JP2000319345A - Thermosetting resin composition and its cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting resin composition having high adhesive strength to a substrate material or the like, and, above all, to provide a sealing agent having excellent adhesiveness to semiconductor, too, where a lead frame plated with gold, palladium or silver is used and therefore exhibiting excellent welder crack resistance. SOLUTION: This thermosetting resin composition comprises a resin expressed by the formula [wherein Rs are each H, a 1-10C hydrocarbon group, an alkoxy group, a halogen atom or hydroxyl group; Xs are each oxygen atom or sulfur atom; Qs are each H or a 1-5C alkyl; (n) is an average value and is a real number of 1.2-8; (y)s are each an integer of 1 or 2; (i)s are each an integer of 1-6; (j)s are each an integer of 1-3 and; Z is hydrogen atom or glycidyl group], and having melt viscosity of 0.5-5.0 poises at 150 deg.C when Z is hydrogen atom and melt viscosity of 0.5-3.0 poises at 150 deg.C when Z is glycidyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an insulating material for electric and electronic parts such as a high-reliability semiconductor encapsulation, and various kinds of materials such as a laminate (printed wiring board) and CFRP (carbon fiber reinforced plastic). The present invention relates to a thermosetting resin composition useful for composite materials, adhesives, paints, and the like, and a cured product thereof.

[0002]

2. Description of the Related Art Phenolic resins and epoxy resins have excellent workability and excellent electrical properties, heat resistance and adhesiveness of the cured products.
Due to its moisture resistance (water resistance) and the like, it is widely used in the fields of electric / electronic parts, structural materials, adhesives, paints, and the like.

However, in recent years, especially in the electric and electronic fields, with the development thereof, high purity, moisture resistance, adhesion,
There is a demand for further improvement of various properties of the resin such as lowering the viscosity for highly filling the filler. Further, as a structural material, a lightweight material having excellent mechanical properties is required for aerospace materials, leisure and sports equipment applications, and the like. To meet these requirements, many proposals have been made on phenolic resins and epoxy resins and thermosetting resin compositions containing them, but they have not been satisfactory yet.

[0004]

DISCLOSURE OF THE INVENTION The present invention relates to an insulating material for electric and electronic parts (such as a highly reliable semiconductor encapsulating material) and a laminate which exhibit excellent moisture resistance (water resistance) and adhesion in the cured product. The present invention provides a thermosetting resin composition useful for various composite materials such as (a printed wiring board) and CFRP, an adhesive, a paint, and the like, and a cured product thereof.

[0005]

Means for Solving the Problems The present inventors have made intensive studies on a method of imparting the above-mentioned properties to a thermosetting resin composition and a cured product thereof, and have completed the present invention. That is, the present invention provides the following equation (1):

[0006]

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(Wherein, a plurality of Rs independently represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group, a halogen atom or a hydroxyl group. A plurality of Xs independently represent an oxygen atom or a sulfur atom. A plurality of Qs independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, n represents an average value, and represents a real number of 1.2 to 8. A plurality of y's independently represent an atom. A plurality of i independently represent an integer of 1 to 6. A plurality of j independently represent an integer of 1 to 3. A plurality of Z represents a hydrogen atom or glycidyl. Wherein Z is a hydrogen atom, the melt viscosity at 150 ° C. is 0.5 poise to 5.0 poise,
Is a glycidyl group, a thermosetting resin composition containing a resin having a melt viscosity at 150 ° C. of not less than 0.5 poise and not more than 3.0 poise; (2) In the formula (1), Z is hydrogen. (1) The thermosetting resin composition according to the above (1), which contains both an atomic resin and a resin wherein Z is a glycidyl group; (3) a copper frame having an outermost layer plated with palladium, gold, silver, or nickel; or (4) The thermosetting resin composition according to the above (1) or (2), for sealing a semiconductor device using the unplated copper frame as a lead frame. Any one
Cured product obtained by curing the thermosetting resin composition according to the item,
(5) A semiconductor device sealed with the thermosetting resin composition of (1) to (3).

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The above formula (1) used in the present invention
Wherein Z is a hydrogen atom (hereinafter referred to as phenolic resin of the present invention) is a phenolic compound represented by the following formula (2)

[0009]

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(Wherein, X represents an oxygen atom or a sulfur atom; a plurality of Qs independently represent a hydrogen atom or a carbon atom
To 5 alkyl groups. j represents an integer of 1 to 3. )
By condensation polymerization of the compound of the formula (1) in the presence of a catalyst and, if necessary, a solvent. When Q in the formula (2) is an alkyl group, a methyl group, an ethyl group, a propyl group,
Examples thereof include a butyl group and a pentyl group, and a methyl group or an ethyl group is preferable. Also, j represents an integer of 1 to 3, and when Q is an alkyl group, j is preferably 1.

