JPH02187416A - Novolak resin-containing composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition, containing a silane- or siloxane- modified novolak resin having a specific structure without causing cracking or deterioration in semiconductors by moisture absorption when used as a sealing material for semiconductors since cured products with remarkably low moisture absorption are provided. CONSTITUTION:The objective composition containing a silane- and/or siloxane- modified epoxy novolak resin and/or silane- or siloxane-modified phenol or cresol novolak resin consisting essentially of units expressed by formula I [X is H or formula II; R<1> is (substituted) lower alkylene; R<2> to R<6> are (substituted) monofunctional hydrocarbon; R<7> is H or methyl; n is 0-5] or cresol novolak resin. Furthermore, in the case of the phenol or cresol novolak resin, the novolak resin expressed by the formula is obtained by, e.g. subjecting a silane- or siloxane-modified phenolic derivative expressed by formula III and an aqueous solution of formaldehyde to hydroformylating reaction in the presence of a catalyst, such as hydrochloric acid.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a composition containing a silane- or siloxane-modified epoxy novolac resin and/or a silane- or siloxane-modified phenol or cresol novolak resin.

Issues to be addressed in the future - In recent years, epoxy resin compositions containing novolac-type epoxy resin and novolac-type phenol resin as a curing agent have been widely used as materials for the electrical and electronic industries, especially semiconductor encapsulation materials. There is a high demand for novolac type epoxy resins and novolac type phenolic resins.

However, as these novolac type resins, orthocresol novolak type and phenol novolac type have been mainly used, but these novolac type resins are used to manufacture the above-mentioned epoxy resin compositions, and semiconductor encapsulation is performed. In today's world, as the degree of integration of integrated circuits increases, there is a strong demand for low moisture absorption of sealing materials in order to suppress cracks that occur during the soldering process. The problem is that it cannot be fully satisfied.

The present invention was made in view of the above circumstances, and an object of the present invention is to provide a novolac resin-containing composition that solves the above-mentioned hygroscopic problem.

As a result of intensive studies to achieve the above object, the present inventor has found that the following general formula (1) obtained by modifying epoxy novolac resin, phenol or cresol novolac resin with silane or siloxane (However, X is a hydrogen atom or -CH2CH-CH, group, \
1 R1 is an unsubstituted or substituted lower alkylene group, R2R3,
R4, R5 and R6 are the same or different unsubstituted or substituted -
a valent hydrocarbon group, R7 represents a hydrogen atom or a methyl group, n
is an integer from 0 to 5), i.e., a silane- or siloxane-modified phenol or cresol novolac resin in which X in formula (1) is a hydrogen atom;
is -CH2CH-CH, a silane or a siloxane-modified epoxy resin has low water absorption, and compositions containing these epoxy novolac resins and/or phenol or cresol novolak resins can produce cured products with very low moisture absorption. The inventors have discovered that even when used for the encapsulation of semiconductors, it is possible to prevent cracks caused by moisture absorption and deterioration of semiconductors due to moisture absorption as much as possible, leading to the present invention.

Accordingly, the present invention provides a composition containing a silane- or siloxane-modified epoxy novolac resin and/or a silane- or siloxane-modified phenol or cresol novolak resin having the unit represented by the above formula (1) as a main constituent unit.

The present invention will be explained in more detail below.

The novolak resin-containing composition according to the present invention can be prepared by the following formula (1
) Contains a phenol or cresol novolak resin whose main constituent units are the units represented by the formula and/or a novolak resin whose main constituent units are the units represented by the formula.

Here, X is a hydrogen atom or -CH, CH-CH, group\
1 , and therefore, the above formula (1) contains an epoxy novolak resin whose main constituent units are the units represented by the formula (1).

As the phenol or cresol novolak resin of the above formula (la), orthosilane- or siloxane-modified phenol or cresol novolak resins, that is, those having phenol or cresol novolak resin as a main structural unit, are particularly preferably used.

