JP6799370B2 - Multivalent hydroxy resin, epoxy resin, their manufacturing method, epoxy resin composition and cured product thereof - Google Patents

Description

The present invention relates to an epoxy resin that provides a cured product having excellent fluidity, moisture resistance, high temperature and low elasticity, flame retardancy, and low dielectric property, a polyvalent hydroxy resin suitable as an intermediate thereof, a method for producing the same, and the like. It relates to the epoxy resin composition used and a cured product thereof, and is suitably used for insulating materials and composite materials in the electrical and electronic fields such as semiconductor encapsulants and printed wiring boards.

Epoxy resins have been used in a wide range of industrial applications, but their required performance has become more sophisticated in recent years. For example, semiconductor encapsulant materials are a typical field of resin compositions containing epoxy resin as the main component, but as the degree of integration of semiconductor elements increases, the package size is becoming larger and thinner, and the mounting method is also increasing. The transition to surface mounting is progressing, and the development of materials with excellent solder heat resistance is desired. Therefore, as a sealing material, in addition to low hygroscopicity, improvement of adhesiveness and adhesion at the interface between different materials such as lead frames and chips is strongly required. Similarly, for circuit board materials, it is desired to develop a material having excellent low dielectric property from the viewpoint of reducing dielectric loss, in addition to improving low hygroscopicity, high heat resistance, and high adhesion from the viewpoint of improving solder heat resistance. There is. In order to meet these demands, various new structures of epoxy resins and curing agents are being studied. More recently, from the viewpoint of reducing the environmental load, there is a movement to eliminate halogen-based flame retardants, and epoxy resins and curing agents having more excellent flame retardancy are required.

Therefore, various epoxy resins and epoxy resin curing agents have been studied from the above background. As a resin using an aromatic vinyl compound, Patent Document 1 discloses a resin composition of a novolak type phenol resin and an aromatic vinyl compound, which is cured from a polyfunctional novolak resin and an aromatic divinyl compound. It is a composition for obtaining a product, and the product does not have solvent solubility or moldability because three-dimensional cross-linking proceeds. Therefore, it cannot be used as a curing agent for an epoxy resin or modified to be used as an epoxy resin, and further, it cannot be used for an electronic material substrate application that requires solvent solubility. Further, Patent Document 2 discloses a method for producing a phenol aralkyl resin in which phenol is reacted with divinylbenzene having a purity of 90% by weight or more. Here, by using divinylbenzene having a high purity, the aralkyl resin can be produced. Although it was possible to improve heat resistance and moisture resistance by increasing the molecular weight and making it polyfunctional, it was difficult to reduce the dielectric constant. Further, Patent Document 3 discloses a polyvalent hydroxy resin obtained by reacting a phenol novolac resin with styrene, but it has not been sufficiently sufficient from the viewpoint of hygroscopicity and heat resistance.

Japanese Unexamined Patent Publication No. 5-117337 Japanese Unexamined Patent Publication No. 8-73570 Japanese Unexamined Patent Publication No. 2012-57079

An object of the present invention is a polyvalent hydroxy resin having excellent fluidity, moisture resistance, high temperature and low elasticity, flame retardancy, low dielectric property, etc. in applications such as lamination, molding, casting, and adhesion. And providing epoxy resin, encapsulation of electrical and electronic parts, circuit board materials, composites that provide a cured product with excellent fluidity and excellent moisture resistance, low elasticity, flame retardancy, low dielectric property, etc. It is an object of the present invention to provide an epoxy resin composition useful for a material or the like, and to provide a cured product thereof.

The present invention is obtained by reacting a phenol compound represented by the following general formula (1) with an aromatic vinyl compound represented by the following general formulas (2) and (3), and the following general formula (4). It is a polyhydric hydroxy resin characterized by being represented.

（Ｒ₁は水素又は炭素数１〜６の炭化水素基を示す。）

(R ₁ indicates hydrogen or a hydrocarbon group having 1 to 6 carbon atoms.)

（Ｒ₁は水素又は炭素数１〜６の炭化水素基を示し、Ｒ₂は式（ａ）で表される置換基を示し、Ｒ₃およびＲ₄は水素を示し、ｎは０〜２０の数を示す。また、ｐはＲ₂が置換するベンゼン環1つ当たりの平均の置換数であり、０．１〜３．０の数を示す。）

(R ₁ represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, R ₂ represents a substituent represented by the formula (a), R ₃ and R ₄ represent hydrogen, and n is 0 to 20. The number is shown. In addition, p is the average number of substitutions per benzene ring substituted by R ₂ , and indicates a number of 0.1 to 3.0.)

A preferred embodiment of the multivalent hydroxy resin has a hydroxyl group equivalent of 200 to 500 g / eq. The content of the unit price hydroxy compound represented by the following general formula (5) is 3% to 20% in terms of area percentage when detected by gel permeation chromatography (GPC; RI). Can be mentioned.

（ここで、ｐ、Ｒ₁は一般式（４）と同意である。）

(Here, p and R ₁ agree with the general formula (4).)

Further, in the present invention, the phenol compound represented by the general formula (1) and the aromatic vinyl compound represented by the general formulas (2) and (3) are mixed in the presence of an acid catalyst of 10 to 1000 wtppm. A polyvalent hydroxy resin represented by the above general formula (4), which comprises reacting at a reaction temperature of 40 to 180 ° C. to add a substituent represented by the above formula (a) to the benzene ring of the phenol compound. It is a manufacturing method of.

