxyaryl methyl group), and Y ² and Y ³ represent the hydroxyaryl methyl group or a hydrogen atom. Therefore, there are three types of the hydroxy compounds having 1, 2 or 3 hydroxyarylmethyl groups.

In the method for producing an epoxy resin of the present invention, a mixture containing any one or two or three of the above three types of hydroxy compounds can be used as a starting material. When a mixture is used, it is preferable that the compound having three hydroxyarylmethyl groups is contained in an amount of 30% by mass or more of the whole. In some cases, the hydroxy compound may ^{contain isocyanuric acid in which all of Y 1} to Y ³ are hydrogen atoms as impurities, but the content of isocyanuric acid should be kept at 30% by mass or less.

In the above formula (4), R ¹¹ and R ¹² represent hydrocarbon groups having 1 to 8 carbon atoms. When R ¹¹ and R ¹² are hydrogen atoms, the glass transition point of the cured product is lowered, which is not preferable. Examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an s-butyl group, a t-butyl group, an n-amyl group, an s-amyl group and a t-amyl group. Examples thereof include a group, a cyclohexyl group, a phenyl group, a benzyl group and the like, and a methyl group, an ethyl group, an n-propyl group, an n-butyl group and an n-amyl group are preferable, and a methyl group and an ethyl group are more preferable. The hydrocarbon group may be a secondary hydrocarbon group or a tertiary hydrocarbon group, but the synthetic reaction may be inhibited by steric hindrance. Further, a substituent having a large number of carbon atoms is preferable because the dielectric constant and the dielectric loss tangent of the cured product can be lowered.

In formula (4), one of R ¹³ , R ¹⁴ , and R ¹⁵ is a hydroxyl group, and the other two are hydrocarbon groups or hydrogen atoms having 1 to 8 carbon atoms.
When R ¹³ or R ¹⁵ is a hydroxyl group, R ¹⁴ is preferably a hydrocarbon group, and when R ¹⁴ is a hydroxyl group, ^{both R 13} and R ¹⁵ are preferably hydrocarbon groups. When both of the above two are hydrogen atoms, a hydrocarbon group having 1 to 8 carbon atoms is added to the ortho position of the methylene group of the formula (4) depending on the reaction for obtaining the hydroxy compound represented by the general formula (3). It may be difficult to selectively introduce it.
Examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an s-butyl group, a t-butyl group, an n-amyl group, an s-amyl group and a t-amyl group. Examples include a group, a cyclohexyl group, a phenyl group, a benzyl group and the like. Of these, substituents having a large number of carbon atoms such as tertiary hydrocarbon groups such as t-butyl group and t-amyl group and aromatic substituents such as phenyl group and benzyl group have low dielectric properties of the cured product. It is preferable to do so. However, when both of the above two are tertiary hydrocarbon groups such as a t-butyl group and a t-amyl group, the reactivity at the time of synthesizing the epoxy resin may be inferior.

Specific examples of the hydroxyarylmethyl group represented by the above formula (4) include, but are not limited to, the groups shown below.

The hydroxy compound represented by the general formula (3) can be obtained by reacting using a known synthetic method. For example, a method of reacting isocyanuric acid with an aromatic represented by the following formula (5a) with paraformaldehyde, a method of reacting isocyanuric acid with a methyl halide aromatic represented by the following formula (5b), and the like can be mentioned. ..

（但し、Ｒ^１１〜Ｒ^１５は式（４）のＲ^１１〜Ｒ^１５とそれぞれ同義であり、Ｚは塩素原子、臭素原子、ヨウ素原子等のハロゲン原子である。）

^(However, R 11 ^{to R 15} have the same meanings respectively as ^R 11 ^{to R 15} in Formula (4), Z a chlorine atom, a bromine atom, a halogen atom such as iodine atom.)

The method for producing an epoxy resin of the present invention is a method of reacting a hydroxy compound represented by the above general formula (3) with epichlorohydrin. The obtained epoxy resin is an epoxy resin represented by the above general formula (1) or an epoxy resin containing the same as a main component. The reaction of reacting the above hydroxy compound with epichlorohydrin can be carried out in the same manner as a normal epoxidation reaction.

For example, after dissolving the above hydroxy compound in excess epichlorohydrin, in the presence of alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, 1 to 150 ° C., preferably 60 to 120 ° C. A method of reacting for 10 hours can be mentioned. The amount of the alkali metal hydroxide used at this time is 0.8 to 1.2 mol, preferably 0.9 to 1. It is in the range of 0 mol. In addition, epichlorohydrin is used in excess with respect to the total amount of hydroxyl groups and NH groups in the hydroxy compound, but is usually 1.5 with respect to 1 mol of the total amount of hydroxyl groups and NH groups in the hydroxy compound. It is in the range of ~ 30 mol, preferably 2-15 mol. After completion of the reaction, excess epichlorohydrin is distilled off, the residue is dissolved in a solvent such as toluene and methyl isobutyl ketone, filtered, washed with water to remove inorganic salts, and then the solvent is distilled off to obtain the desired epoxy. Resin can be obtained. Since the hydroxy compound has a total of three hydroxyl groups and N—H groups in one molecule, the amount of alkali metal hydroxide or epichlorohydrin used per mole of the hydroxy compound is calculated to be three times the number of moles. Will be done.

The epoxy resin of the present invention is represented by the above general formula (1). Wherein, X ¹ is a group represented by the formula (2) (. Referred glycidyloxy arylmethyl group), X ^2, X ³ is a glycidyl group or the glycidyloxy arylmethyl group. The epoxy resin of the present invention may include three types of compounds having one, two or three glycidyloxyarylmethyl groups.

The epoxy resin of the present invention may be any of these three compounds, a mixture of these three, or any two of these three, but glycidyloxyarylmethyl. It is preferable that the compound having three groups is contained in an amount of 30% by mass or more of the whole. In some cases, the epoxy resin ^{may contain trichloroisocyanuric acid, in which all of X 1} to X ³ are glycidyl groups, as an impurity, but the content should be kept at 30% by mass or less. Is good.

The epoxy resin of the present invention is a compound or mixture represented by the above general formula (1), but may contain a polymerized product to some extent.

The epoxy equivalent of the epoxy resin represented by the general formula (1) is 140 to 700 g / eq. It is preferably in the range of 170 to 500 g / eq. And more preferably 200-400 g / eq. Is. If the epoxy equivalent is too small, the dielectric properties deteriorate and the adhesiveness also deteriorates. Further, if the epoxy equivalent is too large, the heat resistance is lowered and the softening point of the resin is raised, so that the handleability is deteriorated, which is not preferable.

Epoxy resins all from X ¹ of X ³ becomes glycidyloxy arylmethyl group, all the Y ¹ to Y ³ in the general formula (3) can be readily obtained from the hydroxy compound is a hydroxy aryl methyl group. The epoxy resin one or two from X ¹ X ³ becomes glycidyloxy arylmethyl group may be obtained from the corresponding hydroxy compound one or two from Y ¹ Y ³ becomes hydroxyaryl methyl It can be easily obtained.

In the above formula (2), R ¹ and R ² represent hydrocarbon groups having 1 to 8 carbon atoms. One of R ³ , R ⁴ , and R ⁵ represents a glycidyloxy group, and the other two represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. As the hydrocarbon groups, R ¹ and R ² are exemplified in the description ^{of R 11} and R ¹² of the above formula (4), ^{and R 3 to} R ^{5 are R 13 to} R ^{15 of the} formula (4). The same as those exemplified in the above description can be mentioned.

The epoxy resin of the present invention can be used as a composition together with a curing agent for various purposes.

The epoxy resin composition of the present invention is an epoxy resin composition composed of an epoxy resin and a curing agent, and contains an epoxy resin represented by the above general formula (1) as an essential component as an epoxy resin component.

