JPH0625245B2 - Glycidyl ether of polyvalent phenol novolak, its production method and use - Google Patents

Description

FIELD OF THE INVENTION This invention relates to particular epoxy resins.

2. Description of the Related Art A resin material for encapsulating a semiconductor integrated circuit is required to have various strict physical properties in order to protect the semiconductor integrated circuit from the external environment.

As a sealing resin, an epoxy resin has become the mainstream in terms of moisture resistance, processability, electrical characteristics, and price. Among them, glycidyl ethers of phenol novolac and cresol novolac are excellent in terms of heat resistance and moisture resistance, and are most widely used at present.

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention However, in recent years, the density and size of semiconductor elements have been rapidly increased, and higher quality resin materials are required. The encapsulating resin material is required to have a low content of hydrolyzable chlorine, a high glass transition temperature and a low elastic modulus. In particular, the high glass transition temperature is required for the following two reasons. First, there is a problem of heat generation by the semiconductor element. That is, the internal temperature of the semiconductor element is 150
It is known that the temperature can reach as high as 0 ° C., and it is expected that the heat generation will increase as the density and size of semiconductor elements increase. Secondly, in the process of manufacturing a semiconductor integrated circuit, heat of about 260 ° C. is applied when soldering wiring or the like. In the future, it may be possible to immerse the semiconductor element in a solder bath for the purpose of automating and simplifying the manufacturing process, and it is required to have heat resistance sufficient to withstand it.

An object of the present invention is to obtain a glycidyl ether of polyhydric phenol novolac which can provide a cured product having a small amount of hydrolyzable chlorine and excellent heat resistance.

Means for Solving the Problem The inventors of the present invention have made earnest studies on glycidyl ethers of polyhydric phenols satisfying the above-mentioned requirements, and as a result, have made glycidyl ethers of polyhydric phenol novolacs having the following specific structures. By doing so, it has been found that such requirements are satisfied.

That is, the present invention has the general formula (In the formula, R is a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms and an aromatic group, and n is an average.
It is a number from 1.5 to 25. ) Relating to the glycidyl ether of the polyhydric phenol novolac.

The polyhydric phenol novolac glycidyl ether of the present invention has the formula Bisphenol (1,3-trimethyl-
1, p-hydroxyphenyl-indan-6-ol)
Is condensed with an aldehyde represented by the general formula RCHO (III) (wherein R is a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms and an aromatic group). To give a polyhydric phenol novolak, and then the polyhydric phenol is subjected to glycidyl etherification with epihalohydrin.

The bisphenol represented by the formula (II) of the present invention can be produced, for example, by the method described in US Pat. No. 3,288,864. That is, the formula A p-isopropenylphenol represented by the following formula in an organic solvent, a Friedel-Crafts catalyst such as boron trifluoride,
It can be obtained by adding aluminum chloride or the like and heating, but it is not limited to this method.

Specific examples of the aldehydes represented by the general formula (III) include formaldehyde, acetaldehyde, benzaldehyde and the like.

In formula (I), the number average number of repeating units n is 1.5 or more on average 2
It is 5 or less, preferably 2 or more and 15 or less. The n
When it exceeds 25, a high molecular weight product is obtained, and the glycidyl ether has a high viscosity even under high temperature conditions, which makes handling difficult. When n is less than 2, the glycidyl ether becomes a semisolid or viscous liquid at room temperature, which makes it difficult to handle. The number average molecular weight is in the range of about 500 to 10,000. The number average molecular weight is determined by the vapor pressure osmotic pressure method, and the number average repeating unit number is calculated from this.

The bisphenol represented by the formula (II) and the general formula of the present invention
In order to polycondensate the aldehydes represented by (III) to form polyhydric phenol novolac, a commonly used method for producing a novolac type phenol resin can be applied, and even in a batch method, as described in JP-A-51-130498. The continuous method may be used. An example of the manufacturing method is encyclopedia
Inorganic acids such as hydrochloric acid, phosphoric acid and sulfuric acid, or paratoluene sulfonic acid, shu, as described in Phenolic Resins, page 10, page 1, of Polymer Science and Technology (Interscience Publishers). It is produced by condensation polymerization of phenols and aldehydes using an organic acid such as an acid or a metal salt such as zinc acetate as a catalyst. If necessary, an aromatic solvent or the like may be used. The polyhydric phenol novolac thus obtained is a novel one and has the general formula (In the formula, R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms,
It is a group selected from the group consisting of aromatic groups, and n is 1.
It is a number from 5 to 25. ) Is represented.