In the method for producing a polyvalent hydroxy resin, 0.1 to 1.0 mol of an aromatic vinyl compound represented by the general formula (2) is obtained with respect to 1 mol of the hydroxy group of the phenol compound represented by the general formula (1). It is good to react.

Further, the present invention is an epoxy resin composition composed of an epoxy resin and a curing agent, wherein the above-mentioned polyvalent hydroxy resin is an essential component as a part or all of the curing agent. Furthermore, the present invention is an epoxy resin cured product obtained by curing this epoxy resin composition.

Further, the present invention is an epoxy resin characterized by being obtained by reacting the above-mentioned multivalent hydroxy resin with epichlorohydrin. Further, the present invention is an epoxy resin composition composed of an epoxy resin and a curing agent, an epoxy resin composition containing the epoxy resin as an essential component, and an epoxy resin cured product obtained by curing the epoxy resin composition. Is.

The epoxy resin cured product obtained by using the epoxy resin composition of the present invention is excellent in moisture resistance, high temperature and low elasticity, flame retardancy, low dielectric property and the like. In addition, this epoxy resin composition gives excellent fluidity during molding. Therefore, the epoxy resin composition of the present invention can be suitably used for applications of encapsulating materials for power semiconductors and applications of circuit board materials compatible with high frequencies.

GPC chart of the multivalent hydroxy resin synthesized in Example 1 FD-MS chart of the multivalent hydroxy resin synthesized in Example 1 GPC chart of the multivalent hydroxy resin synthesized in Comparative Example 1 FD-MS chart of the multivalent hydroxy resin synthesized in Comparative Example 1 GPC chart of epoxy resin synthesized in Example 3 FD-MS chart of the epoxy resin synthesized in Example 3 GPC chart of epoxy resin synthesized in Comparative Example 2 FD-MS chart of the epoxy resin synthesized in Comparative Example 2

First, a method for producing the multivalent hydroxy resin (also referred to as DVBN-P) of the present invention will be described. In the production method of the present invention, the phenol compound represented by the general formula (1) and the aromatic vinyl compound represented by the general formulas (2) and (3) are present in an acid catalyst of 10 to 1000 wtppm. Below, the reaction is carried out at a reaction temperature of 40 to 180 ° C. to produce a polyhydric hydroxy resin represented by the above general formula (4).

The phenol compound used in the method for producing DVBN-P of the present invention is the phenol compound represented by the above general formula (1).
In the general formula (1), R ₁ represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms. Suitable phenolic compounds include, for example, phenol, o-cresol, m-cresol, p-cresol, ethylphenols, isopropylphenols, tertiary butylphenols, allylphenols, phenylphenols and the like. These phenols may be used alone or in combination of two or more.

The aromatic vinyl compound used in the reaction is both divinylbenzene (DVB) and ethylvinylbenzene (EVB) represented by the above general formulas (2) and (3).
Here, DVB and EVB may be a meta-form, a para-form, an ortho-form alone, or a mixture of isomers, respectively. DVB contains a meta-form as a main component, and the meta-form concentration is preferably 40% or more of the total DVB isomers. More preferably, it is 50% or more. EVB contains a meta-form as a main component, and the meta-form concentration is preferably 40% or more of all EVB isomers. More preferably, it is 50% or more.

The ratio of EVB in the aromatic vinyl compound is in the range of 10 to 50 wt% in the total aromatic vinyl compound in consideration of the handleability of the obtained resin, the moldability at the time of preparing the epoxy cured product, and the physical property balance of the curability. preferable. It is more preferably in the range of 15 to 45 wt%, and even more preferably in the range of 20 to 40 wt%. The proportion of DVB is preferably in the range of 50-90 wt% of the total aromatic vinyl compound, in the range of 55-85 wt%.

Further, as the ratio of the phenol compound represented by the above general formula (1) to DVB, the phenol compound is considered in consideration of the handleability of the obtained resin, the moldability at the time of producing the epoxy cured product, and the physical property balance of the curability. The molar ratio of DVB to 1 mol is preferably in the range of 0.1 to 1.0, more preferably in the range of 0.2 to 1.0 mol, and even more preferably in the range of 0.3 to 0.8 mol.

In the above general formula (4), DVB gives a unit (α-dimethylxylylene unit) for binding phenol rings to each other, and thus acts as a cross-linking agent. On the other hand, EVB provides a group R ₂ that replaces the phenol ring, that is, a substituent (ethylstylenyl group) represented by the formula (a). The substitution position of this substituent is mainly the vacant ortho and / or para position with respect to the OH group of the phenol ring.

The reaction between the phenol compound and the aromatic vinyl compound represented by the general formulas (2) and (3) is carried out in the presence of an acid catalyst. As the acid catalyst, a well-known inorganic acid or organic acid can be appropriately selected. For example, mineral acids such as hydrochloric acid, sulfuric acid and phosphoric acid, organic acids such as formic acid, oxalic acid, trifluoroacetic acid, p-toluenesulfonic acid, dimethylsulfate and diethylsulfuric acid, zinc chloride, aluminum chloride, iron chloride and trifluoride. Examples thereof include Lewis acids such as boron carbonate, ion exchange resins, active white clay, silica-alumina, and solid acids such as zeolite. The amount of the acid catalyst used is preferably in the range of 10 to 1000 wtppm, preferably in the range of 50 to 500 wtppm with respect to the total of the phenol compound and the aromatic vinyl compound.

