JP2017066268A - Polyhydric hydroxy resin, epoxy resin, methods of producing them, epoxy resin composition and cured article thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an epoxy resin, a polyhydric epoxy resin and a composition thereof, providing a cured article excellent in flowability, moisture resistance, high temperature low elasticity, fire retardance, low dielectric property or the like and suitable for applications such as encapsulation of electronic components, a circuit board material and a composite material.SOLUTION: The polyhydric hydroxy resin is provided which is obtained by reacting a phenol compound with an aromatic vinyl compound containing divinyl benzene and ethylvinylbenzene in the presence of an acid catalyst of 10 to 1000 wtppm at a reaction temperature of 40 to 180°C and in which a part of phenol core is substituted by an ethyl phenethyl group, a method of producing the polyhydric hydroxy resin and an epoxy resin obtained by epoxidizing an OH group of the polyhydric hydroxy resin by epichlorohydrin are also provided.SELECTED DRAWING: None

Description

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

  Epoxy resins have been used in a wide range of industrial applications, but their required performance has become increasingly sophisticated in recent years. For example, there is a semiconductor sealing material in a typical field of a resin composition mainly composed of an epoxy resin, but as the integration degree of semiconductor elements is improved, the package size is becoming larger and thinner, and the mounting method is also increased. 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 reducing moisture absorption, improvement in adhesion and adhesion at the interface between different materials such as lead frames and chips is strongly demanded. Similarly, for circuit board materials, in addition to improving low heat absorption, high heat resistance, and high adhesion from the viewpoint of improving solder heat resistance, it is desirable to develop materials with excellent low dielectric properties from the viewpoint of reducing dielectric loss. Yes. In order to meet these requirements, various new structures of epoxy resins and curing agents have been studied. Furthermore, recently, from the viewpoint of reducing environmental impact, there has been a movement to eliminate halogen-based flame retardants, and epoxy resins and curing agents with more excellent flame retardancy have been demanded.

  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 novolac 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 crosslinking proceeds. Therefore, it cannot be used as an epoxy resin curing agent or modified to be used as an epoxy resin, and it cannot be used for an electronic material substrate that requires solvent solubility. Patent Document 2 discloses a method for producing a phenol aralkyl resin in which phenol and divinylbenzene having a purity of 90% by weight or more are reacted. 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 molecular weight and polyfunctionalization, it was difficult to reduce the dielectric constant. Furthermore, Patent Document 3 discloses a polyvalent hydroxy resin obtained by reacting a phenol novolac resin with styrene, but it has not been sufficient from the viewpoint of hygroscopicity and heat resistance.

Japanese Patent Laid-Open No. 5-117337 JP-A-8-73570 JP 2012-57079 A

  The object of the present invention is to provide a polyvalent hydroxy resin having excellent fluidity and excellent properties such as moisture resistance, high temperature and low elasticity, flame retardancy, and low dielectric properties in applications such as lamination, molding, casting and adhesion. Providing epoxy resin, sealing fluid and circuit board materials, composites that provide cured products with excellent fluidity, moisture resistance, low elasticity, flame resistance, and low dielectric properties The object is to provide an epoxy resin composition useful for materials and 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). It is a polyvalent hydroxy resin characterized by being expressed.

（Ｒ₁は水素又は炭素数１〜６の炭化水素基を示す。）

(R ₁ represents 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 represents 0-20. In addition, p is an average number of substitution per benzene ring substituted by R ₂ and represents a number of 0.1 to 3.0.)

  As a preferable embodiment of the polyvalent hydroxy resin, the hydroxyl equivalent is 200 to 500 g / eq. Or the content rate of the unit price hydroxy compound represented by the following general formula (5) is 3% to 20% as an 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 are the same as those in the general formula (4).)

  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 combined in the presence of 10 to 1000 wtppm of an acid catalyst. The polyhydric hydroxy resin represented by the above general formula (4), which is reacted at a reaction temperature of 40 to 180 ° C. to add the substituent represented by the above formula (a) to the benzene ring of the phenol compound. It is a manufacturing method.