The novel polyhydric phenol novolac of the present invention can also be used as a curing agent when an epoxy resin is the main ingredient.

In order to glycidyl etherify the polyhydric phenol novolac thus obtained, a method commonly used for producing the glycidyl ether from monohydric or polyhydric phenol can be applied. For example, polyphenols are dissolved in epihalohydrin, and an aqueous alkali metal hydroxide solution is continuously added to this solution, while water and epihalohydrin are distilled from the reaction mixture, and the distilled liquid is separated to remove the aqueous layer. The production method of returning epihalohydrin to the reaction system can be used. Specific examples of epihalohydrin include epichlorohydrin, epibromhydrin and the like, but epichlorohydrin is preferable from the viewpoint of industrial availability.

The polyhydric phenol novolac glycidyl ether of the present invention is used in various applications by blending it with a curing agent, a curing accelerator, an inorganic filler and the like.

As a curing agent, phenol novolac, diaminodiphenylmethane, diaminodiphenyl sulfone, metaphenylenediamine, phthalic anhydride, tetrahydrophthalic anhydride, pyromellitic dianhydride, benzophenone tetracarboxylic acid anhydride, silica as a filler, alumina,
Examples include talc, clay, and glass fiber. Examples of the curing accelerator include imidazoles, tertiary amines and phenols. If necessary, an internal release agent such as stearic acid, calcium stearate, carnauba wax, montan wax, etc., and a flame retardant imparting agent such as glycidyl ether of trabrom bisphenol can be added.

The amount of the curing agent, the filler, the curing accelerator, and the internal release agent varies depending on the type, but as a general rule, the curing agent should be equivalent to the number of moles of epoxy groups in the polyhydric phenol novolac glycidyl ether. The compounding amount that makes the functional groups mols, the compounding amount that the filler is close to the closest packing to the total compounding volume, and the curing accelerator is the compounding amount that is a catalytic amount. The release agent is used in an amount of about 0.2 to 2.0% by weight based on the total amount of the release agent.

The polyhydric phenol novolac glycidyl ether of the present invention is a cured product having a higher glass transition temperature than the conventional orthocresol novolac glycidyl ether or phenol novolac glycidyl ether,
Also, the content of hydrolyzable chlorine is small.

Therefore, the glycidyl ether of polyhydric phenol novolac of the present invention can be suitably used as a sealant for semiconductor integrated circuits by blending the above-mentioned various compounding agents.

Further, a glycidyl ether of the present invention as a main component, and a curing agent such as dicyandiamide, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, hexahydrophthalic anhydride, pyromellitic dianhydride, diethyltriamine, and triethylenetriamine,
The curing accelerator is dissolved in a solvent, glass cloth, glass non-woven cloth, polyester cloth, polyester non-woven cloth, organic such as asbestos paper, and a method of laminating and molding a prepreg that is dried after impregnating an inorganic fiber base material. Different glycidyl ethers can be used as the base compound for laminates.

EXAMPLES The present invention will be described below with reference to examples. The epoxy equivalent in the present invention is defined as gram equivalent per mol of glycidyl ether group. In addition, hydrolyzable chlorine is quantified by back titration with a silver nitrate solution by dissolving the glycidyl ether of a novolac-type substituted phenol resin in dioxane, adding an alcohol solution of potassium hydroxide, and desorbing it when heated at reflux for 30 minutes. It is defined as the weight percentage of chlorine atoms in the compound. The softening point is J
It was measured by IS-K2531 (petroleum asphalt softening point test method (ring and ball method)). The number average molecular weight was measured by the vapor pressure osmosis method.

