JPH0453865A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermosetting resin composition which can give a cured product excellent in wet heat resistance and retaining low-stress properties by mixing a methyl-substituted novolac epoxy resin with a plurality of specified components. CONSTITUTION:The title composition is obtained by mixing 100 pts.wt. methyl- substituted novolac epoxy resin of formula I (wherein the average number of the methyl groups per aromatic ring is 1-3, and m is 0 or 1-20) with 1-900 pts.wt. bisphenol A epoxy resin of formula II (wherein n is 0 or 1-10) and/or bisphenol AD epoxy resin of formula III (wherein n is as defined above), 1-100 pts.wt. organosilicon compound having a structural unit of formula IV (wherein n is 2 or 3; R is 1-20C alkyl, alkoxy or substituted alkyl; and m is 0-4) directly bonded to the Si atom, 10-900 pts.wt. phenol novolac resin of formula V (wherein R' is 1-10C alkyl, alkenyl or the like; and the average number of the R' groups per aromatic ring is 0-3: and k is 1-18) and 0.001-100 pts.wt. organosilicon compound having at least two alkoxy and/or hydroxyl groups directly bonded to the Si atom in the molecule as essential components.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a thermosetting resin composition. In particular, the present invention relates to a highly reliable TAB sealing material.

Recently, as electronic devices such as electronic watches, cameras, calculators, IC cards, word processors, and LCD televisions have become lighter, thinner, smaller, and more sophisticated, the mounting format of semiconductor elements, which are the core of these products, is also changing. be.

The film gear rear (TAB) mounting method follows the trend of increasing the number of terminals in semiconductor devices and increasing the density of mounting, and is used for mounting in watches, calculators, thermal heads, and LCD displays, and is expected to expand in the future. is expected.

The usefulness of the TAB mounting method has not been recognized in all types of applications, and one of the reasons why full-fledged use of the TAB mounting method in applications such as memory has been delayed is because of the high reliability and reliability of the same level as the sealing resin for transfer molding. This may be because there is currently no TAB sealing material on the market that has i.

<Prior art> Conventionally, the sealing materials for TAB include an organosilicon compound having three methoxy groups in an epibis type epoxy resin IJA, a resol type phenolic resin curing agent, and an organic face f1.
Alternatively, a liquid epoxy resin containing an inorganic pigment and an organic solvent has been proposed (Japanese Patent Publication No. 1-36984).

[Problems to be solved by the invention] Semiconductor elements encapsulated with a encapsulating material based on this prior art have lower reliability than semiconductor elements encapsulated with encapsulating resin for transfer molding. Although it is inferior in terms of performance, it has been put into practical use in consumer applications such as calculators and liquid crystal displays, where reliability requirements are not as strict as in memory applications.

However, the reason why TAB encapsulants are widely used in industrial fields including memory applications is that they are low-stress type TABs that have a higher degree of reliability and can be applied to large-sized chips. The situation is such that it is necessary to produce a sealing material.

Means for Solving the Problems> The inventors have developed a new sealant for TAB that is more reliable than conventional TAB oil sealants and has low stress properties. As a result of extensive research in order to obtain an I''A B sealant, the following invention was achieved.

That is, the present invention provides (AJ: 100 parts by weight of methyl-substituted novolac type epoxy resin represented by the following general formula, provided that the average number of methyl groups per aromatic ring is more than 1 and less than 3, (m represents O or an integer of 1 to 20) FB) 1 to 900 parts by weight of a bisphenol AD type epoxy resin of the general formula H) n O (n represents 0 or an integer of 1 to 10), (C ) A bisphenol A-based epoxy resin of organosilicon compound H3 (n represents 0 or an integer from 1 to 10) containing the following structural unit directly bonded to a silicon atom in one molecule, and/or the general formula ( n is 2 or 3; R is the same or different substituent and represents an alkyl group, alkoxy group, or substituted alkyl group having 1 to 20 carbon atoms; m is an integer of 0 to 4) 1 to 100 parts by weight ( D) Phenol novolak resin represented by the following general formula <R' is the same or different substituent, and has 1 carbon number
~10 alkyl groups, alkenyl groups, vinyl groups, and allyl groups. However, the average value of the number of R' groups per aromatic ring is from 0 to 3, and k represents an integer from 1 to 18.) 10 to 900 parts by weight. The present invention relates to a thermosetting resin composition containing as an essential component 0.001 to 100 parts by weight of an organosilicon compound having two or more alkoxy groups and/or hydroxyl groups directly bonded to elementary atoms.

