JPS61275325A - Resin composition for sealing electronic element - Google Patents

Abstract

PURPOSE:The titled composition which can be readily cured by irradiation with a small dose of light to give a cured product excellent in cracking resistance, electrical properties, moisture resistance and adhesiveness, obtained by mixing two photopolymerizable compounds with an epoxy resin, a reaction accelerator and a photopolymerization initiator. CONSTITUTION:100pts.wt. mixture obtained by mixing 5-80pts.wt. photo polymerizable compound (A) having at least one of each of photosensitive groups such as an epoxy group and a (meth)acrylic group in the molecule with 5-90pts. wt. photopolymerizable compound (B) having at least one of each of carboxyl and said photosensitive group in the molecule [e.g., mono(meth)acryloyloxyethyl hexahydrophthalate], 5-90pts.wt. epoxy resin (C) (e.g., bisphenol A epoxy resin) so that the ratio of the number of COOH groups to that of NCO groups is smaller than unity is mixed with 0.01-10pts.wt. reaction accelerator (D) (e.g., 2-methylimidazole) and 0.001-10pts.wt., per total of A+B, photopolymerization initiator (E), e.g., acetophenone (derivative).

Description

[Detailed description of the invention] [Technical field of invention] The present invention relates to a resin composition for electronic device side 1L.

To be more precise, III+! Easy to operate for
The present invention relates to a resin composition for use in Ichiko Motomo period 1 which also has a short curing time.

[Technical background of the invention and its problems]

In recent years, in the field of encapsulation of semiconductor devices, with the increasing integration of semiconductor elements, various functional units of the elements have become finer. The size of the Niko beret itself is rapidly increasing.

Conventionally, element pellets such as LSI were made of epoxy resin, etc. However, a method has been used in which this is mounted on a circuit board.

However, with this method, there is a limit to the increase in density, and since it involves steps such as soldering, it has been difficult to manufacture extremely high-density and micro-sized circuit boards.

As a solution to this problem, a circuit is formed on a substrate such as a ceramic substrate, an unsealed chip such as an LSI is mounted on it, and then the entire circuit is covered with an appropriate resin.
) +I- method is adopted.

In this case, thermosetting resin is used as the resin for Tsukiichi. However, conventionally used thermosetting resins take a long time to harden, so it takes a long time to stop M.

Furthermore, since the curing force method is also complicated, the 1F margin of the resin during curing work is generally low.

In order to shorten the sealing time, it is sufficient to use a resin with a short curing time, but when such a resin is used, its properties as a sealing resin such as crack resistance, electrical properties, and moisture resistance may be affected. decline was inevitable.

[Purpose of the invention]

The present invention was made with the aim of solving the above-mentioned problems.It can be easily cured with a simple operation, and the cured product has excellent crack resistance, electrical properties, The present invention provides a resin composition for encapsulating electronic devices that has moisture resistance, adhesive properties, and the like.

[J of invention! Essential]

The present invention provides (a) 5 to 80 parts by weight of a photopolymerizable compound having an epoxy group and a photosensitive group in the molecule.

(b) 1 part of photopolymerizable compound having a carboxyl group and a photosensitive group in the molecule, 5 to 90 polymers, (c) 1 part of epoxy tree
ii5 to 30 tons and (d) reaction accelerator 0.01 to
10 parts by weight, but (a), (b) and (c)
) component resin overall welfare 100! ]! It shall be one part;
Furthermore, based on the total amount of components (a) and (b), 0.00
The present invention relates to an i4 tL: Jl resin composition for electronic devices, which is obtained by blending (e) a photopolymerization initiator having 1 to 10 moieties.

Resin composition for electronic device JLj II of the present invention (hereinafter referred to as
ffi is a component of (a) a "composition".
) The photopolymerizable compound having an epoxy group and a photosensitive group in its molecule is not particularly limited as long as it has at least one photocurable double bond as an epoxy group and a photosensitive group in one molecule.

Examples of the epoxy group in this compound include those shown below. As a light-curing Fuwajito bond that simultaneously exists in this compound,
For example, the following can be mentioned. Among these.

is preferred.

In addition, in the above structural formula, the hydrogen atom bonded to the carbon atom is 11! It may be substituted with a halogen atom such as fluorine, an alkyl group having 31 to 6 carbon atoms, a phenyl group, or the like.

This compound can be arbitrarily synthesized and constructed by molecular design depending on the purpose, but it can be easily synthesized by reacting commonly used epoxy resin with acrylic acid, methacrylic acid, cinnamic acid, maleic acid, etc. You can also do that.