As the curing agent to be blended in this epoxy resin composition, any curing agent generally known as an epoxy resin curing agent can be used. For example, there are dicyandiamides, polyhydric phenols, acid anhydrides, aromatics and aliphatic amines. Specifically, examples of polyhydric phenols include, for example, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, fluorene bisnaphthol, 4,4'-biphenol, 2,4'-biphenol, 2,2'. -Divalent phenols such as biphenol, hydroquinone, resorcin, naphthalenediol, or tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol novolac, o -There are trivalent or higher phenols represented by cresol novolac, naphthol novolac, polyvinylphenol and the like. Furthermore, phenols, naphthols or bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, fluorene bisnaphthol, 4,4'-biphenol, 2,4'-biphenol, 2,2'-biphenol, hydroquinone, resorcin. , Divalent phenols such as naphthalenediol, formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, polyhydric phenolic compounds synthesized by condensing agents such as p-xylylene glycol and the like. Further, the hydroxy compound represented by the above general formula (3) is also preferably exemplified.

Phthalic anhydrides include phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, humic anhydride, nadicic anhydride, trimellitic anhydride, and phthalic anhydride. And styrene copolymer compounds and the like.

Examples of amines include aromatic amines such as 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylsulfone, m-phenylenediamine, and p-xylylenediamine. There are aliphatic amines such as ethylenediamine, hexamethylenediamine, diethylenetriamine, and triethylenetetramine.

In the epoxy resin composition, one kind or a mixture of two or more kinds of these curing agents can be used. Then, it is advantageous to use the hydroxy compound represented by the above general formula (3) as at least a part of the curing agent as the curing agent component, and in this case, the blending amount thereof is 5 to 100% by mass in the entire curing agent. , Preferably in the range of 60 to 100% by mass.

Further, in the epoxy resin composition of the present invention, another kind of epoxy resin may be blended as an epoxy resin component in addition to the epoxy resin of the present invention represented by the general formula (1). As the epoxy resin in this case, any ordinary epoxy resin having two or more epoxy groups in the molecule can be used. For example, bisphenol A, bisphenol F, 3,3', 5,5'-tetramethyl-bisphenol F, bisphenol S, fluorene bisphenol, fluorenbisnaphthol, 4,4'-biphenol, 2,4'-biphenol. , 2,2'-biphenol, 3,3', 5,5'-tetramethyl-4,4'-biphenol, divalent phenols such as hydroquinone, resorcin, or tris- (4-hydroxyphenyl) methane , 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol novolac, o-cresol novolac and other trivalent or higher phenols, or guru derived from halogenated bisphenols such as tetrabromobisphenol A There are sidyl etherified products and the like. These epoxy resins can be used alone or in admixture of two or more.

The blending amount of the epoxy resin represented by the general formula (1) in the epoxy resin composition of the present invention is preferably in the range of 5 to 100% by mass, preferably 60 to 100% by mass, based on the entire epoxy resin.

The amount of the curing agent used in the epoxy resin composition is preferably in the range of 0.2 to 1.5 mol of the active hydrogen group of the curing agent with respect to 1 mol of the epoxy group of the total epoxy resin, and is 0.3 to 1.4. The moles are more preferable, 0.5 to 1.3 moles are further preferable, and 0.8 to 1.2 moles are particularly preferable. If it is out of this range, curing may be incomplete and good cured physical properties may not be obtained. For example, when a phenol-based curing agent or an amine-based curing agent is used, an active hydrogen group is blended in approximately equal molar amounts with respect to the epoxy group, and when an acid anhydride-based curing agent is used, an acid is added to 1 mol of the epoxy group. The anhydride group is blended in an amount of 0.5 to 1.2 mol, preferably 0.6 to 1.0 mol. When the above phenol resin is used alone, it is preferable to use the phenolic hydroxyl group in the range of 0.9 to 1.1 mol with respect to 1 mol of the epoxy group of the epoxy resin.

The active hydrogen group referred to in the present invention is a functional group having an active hydrogen reactive with an epoxy group (a functional group having a latent active hydrogen that produces active hydrogen by hydrolysis or the like, or a functional group exhibiting an equivalent curing action. Including), and specific examples thereof include an acid anhydride group, a carboxyl group, an amino group, and a phenolic hydroxyl group. Regarding the active hydrogen group, 1 mol of the carboxyl group and the phenolic hydroxyl group are _{calculated as 1 mol, and the amino group (NH 2} ) is calculated as 2 mol. If the active hydrogen group is not clear, the active hydrogen equivalent can be determined by measurement. For example, the active hydrogen equivalent of the curing agent used is measured by reacting a monoepoxy resin such as phenylglycidyl ether with a known epoxy equivalent with a curing agent having an unknown active hydrogen equivalent and measuring the amount of the monoepoxy resin consumed. Can be sought.

For the epoxy resin composition, various commonly known flame retardants can be used for the purpose of improving the flame retardancy of the obtained cured product. Examples of the flame retardants that can be used include halogen-based flame retardants, phosphorus-based flame retardants (phosphorus compounds as flame retardants), nitrogen-based flame retardants, silicone-based flame retardants, inorganic flame retardants, organic metal salt-based flame retardants, and the like. Can be mentioned. From the viewpoint of the environment, halogen-free flame retardants are preferable, and phosphorus-based flame retardants are particularly preferable. These flame retardants are not limited in use, and may be used alone, a plurality of flame retardants of the same system may be used, or different flame retardants may be used in combination. be.

In particular, in an epoxy resin composition further containing a phosphorus compound as a flame retardant, the phosphorus compound is classified into two types, an additive phosphorus flame retardant (phosphorus-containing additive) and a reactive phosphorus compound, and is reactive. The phosphorus compound is further divided into a phosphorus-containing epoxy resin and a phosphorus-containing curing agent. Comparing the additive phosphorus-based flame retardant and the reactive phosphorus compound, the reactive phosphorus compound has a large flame-retardant effect and is reactive in terms of not bleeding out during curing and having good compatibility. It is preferable to use the phosphorus compound of.

As the phosphorus-containing additive, either an inorganic phosphorus compound or an organic phosphorus compound can be used. Examples of the inorganic phosphorus compound include ammonium phosphates such as red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate and ammonium polyphosphate, and nitrogen-containing inorganic phosphorus compounds such as phosphate amide. Be done.

The red phosphorus is preferably surface-treated for the purpose of preventing hydrolysis and the like, and examples of the surface treatment method include (1) magnesium hydroxide, aluminum hydroxide, zinc hydroxide, and hydroxide. Method of coating with an inorganic compound such as titanium, bismuth oxide, bismuth hydroxide, bismuth nitrate or a mixture thereof, (2) Inorganic compounds such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide and titanium hydroxide, and phenol. Method of coating with a mixture of heat-curable resin such as resin, (3) Heat-curable resin such as phenol resin on a film of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide Examples thereof include a method of double coating with.

Examples of the organophosphorus compound include phosphoric acid ester compounds (for example, methyl acid phosphate, ethyl acid phosphate, isopropyl acid phosphate, dibutyl phosphate, monobutyl phosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, and bis (2-). Ethylhexyl) phosphate, monoisodecyl acid phosphate, lauryl acid phosphate, tridecyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, stearyl acid phosphate, isostearyl acid phosphate, butyl pyrophosphate, ethylene glycol acid phosphate, (2- (Hydroxyethyl) methacrylate acid phosphate, etc.), condensed phosphoric acid esters (eg, PX-200; manufactured by Daihachi Chemical Industry Co., Ltd.), phosphonic acid compounds, phosphinic acid compounds, phosphin oxide compounds (eg, diphenylphosphine oxide, triphenyl) In addition to general-purpose organophosphorus compounds such as phosphine oxides, phosphorane compounds (eg, triphenyl (9H-fluoren-9-iriden) phosphorane, etc.), nitrogen-containing organophosphorus compounds (eg, SPS-100, SPB-100) , SPE-100; manufactured by Otsuka Chemical Co., Ltd.), phosphinic acid metal salts (for example, EXOLIT OP1230, EXOLIT OP1240, EXOLIT OP930, EXOLIT OP935; manufactured by Clariant), and phosphorus compounds having an active hydrogen group directly linked to a phosphorus atom. (For example, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter, DOPO), diphenylphosphine oxide, etc.) and phosphorus-containing phenol compounds (for example, 10- (2,5-dihydroxyphenyl). ) -10H-9-Oxa-10-phosphaphenanthrene-10-oxide (hereinafter, DOPO-HQ), 10- (2,7-dihydroxy-1-naphthyl) -10H-9-oxa-10-phosphaphenanthrene -10-Oxide, 10- (1,4-dihydroxy-2-naphthyl) -10H-9-Oxa-10-phosphaphenanthrene-10-oxide (hereinafter, DOPO-NQ), diphenylphosphinyl hydroquinone, diphenylphos Phenyl-1,4-dioxynaphthalin, 1,4-cyclooctylenephosphinyl-1,4- Organic phosphorus compounds such as phenyldiol, 1,5-cyclooctylenephosphinyl-1,4-phenyldiol, etc., and derivatives obtained by reacting these organic phosphorus compounds with compounds such as epoxy resin and phenol resin. Can be mentioned.