The present invention will be explained in detail below.

The methyl-substituted novolac type epoxy resin used in the present invention has the following general formula. The average number of methyl groups per aromatic ring preferably exceeds 1 and is 3 or less, more preferably 1.2 or more and 2.5 or less.

The methyl-substituted novolak epoxy resin used in the present invention can be synthesized by a conventional method by reacting a methyl-substituted novolak phenol resin with epichlorohydrin. The methyl-substituted novolac type phenolic resin is synthesized by the following reaction.

The bisphenol A-based epoxy resin used in the present invention has a general formula (% formula %). According to the total chlorine measurement method according to the association.Alkali component: IN KOH-propylene glycol, solvent nibbutylcarpitol, reflux time 210
2,000 p111 or less, more preferably 1
．． A material having a value of Oooppm or less is used.

It is expressed by CH30 (n represents 0 or an integer from 1 to 10), and may be monodispersed with a constant degree of polymerization n, but it may be a mixture of components with different degrees of polymerization n. There may be.

The bisphenol A-based epoxy resin preferably has fluidity at room temperature, and more preferably has an epoxy equivalent in the range of 170 to 400 (g/equima).

The bisphenol AD type epoxy resin in the present invention is
It is expressed by the general formula (n represents 0 or an integer from 1 to 10), and may be monodispersed with a constant degree of polymerization n, but it may be a mixture of components with different degrees of polymerization n. There may be.

The bisphenol AD type epoxy resin is preferably one that has fluidity at room temperature, and the lower the viscosity, the better from the viewpoint of coating suitability such as screen printability of the liquid compound and dispensability. It is desirable that it be in the range of 163 to 400 (g/equi).

At the same molecular weight, bisphenol AD epoxy resin has a lower viscosity than bisphenol A epoxy resin, and the mechanical properties and heat resistance (glass transition temperature, long-term heat resistance) of the cured product are almost the same. Although it is most preferable to use the latter alone, a mixture of the two or the former may be used alone.

Bisphenol A type epoxy resin and bisphenol AD
The total chlorine content (according to the total chlorine measurement method by the Epoxy Resin Association) of type epoxy resin is 2.0 OOapl or less, more preferably 1.0 OOapl or less. It is preferable to use one having a value of Oo oppn or less.

The blending amount of component B in the thermosetting resin composition of the present invention is 1 to 90 parts by weight per 100 parts by weight of component A.
Preferably, 0 parts by weight of component B is included.

If the amount of component B is less than 1 part by weight, the moisture and heat resistance and reliability will be insufficient, probably due to the influence of stress after curing, and if the amount of force component B exceeds 900 parts by weight, the cured product will deteriorate. Humid heat resistance and reliability deteriorate due to a decrease in glass transition temperature.

The blending amount of component B is more preferably 10 to 500 parts by weight based on 100 parts by weight of component A.

In the present invention, the following m directly bonded to a silicon atom is used.
A silicon-containing epoxy compound containing at least one chain unit in one molecule is used to reduce stress.

/Rm The blending amount of the boxy compound is preferably 100 parts by weight of component A, 1 part by weight or more and 100 parts by weight or less.

The silicon-containing epoxy compound of the present invention has Si-
It can be easily synthesized by the following reaction between a polyorcasiloxane oligomer having an H group and a phenyl glycidyl ether derivative containing an allyl or vinyl group.

(n is 2.3; R is the same or different substituent and represents an alkyl group, alkoxy group, or substituted alkyl group having 1 to 20 carbon atoms - m is an integer of 0 to 4) This silicon-containing epoxy compound If the blending amount exceeds 100 parts by weight, the glass transition temperature of the cured product obtained from the thermosetting resin composition of the present invention will be significantly lower than when the blending amount is 100 parts by weight or less. Undesirable.