Epoxy resins used in this method include 1, for example, bisphenol A type epoxy resin; bisphenol F type epoxy resin; phenol nopola type epoxy resin; alicyclic epoxy resin; nitrogen-containing epoxy resins such as triglycidyl isocyanate and hydantoin epoxy. Resin: 1111 rib group epoxy resin such as hydrogenated bisphenol A type epoxy resin, propylene glycol diglycidyl ether, pentaerythritol polyglycidyl ether;
Epoxy resin obtained by reaction of aromatic, aliphatic or alicyclic carboxylic acid with epichlorohydrin; Spiro ring-containing epoxy resin; Glycidyl ether type epoxy resin which is a reaction product of 0-allylphenol novolak compound and epichlorohydrin; Bisphenol A
Examples include glycidyl ether type epoxy resins which are reaction products of epichlorohydrin and diallyl bisphenol compounds having an allyl group at the ortho position of each hydroxyl group, and at least one resin selected from the group consisting of these is used. be able to.

The blending ratio of component (a) is (a), (b) and (c)
If the component resin Soja is 100 layers, 5-8Of
f! 2 to 20 layers, preferably 2 to 20 layers.

If the blending ratio exceeds 80 parts by weight, the crack resistance of the cured product after after-curing will decrease.

(b) A photopolymerizable compound having a carboxyl group and a photosensitive group in the molecule, which is the Hitotsubashi r & element of the composition of ``Kihatsu'', is a compound having at least one carboxyl group and one photosensitive group in the molecule. Not particularly limited 6 For example, unsaturated carboxylic acid compounds such as acrylic acid, methacrylic acid, fumaric acid, and chlorinated acid;
1. Or glycidyl methacrylate and succinic acid,
A compound obtained by reacting a polybasic acid such as maleic acid or terephthalic acid, and corresponding mono(2-hydroxy-3-methacryloyloxypropyl)hexahydrophthalate, mono(2-hydroxy-3-acryloyloxy) propyl) hexahydrophthalate, mono(
2-hydroxy-3-methacryloyloxypropyl)
Compounds such as maleine (., mono(2-hydroxy-3-acryloyloxypropyl) succinate): Compounds obtained by reacting hydroxyl group-containing methacrylate, hydroxyl group-containing methacrylate, and polysalt acid-free compounds. Phthalic acid monoacryloyloxyethyl ester, hexahydrophthalic acid monoacryloyloxyethyl ester, hexahydrophthalic acid monomethacryloyloxyethyl ester, phthalic acid monoacryloyloxypropyl ester, succinic acid monoacryloyloxyethyl ester, succinic acid monoacrylic acid ester corresponding to Compounds such as methacryloyloxyethyl ester can be mentioned.

The blending ratio of component (b) is (a), (b) and (c
) Resin set of ingredients! If the shadow is 1'00ffi1 part,
It is 1 part by weight of 5 to 90 parts by weight, preferably 20 to 70 parts by weight. The blending ratio is less than 5 parts by weight.

It is not possible to impart sufficient properties such as crack resistance to the cured product after after-curing. If the amount exceeds 90 parts by weight, the strength of the cured product after the after-after-afternoon treatment will be insufficient.

As the epoxy resin (c) which is -a1 & straddle of the composition of the present invention, commonly used epoxy resins can be used.

For example, bisphenol A type epoxy resins: bisphenol F type epoxy resins; phenol/borac type epoxy resins; alicyclic epoxy resins; heterocyclic epoxy resins such as triglycidyl isocyanate and hydantoin epoxy; hydrogenated bisphenol A type epoxy resins, propylene Aliphatic epoxy resins such as glycol diglycidyl ether upentaerythritol monoglycidyl ether; epoxy resins obtained by reaction of aromatic, aliphatic or cycloaliphatic carboxylic acids with epichlorohydrin; spiro ring-containing epoxy resins ; ortho allyl
Glycidyl ether type epoxy resin which is a reaction product of a phenol novolak compound and epichlorohydrin;
Examples include a glycidyl ether type epoxy resin which is a reaction product of a diallylbisphenol compound having an allyl group at the orne position of each water-resistant group of bisphenol A and epichlorohydrin.

The blending ratio of component (c) is (a), (b) and (
c) When the total amount of resin of component is 100 parts by weight, 5 to 9
0 parts by weight, preferably 20 to 70 parts by weight. The blending ratio is 5! If the amount is less than 1 part RF, it is difficult to provide a well-balanced property of the cured product after curing, such as crack resistance, moisture resistance, electrical properties, and mechanical properties. If it exceeds 90 parts by weight, the mechanical strength of the cured product after secondary curing will be extremely low, and it will be difficult to remove the tank. Furthermore, the curing speed is slowed down.