In addition, this reaction is usually carried out at 10 to 250 ° C. for 1 to 20 hours. Furthermore, during the reaction, alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve and ethyl cellosolve, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, dimethyl ether, diethyl ether and diisopropyl ether, Ethers such as tetrahydrofuran and dioxane, aromatic compounds such as benzene, toluene, chlorobenzene and dichlorobenzene can be used as the solvent.

As a specific method for carrying out this reaction, all the raw materials are charged at once and reacted at a predetermined temperature as they are, or a phenol compound and an acid catalyst are charged and the aromatic vinyl compound is maintained at a predetermined temperature. Is generally reacted while dropping. At this time, the dropping time is usually 1 to 10 hours, preferably 5 hours or less. When a solvent is used after the reaction, if necessary, after removing the acid catalyst component, the solvent and the unreacted product can be distilled off to obtain the polyvalent hydroxy resin of the present invention. When no solvent is used, By distilling off the unreacted material, the desired polyvalent hydroxy resin represented by the general formula (4) can be obtained.

The polyvalent hydroxy resin (DVBN-P) obtained by the production method of the present invention can control the hydroxyl group equivalent according to the ratio of two kinds of aromatic vinyl compounds (DVB and EVB). In other words, in a cured epoxy resin product, the hydroxypropyl group generated by the reaction between the epoxy group and the hydroxyl group is said to be easily burned. However, by increasing the hydroxyl group equivalent, the aliphatic carbon of the flammable component derived from the epoxy group is easily burned. The rate is low and a high degree of flame retardancy can be developed. Further, by adding EVB in the aromatic vinyl compound, the aromaticity is further improved, and it is also effective in improving the fluidity, moisture resistance and low dielectric property.

Therefore, a highly flame-retardant epoxy resin composition, particularly an epoxy resin composition for a semiconductor encapsulating material or a circuit board material, can be obtained by using this DVBN-P. That is, a resin composition exhibiting excellent physical properties such as moisture resistance and low elasticity as well as fluidity can be obtained, and a highly reliable semiconductor encapsulation material or circuit board material can be obtained by using the resin composition.

Further, in the DVBN-P of the present invention, although the molecular weight is increased by adding EVB, the melt viscosity range suitable for preparing an epoxy cured product can be maintained from the introduction of the flexible chain structure. This means that when used as a material for encapsulating semiconductors, it exhibits good fluidity, so that good moldability is possible, and when used as a material for circuit boards, it is possible to improve the solubility in organic solvents. is there. Further, they contribute to low functionality and improve various physical properties, for example, improvement of flame retardancy, further low water absorption and low dielectric property, so that a material having excellent reliability can be obtained.

The hydroxyl group equivalent of the DVBN-P of the present invention thus obtained is 200 to 500 g / eq. It is often in the range of 230 to 400 g / eq. Is the range of. If the hydroxyl group equivalent is lower than this range, it is difficult to obtain high flame retardancy, and if it is higher than this range, high flame retardancy can be obtained, but it is inferior in curability and tends to be difficult to use in the above applications. ..

Further, the melt viscosity of DVBN-P of the present invention at 150 ° C. is preferably in the range of 0.01 to 10.0 Pa · s. From the viewpoint of workability, the lower the melt viscosity in the above range, the more preferable.

Further, the softening point is often 40 to 150 ° C, preferably in the range of 50 to 100 ° C. Here, the softening point is measured based on the ring ball method of JIS-K-2207. If it is lower than this, the heat resistance of the cured product is lowered when it is blended with the epoxy resin composition, and if it is higher than this, the fluidity at the time of molding is lowered.

The epoxy resin obtained by the production method of the present invention is represented by the above general formula (4). In the general formulas (1), (4) and (5), common symbols have the same meaning.
R ₂ represents an ethylstyrenyl group represented by the above formula (a). In addition, one of R ₃ and R ₄ in the general formula (4) is H, and the other is Me.
p represents the average number of R ₂ to be substituted with 1 per benzene ring having an OH group, in the range of 0.1 to 3, preferably from 0.2 to 2, more preferably 0.3 It is in the range of 1.5. The total of p in one molecule is 1 or more as an average value, and more preferably 2 or more. The total amount of p in one molecule is preferably 10 or less.

n is the number of repetitions, meaning that n is any of the compounds 1 to 20 alone or a mixture thereof, or 0 to 20 on average (number average). N as an average is preferably 2 to 10. Also, since the average (number average) can be calculated from the epoxy equivalents, the preferred n is also understood from it.

Then, when this DVBN-P is measured by gel permeation chromatography (GPC; RI), it is preferable that the unit price hydroxy compound in the general formula (5) is in the range of 1% to 25% in terms of the area% thereof. .. More preferably, it is in the range of 3% to 20%. It can be said that this unit price hydroxy compound corresponds to the compound in which n is 0 in the general formula (4) and is not crosslinked by DVB. If the content of this unit price hydroxy compound is less than this range, the properties derived from the functional group concentration remain unimproved, and if it is more than this range, the functional group density becomes too low and the curability becomes curable. Tends to decline. In the present invention, it is possible to adjust the hydroxyl group equivalent of DVBN-P to 200 to 500 g / eq by changing the amount of EVB used in these aromatic vinyl compounds. As a result, the epoxy resin composition exhibits excellent physical properties such as flame retardancy, moisture resistance, high temperature and low elasticity, and has excellent flame retardancy and reliability in applications such as semiconductor encapsulation materials and circuit board materials. Give things. This means that when used as a semiconductor encapsulating material, good moldability is possible due to its fluidity, and when used as a circuit board material, its solubility in an organic solvent can be improved. As a result, a material having excellent reliability can be obtained by improving various physical properties, for example, improving flame retardancy, further lower water absorption and lower dielectric property.

