JP3010697B2 - Epoxy resin composition, epoxy resin cured product and use - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an epoxy resin composition having excellent moisture resistance, a partially cured product thereof, a cured product thereof, an adhesive comprising the same, and a joining member coated with the adhesive. About.

[Conventional technology]

Epoxy resins are widely used in the fields of adhesives, paints, molded products, etc. because of their excellent adhesive properties, abrasion resistance, chemical resistance, and the like.

In recent years, high reliability has been required for electrical and electronic parts, aerospace parts, and the like, and therefore, excellent performance is also required for resins used for these parts. For example, in a semiconductor device, particularly a semiconductor device having optical characteristics used as an image sensor or the like, when dust or moisture enters therein, the characteristics are reduced, so that hermetic sealing properties, particularly moisture resistance, are important factors. For this purpose, the semiconductor element is fixed in a hollow box-shaped casing made of ceramics, plastic, etc., and a lid made of glass, ceramics, plastic, etc.
When a semiconductor device is hermetically sealed by bonding the same, an adhesive for hermetic sealing excellent in adhesiveness and humidity resistance is required.

Conventionally, as a resin composition used for such an adhesive for hermetic sealing, an ortho-cresol novolak-based epoxy resin composition, a phenol novolak-based resin composition, a tetraglycidyldiaminodiphenylmethane-based resin composition or a diaminodiphenylsulfone-based resin Compositions and the like have been used.

However, the moisture resistance of the cured resin obtained from these resin compositions, particularly the moisture resistance of the hermetic sealing adhesive, is not yet satisfactory, and there is room for improvement.

[Problems to be solved by the invention]

An object of the present invention is to provide an epoxy resin composition having excellent moisture resistance in addition to the properties inherent to an epoxy resin, a partially cured product thereof, a cured product and an adhesive comprising the same, and the application of the adhesive. It is to provide a joining member.

[Means for solving the problem]

The present invention is the following epoxy resin composition, a partially cured product thereof,
It is a cured product, an adhesive comprising the same, and a joining member to which the adhesive has been applied.

(1) a resin base having a reactive epoxy group, and the following formula [1] An epoxy resin composition comprising a phenol derivative represented by the formula:

(2) The epoxy resin composition according to (1), wherein the compounding amount of the phenol derivative is 0.7 to 1.5 equivalents to the epoxy group of the resin base material.

(3) The epoxy resin composition according to the above (1) or (2), in which the curing reaction has partially progressed.

(4) A cured epoxy resin obtained by curing the epoxy resin composition or the partially cured product according to any one of (1) to (3).

(5) An adhesive comprising the epoxy resin composition, a partially cured product or a cured product according to any one of the above (1) to (4).

(6) A joining member to which the adhesive according to (5) is applied.

As the resin base material used in the present invention, an organic epoxide substance having a reactive epoxy group (oxirane ring) in the molecule can be used.

As such a resin base material, various known epoxy resins can be used.For example, polyepoxy resins obtained by reacting epihalohydrin such as epichlorohydrin or glycerol dichlorohydrin with a compound having a phenolic or alcoholic hydroxyl group can be used. Glycidyl ether; polyglycidyl ester obtained by reacting epihalohydrin or glycerol dichlorohydrin with a polycarboxylic acid; novolak epoxy resin obtained by reacting novolak with epihalohydrin; polymerization of ethylene-type unsaturated epoxy group-containing monomer Or a polyolefin type epoxy resin obtained by copolymerization; an alicyclic epoxy resin; a poly (N-glycidyl) compound; a poly (S-glycidyl) compound; an epoxy resin having an epoxy group bonded to a hetero atom. Is .