Further, as the reactive phosphorus compound used in the phosphorus-containing epoxy resin and the phosphorus-containing curing agent, the phosphorus compound having an active hydrogen group directly linked to the phosphorus atom and the phosphorus-containing phenols are preferable, and they are easily available. For example, DOPO, DOPO-HQ, DOPO-NQ and the like are more preferable.

Examples of the phosphorus-containing epoxy resin include DOPO and JP-A-04-11662, JP-A-05-21470, JP-A-2000-309624, JP-A-2002-265562, and the like. Particularly those obtained by reacting a reactive phosphorus compound such as diphenylphosphine oxide with a quinone compound such as 1,4-benzoquinone or 1,4-naphthoquinone and then reacting with an epoxy resin, if necessary. preferable. Examples of such a phosphorus-containing epoxy resin include Epototo FX-305, Epototo FX-289B, TX-1320A, and Epototo TX-1328 (manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.).

The epoxy equivalent (g / eq.) Of the phosphorus-containing epoxy resin is preferably 200 to 800, preferably 300 to 780, and more preferably 400 to 760. The phosphorus content of the phosphorus-containing epoxy resin is preferably 0.5 to 6% by mass, preferably 2 to 5.5% by mass, and more preferably 3 to 5% by mass.

As the phosphorus-containing curing agent, in addition to the above-mentioned phosphorus-containing phenols, for example, a condensation reaction of DOPO, an aldehyde, and a phenol compound by a production method as shown in Japanese Patent Publication No. 2008-501063 and Japanese Patent No. 4548547. By doing so, a phosphorus-containing phenol compound can be obtained. Examples of such a phosphorus-containing phenol compound include LC-950PM60 (manufactured by Shin-AT & C) and EXB9000A (manufactured by DIC Corporation). Further, a phosphorus-containing active ester compound can be obtained by further reacting aromatic carboxylic acids by a production method as shown in JP2013-185002A. In addition, a phosphorus-containing benzoxazine compound can be obtained by a production method as shown in WO 2008/010429.

The phosphorus content of the phosphorus-containing curing agent is preferably 0.5 to 12% by mass, preferably 2 to 11% by mass, and more preferably 4 to 10% by mass.

The blending amount of the phosphorus compound is appropriately selected depending on the type of the phosphorus compound, the components of the epoxy resin composition, and the desired degree of flame retardancy. When the phosphorus compound is a reactive phosphorus compound, that is, a phosphorus-containing epoxy resin or a phosphorus-containing curing agent, the epoxy resin composition containing all of the epoxy resin, the curing agent, the flame retardant and other fillers and additives, etc. The phosphorus content is preferably 0.2% by mass or more and 6% by mass or less, more preferably 0.4% by mass or more and 4% by mass or less, and 0.5% by mass or more, with respect to the solid content (nonvolatile content). 5% by mass or less is more preferable, and 0.6% by mass or more and 3% by mass or less is particularly preferable. If the phosphorus content is low, it may be difficult to ensure flame retardancy, and if it is too high, the heat resistance may be adversely affected.

Here, the phosphorus-containing epoxy resin is treated as being both a phosphorus compound and an epoxy resin. Similarly, a phosphorus-containing curing agent is also treated as a phosphorus compound and corresponds to both curing agents. Therefore, when a phosphorus-containing curing agent is used, it may not be necessary to use another curing agent or phosphorus compound. Similarly, when a phosphorus-containing epoxy resin is used, it may not be necessary to use an epoxy resin or a phosphorus compound other than the epoxy resin represented by the above general formula (1).

When the phosphorus compound is an additive-based phosphorus flame retardant, the blending amount is in the range of 0.1 to 2 parts by mass when using red phosphorus in 100 parts by mass of the solid content (nonvolatile content) in the epoxy resin composition. When an organophosphorus compound is used, it is preferably blended in the range of 0.1 to 10 parts by mass, and particularly preferably in the range of 0.5 to 6 parts by mass. ..

When a phosphorus compound is used as a flame retardant, hydrotalcite, magnesium hydroxide, a boron compound, zirconium oxide, calcium carbonate, zinc molybdate and the like may be used in combination as the flame retardant aid.

In the present invention, it is preferable to use these phosphorus compounds as the flame retardant, but the flame retardants described below can be used in combination with the phosphorus compound or in place of the phosphorus compound.

Examples of the nitrogen-based flame retardant include triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, and phenothiazine, and triazine compounds, cyanuric acid compounds, and isocyanuric acid compounds are preferable. Examples of the triazine compound include melamine, acetoguanamine, benzoguanamine, melon [2,4,6-tris (cyanoamino) -1,3,5-triazine], and melam [4,4'-iminobis (1,3,5). -Triazine-2,6-diamine)], ethylenedimelamine, melamine polyphosphate, triguanamine, etc., for example, aminotriazine sulfate compounds such as guanylmelamine sulfate, melem sulfate, melam sulfate, aminotriazine-modified phenolic resin (for example). , LA-7052; manufactured by DIC Co., Ltd., etc.), and aminotriazine-modified phenolic resins modified with tung oil, isomerized linseed oil, and the like. Examples of the cyanuric acid compound include cyanuric acid and melamine cyanuric acid. The blending amount of the nitrogen-based flame retardant is appropriately selected depending on the type of the nitrogen-based flame retardant, other components of the epoxy resin composition, and the desired degree of flame retardancy. For example, in the epoxy resin composition. Of the 100 parts by mass of the solid content (nonvolatile content), it is preferably blended in the range of 0.05 to 10 parts by mass, and particularly preferably in the range of 0.1 to 5 parts by mass. When using a nitrogen-based flame retardant, a metal hydroxide, a molybdenum compound, or the like may be used in combination.

The silicone-based flame retardant can be used without particular limitation as long as it is an organic compound containing a silicon atom, and examples thereof include silicone oil, silicone rubber, and silicone resin. The blending amount of the silicone-based flame retardant is appropriately selected depending on the type of the silicone-based flame retardant, other components of the epoxy resin composition, and the desired degree of flame retardancy. For example, in the epoxy resin composition. It is preferable to blend in the range of 0.05 to 20 parts by mass in 100 parts by mass of the solid content (nonvolatile content). When using a silicone flame retardant, a molybdenum compound, alumina or the like may be used in combination.

Examples of the inorganic flame retardant include metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, low melting point glass and the like. Examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, boehmite, calcium hydroxide, barium hydroxide, zirconium hydride and the like. Examples of the metal oxide include zinc molybdate, molybdenum trioxide, zinc tinate, tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, zirconium oxide, zinc oxide, molybdenum oxide, cobalt oxide, and bismuth oxide. Examples thereof include chromium oxide, nickel oxide, copper oxide and tungsten oxide. Examples of the metal carbonate compound include zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, basic magnesium carbonate, aluminum carbonate, iron carbonate, cobalt carbonate, titanium carbonate and the like. Examples of the metal powder include aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper, tungsten, tin and the like. Examples of the boron compound include zinc borate, zinc metaborate, barium metaborate, boric acid, borax and the like. Examples of low melting point glass include hydrated glass, SiO _2- MgO-H ₂ O, PbO-B ₂ O ₃ system, ZnO-P ₂ O _5- MgO system, P ₂ O _5- B ₂ O _3- PbO. -MgO based, _{P-Sn-O-F-based, PbO-V 2 O 5 -TeO} 2 _system, Al ₂ O 3 -H ₂ O system, and a glassy compounds such as lead borosilicate system. The blending amount of the inorganic flame retardant is appropriately selected depending on the type of the inorganic flame retardant, other components of the epoxy resin composition, and the desired degree of flame retardancy. For example, an epoxy resin, a curing agent, and the like. Of the 100 parts by mass of the solid content (nonvolatile content) in the epoxy resin composition containing all of the flame retardant and other fillers and additives, it is preferably blended in the range of 0.05 to 20 parts by mass, and particularly 0. It is preferable to mix in the range of 5 to 15 parts by mass.