Next, the multivalent hydroxy resin of the present invention will be described.
The polyvalent hydroxy resin of the present invention is represented by the above general formula (4). Therefore, unless the production method is specified, the description is the same as that of the polyvalent hydroxyepoxy resin obtained by the production method of the present invention. Advantageously, it is obtained by simultaneously reacting the above-mentioned phenol compound with an aromatic vinyl compound represented by the general formulas (2) and (3).

That is, the hydroxyl group equivalent, melt viscosity, softening point, and content of the unit-valent hydroxy compound of the polyvalent hydroxy resin of the present invention are preferably in the above ranges. Further, the symbols and preferred ranges or groups in the general formula (4) are the same as described above.

Next, the epoxy resin of the present invention will be described.
The epoxy resin (abbreviated as DVBN-E) of the present invention can be obtained by converting the OH group of the polyvalent hydroxy resin (DVBN-P) represented by the general formula (4) into a glycyl ether.

The DVBN-E of the present invention can be obtained by reacting DVBN-P with epichlorohydrin, or by reacting DVBN-P with allyl halide to obtain an allyl ether compound, and then reacting with a peroxide. .. The reaction of reacting DVBN-P with epichlorohydrin can be carried out in the same manner as a normal epoxidation reaction.

For example, after dissolving the above DVBN-P in excess epichlorohydrin, 1 in the range of 20 to 150 ° C., preferably 30 to 80 ° C. in the presence of alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. A method of reacting for 10 hours can be mentioned. The amount of the alkali metal hydroxide used at this time is in the range of 0.8 to 1.5 mol, preferably 0.9 to 1.2 mol, with respect to 1 mol of the hydroxyl group of DVBN-P. Epichlorohydrin is used in excess with respect to 1 mol of hydroxyl groups in DVBN-P, but is usually 1.5 to 30 mol, preferably 2 to 15 mol, relative to 1 mol of hydroxyl groups in DVBN-P. The range. After completion of the reaction, excess epichlorohydrin is distilled off, the residue is dissolved in a solvent such as toluene or methyl isobutyl ketone, filtered, washed with water to remove inorganic salts, and then the solvent is distilled off to obtain the desired epoxy. A resin (DVBN-E) can be obtained.

The epoxy resin composition of the present invention contains at least an epoxy resin and a curing agent, and there are the following three types.
1) A composition containing the DVBN-E as part or all of the epoxy resin.
2) A composition containing the above DVBN-P as a part or all of the curing agent.
3) A composition in which the DVBN-E and DVBN-P are blended as part or all of the epoxy resin and the curing agent.

In the case of the compositions 2) and 3) above, the blending amount of DVBN-P is usually in the range of 2 to 200 parts by weight, preferably 5 to 120 parts by weight with respect to 100 parts by weight of the epoxy resin. If it is less than this, the effect of improving flame retardancy and moisture resistance is small, and if it is more than this, there is a problem that the moldability and the strength of the cured product are lowered.

When DVBN-P is used as the total amount of the curing agent, the blending amount of DVBN-P is usually adjusted in consideration of the equivalent balance between the OH group of DVBN-P and the epoxy group in the epoxy resin. The equivalent ratio of the epoxy resin to 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 or smaller than this, the curability of the epoxy resin composition is lowered, and the heat resistance, mechanical strength, etc. of the cured product are lowered.

A curing agent other than DVBN-P can be used in combination as the curing agent. The blending amount of the other curing agent is determined within a range in which the blending amount of DVBN-P is usually maintained in the range of 2 to 200 parts by weight, preferably 5 to 80 parts by weight with respect to 100 parts by weight of the epoxy resin. Will be done. If the blending amount of DVBN-P is smaller than this, the effect of improving low hygroscopicity, adhesion and flame retardancy is small, and if it is larger than this, there is a problem that the moldability and the strength of the cured product are lowered.

As the curing agent other than DVBN-P, all generally known curing agents for epoxy resins can be used, and there are dicyandiamides, acid anhydrides, polyhydric phenols, aromatics, aliphatic amines and the like. Among these, in fields where high electrical insulation is required, such as semiconductor encapsulants, it is preferable to use polyhydric phenols as a curing agent. Specific examples of the curing agent are shown below.

Examples of the acid anhydride curing agent include phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl anhydride hymic acid, dodecinyl succinic anhydride, and nadic acid anhydride. There are phthalic anhydride and the like.

Examples of polyphenols include divalent phenols such as bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4'-biphenol, 2,2'-biphenol, hydroquinone, resorcin, naphthalenediol, etc. , Tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol novolac, o-cresol novolac, naphthol novolac, polyvinylphenol, etc. There are phenols. Furthermore, divalent phenols such as phenols, naphthols, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4'-biphenol, 2,2'-biphenol, hydroquinone, resorcin, naphthalenediol, etc. There are polyhydric phenolic compounds synthesized by condensing agents such as formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, p-xylylene dichloride, bischloromethylbiphenyl and bischloromethylnaphthalene.