Examples of the polyglycidyl ether include, for example, epihalohydrin or glycerol dichlorohydrin, mononuclear phenols such as resorcinol, hydroquinone, and catechol; bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) sulfone, 1,1, 2,
2-tetrakis (4-hydroxyphenyl) ethane, 2,2
-Reaction with compounds having a phenolic hydroxyl group such as polynuclear phenols such as -bis (4-hydroxyphenyl) propane (bisphenol A), bisphenol F, and 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane And polyglycidyl ether obtained by the reaction. In addition, epihalohydrin or glycerol dichlorohydrin and the like, ethylene glycol, diethylene glycol, triethylene glycol, higher polyoxyethylene glycol, propane-1,2-diol, polyoxypropylene glycol, propane-1,3-diol, neopentyl glycol, Butane-1,4-diol, polyoxybutylene glycol, pentane-1,5-
Diol, hexane-1,6-diol, hexane-2,4,6
Acyclic alcohols such as triol, glycerol, 1,1,1-trimethylolpropane, pentaerythritol, sorbitol, poly (epichlorohydrin); resorcitol, quinitol, bis (4-hydroxycyclohexyl) methane, 2 Alicyclic alcohols such as 1,2-bis (4-hydroxycyclohexyl) propane and 1,1-bis (hydroxymethyl) cyclohexene-3;
N, N-bis (2-hydroxyethyl) aniline, 4,4'-
Examples thereof include polyglycidyl ether obtained by reacting a compound having an alcoholic hydroxyl group such as an alcohol having an aromatic nucleus such as bis (2-hydroxyethylamino) diphenylmethane.

The polyglycidyl ester includes, for example, epihalohydrin or glycerol dichlorohydrin, and oxalic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dimerized or trimerized linole Aliphatic polycarboxylic acids such as acids; alicyclic polycarboxylic acids such as tetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, hexahydrophthalic acid, and 4-methylhexahydrophthalic acid;
Examples thereof include polyglycidyl esters obtained by reacting polycarboxylic acids such as aromatic polycarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid.

Examples of the novolak include formaldehyde,
Novolaks obtained from aldehydes such as acetaldehyde, chloral and furfural aldehyde and phenols such as phenol, 4-chlorophenol, 2-methylphenol and 4-tert-butylphenol are exemplified.

Examples of the alicyclic epoxy resin include alicyclic diepoxy acetal, alicyclic diepoxy adipate, alicyclic diepoxycarboxylate, and vinylcyclohexene dioxide.

Examples of the poly (N-glycidyl) compound include epichlorohydrin, aniline, n-butylamine,
Amines containing at least two or more amino hydrogen atoms such as bis (4-aminophenyl) methane and bis (4-methylaminophenyl) methane; cyclic ureas such as triglycidyl isocyanurate, ethylene urea and 1,3-propylene urea;
Hydantoin (hydantoin) such as 5,5-dimethylhydantoin
(ins) with a N, N'-diglycidyl derivative, and a product obtained by dihydrochlorination with the like.

Examples of the poly (S-glycidyl) compound include di-S-glycidyl derivatives of dithiols such as ethane-1,2-dithiol and bis (4-mercaptoethylphenyl) ether.

As the epoxy resin in which the epoxy group is bonded to a hetero atom, for example, N, N, O- of p-aminophenol
Triglycidyl derivatives or glycidyl ether-glycidyl esters of salicylic acid or phenolphthalein.

Among the above epoxy resins, a novolak epoxy resin, in particular, an orthocresol novolak epoxy resin can be preferably used. In addition, as a resin base,
A commercially available epoxy resin can also be used. The resin base can be used alone or in combination of two or more.

The phenol derivative represented by the formula [1] used in the present invention is used as a curing agent.

The phenol derivative represented by the formula [1] is commercially available, and a commercially available product thereof can also be used.

The epoxy resin composition of the present invention is a resin composition containing the resin main agent and the phenol derivative as essential components. The proportion of the phenol derivative represented by the above formula [1] in the epoxy resin composition of the present invention is preferably 0.7 to 1.5 equivalents, more preferably 0.8 to 1.2 equivalents, based on the epoxy groups in the resin base.

The epoxy resin composition of the present invention comprises, in addition to the above essential components, other components, such as a curing agent, a catalyst, a solvent, and an additive used in a conventional epoxy resin (composition). It can be used within a range that does not impair.