In this case, in the above formula, R1 is an unsubstituted or substituted lower alkylene group, such as a methylene group, ethylene group, trimethylene group, hexamethylene group, etc., or a group bonded to a carbon atom of these groups. Examples include groups in which some or all of the hydrogen atoms are substituted with halogen atoms, etc.

Mata, R'', R', R', R'& HiR
'C Same as above 11 Also, it is an unsubstituted or substituted-valent hydrocarbon group of J% type, and examples of such groups include lower alkyl groups such as methyl group, ethyl group, butyl group, and octyl group, vinyl group, and allyl group. groups, lower alkenyl groups such as 1-propenyl groups, mononuclear and dinuclear aryl groups such as phenyl groups, xylyl groups, tolyl groups, naphthyl groups, benzyl groups, cycloalkyl groups such as cyclobutyl groups and cyclohexyl groups, or Examples include groups in which part or all of the hydrogen atoms bonded to the carbon atoms of the group are replaced with halogen atoms or the like.

Moreover, R7 is a hydrogen atom or a methyl group. Furthermore, n is an integer of 0 to 5.

The molecular weight etc. of the above novolac resin are appropriately selected depending on the purpose of use of the composition, etc., but in particular, in the case of silane- or siloxane-modified phenol or cresol novolac resin, the average molecular weight is 380 to 1900, preferably 7.
It may be in the range of 70 to 1150, and the ○H equivalent may be in the range of 150 to 380, preferably 190 to 270. Also, the softening point is 20 to 140
℃, preferably in the range of 60 to 100℃. On the other hand, in the case of silane- or siloxane-modified epoxy novolak resin, the average molecular weight is 500 to 2,500.
, preferably in the range of 1,000 to 1,500, and the epoxy equivalent may be in the range of 200 to 500, preferably 250 to 350. Further, the softening point is desirably in the range of 20 to 100°C, preferably 40 to 80°C.

The method for producing the novolak resin represented by formula (1) is not particularly limited, but when obtaining the phenol or cresol novolak resin represented by formula (1a).

For example, a silane-modified or siloxane-modified phenol derivative represented by the following formula (2), where % and n are the same as above] and an aqueous formaldehyde solution or anhydrous formaldehyde are combined with oxalic acid, hydrochloric acid, or sulfuric acid.

A method in which the hydroformylation reaction is carried out in the presence of a catalytic amount of an organic acid such as para-toluenesulfonic acid, one or more inorganic acids, or an inorganic acid salt such as zinc acetate is preferably employed.

Further, the epoxy novolac resin of formula (1b) can be obtained by adding epichlorohydrin to the phenol or cresol novolak resin of formula (1a) obtained as described above.
An effective method is to perform a hydrochloric acid reaction by adding an alkali such as an aqueous solution of caustic soda to epoxidize the phenolic water group of the phenol or cresol novolac resin of formula 1 (1a).

The composition of the present invention contains the novolak resin of the above formula (1), but other components of the composition are selected depending on the intended use. for example.

The composition of the present invention can be suitably used as an adhesive, a paint material, or a resist material, and is particularly useful for sealing electrical and electronic components, such as semiconductor devices such as ICs, LSIs, transistor thyristors, and diodes, and for manufacturing printed circuit boards. In this case, it can be prepared as an epoxy resin composition, but when preparing an epoxy resin composition in this way, the components include an epoxy resin, a curing agent, and if necessary, Curing accelerators, fillers, etc. can be used.

Here, as the epoxy resin, orthocresol epoxy novolak resin, epoxyphenol novolac resin, bisphenol type epoxy resin, etc. can be used, and as the curing agent, bisphenol A, phenol novolac resin, cresol novolak resin, and other known curing agents can be used. For example, when using phenol or cresol novolak resin as a curing agent, the molar ratio (a) of the epoxy group (a) of the epoxy resin and the phenolic hydroxyl group (b) of the phenol or cresol novolak resin
/b) can be used in a range of usually 0.5 to 4, preferably 0.8 to 2, optimally 1 to 1.2, but in the present invention, the epoxy resin component The silane or siloxane modified phenol novolac resin of the above formula (1b) is used as part or all of the curing agent, or the silane or siloxane modified phenol or cresol novolak resin of the above formula (la) is used as part or all of the curing agent component. Just use it.