  In the manufacturing method of the said polyvalent hydroxy resin, 0.1-1.0 mol of aromatic vinyl compounds represented by General formula (2) with respect to 1 mol of hydroxy groups of the phenolic compound represented by General formula (1). It is better to react.

  Moreover, this invention is an epoxy resin composition which consists of said polyhydric hydroxy resin as an essential component in the epoxy resin composition which consists of an epoxy resin and a hardening | curing agent as a part or all of a hardening | curing agent. Furthermore, this invention is an epoxy resin hardened | cured material formed by hardening | curing this epoxy resin composition.

  Moreover, this invention is an epoxy resin characterized by being obtained by reaction with the said polyvalent hydroxy resin and epichlorohydrin. Furthermore, the present invention relates to an epoxy resin composition comprising an epoxy resin and a curing agent, an epoxy resin composition comprising the epoxy resin as an essential component, and an epoxy resin cured product obtained by curing the epoxy resin composition. It is.

  The cured epoxy resin obtained 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 provides excellent fluidity during molding. Therefore, the epoxy resin composition of the present invention can be suitably used for a power semiconductor sealing material and a high-frequency circuit board material.

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

  First, a method for producing the polyvalent 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 the presence of 10 to 1000 wtppm of an acid catalyst. Then, the reaction is carried out at a reaction temperature of 40 to 180 ° C. to produce a polyvalent hydroxy resin represented by the general formula (4).

The phenol compound used in the method for producing DVBN-P of the present invention is a phenol compound represented by the above general formula (1).
In the general formula (1), R ₁ represents a hydrocarbon group having 1 to 6 carbon hydrogen or carbon. Suitable phenol 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 general formulas (2) and (3).
Here, DVB and EVB may each be a meta isomer, a para isomer, an ortho isomer, or an isomer mixture. DVB has a meta isomer as a main component, and the meta isomer concentration is preferably 40% or more of all DVB isomers. More preferably, it is 50% or more. EVB has a meta isomer as a main component, and the meta isomer 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, considering the handleability of the resulting resin, the moldability at the time of making the epoxy cured product, and the balance of curable properties. preferable. More preferably, it is the range of 15-45 wt%, More preferably, it is the range of 20-40 wt%. The ratio of DVB is preferably in the range of 50 to 90 wt% in the wholly aromatic vinyl compound, and is in the range of 55 to 85 wt%.

  In addition, the phenol compound represented by the above general formula (1) and the ratio of DVB used are phenol compounds in consideration of the handleability of the resulting resin, the moldability when creating an epoxy cured product, and the balance of curable physical properties. The mole ratio of DVB to 1 mole is preferably in the range of 0.1 to 1.0, more preferably in the range of 0.2 to 1.0 mole, and still more preferably in the range of 0.3 to 0.8 mole.

DVB acts as a crosslinking agent because it provides a unit (α-dimethylxylylene unit) for bonding phenol rings in the above general formula (4). On the other hand, EVB gives a group R ₂ substituted on the phenol ring, that is, a substituent (ethylstyrenyl group) represented by the formula (a). The substitution position of this substituent is mainly an ortho and / or para position in the vacant 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 performed in the presence of an acid catalyst. The acid catalyst can be appropriately selected from known inorganic acids and organic acids. For example, mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid, organic acids such as formic acid, oxalic acid, trifluoroacetic acid, p-toluenesulfonic acid, dimethyl sulfuric acid, diethyl sulfuric acid, zinc chloride, aluminum chloride, iron chloride, trifluoride. Examples thereof include Lewis acids such as boron fluoride or ion exchange resins, activated clays, silica-alumina, solid acids such as zeolite, and the like. The amount of the acid catalyst used may be 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.