Examples of amines include aromatic amines such as 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylsulfone, m-phenylenediamine, and p-xylylenediamine, ethylenediamine, and the like. There are aliphatic amines such as hexamethylenediamine, diethylenetriamine and riethylenetetramine.
One or a mixture of two or more of these curing agents can be used in the above composition.

The epoxy resin used in the above composition is selected from those having two or more epoxy groups in one molecule. For example, divalent phenols such as bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4'-biphenol, 2,2'-biphenol, tetrabromobisphenol A, hydroquinone, resorcin, or tris- (4). -Hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, novolak resins such as phenol, cresol, and naphthol, and trivalent or higher phenols such as phenol, cresol, and aralkyl resin such as naphthol. There are glycidyl etherified products of sex compounds. These epoxy resins can be used alone or in admixture of two or more.

In the case of the compositions 1) and 3) above, another type of epoxy resin may be blended in the epoxy resin composition in addition to DVBN-E as the epoxy resin component. 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, divalent phenols such as bisphenol A, bisphenol S, fluorene bisphenol, 4,4'-biphenol, 2,2'-biphenol, 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, phenolic aralkyl resins, biphenylaralkyl resins, naphthol aralkyl resins Alternatively, there are glucidyl etherified products derived from halogenated bisphenols such as tetrabromobisphenol A. These epoxy resins can be used alone or in admixture of two or more. In the case of the composition containing DVBN-E as an essential component of the present invention, the blending amount of DVBN-E is preferably in the range of 5 to 100%, preferably 60 to 100%, in the entire epoxy resin.

In the epoxy resin composition of the present invention, oligomers or polymer compounds such as polyester, polyamide, polyimide, polyether, polyurethane, petroleum resin, inden resin, inden-kumaron resin, and phenoxy resin are used as other modifiers. It may be blended as appropriate. The amount added is usually in the range of 2 to 30 parts by weight with respect to 100 parts by weight of the epoxy resin.

In addition, the epoxy resin composition of the present invention may contain additives such as an inorganic filler, a pigment, a flame retardant, a rock denaturing agent, a coupling agent, and a fluidity improver. Examples of the inorganic filler include spherical or crushed molten silica, silica powder such as crystalline silica, alumina powder, glass powder, mica, talc, calcium carbonate, alumina, hydrated alumina, and the like, and semiconductor sealing. When used as a stop material, the blending amount is preferably 70% by weight or more, more preferably 80% by weight or more.

Examples of the pigment include organic or inorganic extender pigments and scaly pigments. Examples of the rocking denaturing agent include silicon-based, castor oil-based, aliphatic amide wax, polyethylene oxide wax, and organic bentonite-based.

Further, a curing accelerator can be used in the epoxy resin composition of the present invention, if necessary. Examples include amines, imidazoles, organic phosphines, Lewis acids, etc. Specifically, 1,8-diazabicyclo (5,4,0) undecene-7, triethylenediamine, benzyldimethylamine, tri. Tertiary amines such as ethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2- Imidazoles such as heptadecylimidazole, organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine, tetraphenylphosphonium / tetraphenylborate, tetraphenylphosphonium / ethyltriphenylborate, tetra There are tetra-substituted phosphonium-tetra-substituted borates such as butylphosphonium and tetrabutylborate, tetraphenylborone salts such as 2-ethyl-4-methylimidazole and tetraphenylborate, and N-methylmorpholine and tetraphenylborate. The amount to be added is usually in the range of 0.1 to 5 parts by weight with respect to 100 parts by weight of the epoxy resin.

Further, if necessary, the resin composition of the present invention includes a release agent such as carnauba wax and OP wax, a coupling agent such as γ-glycidoxypropyltrimethoxysilane, a colorant such as carbon black, and trioxide. Flame retardants such as antimony, low stress agents such as silicone oil, lubricants such as calcium stearate, and the like can be used.

The epoxy resin composition of the present invention is made into a varnish state in which an organic solvent is dissolved, and then impregnated with a fibrous material such as a glass cloth, an aramid non-woven fabric, or a polyester non-woven fabric such as a liquid crystal polymer, and then the solvent is removed to remove the prepreg. Can be. Further, depending on the case, a laminate can be obtained by applying it on a sheet-like material such as a copper foil, a stainless steel foil, a polyimide film, or a polyester film.

If the epoxy resin composition of the present invention is heat-cured, it can be made into an epoxy resin cured product, and this cured product is excellent in terms of low hygroscopicity, high heat resistance, adhesion, flame retardancy and the like. Become. This cured product can be obtained by molding the epoxy resin composition by a method such as casting, compression molding, or transfer molding. The temperature at this time is usually in the range of 120 to 220 ° C.

Hereinafter, the present invention will be described in more detail with reference to Examples.
The resin evaluation method is shown below.

1) GPC measurement A TSKgelG4000HXL x 1 and TSKgelG2000HXL x 3 manufactured by Tosoh Corporation were used in series, and the column temperature was set to 40 ° C. Tetrahydrofuran was used as the eluent at a flow rate of 1 ml / min, and an RI (differential refractometer) detector was used as the detector. 0.03 g of the sample was dissolved in 10 ml of THF. From the measured molecular weight distribution, the area percentage corresponding to each n of the general formula was obtained. Identification of each peak was associated with FD-MS measurements.

2) FD-MS
The measurement was carried out according to the electrolytic desorption / ionization mass spectrometry using a JMS-AX505HA device manufactured by JEOL Ltd. The obtained FD-MS spectral data and gel permeation chromatography (GPC) measurement results were used in combination to identify the molecular weight distribution and its peaks.