In addition, a curing accelerator can be blended into the above-mentioned epoxy resin composition as needed. As a curing accelerator,
For example, imidazole and its derivatives, tertiary amine derivatives, phosphine derivatives.

Examples include cycloamidine derivatives, and one or more of these may be used. Among these, organophosphine compounds, particularly triphenylphosphine, are preferred. This organophosphine compound has a phosphorus atom weight ratio of 0.04 per 100 parts by weight of the total amount of resin components.
It is preferred to use it in an amount of ~0.5 parts by weight, especially 0.05-0.3 parts by weight.

Furthermore, the composition of the present invention can also be made into an ultraviolet curable composition by adding an aromatic onium salt.

Furthermore, the composition of the present invention contains inorganic fillers such as silica, talc, mica, silicon nitride, boron nitride, and alumina, adhesion aids, mold release agents, pigments, dyes, antioxidants, flame retardants, One or more types of surface treatment agents, flexibility-imparting agents, and other additives can be appropriately selected depending on the application and the like, and can be blended within the usual range.

The composition of the present invention is prepared by uniformly stirring and mixing the above-mentioned components,
It can be obtained by kneading with a kneader, roll, extruder Shinagawa mixer, planetary mixer, etc.
In this case, there is no particular restriction on the order of blending the components.

In addition, when molding and curing the composition of the present invention, the conditions are selected depending on the type of the composition, etc. For example, when sealing a semiconductor device using the epoxy resin composition as described above, conventional molding methods such as transfer molding, injection molding, and casting methods can be employed. In this case, the molding temperature of the epoxy resin composition is 150 to 190°C, and the post cure temperature is 150 to 190°C.
It is preferable to carry out the reaction at 50 to 190°C for 0 to 5 hours.

Since the novolak resin-containing composition of the present invention contains an epoxy novolac resin and/or a phenol or cresol novolac resin having a silicon atom bonded to a benzene ring via a substituted or unsubstituted lower alkylene group, It provides a cured product with extremely low moisture absorption, and therefore, when used as a semiconductor encapsulant, it can prevent as much as possible the occurrence of cracks during the soldering process due to the moisture absorption of the cured product. It can be suitably used as a material for electrical/electronic parts, a material for coating, etc.

EXAMPLES Hereinafter, the present invention will be specifically explained by showing examples and comparative examples, but the present invention is not limited to the following examples.

[Example 1] An orthosilane-modified phenol novolac resin having the unit shown in the following formula (3) as a main constituent unit was synthesized by the following method.

The following 3-(2
-Hydroxyphenyl)propyltrimethylsilane (124.7 g (0.6 mol)), 49.2 g of 37% formalin aqueous solution, 60 g of ethyl cellosolve acetate, and 1.5 g of oxalic acid were charged and reacted by refluxing at 110° C. for 30 hours. After that, the reaction solution was washed with water, and the solvent and unreacted substances were distilled off from the reaction solution under reduced pressure to obtain a phenolic hydroxyl group equivalent of 223 g/
An orthosilane-modified phenol novolak resin having a softening point of 31.0° C. was obtained.

The analysis results of the molecular weight, infrared absorption spectrum, and nuclear magnetic resonance spectrum of this resin are shown below.

Molecular weight (by gel permeability chromatography using monodisperse polystyrene as standard) Weight average molecular weight Uw=1.86×10″ number Average molecular weight un=1.27×lO3 polydispersity Hw/Mn
= 1, 46 infrared absorption spectrum +max
(an””) 3440 (-OH) 2950 (-
CH2-)1250 and 840 (Si-(CH,)
3) Nuclear magnetic resonance spectrum: δ (ppm) 0, 13
(S, 5i-CH3), 0.43-0.90(br
, (,H,-3i), 1.26~2.10 (br
.

Cl1t-C1l, -5i), 2.4.3-2.90
(br.

CH□-CM, -CH,-5i), 3.73-4.0
3 (br.