Specific examples of the compound of the formula (2) which can be used include: furfural, 3-furaldehyde, 3-methylfurfural, 5-methylfurfural, 5-ethylfurfural, 2-thiophencarboxaldehyde,
Examples thereof include thiophene carboxaldehyde and 3-methyl-2-thiophene carboxaldehyde, but are not limited thereto, and may be used alone or in combination of two or more.

R in the formula (1) is derived from a phenol to be reacted with the compound of the formula (2), and the hydrocarbon group having 1 to 10 carbon atoms is a methyl group, an ethyl group,
Alkyl groups such as propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group or decyl group, allyl group, phenyl group, etc., and methoxy group as alkoxy group, and halogen atom as Examples thereof include a fluorine atom, a chlorine atom, and a bromine atom. I represents an integer of 1 to 6, and when R is a methyl group,
Is preferable, when it is a phenyl group, 1-2 are preferable, and when it is a hydroxyl group, 1-3 are preferable. Specific examples of phenols that can be used include phenol, cresol, xylenol, trimethylphenol, octylphenol, phenylphenol, diphenylphenol, guaiacol, hydroquinone, resorcinol, catechol, naphthol, dihydroxynaphthalene, methylnaphthol, and allylphenol. Phenol or cresol is preferred. In addition, phenols
The present invention is not limited to these, and may be used alone or in combination of two or more. The amount of the phenol to be used is generally 1.2 to 20 mol, preferably 1.4 to 10 mol, per 1 mol of the compound of the formula (2).

Examples of the solvent include water, methanol, ethanol, propanol, isopropanol, toluene, xylene and the like, but are not limited thereto, and they may be used alone or in combination of two or more. When a solvent is used, the amount used is based on 100 parts by weight of phenols.
Usually, it is in the range of 5 to 500 parts by weight, preferably 10 to 300 parts by weight.

The catalyst is preferably a basic substance. Although polycondensation is possible even with an acidic catalyst, a reaction between the compounds of the formula (2) occurs, and the amount of by-products increases. There is also a method using an organometallic compound, but it is disadvantageous in cost. Specific examples of the basic catalyst that can be used include lithium hydroxide,
Alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide, sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, potassium- alkali metal alkoxides such as tert-butoxide, magnesium methoxide, alkaline earth metal alkoxides such as magnesium ethoxide, etc.
Examples thereof include amines such as sodium carbonate, magnesium oxide, and triethylamine, and amino alcohols such as N, N-dimethylethanolamine, but are not limited thereto, and may be used alone or in combination of two or more. . The amount of the catalyst to be used is generally 0.005 to 2.0 mol, preferably 0.01 to 1.1 mol, per 1 mol of phenols.
Range of moles.

The reaction is carried out by adding a catalyst to a mixture of the compound represented by the formula (2), phenols (and, if necessary, a solvent) and heating the mixture. Further, the compound of the formula (2) may be gradually added to the mixture while the mixture of the phenol and the catalyst (if necessary, the solvent) is being heated. The reaction time is usually 2 to 10
0 hours, preferably 4 to 20 hours, and the reaction temperature is usually 50 hours.
To 175 ° C, preferably 75 to 150 ° C. After the completion of the reaction, the reaction mixture is neutralized, and then the unreacted raw materials and the solvents are removed by filtration or heating under reduced pressure to obtain the phenolic resin of the present invention. The phenolic resin of the present invention has a melt viscosity at 150 ° C. of 0.5
The poise is from 5.0 poise to 5.0 poise, preferably from 1.0 poise to 4.0 poise. To achieve such a viscosity range, the ratio of the compound of the formula (2) to the phenols, Adjust temperature, etc. In the case of the phenolic resin of the present invention, those in which n in the formula (1) is 1.2 or more and 8 or less are easy to handle because the viscosity is not too high and the softening point is not too low. Note that n in the formula (1) can be measured by, for example, gel permeation chromatography.

The resin of the formula (1) wherein Z is a glycidyl group (hereinafter referred to as the epoxy resin of the present invention) is obtained by glycidylation of the hydroxyl group of the phenolic resin of the present invention according to a conventionally known method. be able to. Examples of the epihalohydrins used in the glycidylation reaction include epichlorohydrin, epibromohydrin, epiiodohydrin, β-methylepichlorohydrin, β-methylepibromohydrin, β-ethylepichlorohydrin, and the like. Epichlorohydrin, which is easy and inexpensive, is preferred. During the glycidylation, the melt viscosity of the resin generally tends to decrease. The melt viscosity at 150 ° C. of the epoxy resin of the present invention is 0.5 poise or more.
It is 0 poise or less, preferably 0.5 poise to 2.5 poise.