Silicon-containing material H2PtC in the thermosetting resin composition of the present invention
ja catalyst (here, m = 2.3, R = CH = CH2, e H2 CH = CH2) Specific examples of silicon-containing epoxy compounds include the following compounds, but are not particularly limited to these. It's not that I was.

e e H2PtCja catalyst e e CH3 CH3 Among these compounds, the following compounds are particularly preferably used.

In the thermosetting resin composition of the present invention, a phenol novolak resin having the following general formula is used as a curing agent component.

(R' is the same or different substituent and has 1 carbon number
~10 alkyl groups, alkenyl groups, vinyl groups, and allyl groups. However, if the average value of the number of R' groups per aromatic ring is 0 or more and 3 or less, and k represents an integer of 1 or more and 18 or less), the degree of polymerization (=+2) is 3≦. It is desirable that the range is +2≦20, and it may be a mixture of many kinds of components having different molecular weights. More preferred values of k are 1≦ and ≦4.

When k exceeds 18, the viscosity of the thermosetting resin composition of the present invention increases, resulting in poor workability (dispensing properties, screen printing properties), which poses a problem.

Representative examples of the phenol novolac resin of the present invention include those having the following structure.

CH2=CH3i (OC2H5)3 (1<n≦3> The organosilicon compounds having two or more alkoxy groups or hydroxyl groups directly bonded to a silicon atom in one molecule used in the present invention include the following examples: It is not particularly limited to these compounds.

82N (CH2) 2N) ((CH2) 3si (
OCH3) 3, H2N (CH2) 3si (OC
2H5) 3H2N (CH2) 2NH(CH2)3
si (CH3) (OCH3)2, C2H50CON
HC3H6Si (OCH3)3(CH30)3SiC
2H4Si (OCH3)3C4CH2CH2Si (
OCH3)3CF3CH2Si (OCH3)3 (R=-CH2CH2CH3, N82 Nl2 (CH2> 3 (CH2) 3HO-31
-O-3i-OH OH0H Ca Hs ) (t-0, 1, 2, 3 or more integer) CH3-5i-CH3 aHs OH3 OH The thermosetting resin composition of the present invention contains a known curing accelerator. It can be added as necessary.

Specific examples of the curing accelerator include 2-methylimidazole, 2-ethyl-4-methylimidazole, and 2-methylimidazole.
Phenyl-4-methylimidazole, 2-phenyl-4
- imidazole compounds such as methyl-5-hydroxymethylimidazole or acid addition salts thereof such as hydroxybenzoic acid or dihydroxybenzoic acid, NN'-dimethylpiperazine, 2,4.6-)lis(dimethylaminomethyl)phenol, 1 .8 diazabicyclo(5,4
,0>undecene7.4 Amine compounds such as dimethylaminopyridine or acid addition salts thereof such as hydroxybenzoic acid or dihydroxybenzoic acid, triphenylphosphine, tricyclohexylphosphine, bis(
phosphine compounds such as diphenylphosphine)methane, tris(2,6-simethoxyphenyl)phosphine, triphenylphosphine-triphenylborane, tetraphenylphosphonium tetraphenylborate, triethylammonium-tetraphenylborate, pyridinium-tetraphenylborate, etc. boron-containing compounds,
Examples include metal acetylacetonates such as aluminum acetylacetonate and cobalt acetylacetonate.

When the above-mentioned curing accelerator is added to the thermosetting resin composition of the present invention, the total weight of the compound containing an epoxy group is usually 1
0°1 to 00 parts by weight.

100 parts by weight is added.

Other epoxy resins may be added to the thermosetting resin composition of the present invention. The amount added is preferably 100 parts by weight or less based on 100 parts by weight of the total weight of components A, B, and C.

Other epoxy resins are not particularly limited as long as they have one or more epoxy groups per molecule; examples include bisphenol F diglycidyl ether, phenol nophorac polyglycidyl ether, cresol novolac polyglycidyl ether, and resorcin diglycidyl ether. ether, phenylglycidyl ether, ptert
-butyl glycidyl ether, vinylcyclohexene oxide and the like.