  Moreover, this reaction is normally performed at 10-250 degreeC for 1 to 20 hours. Further, during the reaction, alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, ethyl cellosolve, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethyl ether, diethyl ether, 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 raw materials are charged together and reacted at a predetermined temperature as it is, or a phenol compound and an acid catalyst are charged, and an aromatic vinyl compound is maintained at a predetermined temperature. A method of reacting while dropping is generally used. Under the present circumstances, dripping time is 1 to 10 hours normally, and 5 hours or less are preferable. After the reaction, if a solvent is used, if necessary, after removing the acid catalyst component, the solvent and unreacted substances can be distilled off to obtain the polyvalent hydroxy resin of the present invention. The polyvalent hydroxy resin represented by the general formula (4), which is the target product, can be obtained by distilling off the unreacted product.

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

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

  Furthermore, in DVBN-P of this invention, by adding EVB, although molecular weight increases, the melt viscosity range suitable for epoxy cured material preparation etc. can be maintained from introduction | transduction of a flexible chain structure. This indicates good flowability when used as a semiconductor sealing material, and good moldability is possible. When used as a circuit board material, it can improve solubility in organic solvents. is there. In addition, they contribute to low functionality and improve various physical properties, for example, flame retardancy, further low water absorption and low dielectric properties, and thus materials having excellent reliability can be obtained.

  The thus obtained hydroxyl group equivalent of DVBN-P of the present invention is 200 to 500 g / eq. It is good to exist in the range, More preferably, it is 230-400 g / eq. Range. If the hydroxyl equivalent is lower than this range, it is difficult to obtain a high level of flame retardancy. .

  Moreover, the melt viscosity at 150 ° C. of DVBN-P of the present invention is preferably in the range of 0.01 to 10.0 Pa · s. From the viewpoint of workability, the melt viscosity is preferably as low as possible within the above range.

  Furthermore, the softening point is preferably 40 to 150 ° C, and preferably in the range of 50 to 100 ° C. Here, the softening point is measured based on the ring and ball method of JIS-K-2207. When lower than this, when this is mix | blended with an epoxy resin composition, the heat resistance of hardened | cured material will fall, and when higher than this, the fluidity | liquidity at the time of shaping | molding will fall.

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

  n is the number of repetitions, and n is any one compound of 1 to 20 or a mixture thereof, or means 0 to 20 as an average (number average). N as an average is preferably 2 to 10. Moreover, since an average (number average) is calculable from the said epoxy equivalent, preferable n is also understood from it.

  And when this DVBN-P is measured by gel permeation chromatography (GPC; RI), the unit price hydroxy compound in the general formula (5) is preferably in the range of 1% to 25% in area%. . More preferably, it is in the range of 3% to 20%. This unit price hydroxy compound corresponds to a compound in which n is 0 in the general formula (4), and can be said to be a compound not crosslinked by DVB. When the content of the unit price hydroxy compound is less than this range, the property derived from the functional group concentration remains unimproved. When the content is more than this range, the functional group density is too low and the curability is low. There is a tendency to decrease. In the present invention, the hydroxyl equivalent of DVBN-P can be adjusted 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 is excellent in flame retardancy and reliability in applications such as semiconductor sealing materials and circuit board materials. Give things. This means that when used as a semiconductor sealing material, good moldability is possible due to fluidity, and when used as a circuit board material, 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, flame retardancy, further low water absorption and low dielectric property.

Next, the polyvalent hydroxy resin of the present invention will be described.
The polyvalent hydroxy resin of the present invention is represented by the 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 reacting the phenol compound with the aromatic vinyl compounds represented by the general formulas (2) and (3) simultaneously.

  That is, the hydroxyl group equivalent, melt viscosity, softening point, and content of the unit price hydroxy compound of the polyvalent hydroxy resin of the present invention are preferably in the above ranges. Furthermore, 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 glycidyl etherifying the OH group of the polyvalent hydroxy resin (DVBN-P) represented by the general formula (4).

