KR102047682B1

KR102047682B1 - Epoxy resin mixture, epoxy resin composition, and cured product thereof

Info

Publication number: KR102047682B1
Application number: KR1020157008271A
Authority: KR
Inventors: 마사타카 나카니시; 세이지 에바라; 카즈마 이노우에
Original assignee: 닛뽄 가야쿠 가부시키가이샤
Priority date: 2012-11-08
Filing date: 2013-11-07
Publication date: 2019-11-22
Also published as: CN104769000A; CN104769000B; KR20150082188A; JPWO2014073600A1; WO2014073600A1; TWI572666B; TW201439188A; JP6324317B2

Abstract

It aims at providing the epoxy resin mixture and epoxy resin composition which are excellent in fluidity | liquidity, and a hardened | cured material in the said hardened | cured material gives a hardened | cured material excellent in heat resistance and a flame retardance. The epoxy resin mixture of the present invention is 1,1'-bis (2-glycidyloxynaphthyl) and substituted (or unsubstituted) 4,4'-bisglycidyloxybiphenyl (wherein the substituent And in the ring, the number of substituents is 4 or less, and the number of carbons is 4 or less).

Description

Epoxy resin mixture, epoxy resin composition, and cured product thereof {EPOXY RESIN MIXTURE, EPOXY RESIN COMPOSITION, AND CURED PRODUCT THEREOF}

This invention relates to the epoxy resin mixture which gives the composition excellent in fluidity | liquidity, and the hardened | cured material excellent in flame retardancy and heat resistance.

The present invention also relates to an electric and electronic material application requiring high performance, in particular an epoxy resin mixture, an epoxy resin composition, and a cured product thereof suitable as a sealing agent for semiconductors, a thin film substrate material.

Epoxy resin compositions are widely used in the fields of electrical and electronic components, structural materials, adhesives, paints and the like due to their workability and excellent electrical properties, heat resistance, adhesion, moisture resistance (water resistance), and the like of the cured product.

However, in recent years in the field of electric and electronics, the development of high purity resin composition, low viscosity to high moisture resistance, adhesion, dielectric properties, filler (inorganic or organic filler), reactivity to shorten the molding cycle It is required to further improve all the characteristics such as the improvement. Moreover, as a structural material, the material which is lightweight and excellent in mechanical properties is calculated | required in aerospace material, leisure, sports equipment use, etc. In particular, in the field of semiconductor sealing and substrates (substrate itself or its surrounding materials), as the semiconductor changes, it becomes complicated to become thin, stacked, systemized, and three-dimensional. It has been going on, causing high wire inactivity to cause wire sweeping. In addition, it has been adversely affected to the connecting portion of the wire.

Moreover, in the flip chip type package, the method called MUF attracts attention from the viewpoint of a cheap manufacturing method, and seals at once without using an underfill. In this application, it is necessary for the resin to escape through a very narrow gap between the chip and the package substrate, and the refinement of the filler becomes important, and this refinement causes an increase in the viscosity of the system and causes voids.

In addition, in the sealing resin used for the redistribution layer such as the wafer level package, the correlated insulating film used in the buildup layer, etc., the thickness of the layer is thin and the filling of the fine filler is required to lower the linear expansion rate. Therefore, also in this use, the viscosity reduction of a resin composition is required similarly to the above.

"2008 STRJ Reporting Semiconductor Roadmap Expert Committee Report 2008", Chapter 8, p1-1, [online], March 2009, Japan Electronics and Information Technology Industries Association Association Retrieved 30 May 2012], <http://strj-jeita.elisasp.net/strj/nenjihoukoku-2008.cfm> Takakura Nobuyuki et al., Matsushita electrician notation car-related device technology vehicle high temperature operation IC, 74, Japan, May 31, 2001, pages 35-40

Although various methods can be mentioned as a method of low viscosity of a resin composition, Although the low molecular weight of an epoxy resin is generally used as a method of low viscosity of a resin composition, when molecular weight of an epoxy resin is made low, heat resistance falls and at the room temperature Since the shape of is likely to have fluidity, handling at room temperature is difficult, and stickiness emerges when the composition is used, making storage and handling difficult. Moreover, since the ratio of the epoxy part (aliphatic chain) in a molecule | numerator increases, it becomes easy to thermally decompose relatively, and it is easy to have a bad influence in terms of flame retardance.

That is, an object of the present invention is to provide an epoxy resin mixture capable of providing an epoxy resin composition capable of providing a cured product having excellent fluidity and excellent heat resistance and flame retardancy, an epoxy resin composition containing the same, and a cured product thereof. do.

MEANS TO SOLVE THE PROBLEM The present inventors came to complete this invention, as a result of earnestly examining in view of the above fact.

That is, the present invention

(One)

4,4'-bisglycidyloxybiphenyl substituted with 1,1'-bis (2-glycidyloxynaphthyl) and a substituted (or unsubstituted), provided that the substituent Epoxy resin mixture, wherein the number is 4 or less, and the number of carbons is 4 or less),

(2)

The ratio of 1,1'-bis (2-glycidyloxynaphthyl) (A) and substituted (or unsubstituted) 4,4'-glycidyloxybiphenyl (B) according to the above (1) The epoxy resin mixture which is A / B = 1-10,

(3)

In the above (1), 4,4'-biphenol of vinyl and substituted (or unsubstituted) (However, when the substituent has in the aromatic ring, the number of substituents is 4 or less, carbon number is 4 or less) ), An epoxy resin mixture obtained by reacting with epihalohydrin,

(4)

Epoxy resin composition which makes it essential to contain the epoxy resin mixture and hardening | curing agent in any one of said (1)-(3),

(5)

It is essential to contain the epoxy resin mixture and polymerization catalyst in any one of said (1)-(3), The epoxy resin composition characterized by the above-mentioned,

(6)

The hardened | cured material characterized by hardening the epoxy resin composition as described in said (4) or (5) is provided.

(Effects of the Invention)

The epoxy resin mixture of the present invention is very low in viscosity and is an epoxy resin that contributes to the fluidity of the composition, and the cured product is excellent in heat resistance and flame resistance. Therefore, it is useful for various composite materials, adhesives, paints and the like, including insulating materials for electrical and electronic components, laminated boards (printed wiring boards, build-up boards, etc.) and CFRP. In particular, it is very useful for the semiconductor sealing material which protects a semiconductor element.

The epoxy resin mixture of the present invention has 1,1'-bis (2-glycidyloxynaphthyl) and substituted or unsubstituted 4,4'-bisglycidyloxybiphenyl (wherein the aromatic ring has a substituent) In this case, the number of substituents is 4 or less, and the carbon number is 4 or less).

1,1'-bis (2-glycidyloxynaphthyl) is a reactant of binol and epihalohydrin, and also 4,4'-bisglycidyloxybiphenyl (where the aromatic ring has a substituent In this case, the number of substituents is 4 or less, and the number of carbons is 4 or less, 4,4'-biphenol (However, when having an substituent on the aromatic ring, the number of substituents is 4 or less, carbon number is 4 And epihalohydrin.

Here, as a substituent, a C1-C4 alkyl group and an alkoxy group are preferable, A methyl group, an ethyl group, a propyl group, isopropyl group, a butyl group, a methoxy group, an ethoxy group, a propoxy group, etc. are mentioned specifically ,.

As such substituted or unsubstituted 4,4'-bisglycidyloxybiphenyl, the following structure is mentioned specifically ,.