A diluent can be added to the composition of the present invention if necessary. Examples include methylcellosolve, ethylcellosolve, butylcellosolve acetate, ethyllubitol, butylcarpitol, ethyllubitol acetate, γ-butyrolactone, 4-valerolactone,
Examples include propylene carbonate, xylene, toluene, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, and the like.

The composition of the present invention may contain inorganic fillers, pigments,
Various visibility imparting agents such as dyes, mold release agents, antioxidants, flame retardants, and rubbers may be added. Examples of inorganic fillers include natural silica such as crystalline silica and crystallized silica, synthetic high-purity silica, synthetic spherical silica, talc, mica, calcium carbonate, silicon nitride, boron nitride,
1 from alumina etc. 1 or two or more types can be used as appropriate.

The composition of the present invention may be mixed, if necessary, by melting at a high temperature, or by using a kneader, planetary mixer, 3-roll, single-screw or twin-screw extruder, etc. at a temperature between room temperature and 150°C or less. A method of kneading is applied.

Function> In the present invention, a trifunctional epoxy resin with a specific structure,
By using a bifunctional epoxy resin, a silicon-containing epoxy compound, a phenol novolak resin, and an organic gay compound, T
An AB encapsulant is provided.

Method for evaluating characteristics> The method for evaluating characteristics in the present invention is as follows.

1. Create a glass transition temperature test piece (5 am
10 type), the inflection point in the displacement-temperature curve when the temperature was not raised from 30 to 330°C at a rate of 10°C/min was measured and determined as the glass transition temperature.

2. Water absorption rate The weight increase after absorbing water for 100 hours at 121°C1 relative temperature of 100% using a pressure Kutzker test equipment (PCT) was measured for the molded plate (50 mm φ x 3 thick). , the water absorption rate was calculated.

3. Insulation resistance A comb-shaped $ electrode (IP
C-3M-840B type), apply varnish and harden it, apply a voltage of 100 V DC using a Kyokuho megohmmeter (Toa Denpa Kogyo SM to IOE type), and check the resistance after 1 minute. The value was measured and used as the insulation resistance value.

4. Warping of the silicone plate Apply face to a silicone plate (10m x 40m x 0.3m thick) so that it has a thickness of 50cm after curing, and heat cure at 80°C for 50 minutes, 110°C for 20 minutes, and 150°C for 3 hours. Then, using a surface roughness meter (Tokyo Seimitsu ■), the warpage of the silicon plate between 30 surfaces at the center was measured.

<Example> Example 1 Methyl-substituted novolac type epoxy resin with the following structural formula (manufactured by Nippon Kayaku ■, EOCN5200) (average value of n is 1.6
(with m=2 as the main component) 60 parts by weight, bisphenol A type epoxy resin (manufactured by Asahi Kasei ■, X-2317>20 parts by weight, 20 parts by weight of a silicon-containing epoxy compound with the following structural formula, phenol nophora. Ink resin (Meisho Kasei■
51 parts by weight of triphenylphosphine (manufactured by Hokko Chemical Co., Ltd., H-1), 1.5 parts by weight of triphenylphosphine (manufactured by Hokko Chemical Co., Ltd.), a hydrolyzed condensate of γ-glycidoxypropyltrimethoxysilane (manufactured by Thi-Soso Co., Ltd.) with the estimated structural formula below. (Manufactured by Toshi Tau Corning Silicone ■, 5H6018) 1.5 parts by weight, an organic gay compound containing a silanol group represented by the following structural formula (manufactured by Toshi Tau Corning Silicone ■, 5H6018) R RO-3i -0-3i -OR ＼ /l l \ / Si OOSi / \ l l/ \ HOO-5i -0-3i -00H R 15 parts by weight of (R=-CH2CH2CH3, -CeHs) were weighed and mixed, and the mixture was heated on a mixing roll heated to 100°C for 15 minutes. The mixture was melt-kneaded, cooled, and then pulverized to obtain a powdery thermosetting resin composition.

After heating this composition to 100°C for several minutes to melt it,
Vacuum degas and pour into a mold at 120℃ for 1 hour at 150℃.
It was cured by heating at ℃ for 3 hours to obtain a test piece for physical property testing.