As a curing agent that can be used as other components, for example, unmodified aliphatic polyamine, modified aliphatic polyamine, unmodified aromatic polyamine, modified aromatic polyamine, unmodified alicyclic polyamine, modified alicyclic polyamine,
Unmodified polyaminoamide, modified polyaminoamide, compounded amine curing agent, tertiary amine, condensation polymer of amine derivative and formaldehyde (unia formaldehyde, melamine formaldehyde, etc.), unmodified aliphatic acid and acid anhydride, unmodified fat Cyclic acids and acid anhydrides, unmodified aromatic acids and acid anhydrides, modified acids and acid anhydrides, halogenated acid anhydrides and acids, dicyandiamides and derivatives, boron halide complex compounds, organometallic complex compounds, polythiols, Examples include condensation polymers of phenol formaldehyde, phenols and derivatives, other compounds containing a hydroxyl group, isocyanates, blocked isocyanates, ketimines, acid dihydrazides and imidazoles and derivatives.

Specific examples of such a curing agent include unmodified aliphatic polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and diethylaminopropylamine, and modified aliphatic polyamines which are modified products thereof; m-xylenediamine , Diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone, etc. and modified aromatic polyamines which are modified products thereof; mensendiamine, isophoronediamine, N-aminoethylpiperazine, 3,9-bis ( Unmodified such as 3-aminopropyl) -2,4,8,10-tetraoxyspiro (5,5) undecane adduct, bis (4-amino-3-methylcyclohexyl) methane, bis (4-aminocyclohexyl) methane Alicyclic polyamines and their modifications Modified alicyclic polyamines, which are phthalic anhydride, tetrahydrophthalic anhydride,
Hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, dodecylsuccinic anhydride, chlorendic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, ethylene glycol Acid anhydrides such as bis (anhydrotrimate), methylcyclohexenetetracarboxylic anhydride, trimellitic anhydride and polyazeleic anhydride; polymercaptans such as polymercaptan and polysulfide; resole type phenolic resins; bisphenol A And bisphenols such as bisphenol F; hydroxybenzene derivatives such as hydroquinone, pyrogallol and broroglucin; 1,1,3-tris (2-
Methyl-4-glycidoxy-5-t-butylphenyl)
Butane, 1- [α-methyl-α- (4′-glycidoxyphenyl) ethyl] -4- [α ′, α′-bis (4 ″-
Compounds having a glycidoxyphenyl group such as glycidoxyphenyl) ethyl] benzene; and novolak resins such as phenol novolak resin, phenyl novolak resin, cresol novolak resin, and octylphenyl novolak resin.

These curing agents can be used alone or in combination of two or more.

Catalysts that can be used as other components include, for example, 2-methylimidazole, 2-ethyl-4-
Known epoxy resin curing catalysts such as methylimidazole, 2,4,6-tris (dimethylaminomethyl) phenol, and monoethylamine complex can be used.

These catalysts can be used alone or in combination of two or more.

Solvents that can be used as other components include, for example, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene, xylene and mesitylene; amides such as dimethylformamide and dimethylacetamide; ethylene glycol monomethyl ether And ethers such as ethylene glycol monobutyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, esters such as methyl acetate, ethyl acetate and butyl acetate; and alcohols such as methanol, ethanol, isopropyl alcohol and butanol. .

These solvents can be used alone or in combination of two or more.

Additives that can be used as other components include, for example, inorganic fillers such as silica, alumina, talc, clay, zinc oxide, titanium oxide, and glass fiber; antimony oxide, halides, phosphides, and other flame retardants Agents; fillers such as release agents, pigments, silane coupling agents and the like; surface treatment agents and the like.

The epoxy resin composition of the present invention can be produced by mixing the resin base, the phenol derivative, and other components that are blended if necessary.

The epoxy resin composition of the present invention allows the curing reaction to proceed as it is to obtain a partially cured product or a cured product. In this case, a part of the curing reaction proceeds only by mixing the resin base and the phenol derivative. In particular, when dissolved in a solvent, if the solvent is removed by heating as a drying step, the curing reaction proceeds, and a partially cured product is generated.