Examples of the organometallic salt-based flame retardant include ferrocene, an acetylacetonate metal complex, an organometallic carbonyl compound, an organocobalt salt compound, an organosulfonic acid metal salt, a metal atom and an aromatic compound or a heterocyclic compound in an ionic bond or arrangement. Examples thereof include position-bonded compounds. The blending amount of the organic metal salt-based flame retardant is appropriately selected depending on the type of the organic metal salt-based flame retardant, other components of the epoxy resin composition, and the desired degree of flame retardancy. For example, an epoxy resin. , Hardener, flame retardant and other fillers, additives, etc. may be blended in the range of 0.005 to 10 parts by mass in 100 parts by mass of the solid content (nonvolatile content) in the epoxy resin composition. preferable.

Examples of the halogen-based flame retardant include bromine compounds and chlorine compounds, but chlorine compounds are not preferable due to toxicity problems. Examples of the bromine compound include p-dibromobenzene, pentabromodiphenyl ether, octabromodiphenyl ether, tetradecabromo-p-diphenoxybenzene, decabromodiphenyl ether, tetrabromobisphenol A, hexabromocyclododecane, hexabromobenzene, 2, 2'-Ethylene bis (4,5,6,7-tetrabromoisoindolin-1,3-dione (eg, SAYTEX BT-93; manufactured by Albemar)), ethane-1,2-bis (pentabromophenyl) ) (For example, SAYTEX 8010; manufactured by Albemar), brominated epoxy oligomers (for example, SR-T1000, SR-T2000; manufactured by Sakamoto Yakuhin Kogyo), etc. The amount of the halogen-based flame retardant compounded is halogen-based. It is appropriately selected depending on the type of flame retardant, other components of the epoxy resin composition, and the desired degree of flame retardancy. For example, epoxy resin, hardener, flame retardant and other fillers and additives, etc. The halogen content is preferably 5% by mass or more and 15% by mass or less with respect to the solid content (nonvolatile content) in the epoxy resin composition containing all of them. Or, when a halogen-based flame retardant is used as the flame retardant, the flame retardant As auxiliaries, for example, antimony compounds such as antimony trioxide, antimone tetroxide, and antimone pentoxide, tin compounds such as tin oxide and tin hydroxide, molybdenum compounds such as molybdenum oxide and ammonium molybthenate, zirconium oxide, and the like. A zirconium compound such as zirconium hydroxide, a boron compound such as zinc borate and barium metaborate, a silicone oil, a silane coupling agent, a silicon compound such as high molecular weight silicone, and chlorinated polyethylene may be used in combination.

The epoxy resin composition of the present invention contains, if necessary, a curing accelerator, a filler, a thermoplastic resin, a thermosetting resin other than the epoxy resin, a silane coupling agent, an antioxidant, a mold release agent, and a defoaming agent. Other additives such as agents, epoxies, rock-modifying agents, smoothing agents, and pigments can be blended. Further, an organic solvent, a reactive diluent and the like can be blended for adjusting the viscosity.

Examples of the curing accelerator include imidazole derivatives, tertiary amines, phosphorus compounds such as phosphines, metal compounds, Lewis acids, amine complex salts and the like. These curing accelerators may be used alone or in combination of two or more.

The imidazole derivative may be any compound having an imidazole skeleton and is not particularly limited. For example, 2-ethylimidazole, 2-ethyl-4-methylimidazole, bis-2-ethyl-4-methylimidazole, 1-methyl-2-ethylimidazole, 2-isopropylimidazole, 2,4-dimethylimidazole, 2- Alkyl-substituted imidazole compounds such as heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-ethylimidazole, 1-benzyl-2-phenyl Examples thereof include imidazole compounds substituted with an aryl group such as imidazole, benzimidazole, 2-ethyl-4-methyl-1- (2'-cyanoethyl) imidazole, and a hydrocarbon group containing a ring structure such as an aralkyl group.

Examples of tertiary amines include 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2- (dimethylaminomethyl) phenol, 1,8-diazabicyclo [5.4.0] -7-undecene ( DBU) and the like. Examples of phosphines include triphenylphosphine, tricyclohexylphosphine, triphenylphosphine and triphenylborane. Examples of the metal compound include tin octylate and the like.

Among these curing accelerators, 2-dimethylaminopyridine, 4-dimethylaminopyridine and the like are excellent in heat resistance, dielectric properties, solder resistance, etc. when used for build-up materials and circuit boards. Imidazoles are preferred. Further, when used as a semiconductor encapsulating material, triphenylphosphine and DBU are preferable because they are excellent in curability, heat resistance, electrical properties, moisture resistance reliability and the like.

The amount of the curing accelerator to be blended may be appropriately selected according to the purpose of use, but 0.02 to 15 parts by mass is used as necessary with respect to 100 parts by mass of the epoxy resin component in the epoxy resin composition. .. It is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, and even more preferably 0.5 to 5 parts by mass. By using the curing accelerator, the curing temperature can be lowered and the curing time can be shortened.

Examples of the filler include molten silica, crystalline silica, alumina, silicon nitride, boron nitride, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, boehmite, talc, mica, clay, calcium carbonate, magnesium carbonate, barium carbonate, and the like. Inorganic fillers such as zinc oxide, titanium oxide, magnesium oxide, magnesium silicate, calcium silicate, zirconium silicate, barium sulfate, carbon, carbon fiber, glass fiber, alumina fiber, silica alumina fiber, silicon carbide fiber, polyester Examples thereof include fibrous fillers such as fibers, cellulose fibers, aramid fibers, and ceramic fibers, and fine particle rubber. Among these, those which are not decomposed or dissolved by an oxidizing compound such as an aqueous solution of permanganate used for the surface roughening treatment of the cured product are preferable, and in particular, molten silica and crystalline silica are easy to obtain fine particles. preferable. Further, when the blending amount of the filler is particularly large, it is preferable to use molten silica. The molten silica can be used in either a crushed form or a spherical shape, but in order to suppress an increase in the melt viscosity of the molding material while increasing the blending amount of the molten silica, it is more preferable to mainly use a spherical one. Further, in order to increase the blending amount of spherical silica, it is preferable to appropriately adjust the particle size distribution of spherical silica. The filler may be treated with a silane coupling agent or an organic acid such as stearic acid. Generally, the reason for using the filler is the effect of improving the impact resistance of the cured product and the low linear expansion of the cured product. Further, when a metal hydroxide such as aluminum hydroxide, boehmite, or magnesium hydroxide is used, it acts as a flame retardant aid and has an effect of improving flame retardancy. When used for applications such as conductive paste, a conductive filler such as silver powder or copper powder can be used.

The blending amount of the filler is preferably high in consideration of the low linear expansion of the cured product and the flame retardancy. It is preferably 1 to 90% by mass, more preferably 10 to 85% by mass, still more preferably 20 to 80% by mass, based on the solid content (nonvolatile content) in the epoxy resin composition. If the blending amount is large, the impregnation required for the use of the laminated board becomes insufficient, the adhesiveness may be lowered, and the cured product may be brittle, so that sufficient mechanical properties may not be obtained. Further, if the blending amount is small, there is a possibility that the blending effect of the filler may not be obtained, such as improvement of the impact resistance of the cured product.

The average particle size of the inorganic filler is preferably 0.05 to 1.5 μm, more preferably 0.1 to 1 μm. When the average particle size of the inorganic filler is in this range, the fluidity of the epoxy resin composition can be kept good. The average particle size can be measured by a particle size distribution measuring device.