  The DVBN-E of the present invention can be obtained by a method of reacting DVBN-P with epichlorohydrin, or reacting DVBN-P with an allyl halide to form 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 the above DVBN-P is dissolved in excess epichlorohydrin, it is 20 to 150 ° C., preferably 30 to 80 ° C. in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. The method of making it react for 10 hours is mentioned. The amount of alkali metal hydroxide used in this case 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 of 1 mol of hydroxyl group in DVBN-P, but usually 1.5 to 30 mol, preferably 2 to 15 mol, based on 1 mol of hydroxyl group in DVBN-P. It is a range. After completion of the reaction, excess epichlorohydrin is distilled off, the residue is dissolved in a solvent such as toluene, methyl isobutyl ketone, filtered, washed with water to remove inorganic salts, and then the target epoxy is removed by distilling off the solvent. 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) The composition which mix | blended the said DVBN-E as a part or all of an epoxy resin.
2) The composition which mix | blended said DVBN-P as a part or all of a hardening | curing agent.
3) The composition which mix | blended the said DVBN-E and DVBN-P as some or all of an epoxy resin and a hardening | curing agent.

  In the case of the above compositions 2) and 3), the amount of DVBN-P is usually 2 to 200 parts by weight, preferably 5 to 120 parts by weight, based on 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 amount of DVBN-P is usually blended in consideration of the equivalent balance between the OH groups of DVBN-P and the epoxy groups in the epoxy resin. The equivalent ratio of the epoxy resin and the curing agent is usually in the range of 0.2 to 5.0, preferably in the range of 0.5 to 2.0. If it is larger or smaller than this, the curability of the epoxy resin composition is lowered, and the heat resistance, mechanical strength and the like of the cured product are lowered.

  A curing agent other than DVBN-P can be used in combination as a curing agent. The blending amount of the other curing agent is determined so that the blending amount of DVBN-P is usually 2 to 200 parts by weight, preferably 5 to 80 parts by weight with respect to 100 parts by weight of the epoxy resin. Is done. If the amount of DVBN-P is less than this, the effect of improving low hygroscopicity, adhesion and flame retardancy 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.

  As a curing agent other than DVBN-P, any of those generally known as curing agents for epoxy resins can be used, and examples thereof include dicyandiamide, acid anhydrides, polyhydric phenols, aromatic and aliphatic amines. Among these, polyhydric phenols are preferably used as a curing agent in a field where high electrical insulation properties such as a semiconductor sealing material are required. Below, the specific example of a hardening | curing agent is shown.

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

  Examples of the polyhydric phenols include divalent phenols such as bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4′-biphenol, 2,2′-biphenol, hydroquinone, resorcin, and naphthalenediol, or , Tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol novolak, o-cresol novolak, naphthol novolak, polyvinylphenol, 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, There are polyhydric phenolic compounds synthesized by a condensing agent such as formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, p-xylylene dichloride, bischloromethylbiphenyl, bischloromethylnaphthalene, 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, ethylenediamine, There are aliphatic amines such as hexamethylenediamine, diethylenetriamine, and reethylenetetramine.
One or more of these curing agents can be mixed and used in the composition.

  The epoxy resin used in the composition is selected from those having two or more epoxy groups in one molecule. For example, 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 aralkyl resins such as phenol, cresol and naphthol There are glycidyl etherified compounds of the active compound. These epoxy resins can be used alone or in combination of two or more.

  In the case of the above compositions 1) and 3), another 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, all ordinary epoxy resins having two or more epoxy groups in the molecule can be used. Examples include 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 novolak and other trivalent or higher phenols, phenol-based aralkyl resins, biphenyl aralkyl resins, naphthol-based aralkyl resins Alternatively, there are glycidyl ethers derived from halogenated bisphenols such as tetrabromobisphenol A. These epoxy resins can be used alone or in combination of two or more. And in the case of the composition which uses DVBN-E of this invention as an essential component, the compounding quantity of DVBN-E is 5-100% in the whole epoxy resin, Preferably it is good to be the range of 60-100%.

  In the epoxy resin composition of the present invention, an oligomer or a polymer compound such as polyester, polyamide, polyimide, polyether, polyurethane, petroleum resin, indene resin, indene-coumarone resin, phenoxy resin, etc. is used as another modifier. You may mix | blend suitably. The addition amount 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 can contain additives such as inorganic fillers, pigments, refractory agents, thixotropic agents, coupling agents, fluidity improvers and the like. Examples of the inorganic filler include silica powder such as spherical or crushed fused silica and crystalline silica, alumina powder, glass powder, mica, talc, calcium carbonate, alumina, hydrated alumina, and the like. A preferable blending amount when used for a stopper is 70% by weight or more, and more preferably 80% by weight or more.