The glass transition temperature by TMA method is 160°C, and PC
After the T test (121°C, relative humidity 100%, 100 hours), the temperature decreased to 142°C.

The water absorption rate was 220% by weight.

A solvent (
Add 60 parts by weight of xylene/n-butanol/methyl isobutyl ketone mixed solvent (weight ratio 15:20:65),
Dissolved uniformly. This varnish was applied onto the comb-shaped electrode and the film thickness after curing was 1001. II+), PCT exam (12
The insulation resistance between the wires was evaluated before and after (1°C1 relative humidity 100%, 100 hours).

Insulation resistance before PCT test is 5. I x 10”Ω,
The insulation resistance after the PCT test was 3.5×10 13 Ω.

Apply this varnish to a single-sided film carrier (Kap).
ton film thickness 50um, adhesive thickness 204, copper foil thickness 35u
M) was coated on a simulated element (line width, line spacing: 81 JIl, no passivation film, number of bottles - 20) with inner lead bonding, and heated at 80°C for 50 minutes and at 110°C for 20 minutes.
It was cured by heating at 150° C. for 3 hours.

The disconnection defect rate after the PCT test (121°C, relative humidity 100%) was 1. ．． 000 hours and the results as W c
: i b +plot, the 10% failure occurrence time was 370 hours, and the 50% failure occurrence time was 670 hours.

This varnish was applied to a silicon plate, and after curing, the warp of the silicon plate was measured and found to be 26 μm.

Example 2 Methyl-substituted novolak epoxy resin (EOCN520
0) 60 parts by weight, bisphenol AD type epoxy resin (
Silicon-containing epoxy compound 2 used in Example 1, using 20 parts by weight of R1710 manufactured by Mitsui Petrochemical Industries ■
0 parts by weight, phenol novolac resin (H-1) 531
1.5 parts by weight of triphenylphosphine, hydrolyzed condensate of γ-glycidoxypropyltrimethoxysilane (
YA-2>1.5 parts by weight and 1.5 parts by weight of an organosilicon compound containing silanol (SH6018) were weighed and mixed, and a powdered thermosetting resin composition was obtained in the same manner as in Example 1.

After heating this composition to 100°C for several minutes to melt it,
Vacuum degassed, pour into mold, and heat at 120℃ for 1 hour.
The material was cured by heating at 0° C. for 3 hours to obtain a test piece for physical property testing.

The glass transition temperature by the TMA method is 158°C, and the PC
T test (121°C1 relative humidity 100%, 100 hours)
Later, the temperature dropped to 140°C.

The water absorption rate was 221% by weight.

A solvent (
Add 60 parts by weight of xylene/n-butanol/methyl isobutyl ketone mixed solvent (weight ratio 15:20:65),
Dissolved uniformly. This varnish was applied on the comb-shaped electrode, and the film thickness after curing: 1004), PCT test (121'C1
The insulation resistance between the wires was evaluated before and after (100% relative humidity, 100 hours).

The insulation resistance before the PCT test was 5.3 x 10''Ω, and the insulation resistance after the PCT test was 4.0 x 1013Ω.

Apply this varnish to a single-sided film carrier (Kap).
ton film thickness 50u+n, adhesive thickness 204, copper foil thickness 35
A simulated element (μ town) with inner lead bonding (
Line width, line spacing 8 lines, no passivation film, number of bins -2
0), and heated and cured at 80'C for 50 minutes, 110C for 20 minutes, and 150C for 3 hours.

The disconnection defect rate after PCT test (121℃, relative humidity 100%) was tracked for up to 1,000 hours, and the results were published on Web.
When organized using the l plot, the 10% failure occurrence time is 3
50 hours, 50% failure occurrence time was 660 hours.

This varnish was applied to a silicon plate, and after curing, the warpage of the silicon plate was measured and found to be 26n.

Example 3 Methyl-substituted novolak epoxy resin (EOCN520
0) 60 parts by weight, bisphenol A type epoxy resin (X
-2317) 35 parts by weight, 5 parts by weight of the silicon-containing epoxy compound used in Example 1, 55 parts by weight of phenol novolac resin (Hl), 15 parts by weight of triphenylphosphine
Parts by weight, 1.5 parts by weight of a hydrolyzed condensate of γ-glycidoxypropyltrimethoxysilane (YA-2), and 1.5 parts by weight of an organosilicon compound containing a silanol group (SH6018) were weighed and mixed to form a solid line example. A powdered thermosetting resin composition was obtained in the same manner as in Example 1.