3) Softening point An automatic softening point device (manufactured by Meiho Co., Ltd., ASP-M4SP) was used, and the measurement was performed by the ring-ball method according to JIS-K-2207.

4) Melt viscosity Measured at 150 ° C. using a CAP2000H type rotational viscometer manufactured by BROOKFIELD.

5) Measurement of hydroxyl group equivalent Using a potentiometric titrator, acetylation was performed with 1.5 mol / L acetyl chloride at 100 ° C. for 60 minutes using 1,4-dioxane as a solvent, and excess acetyl chloride was removed with water. And titrated with 0.5 mol / L-potassium hydroxide.

6) Measurement of epoxy equivalent Using a potentiometric titrator, methyl ethyl ketone was used as a solvent, a brominated tetraethylammonium acetic acid solution was added, and the potentiometric titrator was used for measurement using a 0.1 mol / L perchloric acid-acetic acid solution.
7) Solvent solubility MEK was added and dissolved so that the resin solid content was 50 wt%. Solubility was observed when left to stand for one week. 〇; Uniform dissolution, Δ; Turbidity in solution, ×; Precipitate.

Example 1
150 g of phenol and 0.045 g of 50% paratoluenesulfonic acid were added to a 1 L 4-neck flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel, and the temperature was raised to 100 ° C. Next, while stirring at 100 ° C., 148 g of 63% DVB (including 55 g of EVB) as an aromatic vinyl compound was added dropwise over 2 hours to react. Further, the reaction was completed by keeping the temperature at 150 ° C. Then, the temperature was lowered to 85 ° C. and washing with water was performed about 4 times. Subsequently, the unreacted product was distilled off under reduced pressure to obtain 252 g of a polyvalent hydroxy resin. Its softening point is 59 ° C., its melt viscosity at 150 ° C. is 0.06 Pa · s, and its hydroxyl group equivalent is 252 g / eq. The GPC area% of the unit price hydroxy resin (unit price hydroxy resin of the general formula (5)) was 11.6. This multivalent hydroxy resin is called DVBN-P1. The GPC chart of DVBN-P1 is shown in FIG. 1, and the FD-MS chart is shown in FIG.

Example 2
206 g of a polyvalent hydroxy resin (DVBN-P2) was obtained in the same manner as in Example 1 except that 150 g of phenol, 0.03 g of 50% paratoluenesulfonic acid and 115 g of 81% DVB (including 21 g of EVB) were used. The softening point of DVBN-P was 68 ° C., the melt viscosity at 150 ° C. was 0.11 Pa · s, and the hydroxyl group equivalent was 211 g / eq. The GPC area% of the unit price hydroxy resin was 6.6.

Comparative Example 1
150 g of phenol and 0.03 g of 50% paratoluenesulfonic acid were added to a 1 L 4-neck flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel, and the temperature was raised to 100 ° C. Next, 185 g of a multivalent hydroxy resin (DVBN-P3) was obtained in the same manner as in Example 1 except that 97 g of 96% DVB (including 4 g of EVB) was used while stirring at 100 ° C. The softening point of DVBN-P3 was 76 ° C., the melt viscosity at 150 ° C. was 0.18 Pa · s, and the hydroxyl group equivalent was 197 g / eq. The GPC area% of the unit price hydroxy resin was 1.0. The GPC chart of DVBN-P3 is shown in FIG. 3, and the FD-MS chart is shown in FIG.

Synthesis Example 1 (Example)
150 g of phenol and 0.04 g of 50% paratoluenesulfonic acid were added to a 1 L 4-neck flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel, and the temperature was raised to 100 ° C. Next, 373 g of a multivalent hydroxy resin (DVBN-P4) was obtained in the same manner as in Example 1 except that 255 g of 57% DVB (including 99 g of EVB) was used while stirring at 100 ° C. The softening point of DVBN-P4 was 76 ° C., the melt viscosity at 150 ° C. was 0.40 Pa · s, and the hydroxyl group equivalent was 314 g / eq. The GPC area% of the unit price hydroxy resin was 7.4.

Synthesis Example 2 (Example)
150 g of phenol and 0.04 g of 50% paratoluenesulfonic acid were added to a 1 L 4-neck flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel, and the temperature was raised to 100 ° C. Next, 359 g of a multivalent hydroxy resin (DVBN-P5) was obtained in the same manner as in Example 1 except that 230 g of 63% DVB (including 85 g of EVB) was used while stirring at 100 ° C. The softening point of DVBN-P5 was 77 ° C., the melt viscosity at 150 ° C. was 0.47 Pa · s, and the hydroxyl group equivalent was 294 g / eq. The GPC area% of the unit price hydroxy resin was 7.2.

Synthesis Example 3 (Example)
150 g of phenol and 0.03 g of 50% paratoluenesulfonic acid were added to a 1 L 4-neck flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel, and the temperature was raised to 100 ° C. Next, 296 g of a multivalent hydroxy resin (DVBN-P6) was obtained in the same manner as in Example 1 except that 179 g of 81% DVB (including 32 g of EVB) was used while stirring at 100 ° C. The softening point of DVBN-P6 is 91 ° C., the melt viscosity at 150 ° C. is 1.37 Pa · s, and the hydroxyl group equivalent is 241 g / eq. The GPC area% of the unit price hydroxy resin was 4.0.