Blending the thermoplastic resin is particularly effective when the epoxy resin composition is molded into a sheet or a film. Examples of the thermoplastic resin include phenoxy resin, polyurethane resin, polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, ABS resin, AS resin, vinyl chloride resin, polyvinyl acetate resin, polymethyl methacrylate resin, and polycarbonate resin. Polyacetal resin, cyclic polyolefin resin, polyamide resin, thermoplastic polyimide resin, polyamideimide resin, polytetrafluoroethylene resin, polyetherimide resin, polyphenylene ether resin, modified polyphenylene ether resin, polyether sulfone resin, polysulfone resin, polyether ether Examples thereof include ketone resins, polyphenylene sulfide resins, and polyvinyl formal resins. A phenoxy resin is preferable from the viewpoint of compatibility with the epoxy resin, and a polyphenylene ether resin or a modified polyphenylene ether resin is preferable from the viewpoint of low dielectric properties.

Examples of other additives include thermosetting resins other than epoxy resins such as phenol resin, melamine resin, urea resin, unsaturated polyester resin, alkyd resin, diallyl phthalate resin, and thermosetting polyimide, and quinacridone-based and azo. Organic pigments such as phthalocyanine, inorganic pigments such as titanium oxide, metal foil pigments, and rust preventive pigments, ultraviolet absorbers such as hindered amines, benzotriazoles, and benzophenones, hindered phenols, and phosphorus. , Sulfur-based, hydrazide-based antioxidants, silane-based, titanium-based coupling agents, stearic acid, palmitic acid, zinc stearate, calcium stearate and other mold release agents, leveling agents, leology control agents, Examples thereof include additives such as pigment dispersants, anti-repellent agents, and antifoaming agents. The blending amount of these other additives is preferably in the range of 0.01 to 20% by mass with respect to the solid content (nonvolatile content) in the epoxy resin composition. Further, an organic solvent or a reactive diluent can also be used for adjusting the viscosity.

Examples of the organic solvent include amides such as N, N-dimethylformamide and N, N-dimethylacetamide, and ethers such as ethylene glycol monomethyl ether, dimethoxydiethylene glycol, ethylene glycol diethyl ether, diethylene glycol diethyl ether and triethylene glycol dimethyl ether. Kinds, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, 1-methoxy-2-propanol, 2-ethyl-1-hexanol, benzyl alcohol, ethylene glycol, propylene glycol, butyl diglycol. , Alcohols such as pine oil, acetates such as butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, cellosolve acetate, ethyl diglycol acetate, propylene glycol monomethyl ether acetate, carbitol acetate, benzyl alcohol acetate, and benzoic acid. Orthoperic acid esters such as methyl and ethyl benzoate, cellosolves such as methyl cellosolve, cellosolve and butyl cellosolve, carbitols such as methylcarbitol, carbitol and butylcarbitol, and fragrances such as benzene, toluene and xylene. Group hydrocarbons, dimethylsulfoxide, acetonitrile, N-methylpyrrolidone and the like can be mentioned.

Examples of the reactive diluent include monofunctional glycidyl ethers such as allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether and trill glycidyl ether, resorcinol diglycidyl ether and neopentyl glycol diglycidyl ether. , 1,4-Butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, propylene glycol diglycidyl ether and other bifunctional glycidyl ethers, glycerol polyglycidyl ether, trimethylol propane Polyfunctional glycidyl ethers such as polyglycidyl ether, trimethylolethane polyglycidyl ether, pentaerythritol polyglycidyl ether, glycidyl esters such as neodecanoic acid glycidyl ester, and glycidyl amines such as phenyldiglycidylamine and trildiglycidylamine Can be mentioned.

The organic solvent is preferably used alone or in a mixture of a plurality of types as a non-volatile content in an amount of 20 to 90% by mass, and the appropriate type and amount used are appropriately selected depending on the intended use. For example, in printed wiring board applications, it is preferable that a polar solvent having a boiling point of 160 ° C. or lower, such as methyl ethyl ketone, acetone, or 1-methoxy-2-propanol, is used, and the amount used is preferably 40 to 80% by mass in terms of non-volatile content. For adhesive film applications, for example, ketones, acetic acid esters, carbitols, aromatic hydrocarbons, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like are preferably used, and the amount used is non-volatile. It is preferably 30 to 60% by mass.
Reactive diluents are mainly used in solvent-free systems to reduce viscosity and adjust gel time. If this amount is large, the curing reaction may not proceed sufficiently and unreacted components may bleed out from the cured product, or the physical properties of the cured product such as mechanical strength may be reduced. Therefore, do not use more than necessary. Is preferable. Therefore, it is preferably 30% by mass or less, more preferably 20% by mass or less, and further preferably 10% by mass or less in the epoxy resin.

The epoxy resin composition of the present invention can be obtained by curing in the same manner as the known epoxy resin composition. As a method for obtaining a cured product, a known method can be taken, and forms such as casting, injection, potting, dipping, drip coating, transfer molding, compression molding, resin sheet, copper foil with resin, and prepreg. A method such as forming a laminated plate by laminating and curing under heat and pressure is preferably used. The curing temperature at that time is usually in the range of 100 to 300 ° C., and the curing time is usually about 10 minutes to 5 hours.

The epoxy resin composition of the present invention can be obtained by uniformly mixing the above components. An epoxy resin composition containing an epoxy resin, a curing agent, and if necessary, various additives can be easily made into a cured product by a method similar to a conventionally known method. Examples of the cured product include molded products such as laminates, cast products, molded products, adhesive layers, insulating layers, and films.

Applications in which epoxy resin compositions are used include printed wiring board materials, resin compositions for flexible wiring boards, insulating materials for circuit boards such as interlayer insulating materials for build-up boards, semiconductor encapsulant materials, conductive pastes, and conductive films. , Build-up adhesive film, resin casting material, adhesive, etc. Among these various applications, in the applications of printed wiring board materials, insulating materials for circuit boards, and adhesive films for build-up, passive components such as capacitors and active components such as IC chips are embedded in the substrate, so-called substrates for built-in electronic components. Can be used as an insulating material for Among these, circuit boards such as printed wiring board materials, resin compositions for flexible wiring boards, and interlayer insulating materials for build-up boards, due to their characteristics such as high flame retardancy, high heat resistance, low dielectric properties, and solvent solubility. It is preferably used as a material for (laminated board) and a semiconductor encapsulation material.

When the epoxy resin composition is in the form of a plate such as a laminated plate, the filler used is preferably in the form of fibers in terms of dimensional stability, bending strength, etc., and glass in which glass fibers are woven into a mesh shape. Fiberglass cloth is more preferable.

By impregnating the fibrous reinforcing base material with the epoxy resin composition, the prepreg of the present invention used in a printed wiring board or the like can be prepared. As the fibrous reinforcing base material, inorganic fibers such as glass and woven fabrics or non-woven fabrics of organic fibers such as polyester resin, polyamine resin, polyacrylic resin, polyimide resin, and aromatic polyamide resin can be used. It is not limited to. The method for producing the prepreg from the epoxy resin composition is not particularly limited. For example, a varnish-like epoxy resin composition containing the organic solvent is further blended with an organic solvent to adjust the viscosity to an appropriate level. It is obtained by preparing a varnish, impregnating the fibrous base material with the resin varnish, and then heat-drying to semi-cure the resin component (B-stage). The heating temperature is preferably 50 to 200 ° C, more preferably 100 to 170 ° C, depending on the type of organic solvent used. The heating time is adjusted according to the type of organic solvent used and the curability of the prepreg, and is preferably 1 to 40 minutes, more preferably 3 to 20 minutes. At this time, the mass ratio of the epoxy resin composition to be used and the reinforcing base material is not particularly limited, but it is usually preferable to adjust the resin content in the prepreg to be 20 to 80% by mass.