[Wherein R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group, G represents a glycidyl group, and t represents an integer of 1 to 4]

And the said substituted or unsubstituted 4,4'- biphenol can specifically mention the following structure.

[Wherein R and t represent the same meaning as described above]

Although stereoisomer exists in a vinyl, you may use either a chiral racemate in order to obtain the epoxy resin mixture of this invention. In addition, the purity is preferably 90 area% or more by GPC, more preferably 93 area% or more, even more preferably 95 area% or more, particularly preferably 98 area% or more. Examples of the impurity include a quinone structure and a naphthol compound of a raw material, but these are each 2% by area or less, preferably 1% by area or less. Purity can be controlled by crystallization or washing. When this purity is low, the characteristic of the epoxy resin mixture of this invention obtained may fall. In addition, the drying loss is preferably 0.2% or less, more preferably 0.1% or less. When there is much drying loss, a manufacturing line may be contaminated in a manufacturing process. As for melting | fusing point, 200-220 degreeC is preferable, More preferably, it is 212-219 degreeC. These commercial items can be obtained from Sigma-Aldrich Co., LLC., SR-CHEM.

4,4'-biphenol (However, when the substituent has in the aromatic ring, the number of substituents is 4 or less, carbon number is 4 or less) is a compound having a 4,4'-biphenol as a basic skeleton, Specific examples thereof include 4,4'-biphenol, 3,3 ', 5,5'-tetramethylbiphenyl-4,4'-diol, 3,3'-dimethylbiphenyl-4,4'-diol, and the like. Can be mentioned. In the present invention, 4,4'-biphenol, 3,3 ', 5,5'-tetramethylbiphenyl-4,4'-diol is preferable from the availability, and from the handleability of the epoxy resin mixture, 4,4'-biphenol is preferred. 4'-biphenol is preferred.

In the epoxy resin mixture of the present invention, 1,1'-bis (2-glycidyloxynaphthyl) (A) and substituted (or unsubstituted) 4,4'-bisglycidyloxybiphenyl ( When it has a substituent in the aromatic ring, the number of substituents is four or less and carbon number is four or less) As for the ratio (weight ratio) of (B), A / B = 1-10 are preferable, More preferably, it is 1.5- 7.5, Especially preferably, it is 2.0-6.0. The range seen from the viewpoint of the balance of heat resistance, flame retardancy, and fluidity is preferable.

As the shape of this epoxy resin mixture, when it is mixed homogeneously, it is preferable to have a solid resin shape with crystallinity, and the softening point at that time becomes like 70-140 degreeC from the problem of handleability and the moldability at the time of hardening. More preferably, it is 80-130 degreeC.

The epoxy resin mixture of the present invention is 1,1'-bis (2-glycidyloxynaphthyl) and substituted (or unsubstituted) 4,4'-bisglycidyloxybiphenyl (wherein the substituent In the case of having a ring, the number of substituents may be 4 or less, and the number of carbons is 4 or less) evenly mixed, and 4,4'-biphenol of vinyl and substituted (or unsubstituted) may be substituted. In the aromatic ring, the number of substituents may be 4 or less, and the number of carbons is 4 or less), and may be obtained by reacting with epihalohydrin. In the present invention, the latter is particularly preferable from the simplicity of manufacture and the connection of molecules.

Although it does not specifically limit as a method of reaction with epihalohydrin, An example of the synthesis | combining method of the epoxy resin mixture of this invention is described below.

Binol (AA) and 4,4'-biphenol in the reaction for obtaining the epoxy resin mixture of the present invention, provided that the number of substituents is 4 or less, and the number of carbons is 4 or less ) (BB) is reacted with epihalohydrin simultaneously to obtain an epoxy resin mixture. As the ratio (weight ratio) of (AA) and (BB) here, AA / BB = 1-10 are preferable, More preferably, it is 1.5-7.5, Especially preferably, it is 2.0-6.0. The range seen from the viewpoint of the balance of heat resistance, flame retardancy, and fluidity is preferable. In addition, the mixture of (AA) and (BB) is called a phenol mixture of this invention below.

As epihalohydrin in reaction which obtains the epoxy resin mixture of this invention, epichlorohydrin which is industrially available is preferable. The amount of epihalohydrin used is usually 3.0 to 15 mol, preferably 3.0 to 10 mol, more preferably 3.5 to 8.5 mol, particularly preferably 4.5 to 1 mol of the hydroxyl group of the phenol mixture of the present invention. ~ 8.5 moles.

If it is less than 3.0 mol, epoxy equivalent may become large, and workability | operativity of the epoxy resin which was possible may deteriorate, and when 15 mol is exceeded, a solvent amount may become large amount.

In the above reaction, the use of an alkali metal hydroxide is preferable for the reaction with epihalohydrin. Examples of alkali metal hydroxides that can be used include sodium hydroxide and potassium hydroxide, and solids may be used or the aqueous solution may be used. However, in the present invention, solids molded in the form of flakes from the surface of water, solubility, and handling are particularly preferred. The use of is preferred.

The use amount of alkali metal hydroxide is 0.90 to 1.5 mol normally with respect to 1 mol of hydroxyl groups of a phenol mixture, Preferably it is 0.95-1.25 mol, More preferably, it is 0.99-1.15 mol.

In order to accelerate the reaction, quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide and trimethylbenzylammonium chloride may be added as a catalyst. As the usage-amount of a quaternary ammonium salt, it is 0.1-15 g normally with respect to 1 mol of hydroxyl groups of the phenol mixture of this invention, Preferably it is 0.2-10 g.

In this reaction, in addition to the said epihalohydrin, a nonpolar proton solvent (dimethyl sulfoxide, dioxane is preferable in this invention, such as dimethyl sulfoxide, dioxane, and dimethyl imidazolidinone), and C1-C5 It is preferable to use dog alcohol together. As C1-C5 alcohol, they are alcohols, such as methanol, ethanol, and isopropyl alcohol (methanol is preferable in this invention). The usage-amount of a nonpolar proton solvent or a C1-C5 alcohol is 2-50 weight% normally with respect to the usage-amount of epihalohydrin, Preferably it is 4-25 weight%. Moreover, you may perform epoxidation, controlling water in system by azeotropic dehydration methods.

When there is much moisture in a reaction system, electrical reliability may fall in the obtained epoxy resin mixture, and it is preferable to control and synthesize moisture to 5% or less. Moreover, when an epoxy resin mixture is obtained using a nonpolar proton solvent, an epoxy resin mixture excellent in electrical reliability is obtained, and therefore a nonpolar proton solvent can be used suitably.

Reaction temperature is 30-90 degreeC normally, Preferably it is 35-80 degreeC. In particular, in the present invention, 60 ° C or more is preferable for higher purity epoxidation, and a reaction under conditions close to reflux conditions is particularly preferable. The reaction time is usually 0.5 to 10 hours, preferably 1 to 8 hours, particularly preferably 1 to 3 hours. If the reaction time is short, the reaction does not proceed to the end, and if the reaction time is long, byproducts may occur.