The glycidylation reaction is carried out, for example, by adding a solid of alkali metal hydroxide such as sodium hydroxide or potassium hydroxide to the mixture of the phenolic resin of the present invention and epihalohydrin at 20 to 120 ° C.
For 1 to 20 hours. At this time, the alkali metal hydroxide may be used in the form of an aqueous solution. In this case, the alkali metal hydroxide is continuously added, and water and epihalohydrin are continuously added to the reaction system under reduced pressure or normal pressure. May be further distilled off, water may be removed, and epihalohydrins may be continuously returned to the reaction system.

In the above method, the amount of the epihalohydrin used is usually 0.5 to 20 mol, preferably 0.7 to 10 mol, per equivalent of the hydroxyl group of the phenolic resin of the present invention. The amount of the alkali metal hydroxide to be used is usually 0.5 to 1 to 1 equivalent of the hydroxyl group of the phenolic resin of the present invention.
It is 5 mol, preferably 0.7 to 1.2 mol. Also,
In the above reaction, dimethyl sulfone, dimethyl sulfoxide, dimethylformamide, 1,3-dimethyl-2-
By adding an aprotic polar solvent such as imidazolidinone, an epoxy resin having a low hydrolyzable halogen concentration can be obtained, which is suitable for use as a sealing material for electronic materials. The amount of the aprotic polar solvent used is usually 5 to 200% by weight, preferably 10 to 100% by weight based on the weight of the epihalohydrin.
% By weight. In addition, the reaction can easily proceed by adding an alcohol such as methanol or ethanol in addition to the above-mentioned solvent. Further, toluene, xylene, dioxane and the like can also be used.

Also, a mixture of the phenolic resin of the present invention and an excess of epihalohydrin is added to tetramethylammonium chloride, tetramethylammonium bromide,
Using a quaternary ammonium salt such as trimethylbenzylammonium chloride as a catalyst,
Sodium hydroxide to the halohydrin ether of the phenolic resin of the present invention obtained by reacting at
The epoxy resin of the present invention can also be obtained by adding a solid or aqueous solution of an alkali metal hydroxide such as potassium hydroxide and reacting at 20 to 120 ° C. for 1 to 20 hours to close the ring of the halohydrin ether. In this case, the amount of the quaternary ammonium salt used is the amount of the hydroxyl group 1 of the phenolic resin of the present invention.
It is usually 0.001 to 0.2 mol, preferably 0.05 to 0.1 mol, per equivalent.

Usually, these reactants are washed with water, or without heating, after removing excess epihalohydrin under heating and reduced pressure, dissolved in a solvent such as toluene, xylene, methyl isobutyl ketone, and the like. Then, an aqueous solution of an alkali metal hydroxide is added to react again. In this case, the amount of the alkali metal hydroxide used is usually 0.0 to 1 equivalent of the hydroxyl group of the phenolic resin of the present invention.
It is 1 to 0.2 mol, preferably 0.05 to 0.1 mol. The reaction temperature is usually 50 to 120 ° C, and the reaction time is usually 0.5 to 2 hours.

After the completion of the reaction, salts produced as by-products are removed by filtration, washing with water, and the like, and a solvent such as toluene, xylene, or methyl isobutyl ketone is distilled off under reduced pressure under heating to obtain an epoxy resin having a small amount of hydrolyzable halogen. Can be. Further, the step of synthesizing the phenolic resin of the present invention and the step of glycidylation can be performed continuously. For example, after reacting the compound of the formula (2) with a phenol by the above-mentioned method, epihalohydrins are directly added to the system without removing unreacted raw materials and solvents by distillation under heating and reduced pressure. The glycidylation may be carried out according to the above-mentioned method, and the glycidylation of the unreacted raw material may be distilled off together with the solvent in the last solvent distillation step.

Hereinafter, the thermosetting resin composition of the present invention will be described. When the thermosetting resin composition of the present invention contains the phenolic resin of the present invention, it contains an epoxy resin and / or a cyanate ester resin as other components. In this case, the phenolic resin of the present invention alone or It can be used in combination with other curing agents. When used in combination, the proportion of the phenolic resin of the present invention in the total curing agent is 1
It is preferably at least 0% by weight, particularly preferably at least 20% by weight. When the thermosetting resin composition of the present invention contains the epoxy resin of the present invention, the epoxy resin of the present invention can be used alone or in combination with another epoxy resin. When used in combination, the proportion of the epoxy resin of the present invention in the epoxy resin is preferably 20% by weight or more, particularly preferably 30% by weight or more.