The epoxy resin composition of the present invention can be used by molding it into a sheet or a film. In this case, it is possible to make a sheet or a film by using a conventionally known method. The method for producing the adhesive sheet is not particularly limited, but for example, the resin varnish is applied onto the support base film that does not dissolve in the resin varnish using a coating machine such as a reverse roll coater, a comma coater, or a die coater. After that, it is obtained by heating and drying to B-stage the resin component. Further, if necessary, another support base film is laminated as a protective film on the coated surface (adhesive layer) and dried to obtain an adhesive sheet having release layers on both sides of the adhesive layer. Examples of the support base film include metal foils such as copper foils, polyolefine films such as polyethylene films and polypropylene films, polyester films such as polyethylene terephthalate films, polycarbonate films, silicone films, and polyimide films. Such as, a polyethylene terephthalate film having no defects, excellent dimensional accuracy, and excellent cost is preferable. Further, a metal foil, particularly a copper foil, in which the laminated plate can be easily multi-layered is preferable. The thickness of the support base film is not particularly limited, but is preferably 10 to 150 μm, more preferably 25 to 50 μm, because it has strength as a support and is less likely to cause laminating defects. The thickness of the protective film is not particularly limited, but is generally 5 to 50 μm. In addition, in order to easily peel off the molded adhesive sheet, it is preferable to perform surface treatment with a mold release agent in advance. The thickness of the resin varnish applied is preferably 5 to 200 μm, more preferably 5 to 100 μm after drying. The heating temperature is preferably 50 to 200 ° C, more preferably 100 to 170 ° C, depending on the type of organic solvent used. The heating time is adjusted according to the type of organic solvent used and the curability of the prepreg, and is preferably 1 to 40 minutes, more preferably 3 to 20 minutes. The adhesive sheet thus obtained is usually an insulating adhesive sheet having insulating properties, but a conductive adhesive sheet can be obtained by mixing a conductive metal or metal-coated fine particles with an epoxy resin composition. You can also get it. The support base film is peeled off after being laminated on a circuit board or after being heat-cured to form an insulating layer. If the support base film is peeled off after the adhesive sheet is heat-cured, it is possible to prevent dust and the like from adhering in the curing process.

A method of manufacturing the laminated board of the present invention using the prepreg of the present invention and the above-mentioned insulating adhesive sheet will be described. For example, when forming a laminated board using prepregs, one or a plurality of prepregs are laminated, and metal foils are arranged on one side or both sides to form a laminate, and the laminate is pressurized and heated. The prepreg can be cured and integrated with the above to obtain a laminated board. Here, as the metal foil, a single metal leaf such as copper, aluminum, brass, nickel or the like, an alloy, or a composite metal leaf can be used. As a condition for heating and pressurizing the laminate, it is sufficient to appropriately adjust and heat and pressurize the epoxy resin composition under the condition that the epoxy resin composition is cured. However, if the pressurization is too low, air bubbles remain inside the obtained laminate. Since the electrical characteristics may deteriorate, it is desirable to pressurize under conditions that satisfy the moldability. The heating temperature is preferably 160 to 250 ° C, more preferably 170 to 220 ° C. The pressurizing pressure is preferably 0.5 to 10 MPa, more preferably 1 to 5 MPa. The heating and pressurizing time is preferably 10 minutes to 4 hours, more preferably 40 minutes to 3 hours. Further, the multilayer plate can be produced by using the single-layer laminated plate thus obtained as an inner layer material. In this case, first, a circuit is formed on the laminated board by an additive method, a subtractive method, or the like, and the formed circuit surface is treated with an acid solution and blackened to obtain an inner layer material. An insulating layer is formed on one side or both side of the circuit forming surface of the inner layer material with a prepreg or an insulating adhesive sheet, and a conductor layer is formed on the surface of the insulating layer to form a multilayer plate.

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, an insulating adhesive sheet is arranged between the circuit forming surface of the inner layer material and the metal foil to form a laminate. Then, by heating and pressurizing this laminate and integrally molding it, a cured product of the insulating adhesive sheet is formed as an insulating layer, and a multi-layered inner layer material is formed. Alternatively, the inner layer material and the metal foil which is the conductor layer are formed, and the cured product of the insulating adhesive sheet is formed as the insulating layer. Here, as the metal foil, the same metal foil as that used for the laminated board used as the inner layer material can be used. Further, the heat and pressure molding can be performed under the same conditions as the molding of the inner layer material.

When forming an insulating layer using the prepreg, a laminated body of one or a plurality of prepregs is arranged on the circuit forming surface of the inner layer material, and a metal foil is further arranged on the outside of the laminated body. To form. Then, by heating and pressurizing this laminate and integrally molding it, a cured product of the prepreg is formed as an insulating layer, and a metal foil on the outer side thereof is formed as a conductor layer. Here, as the metal foil, the same metal foil as that used for the laminated board used as the inner layer board can be used. Further, the heat and pressure molding can be performed under the same conditions as the molding of the inner layer material. A printed wiring board can be molded by further forming a via hole or a circuit on the surface of the multilayer laminated board thus formed by an additive method or a subtractive method. Further, by repeating the above-mentioned construction method using this printed wiring board as an inner layer material, a multi-layer board can be further formed.

When the epoxy resin composition is applied to the laminated board to form an insulating layer, the epoxy resin composition is preferably applied to a thickness of 5 to 100 μm, and then 100 to 200 ° C., preferably 150 to 200 ° C. Then, it is heated and dried for 1 to 120 minutes, preferably 30 to 90 minutes to form a sheet. It is formed by a method generally called a casting method. It is desirable to form the thickness after drying to 5 to 150 μm, preferably 5 to 80 μm. The viscosity of the epoxy resin composition is preferably in the range of 10 to 40,000 mPa · s at 25 ° C., more preferably 200 to 30,000 mPa · s, because a sufficient film thickness can be obtained and uneven coating and streaks are unlikely to occur. Is. A printed wiring board can be formed by further forming a via hole or a circuit on the surface of the multilayer laminated board thus formed by an additive method or a constructive method. Further, by repeating the above-mentioned construction method using this printed wiring board as an inner layer material, a multi-layer laminated board can be further formed.

Sealing materials obtained by using the epoxy resin composition of the present invention include tape-shaped semiconductor chips, potting-type liquid sealing, underfilling, semiconductor interlayer insulating films, and the like, and are suitable for these. Can be used. For example, in semiconductor package molding, an epoxy resin composition is cast or molded using a transfer molding machine, an injection molding machine, or the like, and further heated at 50 to 200 ° C. for 2 to 10 hours to obtain a molded product. The method can be mentioned.

In order to prepare the epoxy resin composition for the semiconductor encapsulant material, the epoxy resin composition is added with a compounding agent such as an inorganic filler, a coupling agent, a mold release agent, etc., which are blended as necessary. An example is a method in which the agents are premixed and then sufficiently melt-mixed using an extruder, a feeder, a roll, or the like until they become uniform. At that time, silica is usually used as the inorganic filler, but in that case, it is preferable to mix the inorganic filler in the epoxy resin composition at a ratio of 70 to 95% by mass. When the epoxy resin composition thus obtained is used as a tape-shaped encapsulant, it is heated to prepare a semi-cured sheet, which is used as an encapsulant tape, and then this encapsulant tape. Can be mentioned as a method in which the resin is placed on a semiconductor chip, heated to 100 to 150 ° C. to be softened, molded, and completely cured at 170 to 250 ° C. When used as a potting type liquid encapsulant, the obtained epoxy resin composition may be dissolved in a solvent as necessary, applied onto a semiconductor chip or an electronic component, and directly cured. ..

Further, the epoxy resin composition of the present invention can be further used as a resist ink. In this case, the epoxy resin composition is blended with a vinyl-based monomer having an ethylenically unsaturated double bond and a cationic polymerization catalyst as a curing agent, and further, a pigment, talc, and a filler are added to form a composition for a solder ink. Then, a method of applying it on a printed circuit board by a screen printing method and then producing a cured product of a solder ink can be mentioned. The curing temperature at this time is preferably in the temperature range of about 20 to 250 ° C.

The present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto as long as the gist thereof is not exceeded. Unless otherwise specified, parts represent parts by mass and% represents% by mass. The measurement methods were as follows.

Hydroxyvalent equivalent: Measured in accordance with JIS K0070 standard, and the unit is (g / eq.).
-Epoxy equivalent: Measured according to JIS K7236 standard, and the unit is (g / eq.).
-Softening point: Measurement was performed in accordance with JIS K7234 standard and ring ball method. Specifically, an automatic softening point device (manufactured by Meitec Corporation, ASP-MG4) was used. The unit is (° C).
-Melting viscosity: Measured at 180 ° C. using a CV-1S type cone plate viscometer manufactured by Toa Kogyo Co., Ltd., and the unit is (mPa · s).