The epoxy resin composition or partially cured product of the present invention cures at normal temperature and normal pressure over a long period of time, but is preferably cured under heating. Curing conditions vary depending on the type of resin base agent, curing agent and other additives, the mixing ratio, etc.,
Generally, the temperature is 80-220 ° C, preferably 100-200 ° C,
The pressure is suitably normal pressure to 6 kg / cm ² , preferably 1 to 4 kg / cm ² .

The epoxy resin composition of the present invention and the cured product obtained from the partially cured product thereof, in addition to the inherent properties of the epoxy resin, are further excellent in moisture resistance, particularly because the water absorption rate and diffusion coefficient are small, It can be used as an adhesive, a paint or a molding material for electric and electronic parts or aerospace parts, as well as a field where a conventional epoxy resin is used, and is particularly excellent as an adhesive for hermetic sealing.

When used as a molding material, a method in which a resin composition is melt-kneaded with a heating roll or the like, and a method in which a kneaded material is cooled and pulverized to form a pulverized product by hot press molding or the like, or a method in which the pulverized material is dissolved in a solvent and molded by casting or the like And other methods.

When used as an adhesive or paint, it is usually dissolved in a solvent to form an adhesive or paint. In this case, a one-pack type or a two-pack type may be used. In the case of an adhesive, a product can be obtained in a state where a paint is applied to the joining member. In this case, it is preferable to form a coating material which is partially cured by heating and drying.

Cured product obtained from the epoxy resin composition of the present invention,
Since it has excellent moisture resistance, and particularly has a low water absorption rate and diffusion coefficient, it is excellent as an adhesive for hermetic sealing, particularly as an adhesive for hermetic sealing for electronic components such as semiconductor devices. Semiconductor devices that require an airtight seal include a charge coupled device (CCD).
d Device), MOS (Metal Oxide Semiconductor), CPD
(Charge Primming Device) etc., and
EPROM (Erasable and Programmable / Read Only Memor
There is a semiconductor device using a semiconductor element having optical characteristics, such as a memory which can be written and erased by light such as y).

FIG. 1 is a sectional view showing a general semiconductor device. In FIG. 1, a semiconductor device 1 includes a semiconductor device (IC chip) on a die pad 3 formed in a box-shaped casing 2.
4 is fixed and connected to a lead 6 by a bonding wire 5, and an opening of the casing 2 is connected to a lid (lid).
7 is bonded (sealed) with a hermetic sealing adhesive 8 and hermetically sealed to form a package 9.

In FIGS. 2 and 3, the bonding member 10 has an adhesive 8 layer formed over the entire periphery of the rear surface of the lid 7.

The semiconductor device 1 shown in FIG. 1 generally requires hermetic sealing so that dust and the like do not enter. In the semiconductor device 1 having the above-described optical characteristics, the lid 7 is made of a transparent material such as glass. Since the light transmittance is required, the adhesive 8 is required to have a hermetic sealing property, particularly moisture resistance, in order to prevent moisture from dewing to reduce the light transmittance.

The adhesive containing the epoxy resin composition of the present invention, its partially cured product or cured product is suitable as an airtight sealing adhesive for such a semiconductor device. Here, the materials of the casing 2 and the lid 7 to be bonded are not limited, and can be applied to any material such as metal, ceramics, glass, and plastic.

1, the package 9 can be formed by applying the adhesive 8 to the casing 2 or the lid 7 and curing the package when the semiconductor device 1 is packaged. As shown in FIGS. 2 and 3, an adhesive 8 is applied to the lid 7 in advance and dried to form a joining member 10. The joining member 10 is attached to the casing 2 and cured by heating and pressing. Then, the package 9 can be formed.

The epoxy resin composition of the present invention, its partially cured product, or cured product is excellent as such an adhesive for hermetic sealing, but is not limited to this application, and is utilized for various applications by utilizing its properties. can do.