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

  Furthermore, a curing accelerator can be used in the epoxy resin composition of the present invention as necessary. Examples include amines, imidazoles, organic phosphines, Lewis acids, etc., specifically 1,8-diazabicyclo (5,4,0) undecene-7, triethylenediamine, benzyldimethylamine, 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, and phenylphosphine, tetraphenylphosphonium tetraphenylborate, tetraphenyl Tetraphenyl such as ruphosphonium / ethyltriphenylborate, tetrabutylphosphonium / tetrabutylborate, tetrasubstituted phosphonium / tetrasubstituted borate, 2-ethyl-4-methylimidazole / tetraphenylborate, N-methylmorpholine / tetraphenylborate, etc. There is boron salt. The addition amount 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, etc. can be used.

  The epoxy resin composition of the present invention is made into a varnish in which an organic solvent is dissolved, and then impregnated into a fibrous material such as glass cloth, aramid nonwoven fabric, polyester nonwoven fabric such as liquid crystal polymer, and the like, and then the solvent is removed. It can be. Moreover, it can be set as a laminated body by apply | coating on sheet-like materials, such as copper foil, stainless steel foil, a polyimide film, and a polyester film depending on the case.

  If the epoxy resin composition of the present invention is cured by heating, an epoxy resin cured product can be obtained, 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, transfer molding or the like. The temperature at this time is usually in the range of 120 to 220 ° C.

Hereinafter, the present invention will be described more specifically with reference to examples.
The evaluation method of resin is shown below.

1) GPC measurement Tosoh Corporation TSKgelG4000HXL × 1 and TSKgelG2000HXL × 3 in series were used, and the column temperature was 40 ° C. Tetrahydrofuran was used as the eluent, the flow rate was 1 ml / min, and an RI (differential refractometer) detector was used as the detector. 0.03 g of sample was dissolved in 10 ml of THF. The area percentage corresponding to each n in the general formula was determined from the measured molecular weight distribution. The identification of each peak was related to the FD-MS measurement result.

2) FD-MS
It measured according to the electrolytic desorption ionization mass spectrometry using the JEOL JMS-AX505HA apparatus. Using the obtained FD-MS spectral data and gel permeation chromatography (GPC) measurement results, the molecular weight distribution and each peak thereof were identified.

3) Softening point It measured by the ring and ball method according to JIS-K-2207 using the automatic softening point apparatus (Amiho Co., Ltd. make, ASP-M4SP).

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, 1,4-dioxane is used as a solvent, acetylation is carried out with 1.5 mol / L acetyl chloride at 100 ° C. for 60 minutes, and excess acetyl chloride is removed with water. And titrated using 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 potential was measured 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 allowed to stand for one week. ◯: Uniform dissolution, Δ: Turbidity in solution, x: Precipitates.

Example 1
To a 1 L four-necked flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel, 150 g of phenol and 0.045 g of 50% paratoluenesulfonic acid were added, and the temperature was raised to 100 ° C. Next, while stirring at 100 ° C., 148 g of 63% DVB (including 55 g of EVB) was dropped as an aromatic vinyl compound over 2 hours to be reacted. Furthermore, the reaction was completed by maintaining the temperature at 150 ° C. Thereafter, the temperature was lowered to 85 ° C. and washing was performed about 4 times. Subsequently, after unreacted substances were distilled off under reduced pressure, 252 g of a polyvalent hydroxy resin was obtained. Its softening point is 59 ° C., melt viscosity at 150 ° C. is 0.06 Pa · s, and hydroxyl 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 polyvalent hydroxy resin is referred to as DVBN-P1. The GPC chart of DVBN-P1 is shown in FIG. 1, and the FD-MS chart is shown in FIG.