In addition, when blending components (a), (b), and (c), the number of epoxy groups and the number of carboxyl groups in each of these components, 17, is equal to
(a) so that ≧1.

If components (b) and (c) are blended, the cured product of the resulting composition will have a significantly low volume resistivity after a constant temperature and humidity test, so this should be avoided.

The reaction promoter (d), which is one component of the present invention, is a reaction promoter between a carboxyl group and an epoxy group. Examples of this reaction accelerator include 2-methylimidazole,
2-Imidazoles such as ethylimidazole, tertiary amines such as triethanolamine, triethylamine, N-methylmorpholine, dialkylaminoethanol, phosphines such as triphe, neal*sphine,
Examples include phenols such as 21B-1-butyl-4-methylphenol, and compounds such as tetra(S-butyl) titanate and stanasoftate.

The blending ratio of this component (d) is (a), (b) and (c).
When the total amount of component resin is 100 parts by weight, 0.00
The amount is 1 to 10 parts by weight, preferably 0.2 to 2 parts by weight. If the blending ratio is less than 0.01 parts by weight, the reaction between epoxy groups and carboxyl groups in the after-cure composition may not occur within 1 minute. If it exceeds 10 parts by weight, the mechanical strength of the final cured product may decrease.

The photopolymerization initiator, which is one component of the composition of the present invention, is not particularly limited. For example, aromatic compounds, hydrocarbons, benzophenone and its derivatives.

Examples include 0-benzoylbenzoic acid ester, acetophenone and its derivatives, benzoin and benzoin ether and its derivatives, xanthone and its derivatives, thioxanthone and its derivatives, disulfide compounds, quinone compounds, halogenated hydrocarbons and amines.

Among these, acetophenone and its derivatives and benzoin ether and its derivatives are preferred.

Examples of acetophenone and its derivatives include acetophenone, 4-methylacetophenone, 3-methylacetophenone, and 3-methoxyacetophenone. Examples of benzoin, benzoin ether, and derivatives thereof include 1.

Examples include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin-n-butyl ether, benzoin triphenylsilyl ether, and the like. These photopolymerization initiators can be used alone or in an appropriate combination of two or more. The blending amount is 0.001 to 1 based on the total amount of components (a) and (b).
It is 0-fold trapping part, preferably 0.01 to 3-fold trapping part.

Furthermore, fillers such as silica, alumina, and glass fibers, antifoaming agents, defoaming agents, pigments, and the like can be added to the composition of the present invention, if necessary.

The composition of the present invention can be obtained by uniformly stirring and mixing the above-mentioned predetermined components of each component using an appropriate method.

Below, an example of use will be described in which the composition of the present invention is used to seal an electronic device.

Using the composition of the present invention, a circuit board containing a chip such as an LSI can be prepared by a method such as dripping. Next, it can be easily primary cured by irradiating it with light for a short period of time. However, the tank has disappeared and is strong enough to withstand normal handling. ,
Stocking becomes easy, and it is possible to after-cure the pre-cured circuit board to a large extent at one time.

The manufacturing process can be simplified and manufacturing costs can also be reduced.

During primary curing, the wavelength of the irradiated light varies depending on the composition, but is usually 180 to 700 nm. Within this range, wavelengths in the ultraviolet region are particularly preferred.

The duration of light irradiation IIv varies depending on the proportion of the composition, the type of light source, etc., but is usually 1 to 1800 seconds, preferably 10 to 60 seconds.

The primary cured product obtained in this manner is then subjected to after-curing to impart excellent properties such as electrical properties, mechanical properties, +M moisture properties, and crack resistance.

The heating temperature and time in after-cure vary depending on the blending ratio of the composition, but are usually 50 to 200°C.
, for 1 to 300 minutes. Preferably 120~
At 150°C, it is 10 to 60 minutes.

If the heating temperature and time are less than 50°C and less than 1 minute, the carboxyl group or epoxy group in one composition will remain in an unreacted state, so the cured product will be
It is difficult to obtain satisfactory characteristics.

If the temperature exceeds 200°C and the duration exceeds 300 minutes, the high temperature may cause deterioration of one composition, and the properties of the cured product may deteriorate.

The composition of the present invention can be applied to LSI devices, which are currently in increasing demand.
It is suitable for integrally sealing electronic elements and circuits such as ICs and LEDs.

The present invention will be described in further detail with reference to Examples and Comparative Examples.

[Examples 1 to 5] Component (a) of the composition of the present invention was prepared as follows.