This composition was heated to 100°C for several minutes to melt it, then vacuum degassed, poured into a mold, and heated at 120°C for 1 hour and 150°C for 3 hours to harden it for physical property testing. A test piece was obtained.

The glass transition temperature by TMA method is 150°C, and P
CT test (121℃, relative humidity 100%, 100 hours)
Later, the temperature dropped to 120°C.

The water absorption rate was 235% by weight.

A solvent (
60 parts by weight of xylene/n-butanol/methyl isobutyl ketone mixed solvent (weight ratio 15:20:65) was added and uniformly dissolved. This varnish was applied on the comb-shaped electrode, and the film thickness after curing: 100uw+), PCT test (121"C
The insulation resistance between the wires was evaluated before and after (100% humidity, 100 hours).

The insulation resistance before the PCT test was 5.5×10”Ω, and the insulation resistance after the PCT test was 3.7×IQ+3Ω.

Apply this varnish to a single-sided film carrier (Ka
Simulated element (line width, line spacing 84, no passivation film, number of bins - 20) with inner lead bonding to p t on film thickness 504, adhesive thickness 204, copper foil thickness 351 Jl) at 80°C for 50 minutes, then at 110°C.
The film was cured by heating at 150°C for 20 minutes and 3 hours at 150°C.

The disconnection defect rate after PCT test (121℃, relative humidity 100%) was tracked for up to 1,000 hours, and the results were published on Web.
When organized using the l plot, the 10% failure occurrence time is 3
10 hours, 50% failure occurrence time was 620 hours.

This varnish was applied to a silicon plate, and after curing, the warp of the silicon plate was measured and found to be 31 μm.

Example 4 Hydrolyzed condensate of γ-glycidoxypropyltrimethoxysilane used in Example 1 (YA-2) 1.5
Part by weight, organosilicon compound containing silanol group (SH6
018) Instead of 1°5 parts by weight, 3.0 parts by weight of γ-glycidoxypropyltrimethoxysilane (manufactured by Toshi-Tau Corning Silicone ■, 5H6040) was used, and the rest was weighed in the same manner as in Example 1. The mixture was mixed, and a powdered thermosetting resin composition was obtained in the same manner as in Example 1.

After heating this composition to 100°C for several minutes to melt it,
Vacuum degassed and poured into a mold, heated at 120°C for 1 hour.
It was heated at 50° C. for 3 hours to harden and obtain a test piece for physical property testing.

The glass transition temperature by TMA method is 161°C, and P
After the C,T test (121°C, relative humidity 100%, 100 hours), the temperature decreased to 141°C.

The water absorption rate was 2.19% by weight.

A solvent (
60 parts by weight of -1r silene/n-butanol/methyl isobutyl ketone mixed solvent (weight ratio 15:20:65) was added and uniformly dissolved. This varnish was applied to the top of the Kuji shape (film thickness after curing: 100 ua), PCT test (1
The insulation resistance between the wires was evaluated before and after (21° C., relative humidity 100%, 100 hours).

Insulation resistance before PCT test was 4.8X1. O to Ω, PCT
The insulation resistance after the test was 1.5×113Ω.

Apply this varnish to a single-sided film carrier (Kap).
ton film thickness 50μ button, adhesive thickness 20μ, copper foil thickness 35μ
A simulated element (μ phantom) with inner lead bonding (
Line width, line spacing 84, no passivation film, number of pins -2
0), heated to 80℃ for 50 minutes, heated to 110℃ for 20 minutes,
It was cured by heating at 150°C for 3 hours.

The disconnection defect rate after PCT test (121℃, relative humidity 100%) was tracked for up to 1,000 hours, and the results were published on Web.
When organized using the l plot, the 10% failure occurrence time is 3
40 hours, and 50% failure occurrence time was 630 hours.