Epihalohydrin, a solvent, and the like are removed from the reactants of these epoxidation reactions by heating or depressurization after or without washing with water. In addition, in order to obtain an epoxy resin mixture containing less hydrolyzable halogen, the recovered epoxy resin mixture may contain a ketone compound having 4 to 7 carbon atoms (for example, methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, cyclohexanone, etc.). It is possible to dissolve using a solvent as a solvent, to add an aqueous solution of alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and to react to make sure the ring closure. In this case, the usage-amount of alkali metal hydroxide is 0.01-0.3 mol normally, Preferably it is 0.05-0.2 mol with respect to 1 mol of hydroxyl groups of the phenol mixture of this invention used for epoxidation. Reaction temperature is 50-120 degreeC normally, and reaction time is 0.5 to 2 hours normally.

After completion | finish of reaction, the produced salt is removed by filtration, water washing, etc., and the epoxy resin mixture of this invention is obtained by further distilling a solvent off under reduced pressure. Moreover, after distilling a solvent off under reduced pressure, it hold | maintains at 110-170 degreeC, and is 100 degrees C or less, More preferably, 80 degrees C or less plate-shaped object (form of plate shape, sheet shape, belt shape, etc.) It is preferable to shape | mold and take out in shapes, such as plate shape, a water droplet shape (marble shape), by casting | flow_spreading or dripping on a phase. Moreover, it does not matter also with the stepwise cooling method of cooling further at 60 degrees C or less after cooling at 80 degrees C or less.

As an external appearance of the most suitable epoxy resin mixture obtained in this invention, it has a crystalline turbid color (specifically, turbidity and not amorphous).

In the epoxy resin mixture of the present invention, 1,1'-bis (2-glycidyloxynaphthyl) and substituted (or unsubstituted) 4,4'-bisglycidyloxybiphenyl (however, In the aromatic ring, if the number of substituents is 4 or less and the number of carbons is 4 or less) at the same time, there is no particular limitation, but in the reaction under the above preferred conditions, the binol structure and the biphenol structure are- There is also a structure (C) bonded via a CH ₂ CH (OH) CH ₂ -structure. When only vinol is simply epoxidized, the structure (D) to which these are similarly bonded arises, and since it is large in molecular weight, it is easy to raise a viscosity, but when co-oxyxation as mentioned above is performed, structure (C) instead of structure (D) It is preferable in the improvement of the fluidity | liquidity made into the objective of this invention by making it easy to lower a viscosity comparatively.

Preferred resin properties of the epoxy resin mixture of the present invention include epoxy equivalent (1,1'-bis (2-glycidyloxynaphthyl), 4,4'-bisglycidyloxy, which is a mixture of the epoxy resin of the present invention obtained). It is preferable that biphenyl (and the average value of the epoxy equivalent of the said structure (C), when it contains the said structure (C)) is 190-350 g / eq., More preferably, it is 200-300 g / eq. . When epoxy equivalent exists in the said range, the epoxy resin excellent in the heat resistance of hardened | cured material and electrical reliability can be obtained. When the epoxy equivalent exceeds 350 g / eq., The compound may not contain the functional group, and many of the compounds having no functional group may be contained, and the epoxy equivalent may not decrease. In addition, most of the compounds which are not closed by these ends contain chlorine in many cases, and the use of electronic materials may cause corrosion of the glass of chlorine ions and the wiring by the same under high temperature and high humidity conditions.

The total chlorine remaining in the epoxy resin is preferably 5000 ppm or less, more preferably 3000 ppm or less, particularly 2000 ppm or less. Moreover, 5 ppm or less is preferable about chlorine ion and sodium ion, respectively, More preferably, it is 3 ppm or less. Although chlorine ions need not be described above, cations such as sodium ions are also a very important factor especially in power device applications, and are a cause of failure mode when high voltage is applied.

The epoxy resin mixture of the present invention has the form of a resin phase having a softening point. Here, as a softening point, 55-130 degreeC is preferable, More preferably, it is 60-120 degreeC. If the softening point is too low, blocking during storage may be a problem. On the contrary, when a softening point is too high, handling may fall at the time of kneading with another resin. Moreover, it is preferable that melt viscosity is 2 Pa * s or less (ICI melt viscosity 150 degreeC cornplate method). When mixing and using an inorganic material (filler etc.), fluidity | liquidity falls, and also the cloth of glass cloth etc. becomes finer and the impregnation property may fall.

Hereinafter, it describes about the epoxy resin composition (henceforth curable resin composition) of this invention containing the epoxy resin mixture of this invention.

In curable resin composition of this invention, a hardening | curing agent or a polymerization catalyst is used as an essential component.

In curable resin composition of this invention, it can be classified roughly into 2 types, and is represented by curable resin composition A and curable resin composition B below.

In curable resin composition A, it is a composition which uses the epoxy resin mixture and hardening | curing agent of this invention as an essential component.

In curable resin composition B, it is a composition which has an epoxy resin mixture and a polymerization catalyst of this invention as an essential component.

As a polymerization catalyst which curable resin composition B of this invention can contain, if it is a catalyst to superpose | polymerize with heat or light, it can use without limitation, Specifically, a hardening accelerator or an acidic curing catalyst can be used.

Specific examples of curing accelerators that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, and 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, and 1,8. Tertiary amines such as -diaza-bicyclo (5,4,0) undecene-7, phosphines such as triphenylphosphine, tetrabutylammonium salt, triisopropylmethylammonium salt, trimethyldecanylammonium salt, cetyltrimethyl Quaternary phosphonium salts such as quaternary ammonium salts such as ammonium salts, triphenylbenzylphosphonium salts, triphenylethylphosphonium salts, and tetrabutylphosphonium salts (the counter ions of quaternary salts are specifically designated as halogens, organic acid ions, hydroxide ions, etc.). Although not particularly preferred, organic acid ions, hydroxide ions are preferred), and metal compounds such as octylic acid tin and the like. When using a hardening accelerator, 0.01-5.0 weight part is used as needed with respect to 100 weight part of epoxy resins.

As an acidic curing catalyst, a cationic polymerization initiator is preferable and a light or thermal cationic polymerization initiator is especially preferable. It can be used as curable resin composition B mentioned later by mix | blending the cationic polymerization initiator activated by active energy ray and / or the cationic polymerization initiator activated by heat.

Examples of the cationic polymerization initiator for initiating the cationic polymerization of the curable resin composition B of the present invention by irradiation with an active energy ray include diazonium salt, iodonium salt, sulfonium salt, selenium salt, pyridinium salt, ferrocenium salt, phosphonium salt, and thiopy. A lignium salt etc. are mentioned, Preferably it is an iodonium salt and a sulfonium salt, More preferably, it is a diaryl iodonium salt and a dialkyl phenacyl sulfonium salt, Especially a diaryl iodonium salt can be used suitably.

When using a cationic polymerization initiator such as iodonium salts and sulfonium salts in cationically curable resin composition of the present invention, as the anion _{^{_{^{BF 4 -, AsF 6 -,}}}} SbF 6 -, PF 6 - and _{B (C 6 F 5) 4} - a can be mentioned, preferably such as is SbF ₆ ^-, PF ₆ ^- or _{B (C 6 F 5) 4} - , and particularly preferably from SbF ₆ ^- or _{B (C 6 F 5) 4} - a.

As a specific example of a photocationic polymerization initiator, bis (dodecylphenyl) iodonium hexafluoro antimonate (made by GE TOSHIBA SILICONES CO., LTD., The main component of UV-9380C), tolyl cumyl iodonium tetrakis (penta) Fluorophenyl) borate (made by ROHDIA, PHOTOINITIATO R2074), bis (alkyl (C = 10-14) phenyl iodonium) hexafluoroantimonate (photocationic polymerization initiator WPI-016 made by Wako Pure Chemical Industries, Ltd.) ), And the like.