@-c! ! , -@), 5.67~6.03 (br
, 011).

6.56 to 7.13 (br, benzene nucleus) Next, the orthosilane-modified phenol novolac resin obtained above and the epoxy equivalent of 192. Epoxidized orthocresol novolac resin (EOCN-4400,
Nippon Kayaku layer) and triphenylphosphine as a curing catalyst were mixed at the compounding ratio shown in Table 1 to prepare a curable composition.

After heating and curing this composition at 180°C for 30 minutes, the cured product was immersed in water boiled at 100°C for 24 hours.
The water absorption rate at that time was measured. The results are shown in Table 1.

[Comparative Example 1] Phenolic hydroxyl group: 1123. The compounding ratio of orthocresol novolak resin (OCN-80, Nippon Kayaku) with a softening point of 80.0°C, the epoxidized orthocresol novolac resin used in Example 1, and triphenylphosphine as a curing catalyst as shown in Table 1. A curable composition was prepared.

This composition was cured in the same manner as in Example 1, and a water absorption test was conducted.

The results are also listed in Table 1.

Table 1 From the results shown in Table 1, the cured product using the orthosilane-modified phenol novolac resin according to the present invention has a higher absorption rate than the cured product using the ortho-cresol novolac resin having a methyl group at the ortho position of the benzene ring. The rate was extremely low, indicating the effect of silane modification.

[Example 2] A parasilane-modified epoxy novolank resin having the unit shown in the following formula (4) as a main constituent unit was synthesized by the following method.

In a 200 d capacity flask equipped with a cold 46 Reflags condenser, a thermometer, a stirrer and a dropping funnel, a phenolic hydroxyl group equivalent of 211 g/
Equivalents of 20 g of silane-modified phenolic novolac resin (0.095 mol as phenolic hydroxyl groups), 48.9 g (0,524 mol) of epichlorohydrin and 0.09 g (0,25 mol) of cetyltrimethylammonium bromide.
After reacting at 110°C for 6 hours, the reaction solution temperature was lowered to 70'C, and the reaction system was heated to 160°C.
While reducing the pressure to oaHH, 7.6 g of a 50% by weight aqueous solution of caustic soda (0.095-1 L as NaOH) was added dropwise, and water was removed from the system during the reaction. After completion of the dropwise addition, the mixture was refluxed for 90 minutes to react under reduced pressure of 160 mmHg at 70° C. while removing water from the system. The solution was then heated to 25°C.
100 g of toluene was added, by-product salt and unnecessary substances were separated, and the solvent and excess epichlorohydrin were distilled off under reduced pressure.

Next, 14.3 g of methyl isobutyl ketone, 9.5 g of acetone, and 1.0.9 g of a 10% by weight aqueous solution of caustic soda (0.027 mo/L/L as NaOH) were then added to the residue in the flask. , 3 at 60-65°C
After stirring for an hour and removing the aqueous layer, add the same amount of caustic soda aqueous solution as before and repeat the same operation to remove the aqueous layer.
Next, the organic layer was mixed with a 30% aqueous solution of disodium hydrogen phosphate,
Subsequently, after washing with an aqueous magnesium sulfate solution, the resin was evaporated and dried to obtain 21.9 g of a parasilane-modified epoxy novolac resin having an epoxy equivalent of 273 g/equivalent, a softening point of 54.7° C., and a hydrolyzable chlorine content of 0.0029%. .

The analysis results of the molecular weight, infrared absorption spectrum, and nuclear magnetic resonance spectrum of this resin are shown below.

Molecular weight (by gel permeation chromatography using monodisperse polystyrene as standard) Weight average molecular weight V = 1,91 x 103 Number Average molecular weight v1n = 0.62 x 103 Polydispersity VLw
/VIn=3, 06 infrared absorption spectrum: 9
wax (am-”)34.50 (-0CH2
) 2950 (-CH2-) 1240 and 8
50 (S i -(CH,)-) Nuclear magnetic resonance spectrum: δ (ppm) 0-13 ~ O-00 (br -5i-(:'As)
, 1-67~2.17 (br, CH2-5i),
2.33-2.83 Next, the parasilane-modified epoxy novolac resin obtained above, a phenol novolak resin with a phenol equivalent of 110, and triphenylphosphine as a curing catalyst were mixed at the compounding ratio shown in Table 2 to obtain a curable A composition was prepared.