It can be used in combination with the phenolic resin of the present invention.
As other curing agents or curing agents for epoxy resin,
For example, amine compound, acid anhydride compound, amide compound
And phenolic compounds. Can be used
Specific examples of the curing agent include diaminodiphenylmethane,
Diethylenetriamine, triethylenetetramine, dia
Minodiphenyl sulfone, isophorone diamine, dicia
Diamide, linolenic acid dimer and ethylenediamine
Polyamide resin, phthalic anhydride,
Limellitic acid, pyromellitic anhydride, maleic anhydride,
Tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride
Talic acid, methyl nadic anhydride, hexahydroanhydride lid
Luic acid, methyl hexahydrophthalic anhydride, bisphenol
(Bisphenol A, bisphenol F, bisphenol
Nord S, biphenol, bisphenol AD, etc.)
Enols (phenol, alkyl-substituted phenol, aromatic
Aromatic substituted phenol, naphthol, alkyl substituted naphtho
, Dihydroxybenzene, alkyl-substituted dihydroxy
Sibenzene, dihydroxynaphthalene, etc.) and various alde
Hyd (formaldehyde, acetaldehyde, alkyl
Aldehydes, benzaldehydes, alkyl-substituted benzures
Aldehyde, hydroxybenzaldehyde, naphthaldehyde
Hide, glutaraldehyde, phthalaldehyde, croto
Polycondensate with aldehyde, cinnamaldehyde, etc.)
Phenols and various diene compounds (dicyclopentadie
, Terpenes, vinylcyclohexene, norbornadi
Ene, vinyl norbornene, tetrahydroindene, di
Vinylbenzene, divinylbiphenyl, diisopropeni
Polymerization with rubiphenyl, butadiene, isoprene, etc.)
Substances, phenols and ketones (acetone, methyl ethyl
Ketone, methyl isobutyl ketone, acetophenone,
Polycondensates with benzophenone), phenols and aromatics
Dimethanols (benzene dimethanol, α, α,
α ', α'-benzenedimethanol, biphenyldimeta
Knol, α, α, α ′, α′-biphenyldimethanol
Condensates with phenols and aromatic dichloromethyl
(Α, α'-dichloroxylene, bischloromethyl
Polycondensates with bisphenyl, etc., bisphenols and various
Polycondensates of aldehydes and their modified products, imidazo
-R, BF ₃-Amine complexes, guanidine derivatives, etc.
However, the present invention is not limited to these.

Specific examples of the epoxy resin used in the thermosetting resin composition of the present invention include bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.) and phenols (phenol, alkyl-substituted phenol). , Aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc. and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, Polycondensates with phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.) Compounds with dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc., phenols and ketones (acetone, Polycondensates with methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc., phenols and aromatic dimethanols (benzenedimethanol, α, α,
polycondensates with α ′, α′-benzenedimethanol, biphenyldimethanol, α, α, α ′, α′-biphenyldimethanol, phenols and aromatic dichloromethyls (α, α′-dichloro) Xylene, bischloromethylbiphenyl, etc.), polycondensates of bisphenols and various aldehydes, glycidyl ether-based epoxy resins obtained by glycidylation of alcohols, etc., alicyclic epoxy resins, glycidylamine-based epoxy resins, glycidyl An ester-based epoxy resin may be used, but the epoxy resin is not limited to these as long as it is a commonly used epoxy resin. These may be used alone or in combination of two or more.

When the thermosetting resin composition of the present invention contains an epoxy resin, if necessary, a composition generally used as a curing accelerator for the epoxy resin may be contained.
As a curing accelerator, for example, 2-methylimidazole,
Imidazole-based compounds such as 2-ethylimidazole, boron trifluoride complexes, phosphorus-based compounds such as triphenylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine / triphenylborane, and tetraphenylphosphonium / tetraphenylborate; Tertiary amine compounds and the like are used, and the amount of the tertiary amine compound is 0.01 to 15 parts by weight per 100 parts by weight of the epoxy resin.
Parts by weight, preferably 0.1 to 10 parts by weight.

Specific examples of the cyanate ester resin used in the thermosetting resin composition of the present invention include dicyanatobenzene, tricyanatobenzene, dicyanatonaphthalene, dicyanatobiphenyl, 2,2′-bis ( 4-cyanatophenyl) propane, bis (4-cyanatophenyl) methane, bis (3,5-dimethyl-4-cyanatophenyl) methane, 2,2′-bis (3,5-dimethyl-4-cyanatophenyl) propane , 2,2'-bis (4-cyanatophenyl) ethane, 2,2'-bis (4-cyanatophenyl) hexafluoropropane, bis (4-cyanatophenyl) sulfone, bis (4-cyanatophenyl) thioether ,
Phenol novolak cyanate and phenol / dicyclopentadiene cocondensate in which a hydroxyl group is converted to a cyanate group are exemplified, but not limited thereto.