A compound which is activated by heat to initiate cationic polymerization, that is, a thermal cationic polymerization initiator, may be used in the curable resin composition B of the present invention. As this thermocationic polymerization initiator, various onium salts, such as a quaternary ammonium salt, a phosphonium salt, and a sulfonium salt, the combination of an alkoxysilane and an aluminum complex, etc. can be illustrated. Available products include ADEKA OPTON CP-66 and ADEKA OPTON CP-77 (all trade names, manufactured by ADEKA CORPORATION), Sanaid SI-60L, Sanaid SI-80L, and Sanaid SI-100L (all trade names, SANSHIN CHEMICAL INDUSTRY CO., LTD. And CI series (made by NIPPON SODA CO., LTD.), Etc. are mentioned.

Hereinafter, curable resin composition A, B of this invention is demonstrated, respectively.

In curable resin composition A and curable resin composition B, another epoxy resin can be used together other than the epoxy resin mixture of this invention. When using together, 30 weight% or more is preferable and, as for the ratio to the total epoxy resin of the epoxy resin mixture of this invention, 40 weight% or more is especially preferable. However, when using the epoxy resin mixture of this invention as a modifier of curable resin composition, it adds in 1 to 30weight% of a ratio.

Specific examples of other epoxy resins include novolak type epoxy resins, bisphenol A type epoxy resins, biphenyl type epoxy resins, triphenylmethane type epoxy resins, and phenol aralkyl type epoxy resins. Specifically, bisphenol A, bisphenol S, thiodiphenol, fluorene bisphenol, terpendiphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3 ', 5,5'-tetramethyl- [1,1'-biphenyl] -4,4'-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4- Hydroxyphenyl) ethane, phenols (phenol, alkyl substituted phenol, naphthol, alkyl substituted naphthol, dihydroxybenzene, dihydroxynaphthalene etc.), formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxy Benzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4'-bis (chloromethyl) -1,1'-biphenyl, 4,4'-bis ( Polycondensates such as methoxymethyl) -1,1'-biphenyl, 1,4-bis (chloromethyl) benzene, 1,4-bis (methoxymethyl) benzene, and modified substances thereof, tetrabromo bisphenol A Halogenated bisphenols, such as alcohol Silsesquioxane-based epoxy resins, such as glycidyl ether derivatives, alicyclic epoxy resins, glycidylamine epoxy resins, and glycidyl ester epoxy resins derived from the above compounds (chain, cyclic, ladder, or at least two of them) Although the solid or liquid epoxy resin, such as glycidyl group and / or epoxycyclohexane structure, is mentioned for the siloxane structure of the above-mentioned mixed structure, It is not limited to these.

Hereinafter, each curable resin composition is mentioned.

Thermosetting with Curing Agent (Curable Resin Composition A)

As a hardening | curing agent which curable resin composition A of this invention contains, a phenol resin, a phenol type compound, an amine compound, an acid anhydride type compound, an amide type compound, a carboxylic acid type compound, etc. are mentioned, for example.

As a specific example of the hardening | curing agent which can be used, it is as follows.

Phenol resins, phenolic compounds; Bisphenol A, bisphenol F, bisphenol S, fluorenebisphenol, terpendiphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3 ', 5,5'-tetramethyl- [1,1 '-Biphenyl] -4,4'-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) Ethane, phenols (phenol, alkyl substituted phenol, naphthol, alkyl substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.), formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p- Hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4'-bis (chloromethyl) -1,1'-biphenyl, 4,4'-bis (methoxymethyl) Polycondensates such as -1,1'-biphenyl, 1,4'-bis (chloromethyl) benzene, 1,4'-bis (methoxymethyl) benzene, modified substances thereof, and tetrabromobisphenol A Of halogenated bisphenols, terpenes and phenols There can be a compound of the polyphenols or the like, not limited to these. These may be used independently and may use 2 or more types.

Preferable phenol resins include phenol aralkyl resins (resin having an aromatic alkylene structure), and particularly preferably a structure having at least one selected from phenol, naphthol and cresol, and the alkylene moiety serving as the linker is benzene. At least one member selected from a structure, a biphenyl structure and a naphthalene structure (specifically, xylloc, naphthol xylox, phenol biphenylene novolak resin, cresol-biphenylene novolak resin, phenol-naphthalene novolak) Resins, etc.).

Amine compounds and amide compounds; Nitrogen-containing compounds such as diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, polyamide resin synthesized by dimer of linolenic acid and ethylenediamine; Although it is mentioned, it is not limited to these. These may be used independently and may use 2 or more types.

Acid anhydride compounds and carboxylic acid compounds; Phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydro phthalic anhydride, methyltetrahydro phthalic anhydride, methylnadic acid anhydride, nadic anhydride, hexahydro phthalic anhydride, methylhexahydro phthalic anhydride, butanetetra Carboxylic acid anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane Acid anhydrides such as -1,3,4-tricarboxylic acid-3,4-anhydride; Although the carboxylic acid resin obtained by addition reaction of various alcohol, carbinol modified silicone, and the above-mentioned acid anhydride is mentioned, It is not limited to these. These may be used independently and may use 2 or more types.

As other hardening | curing agent which can be used together, the compound of imidazole, a trifluoro borane amine complex, a guanidine derivative, etc. are mentioned, but it is not limited to these. These may be used independently and may use 2 or more types.

Especially in this invention, use of a phenol resin is preferable from a reliability viewpoint.

In the curable resin composition A of this invention, 0.7-1.2 equivalent is preferable with respect to 1 equivalent of epoxy groups of all epoxy resins. When less than 0.7 equivalent with respect to 1 equivalent of epoxy groups or when exceeding 1.2 equivalent, hardening may be incomplete and the favorable hardening property may not be obtained.

In curable resin composition A of this invention, even if it uses a hardening accelerator together with a hardening | curing agent, it does not interfere. The above-mentioned thing is mentioned as a specific example of the hardening accelerator which can be used. When using a hardening accelerator, 0.01-5.0 weight part is used as needed with respect to 100 weight part of epoxy resins.

Curable resin composition A of this invention can also be made to contain a phosphorus containing compound as a flame retardance provision component. As a phosphorus containing compound, a reactive type may be sufficient and an additive type may be sufficient. Specific examples of the phosphorus-containing compound include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, tricylelenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylenyl phosphate, and 1,3-phenylene bis (dike Phosphoric acid esters such as silenyl phosphate), 1,4-phenylene bis (dixylenyl phosphate), and 4,4'-biphenyl (dixylenyl phosphate); 9,10-dihydro-9-oxa-10-phosphorphenanthrene-10-oxide, 10 (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphphenanthrene-10-oxide Phosphanes, such as these; Although phosphorus containing epoxy compounds, red phosphorus, etc. which are obtained by making an epoxy resin react with active hydrogen of the said phosphanes are mentioned, Phosphoric acid esters, phosphanes, or a phosphorus containing epoxy compound are preferable, and 1, 3- phenylene bis (dixylene Especially preferred is phosphate), 1,4-phenylenebis (dixylenylphosphate), 4,4'-biphenyl (dixylenylphosphate) or phosphorus containing epoxy compounds. As for content of a phosphorus containing compound, phosphorus containing compound / all the epoxy resin = 0.1-0.6 (weight ratio) are preferable. In 0.1 or less, flame retardancy is inadequate, and in 0.6 or more, the hygroscopicity and dielectric property of hardened | cured material may fall.