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

Comparative Example 1
To a 1 L four-necked flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel, 150 g of phenol and 0.03 g of 50% paratoluenesulfonic acid were added, and the temperature was raised to 100 ° C. Next, 185 g of a polyvalent 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. DVBN-P3 has a softening point of 76 ° C., a melt viscosity at 150 ° C. of 0.18 Pa · s, and a hydroxyl group equivalent of 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)
To a 1 L four-necked flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel, 150 g of phenol and 0.04 g of 50% paratoluenesulfonic acid were added, and the temperature was raised to 100 ° C. Next, with stirring at 100 ° C., 373 g of a polyvalent hydroxy resin (DVBN-P4) was obtained in the same manner as in Example 1 except that 255% DVB 255 g (including EVB 99 g) was used. DVBN-P4 has a softening point of 76 ° C., a melt viscosity at 150 ° C. of 0.40 Pa · s, and a hydroxyl group equivalent of 314 g / eq. The GPC area% of the unit price hydroxy resin was 7.4.

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

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

Synthesis example 4
To a 1 L four-necked flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel, 150 g of phenol and 0.03 g of 50% paratoluenesulfonic acid were added, and the temperature was raised to 100 ° C. Next, 262 g of polyvalent hydroxy resin (DVBN-P7) was obtained in the same manner as in Example 1 except that 151 g (including 6 g of EVB) of 96% DVB 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 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 stirred and dissolved in a 1 L four-necked flask equipped with a stirrer, a condenser, a thermometer, and a dropping funnel. After uniformly dissolving, maintaining at 65 ° C. under a reduced pressure of 130 mmHg, 32 g of a 48% sodium hydroxide aqueous solution is dropped over 4 hours, and water and epichlorohydrin refluxed during the dropping are separated in a separation tank, and epichlorohydrin is a reaction vessel. The water was removed from the system and reacted. After completion of the reaction, the salt produced by filtration was removed, and after further washing with water, 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 four-necked flask equipped with a stirrer, a condenser, a thermometer, and a dropping funnel and dissolved by stirring. After uniformly dissolving, 107 g of epoxy resin (DVBN-E2) was obtained in the same manner as in Example 3 except that 35 g of 48% sodium hydroxide aqueous solution was added dropwise over 4 hours while maintaining at 65 ° C. under a reduced pressure of 130 mmHg. . 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 added to a 1 L four-necked flask equipped with a stirrer, a condenser, a thermometer, and a dropping funnel and dissolved by stirring. After uniform dissolution, 101 g of epoxy resin (DVBN-E3) was obtained in the same manner as in Example 3 except that 39 g of 48% aqueous sodium hydroxide solution was added dropwise over 4 hours while maintaining at 65 ° C. under a 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 stirred and dissolved in a 1 L four-necked flask equipped with a stirrer, a condenser, a thermometer, and a dropping funnel. After uniform dissolution, 104 g of epoxy resin (DVBN-E4) was obtained in the same manner as in Example 3 except that 42 g of 48% aqueous sodium hydroxide solution was added dropwise over 4 hours while maintaining at 65 ° C. under a reduced pressure of 130 mmHg. . 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. FIG. 7 shows a GPC chart of DVBN-E4, and FIG. 8 shows an FD-MS chart.

Examples 6 to 10 and Comparative Examples 3 to 5
An o-cresol novolac type epoxy resin (OCNE; epoxy equivalent 202, softening point 74 ° C.) was used as an epoxy resin component, and Examples 1, 2, Comparative Example 1, and Synthesis Examples 1, 2, 3, 4 were used as curing agents. 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 formulation shown in Table 1 to obtain an epoxy resin composition. This epoxy resin composition was molded at 175 ° C. and post-cured at 200 ° C. for 5 hours to obtain a cured product test piece, which was then subjected to various physical property measurements. The results are shown in Table 2. The number of the compounding amount is part by weight.

Cured product evaluation method 1) Gel time (GT)
Add the epoxy resin composition onto the plate of the gelation tester (Nisshin Kagaku Co., Ltd.) that has been heated to 175 ° C., and stir at a speed of 2 revolutions per second using a fluororesin rod. The gelation time required for the epoxy resin composition to cure was examined.