In the case where the thermosetting resin composition of the present invention contains a cyanate resin, zinc naphthenate, cobalt naphthenate, naphthenate and the like are used in order to form a sym-triazine ring by trimerizing a cyanate group if necessary. A catalyst such as copper acid, lead naphthenate, zinc octylate, tin octylate, lead acetylacetonate, dibutyltin maleate and the like can be contained. The catalyst is used in an amount of usually 0.0001 to 0.10 part by weight, preferably 0.00015 to 0.0015 part by weight, based on 100 parts by weight of the total weight of the thermosetting resin composition.

Further, known additives can be added to the thermosetting resin composition of the present invention, if necessary. Specific examples of additives that can be used include polybutadiene and modified products thereof, modified acrylonitrile copolymer, polyphenylene ether, polystyrene, polyethylene, polyimide, fluororesin, maleimide compounds, silicone gel, silicone oil, silica, and alumina. , Calcium carbonate, quartz powder, aluminum powder, graphite, talc, clay, iron oxide, titanium oxide, aluminum nitride, asbestos, mica, glass powder, glass fiber, glass nonwoven fabric or inorganic filler such as carbon fiber, silane coupling And a colorant such as carbon black, phthalocyanine blue, and phthalocyanine green.

The thermosetting resin composition of the present invention can be obtained by uniformly mixing the above components at a predetermined ratio.
Mixing may be carried out, if necessary, from 20 to 100 from the softening point of the above components
It can be performed by heating and melting at a temperature as high as about ° C. Further, the respective components of the thermosetting resin composition can be mixed by uniformly dispersing or dissolving the components in a solvent or the like. Although the solvent is not particularly limited, specific examples that can be used include toluene, xylene, methyl ethyl ketone,
Examples include methyl isobutyl ketone, dioxane, methyl cellosolve, and dimethylformamide. These solvents are usually 5 to 300 parts by weight based on 100 parts by weight of the resin component,
Preferably, 10 to 150 parts by weight is used.

The cured product of the present invention can be obtained by treating the above-mentioned thermosetting resin composition at room temperature to 250 ° C. for 30 seconds to 50 hours. Alternatively, the components of the thermosetting resin composition may be uniformly dispersed or dissolved in a solvent or the like, and after removing the solvent, the composition may be cured under the above-described conditions.

The cured product of the present invention thus obtained has moisture resistance and high adhesiveness. Therefore, the thermosetting resin composition of the present invention can be used in a wide range of fields where moisture resistance and adhesiveness are required. Specifically, it is useful as a compounding component of all electric and electronic materials such as an insulating material, a laminate, and a sealing material, but the outermost layer is a copper frame plated with palladium, gold, silver, or nickel, or the above-mentioned plating is applied. It is preferably used to seal a semiconductor device using no copper frame as a lead frame. Further, the semiconductor device of the present invention has a cured product of the epoxy resin composition of the present invention, such as a device sealed with the epoxy resin composition of the present invention. As a semiconductor device, for example, DIP (dual inline package), QFP (quad flat package), BGA (ball grid array), CSP
(Chip size package), SOP (small outline package) and the like.

[0032]

The present invention will be described in more detail with reference to Synthesis Examples and Examples. Note that the present invention is not limited to these examples. In the synthesis examples, the epoxy equivalent, melt viscosity, softening point, and hydrolyzable chlorine concentration were measured under the following conditions. 1) Epoxy equivalent It measured by the method according to JISK-7236. 2) Melt viscosity Melt viscosity in the cone plate method at 150 ° C Measurement machine: cone plate (ICI) high temperature viscometer (RESE)
ARCH EQUIPMENT (LONDON) LTD. : 3 (measurement range: 0 to 20 poise) Sample amount: 0.15 ± 0.005 (g) 3) Softening point Measured by a method according to JIS K-7234 4) Hydrolyzable chlorine concentration 1N in dioxane solution of sample The value obtained by measuring the amount of chlorine liberated by adding a KOH ethanol solution and refluxing for 30 minutes by a silver nitrate titration method and dividing by the weight of the sample.

Synthesis Example 1 188 parts by weight of phenol, 50 parts by weight of water, 9.6 parts by weight of furfural, and 20 parts by weight of sodium hydroxide were charged into a flask equipped with a stirrer, a reflux condenser, and a stirrer, and stirred and dissolved. After heating and reacting for 8 hours under reflux,
Neutralized with concentrated hydrochloric acid. Then, methyl isobutyl ketone 30
After adding 0 parts by weight and removing the separated aqueous layer, washing with water was repeated several times to remove sodium chloride, and methyl isobutyl ketone and unreacted phenol were removed from the oil layer under heating and reduced pressure. n = 1.2
Was obtained in an amount of 26 parts by weight.
The obtained resin had a softening point of 62 ° C. and a melt viscosity of 0.3 poise.