In addition, you may add antioxidant to curable resin composition A of this invention as needed. As antioxidant which can be used, a phenol type, sulfur type, phosphorus antioxidant can be mentioned. Antioxidants can be used individually or in combination of 2 or more types. The usage-amount of antioxidant is 0.008-1 weight part normally with respect to 100 weight part with respect to the resin component in curable resin composition of this invention, Preferably it is 0.01-0.5 weight part.

Specific examples of phenolic antioxidants include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, stearyl-β- ( 3,5-di-t-butyl-4-hydroxyphenyl) propionate, isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,4- Bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 2,4-bis [(octylthio) methyl monophenols such as] -o-cresol; 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 4,4'-thiobis (3- Methyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), triethylene glycol-bis [3- (3-t-butyl-5-methyl -4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N'- Hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide), 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydrate Hydroxyphenyl) propionate], 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, 3,9-bis [1,1-dimethyl-2- {β- (3 -t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane, bis (3,5-di-t-butyl Bisphenols such as 4-hydroxybenzylsulfonic acid ethyl) calcium; 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t- Butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, bis [3,3' -Bis- (4'-hydroxy-3'-t-butylphenyl) butylic acid] glycol ester, tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, 1,3,5-tris (3 ', 5'-di-t-butyl-4'-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, toco Polymeric phenols, such as phenol, are illustrated.

Specific examples of sulfur-based antioxidants include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate Etc. are illustrated.

Specific examples of phosphorus antioxidants include triphenylphosphite, diphenylisodecylphosphite, phenyldiisodecylphosphite, tris (nonylphenyl) phosphite, diisodecylpentaerythritol phosphite, and tris (2,4-di- t-butylphenyl) phosphite, cyclic neopentane tetrayl bis (octadecyl) phosphite, cyclic neopentane tetrayl ratio (2,4-di-t-butylphenyl) phosphite, cyclic neopentane tetrayl ratio ( 2,4-di-t-butyl-4-methylphenyl) phosphite, bis [2-t-butyl-6-methyl-4- {2- (octadecyloxycarbonyl) ethyl} phenyl] hydrogenphosphite Phosphites such as these; 9,10-dihydro-9-oxa-10-phosphperphenanthrene-10-oxide, 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9,10-dihydro-9 Oxaphosphphenanthrene oxides such as -oxa-10-phosphanephenanthrene-10-oxide and 10-decyloxy-9,10-dihydro-9-oxa-10-phosphphenanthrene-10-oxide Etc. are illustrated.

These antioxidants can be used alone, respectively, but may be used in combination of two or more thereof. In particular, phosphorus antioxidant is preferable in the present invention.

In addition, you may add a light stabilizer to curable resin composition A of this invention as needed.

As a light stabilizer, a hindered amine light stabilizer, especially HALS etc. are suitable. Although it does not specifically limit as HALS, As a typical thing, Dibutylamine 1,3,5-triazine N, N'-bis (2,2,6,6- tetramethyl-4- piperidyl-1, Polycondensate of 6-hexamethylenediamine with N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, dimethyl succinate dimethyl-1- (2-hydroxyethyl) -4-hydroxy- 2,2,6,6-tetramethylpiperidine polycondensate, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl } {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, bis ( 2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy -2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonic acid bis ( 1,2,2,6, 6-pentamethyl-4-piperidyl) etc. Only 1 type may be used for HALS and 2 or more types may be used together.

Moreover, binder resin can also be mix | blended with curable resin composition A of this invention as needed. As the binder resin, butyral resin, acetal resin, acrylic resin, epoxy-nylon resin, NBR-phenol resin, epoxy-NBR resin, polyamide resin, polyimide resin, silicone resin and the like, It is not limited to these. It is preferable that the compounding quantity of binder resin is a range which does not impair flame retardance and heat resistance of hardened | cured material, and is 0.05-50 weight part normally with respect to 100 weight part of epoxy resin components, Preferably 0.05-20 weight part is used as needed.

An inorganic filler can be added to curable resin composition A of this invention as needed. As the inorganic filler, powders such as crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, forsterite, steatite, spinel, titania, talc or spheronized particles Although beads etc. are mentioned, It is not limited to these. These may be used independently and may use 2 or more types. The content of these inorganic fillers which occupies 0 to 95 weight% in curable resin composition of this invention is used. Moreover, in curable resin composition of this invention, various compounding agents, such as a silane coupling agent, a stearic acid, palmitic acid, zinc stearate, calcium stearate, various compounding agents, such as surfactant, dye, a pigment, and a ultraviolet absorber, various thermosetting resins Can be added.

Curable resin composition A of this invention is obtained by mixing each component uniformly. Curable resin composition A of this invention can be easily made into the hardened | cured material by the method similar to the method known conventionally. For example, the epoxy resin mixture of the present invention, a curing agent and, if necessary, a curing accelerator, a phosphorus-containing compound, a binder resin, an inorganic filler, and a compounding agent are sufficiently mixed until necessary, using an extruder, a kneader, a roll, or the like as necessary. To obtain a curable resin composition, and after molding and melting the curable resin composition (without melting in the case of liquid phase) using a mold or transfer molding machine or the like, and further heating at 80 to 200 ° C for 2 to 10 hours Hardened | cured material can be obtained.

Furthermore, curable resin composition A of this invention is melt | dissolved in solvents, such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone, as needed. Hardened | cured material of curable resin composition A of this invention by making a composition varnish, hot-press molding the prepreg obtained by impregnating and heat-drying the base material of glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. You can do The solvent at this time is 10 to 70 weight% normally in the mixture of curable resin composition of this invention and the said solvent, The quantity which preferably occupies 15 to 70 weight% is used. Moreover, if it is a liquid composition, the epoxy resin hardened | cured material containing carbon fiber can also be obtained as it is, for example by an RTM system.

Moreover, curable resin composition A of this invention can be used also as a modifier of a film type composition. Specifically, it can be used when improving the flexibility and the like in the B-stage. Such a film-shaped resin composition is obtained as a sheet-shaped adhesive agent by apply | coating curable resin composition A of this invention on the peeling film as said curable resin composition varnish, removing a solvent under heating, and performing B stage formation. This sheet adhesive can be used as an interlayer insulation layer in a multilayer substrate or the like.

Curable Resin Composition B (Cation Curing with Acid Curing Catalyst)

Curable resin composition B of this invention hardened | cured using an acidic curing catalyst contains a photoinitiator or a thermal polymerization initiator as an acidic curing catalyst. Moreover, you may contain various well-known compounds, materials, etc., such as a diluent, a polymerizable monomer, a polymerizable oligomer, a polymerization start adjuvant, and a photosensitizer. Moreover, you may contain various well-known additives, such as an inorganic filler, a coloring pigment, a ultraviolet absorber, antioxidant, and a stabilizer as needed.

As an acidic curing catalyst, a cationic polymerization initiator is preferable and a light or thermal cationic polymerization initiator is especially preferable. It can be used as curable resin composition B by mix | blending the cationic polymerization initiator activated by active energy ray and / or the cationic polymerization initiator activated by heat.

Said thing is mentioned as a cationic polymerization initiator which starts cationic polymerization of curable resin composition B of this invention by irradiation of an active energy ray.