〔The invention's effect〕

According to the present invention, the phenol derivative represented by the above formula [1] is used as a curing agent, so that in addition to the inherent properties of the epoxy resin, it has excellent moisture resistance, water absorption rate and diffusion coefficient. Epoxy resin composition, a partially cured product thereof, a cured product thereof, and an adhesive comprising the same, and a joining member coated with the adhesive.

〔Example〕

Next, examples of the present invention will be described. The main resin and curing agent used in each example are as follows.

Resin base agent: a) Orthocresol novolak epoxy manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent = 205-230, trade name; EOCN104)
S), hereinafter referred to as “resin base material a”.

Structural formula; Curing agent: a) A phenol derivative in which the methyl group of the formula [1] is replaced by a hydrogen atom (hereinafter referred to as phenol derivative a).

b) A phenol derivative of the formula [1] (hereinafter referred to as phenol derivative b).

c) Phenol novolak (hydroxyl equivalent = 100-110, trade name; PN-100) manufactured by Nippon Kayaku Co., Ltd., hereinafter referred to as curing agent c.

Structural formula; Comparative Example 1 100 parts by weight of resin base material a, 45 parts by weight of phenol derivative a and 1 part by weight of 2-ethyl-4-methylimidazole as a catalyst were melt-kneaded at 110 ° C. using a heating roll, and then the kneaded product was cooled. Crushed.

The obtained pulverized product was cured into a 10 mm × 10 mm × 1.5 mm sheet by hot press molding (150 ° C. × 4 hours). This cured sheet was subjected to a boiling water absorption test by the following method. Table 1 shows the results. The pulverized product obtained by cooling and pulverizing the kneaded product was in an uncured state.

Boiling water absorption test The cured sheet was immersed in boiling distilled water, and the weight change due to water absorption was measured every several hours to several tens of hours until the weight change disappeared (saturated water absorption state). Square root of time Water absorption rate from the ratio of initial water absorption (m) to water From the initial water absorption rate and the saturated water absorption (ms). Was asked respectively.

Example 1 A cured sheet was produced in the same manner as in Comparative Example 1, except that 47 parts by weight of the phenol derivative b was used instead of 45 parts by weight of the phenol derivative a, and a boiling water absorption test was conducted in the same manner. . Table 1 shows the results.

Comparative Example 2 A cured sheet was produced in the same manner as in Comparative Example 1 except that 48 parts by weight of the curing agent a was used instead of 45 parts by weight of the phenol derivative a, and the boiling water absorption test was performed in the same manner. . Table 1 shows the results.

[Brief description of the drawings]

FIG. 1 is a sectional view of a semiconductor device, FIG. 2 is a bottom view of a joining member, and FIG. 3 is a sectional view taken along line AA of FIG. In the drawings, the same reference numerals denote the same or corresponding parts, 1 is a semiconductor device, 2 is a casing, 3 is a die pad, 4 is a semiconductor element, 5 is a bonding wire, 6 is a lead, 7 is a lid, 8 is an adhesive, 9 is a package, 10 is a joining member.

────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Runa Aragaki 580-32 Takuji, Nagaura, Sodegaura-cho, Kimitsu-gun, Chiba Pref. Mitsui Petrochemical Industry Co., Ltd. (56) References JP-A-3-115424 (JP, A) JP-A-3-198353 (JP, A) JP-A-2-38413 (JP, A) JP-A 1-292029 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) ) C08G 59/62 C09J 163/00-163/10

Claims (6)

(57) [Claims] 1. A resin base having a reactive epoxy group, and a compound represented by the following formula [1]: An epoxy resin composition comprising a phenol derivative represented by the formula: 2. The epoxy resin composition according to claim 1, wherein the amount of the phenol derivative is 0.7 to 1.5 equivalents relative to the epoxy group of the resin base. 3. The epoxy resin composition according to claim 1, wherein the curing reaction partially proceeds. 4. A cured epoxy resin obtained by curing the epoxy resin composition or the partially cured product according to any one of (1) to (3). 5. An adhesive comprising the epoxy resin composition, a partially cured product or a cured product according to any one of (1) to (4). 6. A joining member to which the adhesive according to claim (5) is applied.