-Adhesive strength: Copper foil peel strength was measured in accordance with JIS C6481.
-Glass transition temperature, coefficient of linear expansion: Temperature rise of 10 ° C./min with a thermomechanical analyzer (EXSTAR6000 TMA / SS120U, manufactured by Hitachi High-Tech Science Co., Ltd.) according to IPC-TM-650 2.4.24.1. The temperature of the TMA extrapolation value when the measurement was performed under the conditions was defined as the glass transition temperature (Tg). The coefficient of linear expansion less than Tg was represented by α1, and the coefficient of linear expansion after Tg was represented by α2.
Relative permittivity (Dk) and dielectric loss tangent (Df): Dielectric constant and dielectric at a frequency of 1 GHz using a material analyzer (manufactured by Agilent Technologies) according to IPC-TM-650 2.5.5.9. It was evaluated by asking for a straight contact.
-Combustibility: Evaluated by the vertical method according to UL94.
-Water absorption: Compliant with JIS K7209 standard. As the test piece, a sample used for measuring the dielectric constant and the dielectric loss tangent was used, and the test piece was immersed in water at 23 ° C. for 24 hours for measurement.

-GPC: A main body (manufactured by Tosoh Corporation, HLC-8220GPC) equipped with columns (manufactured by Tosoh Corporation, TSKgelG4000HXL, TSKgelG3000HXL, TSKgelG2000HXL) in series was used, and the column temperature was set to 40 ° C. Tetrahydrofuran was used as the eluent, the flow rate was 1 mL / min, and an RI detector was used as the detector. It was converted from the calibration curve obtained from standard monodisperse polystyrene.
^{-IR: Absorbance of a wave number of 650 to 4000 cm -1} was measured by a total reflection measurement method (ATR method) of a Fourier transform infrared spectrophotometer (Spectrum One FT-IR Spectrometer 1760X, manufactured by Perkin Eler Precision).
^{-NMR: A liquid measurement of 1} H was carried out using _{CDCL 3} as a solvent by a Fourier transformed nuclear magnetic resonance apparatus (manufactured by JEOL, JNM-ECA400).

Synthesis example 1
In a reaction device equipped with a stirrer, a thermometer, a nitrogen gas introduction device, and a cooling tube, at room temperature, 6-t-butyl-2,4-xylenol 217.5 parts, isocyanuric acid 50.0 parts, 92%. 45.5 parts of paraformaldehyde, 1.3 parts of hexamethylenetetramine, 629 parts of dimethylformamide, and 11.4 parts of pure water were charged, and the mixture was refluxed at about 116 ° C. with stirring under a nitrogen stream and reacted for 40 hours. After the reaction, the crystals are cooled to about 5 ° C. with stirring to precipitate crystals, the crystals are filtered, further washed with methanol, dried under reduced pressure, and in the form of a white powder, hydroxy represented by the following formula (6). Compound (P1) was obtained. The hydroxyl group equivalent of P1 was 233.

Synthesis example 2
In Synthesis Example 1, except that 6-t-butyl-2,4-xylenol was changed to 72.5 parts, 92% paraformaldehyde was changed to 15.2 parts, dimethylformamide was changed to 278 parts, and pure water was changed to 3.8 parts. In the same manner as in Synthesis Example 1, a mixture (P2) of isocyanuric acid represented by the following formula (7) and a hydroxy compound was obtained. The hydroxyl group equivalent of P2 was 106. As a result of analyzing P2 using GPC, a hydroxy compound in which isocyanuric acid is 11%, one of the substituents Y is a hydroxyarylmethyl group is 50%, and two of the substituents Y are hydroxyarylmethyl groups. Was 26%, and the hydroxy compound in which all three substituents Y were hydroxyarylmethyl groups was 13%.

Synthesis example 3
In Synthesis Example 1, the same as in Synthesis Example 1 except that 217.5 parts of 6-t-butyl-2,4-xylenol was changed to 316.5 parts of 2,4,6-trimethylphenol and dimethylformamide was changed to 827 parts. Then, a hydroxy compound (P3) represented by the following formula (8) was obtained. The hydroxyl group equivalent of P3 was 191.

Synthesis example 4
In Synthesis Example 1, the same as in Synthesis Example 1 except that 217.5 parts of 6-t-butyl-2,4-xylenol was changed to 316.5 parts of 2,3,5-trimethylphenol and dimethylformamide was changed to 827 parts. Then, a hydroxy compound (P4) represented by the following formula (9) was obtained. The hydroxyl group equivalent of P4 was 191.

Synthesis example 5
To the same reactor as in Synthesis Example 1, 300 parts of 4- (hydroxymethyl) -3,5-dimethylphenol (manufactured by Wako Pure Chemical Industries, Ltd., reagent) and 1000 mL of dichloromethane were added and dissolved. 665 parts of 48% hydrobromic acid was charged and stirred at 50 ° C. for 24 hours under a nitrogen atmosphere. After washing the organic layer with water three times, the solvent was distilled off to obtain 4- (bromomethyl) -3,5-dimethylphenol (intermediate 1).
375 parts of Intermediate 1, 110 parts of sodium carbonate, and 853 parts of dimethylformamide were charged in the same reactor as in Synthesis Example 1, and reacted at about 60 ° C. for 10 hours with stirring under a nitrogen stream. After completion of the reaction, 853 parts of water was charged and cooled to about 5 ° C. with stirring to precipitate crystals, then the crystals were filtered, further washed with methanol and water, dried under reduced pressure, and white powdered according to the following formula. The hydroxy compound (P5) represented by (10) was obtained. The hydroxyl group equivalent of P5 was 177.

Synthesis example 6
In Synthesis Example 1, the following formula (11) was applied in the same manner as in Synthesis Example 1 except that 217.5 parts of 6-t-butyl-2,4-xylenol was changed to 114.8 parts of phenol and dimethylformamide was changed to 194 parts. ) Was obtained. The hydroxyl group equivalent of P6 was 149.

Synthesis example 7
In Synthesis Example 1, 217.5 parts of 6-t-butyl-2,4-xylenol was changed to 149.1 parts of 2,6-xylenol, and dimethylformamide was changed to 492 parts in the same manner as in Synthesis Example 1. A hydroxy compound (P7) represented by the following formula (12) was obtained. The hydroxyl group equivalent of P7 was 177.

Synthesis example 8
In Synthesis Example 1, 217.5 parts of 6-t-butyl-2,4-xylenol was changed to 149.1 parts of 2,5-xylenol, and dimethylformamide was changed to 492 parts in the same manner as in Synthesis Example 1. A hydroxy compound (P8) represented by the following formula (13) was obtained. The hydroxyl group equivalent of P8 was 177.

Synthesis example 9
Synthesis Example 1 except that 217.5 parts of 6-t-butyl-2,4-xylenol was changed to 200.4 parts of 6-t-butyl-2-methylphenol and dimethylformamide was changed to 594 parts in Synthesis Example 1. In the same manner as above, a hydroxy compound (P9) represented by the following formula (14) was obtained. The hydroxyl group equivalent of P9 was 219.