X-ray, an electron beam, an ultraviolet-ray, visible light, etc. can also be used as an active energy ray at the time of hardening curable resin composition B of this invention, Preferably it is an ultraviolet-ray or a visible light, Especially preferably, it is an ultraviolet-ray. When using ultraviolet-ray, the wavelength range is not specifically limited, Preferably it is 150-400 nm, More preferably, it is 200-380 nm. When ultraviolet rays are used, cationic polymerization can be efficiently initiated.

Moreover, in order to further improve the activity of a photocationic polymerization initiator, curable resin composition B of this invention can also use together a sensitizer. As the sensitizer which can be used in the present invention, it is possible to use, for example, a compound disclosed in Clübero Advanced Polymer Science (Adv. In Polymer Sci., 62, 1 (1984)). Specific examples include pyrene, perylene, acridine orange, thioxanthone, 2-chlorothioxanthone and benzoflavin. Moreover, the compound widely used as an optical radical polymerization initiator can also be used, Specifically, such as benzophenone, 2, 4- diethyl thioxanthone, 2-isopropyl thioxanthone, 2, 4- dichloro thioxanthone, etc. Benzoin ethers such as thioxanthones, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyl dimethylke such as 2,2-dimethoxy-1,2-diphenylethan-1-one Dehydration, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl (Alpha)-hydroxyalkyl phenones, such as a phenyl ketone, (alpha)-dicarbonyl compounds, such as camphor quinone, etc. are mentioned. In this invention, thioxanthones and (alpha)-hydroxyalkyl phenones can be used especially suitably.

The compounding quantity of the photocationic polymerization initiator in curable resin composition B of this invention can be suitably adjusted according to the kind and irradiation amount of an active energy ray. For example, in the case of ultraviolet-ray, it is preferable to set it as 0.1-10 mass parts with respect to a total of 100 mass parts of a cation curable resin composition, More preferably, it is 0.5-5 parts, More preferably, it is 1-3 parts. When the amount of the cationic polymerization initiator is less than 0.1 part, the curability may decrease. On the contrary, when the amount of the cationic polymerization initiator is more than 10 parts by mass, the components necessary for the cured product are reduced to decrease the physical properties of the cured product and the coloring of the cured product becomes severe. There is a case.

The compounding quantity at the time of adding a sensitizer to curable resin composition B of this invention can be suitably adjusted according to the kind and irradiation amount of an active energy ray. For example, in the case of ultraviolet-ray, it is preferable to set it as 5 mass parts or less with respect to 100 mass parts of total of curable resin composition B, More preferably, it is 0.2-2 parts. When the compounding quantity of a sensitizer is more than 5 mass parts, the component really needed for hardened | cured material may be reduced, and the physical property of hardened | cured material may fall, or the coloring of hardened | cured material may become severe.

When the active energy ray is ultraviolet light or visible light, the cation curable resin composition is exposed to air, but at this time, the humidity of the atmosphere is preferably low, and the humidity is preferably 80% R.H. 70% R.H. It is more preferable that it is below. In the case where ultraviolet rays or visible light are provided in the production line, a method of sending dry air immediately in front of the light irradiation device or a method of lowering the humidity by attaching a heating device can also be adopted.

The compound mentioned above is mentioned as a compound which is activated by heat and starts cationic polymerization.

It is preferable to make the compounding ratio of the thermocationic polymerization initiator into curable resin composition B of this invention into 0.01-10 mass parts with respect to 100 mass parts of cation curable resin compositions, More preferably, it is 0.1-5 parts, More preferably Is 0.5 to 3 parts. When this compounding ratio is less than 0.01 mass part, even if this is activated by the action of heat, the ring-opening reaction of a ring-opening polymerizable group may not fully advance. Moreover, even if it mix | blends more than 10 mass parts, the effect | action which advances superposition | polymerization does not become high anymore, and the physical property of hardened | cured material may fall.

Moreover, various compounding agents, such as an inorganic filler, a silane coupling material, a mold release agent, a pigment, and various thermosetting resins can be added to curable resin composition B of this invention as needed.

Curable resin composition B of this invention is obtained by mixing each component uniformly. Moreover, after melt | dissolving in homogeneous solvents, such as polyethyleneglycol monoethyl ether, cyclohexanone, (gamma) butyrolactone, and making it uniform, it is also possible to remove and use a solvent by drying. The solvent at this time is 10 to 70 weight% normally in the mixture of curable resin composition B and the said solvent of this invention, The quantity which preferably occupies 15 to 70 weight% is used. Although curable resin composition B of this invention can be hardened by ultraviolet irradiation, since it changes with curable resin composition about the amount of ultraviolet irradiation, it is determined by each hardening condition. What is necessary is just the irradiation amount which hardens a photocurable curable resin composition, and the adhesive strength of hardened | cured material should just satisfy favorable curing conditions. Since it is necessary to transmit the light to the detail at the time of hardening, high transparency is calculated | required in the epoxy resin mixture and curable resin composition B of this invention. Moreover, in these epoxy resin photocuring, it is difficult to harden | cure completely completely only by light irradiation, and in the application which heat resistance is calculated | required, it is necessary to complete | finish reaction hardening completely by heating after light irradiation.

The heating after the said light irradiation should just be in the hardening temperature area | region of normal curable resin composition B. For example, the range of 30 minutes-7 days is suitable at normal temperature-150 degreeC. Although it changes by mix | blending of curable resin composition B, it is effective in the hardening promotion after light irradiation especially in a high temperature range, and it is effective in the heat processing of a short time. In addition, the lower the temperature, the longer the heat treatment is required. The effect of aging processing also occurs by such a thermal after cure.

Moreover, since the shape of the hardened | cured material obtained by hardening | curing these curable resin composition B can also be taken in various ways according to a use, it is not specifically limited, For example, it can also be set as shapes, such as a film shape, a sheet shape, a bulk shape. The method of molding varies depending on the part to be adapted and the member. For example, molding methods such as cast method, casting method, screen printing method, spin coating method, spray method, transfer method and dispenser method can be used. It is not limited. As the molding mold, an abrasive glass, a hard stainless abrasive plate, a polycarbonate plate, a polyethylene terephthalate plate, a polymethyl methacrylate plate, or the like can be applied. Moreover, in order to improve mold release property with a shaping | molding mold, a polyethylene terephthalate film, a polycarbonate film, a polyvinyl chloride film, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a polyimide film, etc. can be applied.

For example, when using for a cationic curable resist, first, the photocationic curable resin composition B of this invention which melt | dissolved in organic solvents, such as polyethyleneglycol monoethyl ether, cyclohexanone, or (gamma) butyrolactone, is a copper clad laminated board or ceramic The coating film is formed by apply | coating the composition of this invention in the film thickness of 5-160 micrometers by methods, such as screen printing and a spin coat method, on board | substrates, such as a glass substrate or a glass substrate. Then, after preliminarily drying the coating film at 60 ~ 110 ℃, irradiated with ultraviolet light (for example, low-pressure mercury lamp, high-pressure mercury lamp, ultra-high pressure mercury lamp, xenon lamp, laser light, etc.) through the neger film drawn a desired pattern, Subsequently, a post-exposure baking process is performed at 70-120 degreeC. Thereafter, the unexposed portion is dissolved (developed) with a solvent such as polyethylene glycol monoethyl ether and then, if necessary, sufficient by irradiation with ultraviolet rays and / or heating (for example, 0.5 to 3 hours at 100 to 200 ° C). Curing is further performed to obtain a cured product. Thus, it is also possible to obtain a printed wiring board.