Synthesis Example 2 Epichlorohydrin (ECH; the same applies hereinafter) was added to 137 parts by weight of the polycondensate (PH1) obtained in Synthesis Example 1.
Parts by weight, dimethyl sulfoxide (DMSO, the same applies hereinafter)
Charge 150 parts by weight into a reaction vessel, heat, stir, dissolve,
While maintaining the temperature at 45 ° C., the inside of the reaction system was 45 Torr.
, 100 parts by weight of a 40% by weight aqueous sodium hydroxide solution was continuously added dropwise over 4 hours. At this time, after cooling and separating the ECH and water distilled off by azeotropic distillation, the reaction was performed while returning only the organic layer, ECH, into the reaction system. After the completion of the dropwise addition of the aqueous sodium hydroxide solution, the reaction was further performed at 45 ° C. for 3 hours and at 70 ° C. for 30 minutes. Then, washing with water was repeated to remove by-product salts and dimethyl sulfoxide.
Excess epichlorohydrin was distilled off from the oil layer under heating and reduced pressure, and 500 parts by weight of methyl isobutyl ketone was added to the residue and dissolved. This methyl isobutyl ketone solution is heated to 70 ° C. and a 30% aqueous sodium hydroxide solution 1
After adding 0 parts by weight and reacting for 1 hour, washing of the reaction solution with water was repeated until the washing solution became neutral. Then, methyl isobutyl ketone is distilled off from the oil layer under heating and reduced pressure to obtain a highly viscous liquid epoxy resin (EH1) at room temperature.
170 parts by weight were obtained. Epoxy resin (EH1) has an epoxy equivalent of 206 g / eq and a hydrolyzable chlorine concentration of 420
ppm.

Synthesis Example 3 The same operation as in Synthesis Example 1 was carried out except that furfural was changed to 29 parts by weight.
= 1.5 parts by weight of phenolic resin (PH2) was obtained. The obtained resin had a softening point of 72 ° C. and a melt viscosity of 0.6 poise.

Synthesis Example 4 The same operation as in Synthesis Example 2 was carried out except that the phenolic resin (PH1) was changed to 141 parts by weight of the phenolic resin (PH2) to obtain a semi-solid epoxy resin (EH2) at room temperature. ) 180 parts by weight were obtained. Epoxy resin (EH
The epoxy equivalent of 2) is 207 g / eq, and the melt viscosity is 0.2.
The concentration of 4 poises and hydrolyzable chlorine was 440 ppm.

Synthesis Example 5 The same operation as in Synthesis Example 1 was carried out except that the furfural was changed to 58 parts by weight.
= 1.8 phenol resin (PH3) was obtained. The obtained resin had a softening point of 83 ° C. and a melt viscosity of 1.8 poise.

Synthesis Example 6 The same operation as in Synthesis Example 2 was carried out except that the phenolic resin (PH1) was changed to 144 parts by weight of the phenolic resin (PH3).
0 parts by weight were obtained. The epoxy equivalent of the epoxy resin (EH3) is 220 g / eq, the softening point is 56 ° C., and the melt viscosity is 1.
One poise, the concentration of hydrolyzable chlorine was 440 ppm.

Synthesis Example 7 The same operation as in Synthesis Example 1 was carried out except that furfural was changed to 74 parts by weight.
= 2.2 phenol resin (PH4) was obtained. The obtained resin had a softening point of 85 ° C. and a melt viscosity of 2.6 poise.

Synthesis Example 8 The same operation as in Synthesis Example 2 was carried out except that the phenolic resin (PH1) was changed to 148 parts by weight of the phenolic resin (PH4).
0 parts by weight were obtained. The epoxy equivalent of the epoxy resin (EH4) is 220 g / eq, the softening point is 63 ° C., and the melt viscosity is 1.
The concentration of 6 poises and hydrolyzable chlorine was 410 ppm.

Synthesis Example 9 In Synthesis Example 1, phenol was converted to o-cresol 216.
When the same operation was performed except that the furfural was changed to 72 parts by weight, n = 1.8 in the formula (1) was used.
173 parts by weight of a phenolic resin (PH5). The obtained resin has a softening point of 75 ° C. and a melt viscosity of 1.0.
Poise.

Synthesis Example 10 The same operation as in Synthesis Example 2 was carried out except that the phenolic resin (PH1) was changed to 160 parts by weight of the phenolic resin (PH5).
6 parts by weight were obtained. The epoxy equivalent of the epoxy resin (EH5) is 237 g / eq, the softening point is 59 ° C., and the melt viscosity is 1.
The concentration of 0 poise and hydrolyzable chlorine was 370 ppm.