This varnish was applied to a silicon plate, and after curing, the warp of the silicon plate was measured and found to be 28 μm.

Comparative example 1 Bisphenol A type epoxy resin (X-2317) 10
0 parts by weight, 56 parts by weight of phenol novolac resin (H-1), 15 parts by weight of triphenylphosphine, hydrolysis wire metal of γ-glycid A dipropyltrimethoxysilane (
1.5 parts by weight of YA-2) and 1.5 parts by weight of an organosilicon compound containing a silanol group (SH6018) were weighed and mixed, and the mixture was melted at 100°C for 15 minutes to obtain a thermosetting resin composition.

After heating this composition to 100°C for several minutes to melt it,
Vacuum degassed, pour into mold, and heat at 120℃ for 1 hour.
It was heated at 0° C. for 3 hours to harden and obtain a test piece for physical property testing.

The glass transition temperature by TMA method is 131°C, and PC
After the T test (121°C, relative humidity 100%, 100 hours), the temperature decreased to 105°C.

The water absorption rate was 265% by weight.

Add 40 parts by weight of the above thermosetting resin composition to a solvent (xylene/n-butanol/methyl isobutyl ketone mixed solvent,
603° C. (weight ratio 15:20:65) was added and uniformly dissolved. This varnish was applied onto a comb-shaped electrode, and the film thickness after curing was 1004), and the insulation resistance between the wires was evaluated before and after a PCT test (121°C, 100% relative humidity, 100 hours). Insulation resistance before PCT test is 4.0×10”Ω,
The insulation resistance after the PCT test was 45×10 13 Ω.

Apply this varnish to a single-sided film carrier (Kap).
A simulated element (line width, line spacing 8IJI+, no passivation film,
Number of pins - 20) and heated at 80°C for 50 minutes, then at 110°C.
The film was cured by heating at 150°C for 20 minutes and 3 hours at 150°C.

The disconnection defect rate after PCT test (121℃, relative humidity 100%) was tracked for up to 1,000 hours, and the results were published on Web.
When organized using the l plot, the 10% failure occurrence time is 2
The time to occurrence of 50% failure was 520 hours.

This varnish was applied to a silicon plate, and after curing, the warp of the silicon plate was measured and found to be 27-1.

Comparative Example 2 Methyl-substituted novolak epoxy resin (EOCN520
0) 100 parts by weight, phenol novolak resin (H-1
) 55 parts by weight, triphenylphosphine 15 parts by weight, γ
- 1.5 parts by weight of a hydrolyzed clamp of glycidoxypropyltrimethoxysilane (YA-2) and 1.5 parts by weight of an organosilicon compound containing a silanol group (SH6018) were weighed and mixed, and the same procedure as in Example 1 was carried out. A powdered thermosetting resin composition was obtained by the procedure.

After heating this composition to 100°C for several minutes to melt it,
Vacuum degassed, pour into mold, and heat at 120℃ for 1 hour.
It was heated at 0° C. for 3 hours to harden and obtain a test piece for physical property testing.

The glass transition temperature by TMA method is 178°C, and PC
T test (121°C5 relative humidity 100%, 100 hours)
Later, the temperature dropped to 155°C.

The water absorption rate was 2.28% by weight.6 A solvent (
Add 60 parts by weight of xylene/n-butanol/methyl isobutyl ketone mixed solvent (weight ratio 15:20:65),
Dissolved uniformly. This varnish was applied onto the comb-shaped electrode, and the film thickness after curing: 100 μm) was performed, and the PCT test (121°C,
The insulation resistance between the wires was evaluated before and after (100% relative humidity, 100 hours).

The insulation resistance before the PCT test was 4.8×10”Ω, and the insulation resistance after the PCT test was 8.2×IQ+2Ω.

Apply this varnish to a single-sided film carrier (Kap).
ton film thickness 504, adhesive layer 204, copper foil thickness 354)
The simulated element (line width,
Line spacing 84, no passivation film, number of pins = 20)
50 minutes at 80℃, 20 minutes at 110℃, 150℃
It was cured by heating at °C for 3 hours.