The hardened | cured material formed by hardening | curing curable resin composition A and curable resin composition B of this invention can be used for various uses.

Typical uses where the curable resin composition A or the curable resin composition B is used include, for example, adhesives, paints, coating agents, molding materials (including sheets, films, FRP, etc.), insulating materials (printed substrates, wire coatings, etc.). And additives to other resins, etc., besides the sealant. Examples of the adhesive include adhesives for civil engineering, construction, automobiles, general office, medical adhesives, and electronic materials. Among these, as adhesives for electronic materials, mounting such as interlayer adhesives of multilayer substrates such as build-up substrates, die bonding agents, semiconductor adhesives such as underfills, BGA reinforcement underfills, anisotropic conductive films (ACF), and anisotropic conductive pastes (ACP), etc. And adhesives for use.

As a sealant and a substrate, potting sealing such as a capacitor, a transistor, a diode, a light emitting diode, an IC, an LSI, potting sealing, flip chip, etc., such as an IC, an LSI type of COB, COF, TAB, etc. Sealing (including reinforcing underfill) and package substrates for mounting IC packages such as underfill, QFP, BGA, CSP, and the like. Moreover, it is also suitable for the board | substrate application which requires the functionality, such as a network board and a module board | substrate.

Example

Next, although an Example demonstrates this invention further more concretely, a part is a weight part below unless there is particular notice. In addition, this invention is not limited to these Examples.

It describes about the various analysis methods used by the Example below.

Epoxy equivalent: According to JIS K 7236 (ISO 3001)

ICI melt viscosity: Complies with JIS K 7117-2 (ISO 3219)

Softening point: Complies with JIS K 7234

GPC:

Column (Shodex KF-603, KF-602.5, KF-602, KF-601x2)

The connecting eluent is tetrahydrofuran

Flow rate is 0.5ml / min

Column temperature is 40 ℃

Detection: Differential Refraction Detector (RI)

Hereinafter, an Example and a comparative example demonstrate this invention concretely.

(Example 1)

214.7 parts of binol, 46.6 parts of 4,4'-biphenol, 740 parts of epichlorohydrin, 296 parts of dimethyl sulfoxide were added, adding nitrogen purge to the flask provided with the stirrer, the reflux condenser, and the stirring apparatus, under stirring. It melt | dissolved and it heated up to 45 degreeC. Subsequently, 84 parts of flake shaped sodium hydroxides were added over 90 minutes, and reaction was further performed at 45 degreeC for 2 hours and 70 degreeC for 75 minutes. After completion | finish of reaction, solvents, such as excess epichlorohydrin, were distilled off under reduced pressure using the rotary evaporator from the oil layer. 800 parts of methyl isobutyl ketones were added and dissolved in the residue, and it heated up to 75 degreeC after water washing. After stirring, 30 parts of 30% by weight aqueous sodium hydroxide solution was added under stirring, and the reaction was carried out for 1 hour, followed by washing with water until the wash water of the oil layer became neutral, and methylisobutyl ketone or the like under reduced pressure using a rotary evaporator from the obtained solution. By distilling off, 360 parts of epoxy resin mixtures (EP1) of this invention were obtained. The epoxy equivalent of the obtained epoxy resin was 207 g / eq., The softening point 87.5 degreeC, and the ICI melt viscosity in 150 degreeC was 0.03 Pa.s or less.

Synthesis Example 1

214 parts of binol, 555 parts of epichlorohydrin (4 molar equivalents to phenol resin), and 55 parts of methanol were added while nitrogen purging to the flask equipped with the stirrer, the reflux condenser, and the stirrer. It heated up to -75 degreeC. Subsequently, after dividingly adding 60 parts of flake shaped sodium hydroxide over 90 minutes, 75 degreeC reaction was further performed. After completion | finish of reaction, water washing was performed with 400 parts of water, and solvents, such as excess epichlorohydrin, were distilled off under reduced pressure using the rotary evaporator from the oil layer. 500 parts of methyl isobutyl ketones were added and dissolved in the residue, and it heated up to 75 degreeC. After stirring, 10 parts of 30% by weight aqueous sodium hydroxide solution and 10 parts of methanol were added under stirring, and the reaction was carried out for 1 hour, followed by washing with water until the wash water of the oil layer became neutral, using a rotary evaporator to obtain methyl under reduced pressure. 403 parts of epoxy resin mixtures (EP2) were obtained by distilling isobutyl ketone etc. out. The epoxy equivalent of the obtained epoxy resin was 230 g / eq., The softening point of 58 degreeC, and ICI melt viscosity in 150 degreeC was 0.07 Pa.s.

Synthesis Example 2

It synthesize | combined like Example 21 except having changed 214.7 parts of binols and 46.6 parts of 4,4'- biphenols to 242 parts of 3,3 ', 5,5'- tetramethylbiphenyl-4,4'- diol. As a result, 349 parts of epoxy resins (EP3) were obtained. The epoxy equivalent of the obtained epoxy resin was 190 g / eq., The softening point 107 degreeC, and the ICI melt viscosity in 150 degreeC was 0.03 Pa.s or less.

Example 2 and Comparative Examples 1 and 2

The epoxy resin obtained above was mix | blended in the ratio (weight part) of Table 1, it mixed and kneaded uniformly using the mixing roll, and the epoxy resin composition for sealing was obtained. This epoxy resin composition was pulverized with a mixer and further tableted with a tablet machine. This tablet-ized epoxy resin composition was transfer-molded (175 degreeC x 60 second), and after demolding, it hardened | cured on conditions of 160 degreeC x 2 hours + 180 degreeC x 6 hours, and obtained the test piece for evaluation.

In addition, the physical property of hardened | cured material was measured with the following method.

Heat resistance (TMA): Measured in accordance with JIS K 7244.

Heat resistance (HDT): Measured in accordance with JIS K 7191.

The epoxy resin of this invention which is a mixture of a binol structure and a biphenol structure is compared with the hardened | cured material (comparative example 1) using the epoxy resin of a binol structure, and the hardened | cured material (comparative example 2) using the epoxy resin of a biphenol structure. It can be seen that it has a structure that exhibits high heat resistance and low linear expansion rate and is compatible with high heat resistance and dimensional stability.

Example 3 and Comparative Examples 3 and 4

The epoxy resin obtained above was mix | blended in the ratio (weight part) of Table 2, and it mixed uniformly and knead | mixed using the mixing roll, and obtained the epoxy resin composition for sealing. This epoxy resin composition was pulverized with a mixer and further tableted with a tablet machine. This tablet-ized epoxy resin composition was transfer-molded (175 degreeC x 60 second), and after demolding, it hardened | cured on conditions of 160 degreeC x 2 hours + 180 degreeC x 6 hours, and obtained the test piece for evaluation. The flame retardancy test results are also shown in Table 2. In addition, the hardening accelerator C1 is the same as the above.

Flame retardance: It performed in accordance with UL94. However, the sample size was 12.5 mm in width x 150 mm in length, and thickness tested by 0.8 mm.

Afterglow time: The total of afterglow time after inoculating 10 times to 5 sets of samples.

Heat resistance (DMA)

Dynamic Viscoelasticity Meter: TA-instruments, DMA-2980

Measuring Temperature Range: -30 ~ 280 ℃

Warming rate: 2 ℃ / min

Test piece size: The thing cut out to 5 mm x 50 mm was used (thickness about 800 micrometers).