Synthesis example 4
150 g of phenol and 0.03 g of 50% paratoluenesulfonic acid were added to a 1 L 4-neck flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel, and the temperature was raised to 100 ° C. Next, 262 g of a multivalent hydroxy resin (DVBN-P7) was obtained in the same manner as in Example 1 except that 151 g of 96% DVB (including 6 g of EVB) was used while stirring at 100 ° C. The softening point of DVBN-P7 is 103 ° C., the melt viscosity at 150 ° C. is 4.37 Pa · s, and the hydroxyl group equivalent is 213 g / eq. The GPC area% of the unit price hydroxy resin was 1.0.

Example 3
100 g of DVBN-P4 obtained in Synthesis Example 1, 411 g of epichlorohydrin, and 62 g of diethylene glycol dimethyl ether were placed in a 1 L 4-neck flask equipped with a stirrer, a condenser, a thermometer, and a dropping funnel, and dissolved by stirring. After uniformly dissolving, the temperature was maintained at 65 ° C. under reduced pressure of 130 mmHg, 32 g of a 48% sodium hydroxide aqueous solution was added dropwise over 4 hours, and the water distilled from reflux and epichlorohydrin were separated in a separation tank during the addition, and epichlorohydrin was placed in a reaction vessel. The water reacted except outside the system. After completion of the reaction, the salt produced by filtration was removed, the mixture was further washed with water, and epichlorohydrin was distilled off to obtain 106 g of an epoxy resin (DVBN-E1). The epoxy equivalent of the obtained resin was 354 g / eq. The softening point was 64 ° C., and the melt viscosity at 150 ° C. was 0.26 Pa · s. The GPC chart of DVBN-E1 is shown in FIG. 5, and the FD-MS chart is shown in FIG.

Example 4
100 g of DVBN-P5 obtained in Synthesis Example 2, 410 g of epichlorohydrin, and 62 g of diethylene glycol dimethyl ether were placed in a 1 L 4-neck flask equipped with a stirrer, a condenser, a thermometer, and a dropping funnel and dissolved by stirring. After being uniformly dissolved, 107 g of epoxy resin (DVBN-E2) was obtained in the same manner as in Example 3 except that the temperature was maintained at 65 ° C. under reduced pressure of 130 mmHg and 35 g of a 48% sodium hydroxide aqueous solution was added dropwise over 4 hours. .. The epoxy equivalent of the obtained resin was 327 g / eq. The softening point was 68 ° C., and the melt viscosity at 150 ° C. was 0.34 Pa · s.

Example 5
100 g of DVBN-P6 obtained in Synthesis Example 3, 409 g of epichlorohydrin, and 61 g of diethylene glycol dimethyl ether were placed in a 1 L 4-neck flask equipped with a stirrer, a condenser, a thermometer, and a dropping funnel and dissolved by stirring. After being uniformly dissolved, 101 g of epoxy resin (DVBN-E3) was obtained in the same manner as in Example 3 except that 39 g of a 48% sodium hydroxide aqueous solution was added dropwise over 4 hours while maintaining the temperature at 65 ° C. under reduced pressure of 130 mmHg. .. The epoxy equivalent of the obtained resin was 303 g / eq. The softening point was 78 ° C., and the melt viscosity at 150 ° C. was 0.69 Pa · s.

Comparative Example 2
100 g of DVBN-P7 obtained in Synthesis Example 4, 443 g of epichlorohydrin, and 66 g of diethylene glycol dimethyl ether were placed in a 1 L 4-neck flask equipped with a stirrer, a condenser, a thermometer, and a dropping funnel and dissolved by stirring. After being uniformly dissolved, 104 g of epoxy resin (DVBN-E4) was obtained in the same manner as in Example 3 except that the temperature was maintained at 65 ° C. under reduced pressure of 130 mmHg and 42 g of a 48% sodium hydroxide aqueous solution was added dropwise over 4 hours. .. The epoxy equivalent of the obtained resin was 280 g / eq. The softening point was 85 ° C., and the melt viscosity at 150 ° C. was 1.14 Pa · s. The GPC chart of DVBN-E4 is shown in FIG. 7, and the FD-MS chart is shown in FIG.

Examples 6-10 and Comparative Examples 3-5
In Example 1, 2, Comparative Example 1, and Synthesis Examples 1, 2, 3, and 4 using an o-cresol novolac type epoxy resin (OCNE; epoxy equivalent 202, softening point 74 ° C.) as an epoxy resin component and as a curing agent. The obtained polyvalent hydroxy resin or phenol aralkyl resin (PA; OH equivalent 175, softening point 67 ° C.) was used. Triphenylphosphine as a curing accelerator was kneaded with the formulations shown in Table 1 to obtain an epoxy resin composition. This epoxy resin composition was molded at 175 ° C., post-cured at 200 ° C. for 5 hours to obtain a cured product test piece, and then subjected to various physical property measurements. The results are shown in Table 2. The compounding amount is the part by weight.

Evaluation method of cured product 1) Gel time (GT)
The epoxy resin composition was added onto a plate of a gelling tester (manufactured by Nissin Scientific Co., Ltd.) heated to 175 ° C., and the mixture was stirred at a rate of 2 rotations per second using a fluororesin rod. The gelation time required for the epoxy resin composition to cure was investigated.

2) Spiral flow (SF)
Using a transfer molding machine, an epoxy resin composition containing spherical silica (average particle size 18 μm) as a filler was injected into a spiral flow mold at 175 ° C., and the flow distance was measured.