The materials used in the examples are shown below.
(Epoxy resin)
TX-1328: Phosphorus-containing epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., TX-1328, phosphorus content 3%, epoxy equivalent 282)
ECN: Cresol novolac type epoxy resin (manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., YDCN-700-3, softening point 73 ° C., epoxy equivalent 203)

(Hardener)
PN1: Phenolic novolak resin (manufactured by Showa Denko KK, Shonor BRG-557, softening point 80 ° C., phenolic hydroxyl group equivalent 105)
PN2: Aromatic modified novolak resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., softening point 65 ° C., phenolic hydroxyl group equivalent 230)
PN3: Phenolic novolak (manufactured by Gun Ei Chemical Industry Co., Ltd., PSM-4261, softening point 80 ° C., phenolic hydroxyl group equivalent 103)
DICY: dicyandiamide (manufactured by Nippon Carbide Industry Co., Ltd., active hydrogen equivalent 21)
SMA: Styrene / maleic anhydride polymerized resin (manufactured by Cray Valley, EF-30, acid value 280 mgKOH / g)
AE: Active ester (manufactured by DIC Corporation, Epicron HPC-8000-65T, active ester equivalent 223)
DOPO-PN: Phosphorus-containing phenolic curing agent (manufactured by Shin-AT & C, LC-950PM60, phosphorus content 9.2%, phenolic hydroxyl group equivalent 341)

(Curing accelerator)
2E4MZ: 2-Ethyl-4-methylimidazole (manufactured by Shikoku Chemicals Corporation, Curesol 2E4MZ)
TPP: Triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd., reagent)

Filler 1: Spherical silica (manufactured by Denki Kagaku Kogyo Co., Ltd., FB-8S)
Filler 2: Carbon black (manufactured by Mitsubishi Chemical Corporation, MA-100)

Example 1
100 parts of hydroxy compound P1, 396.5 parts of epichlorohydrin, and 4 parts of ion-exchanged water were placed in a glass separable flask, and the temperature was raised to 50 ° C. with stirring. After being uniformly dissolved, 3.6 parts of a 49% aqueous sodium hydroxide solution was charged and the reaction was carried out for 3 hours. Next, after raising the temperature to 64 ° C., the pressure was reduced to the extent that reflux of water occurred, and 35.7 parts of a 49% sodium hydroxide aqueous solution was added dropwise over 3 hours. Epichlorohydrin was separated in a separation tank, epichlorohydrin was returned to the reaction vessel, and water was removed from the system to react. After completion of the reaction, the temperature was raised to 70 ° C. for dehydration, and then the temperature was set to 135 ° C. to recover the remaining epichlorohydrin. The pressure was returned to normal pressure, and 204 parts of methyl isobutyl ketone (MIBK) was added and dissolved. 127 parts of ion-exchanged water was added, and the mixture was stirred and allowed to stand to dissolve by-produced salt in water and removed. Next, 2.9 parts of a 49% aqueous sodium hydroxide solution was charged and stirred at 80 ° C. for 90 minutes to carry out a purification reaction. MIBK was added and washed with water several times to remove ionic impurities. The solvent was recovered to obtain the desired epoxy resin (E1). The obtained epoxy resin E1 had an epoxy equivalent of 304, a softening point of 135 ° C., and a melt viscosity of 2600 mPa · s.
The results of GPC measurement, IR measurement and NMR measurement of the epoxy resin E1 are shown in FIGS. 1 to 3.

Examples 2-5, Comparative Examples 1-4
Epoxy resins E2 to E5 were obtained in the same manner as in Example 1 according to the charged amounts (parts) of each raw material shown in Table 1, except that P2 to P5 were used as the hydroxy compounds. In the table, "epichlorohydrin" and "NAOHaq" are the amounts of epichlorohydrin and 49% sodium hydroxide aqueous solution charged with respect to 100 parts of the hydroxy compound.
Similarly, the hydroxy compounds P6 to P9 were used to obtain epoxy resins EH1 to EH4. Table 1 shows the epoxy equivalents, softening points, and melt viscosities of the obtained epoxy resin.

Example 6
39.4 parts of E1 as an epoxy resin, 21.2 parts of TX-1328, 13.6 parts of PN1 as a curing agent, 25.7 parts of DOPO-PN, and 0.1 part of 2E4MZ as a curing accelerator. , MEK, propylene glycol monomethyl ether, and N, N-dimethylformamide to adjust the resin concentration to 50% to obtain an epoxy resin composition varnish.
The obtained epoxy resin composition varnish was impregnated into a glass cloth (manufactured by Nitto Boseki Co., Ltd., WEA2116, 0.1 mm thick). The impregnated glass cloth was dried in a hot air circulation oven at 150 ° C. for 11 minutes to obtain a prepreg. Eight obtained prepregs were overlaid with copper foil (Mitsui Mining & Smelting Co., Ltd., 3EC-III, thickness 35 μm) and vacuum pressed at 2 MPa under the temperature conditions of 130 ° C for 15 minutes + 190 ° C for 80 minutes. A laminated plate having a thickness of 1 mm was obtained. Table 2 shows the measurement results of Tg, α1, α2, adhesive strength, and flame retardancy of the laminated board.

The obtained prepreg was loosened and sieved to obtain a powdery prepreg powder of 100 mesh pass. The obtained prepreg powder was placed in a fluororesin mold and vacuum pressed at 2 MPa under the temperature conditions of 130 ° C. × 15 minutes + 190 ° C. × 80 minutes to obtain a 50 mm square × 2 mm thick test piece. Table 2 shows the measurement results of Dk, Df, and water absorption of the test piece.

Example 7 to Example 14
Except for using E2 to E5 as the epoxy resin, the epoxy resin was blended in the blending amounts (parts) shown in Table 2, and an epoxy resin composition varnish was obtained in the same manner as in Example 6, and a laminated board and a test piece were further obtained. .. The same test as in Example 6 was performed, and the results are shown in Table 2.

Comparative Examples 5-12
Except for using EH1 to EH4 as the epoxy resin, they were blended in the blending amounts (parts) shown in Table 3, and the epoxy resin composition varnish was obtained in the same manner as in Example 6, and a laminated plate and a test piece were further obtained. .. The same test as in Example 6 was performed, and the results are shown in Table 3.

Examples 15-16, Comparative Examples 13-14
E1, E3, EH1, and EH2 were used as the epoxy resin, and an epoxy resin composition was obtained by the formulation shown in Table 4. This epoxy resin composition was molded at 175 ° C. and further post-cured at 180 ° C. for 12 hours to obtain a cured product test piece. The measurement results of various physical property measurements are shown in Table 4. The water absorption rate was measured after 100 hours, not after 24 hours.

The epoxy resin of the present invention, the epoxy resin composition obtained from the epoxy resin composition, and the cured product obtained from the epoxy resin composition are excellent in adhesiveness, flexibility, heat resistance, chemical resistance, insulating property, and curing reactivity. It is used for paints, civil engineering bonding, casting, electrical and electronic materials, film materials, etc. In particular, it is useful for printed wiring board applications, which are one of the electrical and electronic materials, because it exhibits high heat resistance and good electrical characteristics.

Claims (9)

An epoxy resin represented by the following general formula (1).

(However, X ¹ is a group represented by the following formula (2), and X ² and X ³ are independently glycidyl groups or groups represented by the following formula (2).)

(However, R ¹ and R ² independently represent hydrocarbon groups having 1 to 8 carbon atoms, one of R ³ , R ⁴ , and R ⁵ represents a glycidyloxy group, and the other two independently represent hydrogen. Represents an atom or a hydrocarbon group having 1 to 8 carbon atoms. Epoxy equivalent is 140 g / eq. As mentioned above, 700 g / eq. The epoxy resin according to claim 1, which is in the following range. A method for producing an epoxy resin, which comprises reacting epichlorohydrin with a hydroxy compound represented by the following general formula (3).

(However, Y ¹ is a group represented by the following formula (4), and Y ² and Y ³ are independently hydrogen atoms or groups represented by the following formula (4).)

(However, R ¹¹ and R ¹² independently represent hydrocarbon groups having 1 to 8 carbon atoms, one of R ¹³ , R ¹⁴ , and R ¹⁵ represents a hydroxyl group, and the other two independently represent hydrogen atoms or hydrogen atoms or each other. Represents a hydrocarbon group having 1 to 8 carbon atoms.) An epoxy resin composition comprising an epoxy resin and a curing agent, wherein the epoxy resin according to claim 1 or 2 is blended as an essential component. The epoxy resin composition according to claim 4, wherein the active hydrogen group of the curing agent is 0.2 to 1.5 mol with respect to 1 mol of the epoxy group of all the epoxy resins in the epoxy resin composition. A cured product obtained by curing the epoxy resin composition according to claim 4 or 5. A sealing material using the epoxy resin composition according to claim 4 or 5. A prepreg using the epoxy resin composition according to claim 4 or 5. A laminated board using the epoxy resin composition according to claim 4 or 5.

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