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

3) Glass transition point (Tg) and linear expansion coefficient (CTE) by TMA measurement
Using a TMA120C type thermomechanical measuring device manufactured by Seiko Instruments Inc., Tg was obtained under the condition of a temperature rising rate of 10 ° C./min. 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), viscoelasticity (ε ′) by DMA measurement
Using a Seiko Instruments DMA thermomechanical measuring device, Tg was determined under the condition of a heating 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) and 10 wt% weight loss temperature (Td10) by TGDTA measurement
A 5 wt% weight reduction temperature (Td5) and a 10 wt% weight reduction temperature (Td10) were obtained from a weight reduction curve under the condition of a temperature increase rate of 10 ° C./min using a Seiko Instruments TGDTA thermomechanical measurement apparatus.

6) Water absorption rate The conditions of 25 ° C. and 50% relative humidity were taken as the standard state, and the weight change rate after 100 hours of moisture absorption at 85 ° C. and 85% relative humidity.

7) Capacitance method dielectric constant (Dk), dielectric loss tangent (Df)
Using the impedance material analyzer apparatus made from Agilent, the dielectric constant and dielectric loss tangent of the hardened | cured material after storage in a constant temperature and humidity chamber of 25 degreeC and 60% of humidity were measured at 1 GHz.

Examples 11-14 and Comparative Examples 5-7
As the epoxy resin component, DVBN-E1, DVBN-E2, DVBN-E3 obtained in Examples 3, 4, and 5, DVBN-E4 obtained in Comparative Example 2, 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.), as a curing agent component, phenol novolac resin (PN; OH equivalent 108, softening point 90 ° C.), or DVBN-P5 synthesized in Synthesis Example 2 was used. Furthermore, 2-ethyl-4-methylimidazole was used as a curing accelerator, and an epoxy resin composition was obtained with the formulation shown in Table 3. The numerical value in a table | surface shows the weight part in a mixing | blending.

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

Claims (10)

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),

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

The following general formula (4)

(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 or a methyl group, and n represents 0 ) Represents a number of ˜20, and p represents a number of 0.1 to 3.0.
The polyvalent hydroxy resin characterized by these.   Hydroxyl equivalent weight is 200 to 500 g / eq. The polyvalent hydroxy resin according to claim 1, wherein the polyvalent hydroxy resin is in the range of The following general formula (5)

(Here, p represents a number of 0.1 to 3.0, and R ₁ represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms.)
The content rate of the unit price hydroxy compound represented by the formula is 3% to 20% as an area percentage when detected by gel permeation chromatography (GPC; RI). Polyvalent hydroxy resin. A phenol compound represented by the following general formula (1) and an aromatic vinyl compound represented by the following general formulas (2) and (3) are reacted at a reaction temperature of 40 to 180 in the presence of an acid catalyst of 10 to 1000 wtppm. A method for producing a polyvalent hydroxy resin represented by the following general formula (4), wherein the substituent represented by the formula (a) is added to the benzene ring of the phenol compound by reacting at a temperature of 0 ° C.

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

(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 or a methyl group, and n represents 0 ) Represents a number of ˜20, and p represents a number of 0.1 to 3.0.   The aromatic vinyl compound represented by the general formula (2) is allowed to react with 1 mol of the hydroxy group of the phenol compound represented by the general formula (1). 4. A method for producing a polyvalent hydroxy resin according to 4.   An epoxy resin composition comprising an epoxy resin and a curing agent, wherein the polyvalent hydroxy resin according to any one of claims 1 to 3 is an essential component as part or all of the curing agent. object.   A cured epoxy resin obtained by curing the epoxy resin composition according to claim 6.   An epoxy resin, wherein the polyvalent hydroxy resin according to any one of claims 1 to 3 is reacted with epichlorohydrin to convert the hydroxy group of the polyvalent hydroxy resin into a glycidyl group.   An epoxy resin composition comprising an epoxy resin and a curing agent, wherein the epoxy resin according to claim 8 is blended as an essential component.   An epoxy resin cured product obtained by curing the epoxy resin composition according to claim 9.

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