3) Glass transition point (Tg) and coefficient of linear expansion (CTE) measured by TMA
Tg was determined by Seiko Instruments' TMA120C type thermomechanical measuring device under the condition of a heating rate of 10 ° C./min, and α1 (CTE of Tg or less) was an average value in the range of 40 to 60 ° C., and α2 (Tg). The above CTE) was determined from the average value in the range of Tg plus 50 ° C. to 70 ° C.

4) Glass transition point (Tg) and viscoelasticity (ε') measured by DMA
Tg was determined by a DMA thermomechanical measuring device manufactured by Seiko Instruments Inc. under the condition of a temperature rising rate of 4 ° C./min, and viscoelasticity ε'at 40 ° C. and viscoelasticity ε'at 260 ° C. were determined.

5) 5 wt% weight loss temperature (Td5) measured by TGDTA, 10 wt% weight loss temperature (Td10)
A 5 wt% weight loss temperature (Td5) and a 10 wt% weight loss temperature (Td10) were determined from the weight loss curve under the condition of a temperature rising rate of 10 ° C./min by a TGDTA thermomechanical measuring device manufactured by Seiko Instruments Inc.

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

7) Permittivity by capacitance method (Dk), dielectric loss tangent (Df)
Using an impedance material analyzer manufactured by Agilent, the dielectric constant and dielectric loss tangent of the cured product after storage in a constant temperature and humidity chamber at 25 ° C. and 60% humidity were measured at 1 GHz.

Examples 11-14 and Comparative Examples 5-7
As the epoxy resin components, DVBN-E1, DVBN-E2, DVBN-E3 obtained in Examples 3, 4 and 5, DVBN-E4 obtained in Comparative Example 2, and phenol aralkyl type epoxy resin (PA-E; epoxy equivalent 202). , Softening point 75 ° C.), or biphenyl aralkyl type epoxy resin (BPAR-E; epoxy equivalent 272, softening point 75 ° C.), phenol novolac resin (PN; OH equivalent 108, softening point 90 ° C.) as a curing agent component, or The DVBN-P5 synthesized in Synthesis Example 2 was used. Further, 2-ethyl-4-methylimidazole was used as a curing accelerator, and an epoxy resin composition was obtained by the formulation shown in Table 3. The numerical values in the table indicate the parts by weight in the formulation.

This epoxy resin composition was molded at 175 ° C., post-cured at 200 ° C. for 5 hours to obtain a cured product test piece, and then subjected to various physical property measurements. The results are shown in Table 4.

Claims (7)

The phenol compound represented by the following general formula (1) and the aromatic vinyl compound represented by the following general formulas (2) and (3) (however, represented by the general formula (3) among all aromatic vinyl compounds). The proportion of the aromatic vinyl compound is in the range of 15 to 45 wt%), which is obtained by reacting in the presence of an acid catalyst .

(R ₁ indicates hydrogen .)

The following general formula (4)

(R ₁ represents hydrogen , R ₂ represents a substituent represented by the formula (a), R ₃ and R ₄ represent hydrogen or a methyl group, and n represents a number from 0 to 20 and p. Indicates a number of 0.1 to 3.0.)
An epoxy resin characterized in that the hydroxy group of the polyvalent hydroxy resin is made into a glycidyl group by reacting the polyvalent hydroxy resin represented by (1) with epichlorohydrin. The hydroxyl group equivalent of the multivalent hydroxy resin is 200 to 500 g / eq. The epoxy resin according to claim 1, wherein the epoxy resin is in the range of 1. The following general formula (5) in the multivalent hydroxy resin

(Here, p indicates a number of 0.1 to 3.0, and R ₁ indicates hydrogen .)
The first or second claim, wherein the content of the unit price hydroxy compound represented by is 3% to 20% in terms of area percentage when detected by gel permeation chromatography (GPC; RI). Epoxy resin. The phenol compound represented by the following general formula (1) and the aromatic vinyl compound represented by the following general formulas (2) and (3) (however, represented by the general formula (3) among all aromatic vinyl compounds). The ratio of the aromatic vinyl compound is in the range of 15 to 45 wt%.) Is reacted at a reaction temperature of 40 to 180 ° C. in the presence of an acid catalyst of 10 to 1000 wtppm, and is represented by the formula (a). The substituent is added to the benzene ring of the phenol compound to obtain a polyvalent hydroxy resin represented by the following general formula (4), and the polyvalent hydroxy resin is reacted with epichlorohydrin to obtain the hydroxy of the polyvalent hydroxy resin. A method for producing an epoxy resin, wherein the group is a glycidyl group.

(R ₁ indicates hydrogen .)

(R ₁ represents hydrogen , R ₂ represents a substituent represented by the formula (a), R ₃ and R ₄ represent hydrogen or a methyl group, and n represents a number from 0 to 20 and p. Indicates a number of 0.1 to 3.0.) The claim is characterized in that 0.1 to 1.0 mol of an aromatic vinyl compound represented by the general formula (2) is reacted with 1 mol of the hydroxy group of the phenol compound represented by the general formula (1). The method for producing an epoxy resin according to 4. An epoxy resin composition comprising an epoxy resin and a curing agent, wherein the epoxy resin according to any one of claims 1 to 3 is blended as an essential component. An epoxy resin cured product obtained by curing the epoxy resin composition according to claim 6.

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