Synthesis Example 11 In Synthesis Example 1, phenol was converted to o-cresol 216.
When the same operation was carried out except that the furfural was changed to 58 parts by weight, n = 1.6 in the formula (1).
139 parts by weight of a phenolic resin (PH6) was obtained. The resulting resin has a softening point of 74 ° C. and a melt viscosity of 0.8.
Poise.

Synthesis Example 12 The same operation as in Synthesis Example 2 was carried out except that the phenolic resin (PH1) was changed to 159 parts by weight of the phenolic resin (PH6).
0 parts by weight were obtained. The epoxy resin (EH6) has an epoxy equivalent of 237 g / eq, a softening point of 55 ° C., and a melt viscosity of 0.5.
The concentration of hydrolyzable chlorine at 6 poise was 370 ppm.

Examples 1 and 2 and Comparative Examples 1 and 2 Mixtures mixed at the weight ratios shown in Table 1 were kneaded with a biaxial roll, pulverized and tableted, and a resin molded product was prepared by transfer molding. ℃ 2 hours, 1 more
Cured at 80 ° C. for 8 hours.

The results of measuring the physical properties of the cured product thus obtained are shown in Table 1. In addition, the measurement of the physical property value was performed by the following method. Moisture absorption: Weight increase rate (%) after leaving a disk-shaped test specimen of 5 cm in diameter x 4 mm in thickness at 121 ° C / 100% RH for 24 hours Copper foil peel strength: 180 ° peel test Measurement temperature; 30 ℃ Pulling speed; 200 mm / min Copper foil; JTC foil 70 μm manufactured by Nikko Gould Co., Ltd.

Table 1 Example Comparative Example 12 12 Epoxy resin EH3 EH5 ECN EBP (parts by weight) 67.7 69.3 65.0 65.1 Hardener PN PN PN PN (parts by weight) 32.3 30. 7 35.0 34.9 TPP (parts by weight) 0.7 0.7 0.7 1.3 Evaluation result Moisture absorption (%) 2.0 1.8 1.8 2.2 Copper foil peel strength (Kg / cm) 2.6 2.5 2.2 2.4

The abbreviations in Table 1 and the following Tables 2 and 3 indicate the following. ECN: EOCN-1020 (Nippon Kayaku Co., Ltd. epoxy equivalent 220 g / eq, softening point 55 ° C.) BPN: YX-4000H (Yukaka Epoxy Co., Ltd.)
Epoxy equivalent: 196) PN: Phenol novolak (softening point: 80 ° C, hydroxyl equivalent: 103 g / eq, manufactured by Nippon Kayaku Co., Ltd.) TPP: Triphenylphosphine (Junsei Chemical Co., Ltd.) ZA-30: crushed silica (manufactured by Tatsumori Co., Ltd.) Release agent: fine powder carnauba (manufactured by Toago Kasei Co., Ltd.) KBM-303: silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd.) Pd: Lead frame with copper lead frame plated with nickel and palladium in this order Au copper lead frame with lead frame plated with nickel, palladium and gold in this order

Examples 3 to 4 and Comparative Examples 3 to 4 A mixture blended in the proportions shown in Table 2 was kneaded with a biaxial roll, crushed and tableted, and a part of a copper lead frame as shown in FIG. 175 by transfer molding
Seal at 60 ° C for 60 seconds, and at 160 ° C for 2 hours,
By post-curing at 80 ° C. for 8 hours, a test piece for evaluating the adhesive strength as shown in FIG. 2 was obtained. The lead frame is made of copper plated with nickel and palladium in this order.
Further, two kinds of palladium plated with gold were used.

The adhesive strength was measured by fixing the resin-sealed portion of the obtained test piece and pulling the pulled-out portion with a universal tensile tester at a crosshead speed of 3 mm / min. The bonding area at this time is 74.25 mm ² . Table 2 shows the measurement results.

Table 2 Example Comparative Example 3434 Epoxy resin EH3 EH5 ECN EBP (parts by weight) 16.4 16.8 15.7 15.6 Curing agent PN PN PN PN (parts by weight) 7.4 7. 4 8.5 8.4 TPP (parts by weight) 0.2 0.2 0.2 0.4 FB-74 (parts by weight) 52.5 52.5 52.5 52.5 ZA-30 (parts by weight) 22.5 22.5 22.5 22.5 Release agent (parts by weight) 0.3 0.3 0.3 0.3 KBM-303 (parts by weight) 0.3 0.3 0.3 0.3 Evaluation result Pd (g / mm ² ) 330 300 260 290 Au (g / mm ² ) 270 280 210 210