A mixture of 1 kg of epoxy resin Epicoat 828 (manufactured by Shell Chemical Co., Ltd., epoxy value 19B) and 20 g of aluminum acetylacetonado was heated to 120°C. Then, 364 g of acrylic acid was added dropwise to the mixture over 20 minutes, and then
The mixture was heated and stirred at 20°C for 10 hours to obtain component (a). The reaction rate was 85%.

Component (a) obtained in this manner, (b) hexahydrophthalic acid monomethacryloyloxy ester 4-Az ester, (c) Epicote 828 (U product name, manufactured by Shell Chemical Co., Ltd., epoxy value 138), (d ) Grocure 117
3 (registered trademark, manufactured by Merck Japan) and (e)+・
Each component of liphenylphosphine was added in the proportions shown in Table 1.
The mixture was mixed uniformly to obtain a composition of the present invention.

Using this composition, the tests described above were conducted. The results are shown in Table 2.

(1) Crack resistance test Three micro glass pieces of 8.5 x 8.5 x O, 2B (m error) were tested. It was fixed on a slide glass of 5×25×1 (nm) at loam intervals. This micro glass piece was sealed with M1 composition and irradiated with light for 1 minute using a Bow/CV high pressure mercury lamp. Thereafter, after-curing was performed at 150° C. for 30 minutes to prepare a test piece. Using this test piece, -20℃ and 80℃ were tested using a TST tester.
under IO cycle conditions for 30 minutes each.
In Table 2, the denominator indicates the number of samples, and the numerator indicates the number of defective products with cracks.

(2) Electrical property test The composition was applied to a copper plate, irradiated with light for 1 minute using an 80w/cw high-pressure mercury lamp, and then after-cured for 30 minutes at 150'C to obtain a test piece. Using this test piece, the volume resistance at 25°C and 60°C was measured and the electrical properties were evaluated.

(3) Using the test piece prepared in constant temperature and humidity test (2), the temperature was 60°C and the humidity was 9°C.
After being exposed to 0% constant temperature and humidity conditions for 100 hours, 25℃
The volume resistivity at 60° C. was measured to evaluate the 16I humidity.

(4) Adhesion test The composition was applied to a glass plate-L and cured under the same conditions as in (2) to obtain a test piece. In Table 2, the denominator is the number of squares before the test, and one numerator is the number of squares remaining on the glass plate after the test. .

Comparative Example 1 Ehiko) 828501, la M, hexahydrophthalic acid monomethacryloyloxyethyl ester 5
0 weight 4 parts, Darocure-11734 weight #i part, triphenylphosphine 0.5 weight! I! , parts were mixed to obtain a composition of a comparative example. This composition was used to seal the test piece used in the crack resistance test of Example 1. This was irradiated with an 8 Qw/cw high pressure mercury lamp for 1 minute, but curing was insufficient and tack remained.

Comparative Example 2 Ehicoat 82840j TZ amount fi, 80 parts by weight of hegisahydrophthalic acid monomethacryloyloxyethyl ester, Talocure 11F 34ffi & 1 part, and 0.5 parts of triphenylphosphine were mixed together with the composition of Comparative Example. did. This composition was used to seal the test piece used in the crack resistance test of Example 1. This was irradiated with an 80w/cw high pressure mercury lamp for 1 minute. This resulted in a cured product that was sufficiently resistant to normal handling. Each test in Example 1 was conducted using this cured product which was further after-cured at 150° C. for 30 minutes.

The results are shown in Table 3.

〔Effect of the invention〕

The composition of the present invention can be easily cured with a small amount of light irradiation, and therefore, circuits of arbitrary shapes can be efficiently formed.

Furthermore, the cured product obtained by curing the composition of Invention 1 had excellent crack resistance, electrical properties, IIF11 wettability, and adhesiveness.

Table 1

Claims (1)

[Scope of Claims] 1. (a) 5 to 80 parts by weight of a photopolymerizable compound having an epoxy group and a photosensitive group in the molecule, (b) 5 to 80 parts by weight of a photopolymerizable compound having a carboxyl group and a photosensitive group in the molecule 90 parts by weight, (c) 5 to 90 parts by weight of an epoxy resin, and (d) 0.01 to 10 parts by weight of a reaction accelerator, provided that (a)
, (b) and (c) components shall be 100 parts by weight, and (e) photopolymerization of 0.001 to 10 parts by weight based on the total amount of components (a) and (b). A resin composition for encapsulating electronic devices, characterized in that it is obtained by blending an initiator. 2. The composition according to claim 1, wherein the photosensitive groups in component (a) and component (b) are each an acrylic group or a methacrylic group.