Tg: The peak point of Tan-δ was made into Tg.

The epoxy resin mixture of this invention which is a mixture of a binol structure and a biphenol structure from these results is a hardened | cured material (comparative example 3) using the epoxy resin of a binol structure, the hardened | cured material using the epoxy resin of a biphenol structure (comparative example 4). It can be seen that it has a structure compatible with high heat resistance and high flame retardance compared to

Example 4 and Comparative Example 5

The epoxy resin obtained above was mix | blended in the ratio (weight part) of Table 3, it mixed uniformly and knead | mixed using the mixing roll, and obtained the epoxy resin composition for sealing. This epoxy resin composition was pulverized with a mixer and further tableted with a tablet machine. Spiral flow was measured for this tableted epoxy resin composition on the conditions of 175 degreeC and molding pressure of 70 kg / cm <2> with the transfer molding machine. In addition, a hardening | curing agent P2, a hardening accelerator C1, an inorganic filler, a coupling agent, and a mold release agent are the same as the above.

These results show that the epoxy resin of this invention which is a mixture of a binol structure and a biphenol structure generally has high fluidity compared with the hardened | cured material (comparative example 5) using the epoxy resin of the high fluidity nonphenol structure. (Spiral flows despite the same gel time).

Example 5 and Comparative Examples 6, 7, 8, 9

The epoxy resin shown below was mix | blended in the ratio (weight part) of Table 4, it mixed uniformly and knead | mixed using the mixing roll, and the epoxy resin composition for sealing was obtained. This epoxy resin composition was pulverized with a mixer and further tableted with a tablet machine. This tablet-ized epoxy resin composition was transfer-molded (175 degreeC x 60 second), and after demolding, it hardened | cured on conditions of 160 degreeC x 2 hours + 180 degreeC x 6 hours, and obtained the test piece for evaluation.

Heat resistance (TMA): Measured in accordance with JIS K 7244.

Absorption rate: percentage of weight increase after 24 hours immersion in water at 100 ° C

EP4: A mixture of an ortho cresol novolak-type epoxy resin and a biphenol-type epoxy resin (epoxy equivalent 205 g / eq. Softening point 91 DEG C.

EP5: A mixture of a phenol aralkyl type epoxy resin and a nonphenol type epoxy resin (epoxy equivalent 214 g / eq. Softening point 102 ° C. ICI melt viscosity 0.09 Pa · s)

EP6: Mixture of biphenyl type phenol aralkyl type epoxy resin and biphenol type epoxy resin (epoxy equivalent 240g / eq. Softening point 93 degreeC ICI melt viscosity 0.03 Pa.s)

The structural formula of the phenol aralkyl type epoxy resin is the same as the following formula (A), and the structural formula of the biphenyl type phenol aralkyl type epoxy resin is the following formula (B).

From the results, the epoxy resin of the present invention is superior in heat resistance and the water absorption is generally deteriorated when the heat resistance is improved, compared with the same modified resin having a different structure. It turns out that the characteristic is excellent.

Example 6

207 parts of epoxy resin EP1, 103 parts of P1 and 2 parts of C1 were mix | blended, and it mixed uniformly and knead | mixed using the mixing roll, and obtained the epoxy resin composition for sealing. This epoxy resin composition was pulverized with a mixer and further tableted with a tablet machine. This tablet-ized epoxy resin composition was transfer-molded (175 degreeC x 60 second), and after demolding, it hardened | cured on conditions of 160 degreeC x 2 hours + 180 degreeC x 6 hours, and obtained the test piece for evaluation.

Mechanical strength: Bending test The bending strength at 120 ° C according to JIS K 6911 is measured.

-Linear expansion rate: TMA was measured based on JISK7244, and the (alpha) ₁ was measured.

Moisture absorption rate: The amount of weight increase was measured for 24 hours in a constant temperature and humidity bath at 85 ° C and 85%.

Cracking resistance: measured in accordance with ASTM E-399 for K1c

Impact resistance: Izod impact test conforms to JIS K 6911

Molding shrinkage: Measures the difference between mold and JIS K 6911

Gel time: measured on a hot plate at 175 ° C

Mechanical strength: 82 MPa

Linear expansion rate: 57 ppm

Moisture absorption rate: 0.75%

Crack resistance: 19Nmm ^-1.5

Impact resistance: 5.7kJ / ㎡

Molding shrinkage: 1.75%

Gel time: 59 seconds

Example 7 and Comparative Examples 10 and 11

The epoxy resin obtained above was mix | blended in the ratio (weight part) of Table 5, and it mixed uniformly and knead | mixed using the mixing roll, and obtained the epoxy resin composition for sealing. This epoxy resin composition was pulverized with a mixer and further tableted with a tablet machine. Spiral flow was measured for this tableted epoxy resin composition on the conditions of 175 degreeC and molding pressure of 70 kg / cm <2> with the transfer molding machine. In addition, a hardening | curing agent P2, a hardening accelerator C1, an inorganic filler, a coupling agent, and a mold release agent are the same as the above.

From the results, it can be seen that the epoxy resin of the present invention, which is a mixture of a binol structure and a biphenol structure, has a high fluidity compared to a cured product using an epoxy resin of another structure (spiral flow despite the almost same gel time). Iii).

From the above results, it is clear that the composition using the epoxy resin mixture of the present invention is excellent in fluidity and the cured product is particularly excellent in flame retardancy and heat resistance, so that a semiconductor sealing material requiring high functionalization and a thin film substrate material requiring high filler filling ( And interlayer insulating films).

Although this invention was demonstrated in detail with reference to the specific embodiment, it is clear for those skilled in the art for various changes and correction to be possible, without leaving | separating the mind and range of this invention.

In addition, this application is based on the JP Patent application (Japanese Patent Application 2012-246258) of an application on November 8, 2012, The whole is taken in into consideration. Also, all references cited herein are incorporated in their entirety.

The epoxy resin composition containing the epoxy resin mixture of this invention is useful for various composite materials, adhesives, paints, etc., including insulation materials for electrical and electronic components, laminated boards (printed wiring boards, buildup boards, etc.) and CFRP.

Claims

1,1'-bis (2-glycidyloxy-naphthyl) (A) and a compound represented by the following formula (1) (B) and, by playing structure and biphenol structure is -CH ₂ CH (OH) Epoxy resin mixtures which simultaneously contain a compound having structure (C) bonded through a CH ₂ -structure:

(One)
[In formula (1), R represents a hydrogen atom, a C1-C4 alkyl group, G represents a glycidyl group, and t represents an integer of 1-4.].

The method of claim 1,
Epoxy resin mixture, wherein the ratio of 1,1'-bis (2-glycidyloxynaphthyl) (A) and the compound (B) represented by said Formula (1) is A / B = 1-10. .

The method of claim 1,
An epoxy resin mixture obtained by mixing a vinyl and a compound represented by the following formula (2) and reacting with epihalohydrin:

(2)
[In formula (2), R represents a hydrogen atom and a C1-C4 alkyl group, t shows the integer of 1-4.].

The epoxy resin composition containing the epoxy resin mixture and hardening | curing agent in any one of Claims 1-3.

The epoxy resin composition containing the epoxy resin mixture and polymerization catalyst of any one of Claims 1-3.

Hardened | cured material characterized by hardening the epoxy resin composition of Claim 4.

Hardened | cured material characterized by hardening the epoxy resin composition of Claim 5.