We tracked the disconnection defect rate after PCT test (121°C1 relative humidity 100%) for up to 1,000 hours and reported the results to Wei.
When organized using a b+ plot, the 10% failure occurrence time was 310 hours, and the 50% failure occurrence time was 610 hours.

This varnish was applied to a silicon plate, and after curing, the warp of the silicon plate was measured and found to be 40 u.

Comparative Example 3 Hydrolyzed fastener of γ-glycidoxypropyltrimethoxysilane used in Comparative Example 2 (YA-2) 1.5
Part by weight, organosilicon compound containing silanol group (SH6
018) Instead of 1.5 parts by weight, γ-glycidoxy 10
Pyrtrimethoxysilane (SH6040) was used, and the other ingredients were measured and mixed in the same manner as in Comparative Example 2, and a powdered thermosetting resin composition was obtained in the same manner as in Example 1.

This composition was heated to 100°C for several minutes to melt it, then vacuum degassed, poured into a mold, and heated at 120°C for 1 hour.
The material was cured by heating at 150°C for 3 hours to obtain a test piece for physical property testing.

The glass transition mixture by the T''M A method is 178°C, and the PCT test (121°C1 relative humidity 100%, ],
After 0 hours), the temperature decreased to 154°C.

The water absorption rate was 229% by weight.

A solvent (
60 parts by weight of xylene/n-butanol/methyl isobutyl ketone mixed heating medium (weight ratio 15:20:65) was added and uniformly dissolved. This varnish was applied onto the comb-shaped electrode, and the film thickness after curing: 100 μtI) was applied to the PCT test (121 μtI).
The insulation resistance between the wires was evaluated before and after (100% relative humidity, 100 hours).

The insulation resistance before the PCT test was 5.3 x 10"Ω, and the insulation resistance after the PCT test was 5.0 x 10"Ω.
On film thickness 50un, adhesive thickness 20μ, copper foil thickness 35μ
fI) with inner lead bonding to the simulated element (
Line width, line spacing 8 μm, no passivation film, number of pins -
20 bottles), heated at 80°C for 50 minutes, and heated at 110°C for 20 minutes.
It was cured by heating at 150°C for 3 hours.

The disconnection defect rate after PCT test (121℃, relative humidity 100%) was tracked for up to 1,000 hours, and the results were published on Web.
When organized using the l plot, the 10% failure occurrence time is 3
00 hours, and the 50% failure occurrence time was 600 hours.

This varnish was applied to a silicon plate, and after curing, the warp of the silicon plate was measured and found to be 41 μm.

<Effects of the Invention> The cured product obtained from the thermosetting resin composition of the present invention has excellent heat and humidity resistance and maintains low stress properties. High reliability is achieved by sealing with a thermosetting resin composition.

Claims (1)

[Claims] (A) 100 parts by weight of a methyl-substituted novolak epoxy resin represented by the general formula below, ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (However, the average number of methyl groups per aromatic ring The number is greater than 1 and less than or equal to 3, and m represents 0 or an integer from 1 to 20.) (B) General formula, ▲Mathematical formula, chemical formula, table, etc.▼ (n is 0 or more than 1 and less than 10) bisphenol A-based epoxy resins (representing an integer), and/or bisphenol AD-based epoxy resins with general formulas, ▲mathematical formulas, chemical formulas, tables, etc.▼ (n represents 0 or an integer from 1 to 10) 1 to 900 Parts by weight, (C) An organosilicon compound containing the following structural units directly bonded to a silicon atom in one molecule ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (n is 2 or 3; R is the same or different substitution group, representing an alkyl group, alkoxy group, or substituted alkyl group having 1 to 20 carbon atoms; m is an integer of 0 to 4) 1 to 100 parts by weight (D) Phenol novolak resin represented by the following general formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (R' is the same or different substituent and has 1 carbon number)
~10 alkyl groups, alkenyl groups, vinyl groups, allyl groups, provided that the average number of R' groups per aromatic ring is 0 or more and 3 or less, and k is an integer of 1 or more and 18 or less ) 10 to 900 parts by weight (E) Thermosetting containing as an essential component 0.001 to 100 parts by weight of an organosilicon compound having two or more alkoxy groups and/or hydroxyl groups directly bonded to a silicon atom in one molecule Resin composition.