Examples 5 to 6 and Comparative Examples 5 to 6 A mixture blended at the ratios shown in Table 3 was kneaded with a biaxial roll, pulverized and tableted, and the following lead frame was subjected to transfer molding at 175 ° C. × 60. Sealing was performed under the conditions of seconds, and post-curing was performed at 160 ° C. for 2 hours and further at 180 ° C. for 8 hours to obtain a test piece for evaluating solder crack resistance. In addition, as a lead frame for evaluating solder crack resistance, a copper 96-pin QFP (14 × 14 × 1.35 mm thick, chip size: 7 × 7 × 0.4 m thick)
m) A lead frame plated with nickel and palladium in this order was used. The test piece obtained as described above was left in a thermostat set at 85 ° C./85% relative humidity for 12 hours to absorb moisture, and then immersed in a 220 ° C. solder bath for 10 minutes. Regarding the package cracks generated at this time, those in which cracks were visually observed were rated as ×, and were not visually recognized, but those in which cracks were recognized in observation with an ultrasonic flaw detector were Δ, visually, When no cracks were observed in any of the ultrasonic flaw detectors, it was rated as ○.

Table 3 Example Comparative Example 5 6 5 6 Epoxy resin EH3 EH5 ECN EBP (parts by weight) 11.3 11.3 10.6 10.5 Curing agent PN PN PN PN (parts by weight) 5.3 5. 0 5.7 5.7 TPP (parts by weight) 0.1 0.1 0.1 0.2 FB-74 (parts by weight) 58.1 58.1 58.1 58.1 ZA-30 (parts by weight) 24.9 24.9 24.9 24.9 Release agent (parts by weight) 0.3 0.3 0.3 0.3 KBM-303 (parts by weight) 0.3 0.3 0.3 0.3 Evaluation result Pd ○ ○ × ○ Au ○ ○ × △

As is clear from the above results, the thermosetting resin composition of the present invention shows good adhesiveness in the cured product. In particular, the adhesiveness to gold and palladium is remarkable, and as a result, a product having more excellent solder crack resistance than others is obtained.

[0055]

Since the thermosetting resin composition of the present invention has excellent moisture resistance (water resistance) and adhesiveness in the cured product, the insulating material for electric and electronic parts (such as a highly reliable semiconductor sealing material). It is extremely useful when used for laminated boards (such as printed wiring boards) and various composite materials including CFRP, adhesives, paints, and the like. In particular, when used as a semiconductor encapsulant, it has excellent solder crack resistance.

[Brief description of the drawings]

FIG. 1 is a copper lead frame used in Examples 3 and 4 and Comparative Examples 3 and 4.

FIG. 2 is a test piece for evaluating adhesive strength used in Examples 3 and 4 and Comparative Examples 3 and 4.

Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat II (Reference) H01L 23/31 F-term (Reference) 4J002 CC03X CD06W GQ05 4J033 CA01 CA04 CA11 CA12 CA13 CA14 CA22 CA34 CB18 CC01 CC07 HB06 4J036 AA04 AF06 AF07 AF08 AF16 AF33 AF35 BA01 DA01 DB06 DB15 DB27 DC03 DC06 DC09 DC19 DC26 DC31 DC41 FB07 FB13 JA07 4M109 AA01 BA01 CA21 EA03 EB03 EB04 EB06 EB07 EB09 EB12 EB19 EC01 EC03 EC09 FA10

Claims (5)

[Claims] (1) Formula (1) (Wherein, a plurality of Rs are independently a hydrogen atom,
Represents a hydrocarbon group, an alkoxy group, a halogen atom or a hydroxyl group of 10 to 10. A plurality of Xs independently represent an oxygen atom or a sulfur atom. A plurality of Qs independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. n is an average value and indicates a real number of 1.2 to 8. A plurality of y's independently represent an integer of 1 to 2. A plurality of i's independently represent an integer of 1 to 6. A plurality of j are independently 1 to 3
Indicates an integer. A plurality of Z represents a hydrogen atom or a glycidyl group. In the case where Z is a hydrogen atom, its melt viscosity at 150 ° C. is 0.5
When it is not less than poise and not more than 5.0 poise and Z is a glycidyl group, its melt viscosity at 150 ° C. is 0.5
A thermosetting resin composition containing a resin having a poise of not less than 3.0 poise. 2. The thermosetting resin composition according to claim 1, wherein in the formula (1), both a resin in which Z is a hydrogen atom and a resin in which Z is a glycidyl group are contained. 3. The semiconductor device according to claim 1, wherein a copper frame having an outermost layer plated with palladium, gold, silver or nickel, or a semiconductor device using the unplated copper frame as a lead frame is sealed. Thermosetting resin composition. 4. A cured product obtained by curing the thermosetting resin composition according to claim 1. 5. A semiconductor device encapsulated with the thermosetting resin composition according to claim 1.