This composition was cured under the same conditions as in Example 1, and a water absorption test was conducted. The results are shown in Table 2.

[Example 3] An orthosilane-modified epoxy novolac resin having the unit shown in the following formula (4) as a main constituent unit was synthesized by the following method.

20 g of a silane-modified phenol novolak resin with a phenolic hydroxyl group equivalent of 281 g/equivalent ( 0.095 mo/L/) as phenolic hydroxyl group, x, piccl/l
36.3 g (0,392 mol) of phosphorus, 0.07 g (0,197 mol) of cetyltrimethylammonium bromide
mmol) and 5.9 g of a 50% by weight aqueous solution of caustic soda
(0.074 mol as NaOH), 21.0 g of orthosilane-modified epoxy novolac resin having properties of epoxy equivalent: 305 g/equivalent, softening point: 27.0° C., and hydrolyzable chlorine content: 0.0019% was obtained.

The analysis results of the molecular weight, infrared absorption spectrum, and nuclear magnetic resonance spectrum of this orthosilane-modified epoxy novolak resin are shown below.

Molecular weight (by gel permeation chromatography using monodisperse polystyrene as standard) Weight average molecule M viw = 2, 10 x 1
03 number average molecular weight! ]n=1.05X103 polydispersity Kl! w/Un = 2, OO infrared absorption spectrum: vmax (Rho 1) 3450 (-QC:H
2) 2950 (-CH,-) 1250 and 840 (
S i -(CH))3) Nuclear magnetic resonance spectrum: δ
(ρpm) 0.05 (S, 5i-CI+3), 0
．． 3 G ~ 0.83 (br, CH, -5i), 1.
26-2. OO(br.

(br, benzene nucleus) The orthosilane-modified epoxy novolac resin obtained above, the same phenol novolak resin as in Example 2, and triphenylphosphine were mixed at the compounding ratio shown in Table 2, and then cured in the same manner to obtain water absorbent I conducted a test. Second result
Shown in the table.

[Comparative Example 2] Epoxy equivalent used in Example 1: 192. Softening point 48.
Epoxidized orthocresol novolak resin (E
OCN-4400, Nippon Kayaku Layer), the same phenol novolak resin with a phenol equivalent of 110 as used in Examples 2 and 3, and triphenylphosphine were mixed at the blending ratio shown in Table 2, and then the mixture was mixed in the same manner as in Examples. After curing, a water absorption test was conducted.

The results are also listed in Table 2.

Table 2 From the results shown in Table 2, the cured product using the orthosilane-modified epoxy novolac resin according to the present invention has a higher performance than the cured product using the epoxidized ortho-cresol novolac resin having a methyl group at the ortho position of the benzene ring. The water absorption rate was less than half that of the previous one, indicating the effect of silane modification, and the parasilane-modified epoxy novolak resin modified with silane at the para position also showed the same low water absorption rate as the one modified with silane at the ortho position, indicating the effect of silane modification. was recognized.

hand Continued Ministry 17 Positive book (self from) Applicant: Shin-Etsu Chemical Co., Ltd. Agent: Patent Attorney Takashi Kojima 1.Display of the incident 1999 Patent Application No. 6299 2. Name of the invention Novolac resin-containing composition 3. Person who makes corrections Relationship with the incident

Claims (1)

[Claims] 1. The following general formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, ^2,
R^3, R^4, R^5 and R^6 are the same or different unsubstituted or substituted monovalent hydrocarbon groups, R^7 is a hydrogen atom or a methyl group, and n is an integer of 0 to 5. A novolak resin-containing composition comprising a silane- or siloxane-modified epoxy novolac resin and/or a silane- or siloxane-modified phenol or cresol novolak resin whose main constituent unit is a unit represented by the following.