Example 1 (1) Synthesis of polyhydric phenol novolac 1 equipped with a thermometer, a cooling pipe, a dropping funnel, and a stirrer 1
Add 1,3,3-trimethyl-1, p-hydroxyphenyl-indan-6-ol (purity 92%) 0.5 to the flask.
This was dissolved in 150 g of toluene, 0.01 mol of p-toluenesulfonic acid was added as a catalyst, and the mixture was heated to about 100 ° C.
Then, 37% formalin aqueous solution (formaldehyde 0.15
(Including mol) was continuously added from a dropping funnel in 1 hour. After keeping the temperature for 5 hours after dropping, the catalyst was neutralized with an aqueous solution of NaOH, and unreacted substances and water were removed by concentration to obtain a solid resin at room temperature. The softening point of this resin was 101 ° C. and the number average molecular weight was 690. This resin was subjected to ¹⁸ C-NMR measurement using deuterium-substituted acetone as a solvent. The chart is shown in FIG.

Assignment of peaks in the ¹⁸ C-NMR chart in FIG. 1 is as follows.

30.5ppm, 40.0ppm, 59.9ppm 50.0ppm, 30.3ppm, 31.0ppm Aromatic ring carbon: About 111-157ppm (2) Synthesis of glycidyl ether of polyhydric phenol novolac Thermometer, separation tube, dropping funnel and stirrer were attached. 1
In a flask, 1.0 mol of the polyhydric phenol obtained in (1) (as a phenolic hydroxyl group) is dissolved in 7.0 mol of epichlorohydrin. Keeping the temperature at 80 ℃ and the pressure at 250mmHg, 8
Aqueous 48% NaOH solution was added continuously over time. During this time, epichlorohydrin and water were azeotropically liquefied to be liquefied and separated into an organic layer and an aqueous layer by a separation tube, the aqueous layer was removed outside the system, and the organic layer was circulated inside the system. After completion of the reaction, the temperature was kept for 1 hour to evaporate and remove unreacted epichlorohydrin, and the reaction product was dissolved in methyl isobutyl ketone. Next, after removing the by-product salt, methyl isobutyl ketone was evaporated and removed to obtain a solid resin at room temperature.

The softening point of this resin was 82 ° C., the number average molecular weight was 1170, the epoxy equivalent was 227, and the hydrolyzable chlorine was 0.06 wt%. Further, this resin was dissolved in deuterium-substituted chloroform and ¹⁸ C-NMR was measured. The chart is shown in FIG.

Assignment of peaks in the ¹⁸ C-NMR chart in FIG. 2 is as follows.

30.6ppm, 42.2ppm, 59.7ppm, 50.1ppm, 30.5ppm, 30.8ppm, 68.8ppm, 50.0ppm, 44.5ppm, aromatic ring carbon: about 108 to 158ppm (3) Obtained by viscoelasticity measurement (2) of cured product Glycidyl ether of polyhydric phenol
1.0 mol (specifically, 227 g as an epoxy group)
Phenol novolac 1.0 mol (with phenolic hydroxyl group
And 0.8 parts by weight as a curing accelerator based on the total amount
SuPhenol (made by Sumitomo Chemical Co., Ltd., Sumicure
D) was roll-kneaded to obtain a composition. Then add this composition
It was molded into a 1 mm sheet by pressure and heating. This molding
The product was post-cured at 170 ° C. for 5 hours to prepare a cured molded product.
The viscoelasticity measurement result of this molded product is shown in FIG. Glass roll
The transfer temperature was (225 ° C).

Comparative Example 1 Commercially available cresol novolac glycidyl ether
Sumiepoxy manufactured by Tomo Chemical Co., Ltd. ESCN-22
0) as the main agent and cured with the same formulation as in (3) of Example 1
A molded product was made. Fig. 3 shows the results of measuring the viscoelasticity of this molded product.
Shown in. The glass transition temperature was 198 ° C.

Comparative Example 2 1,3,3-trimethyl-1, p-hydroxyphenyl-indan-6-ol (purity 92%) was used as a raw material.
The glycidyl ether of polyhydric phenol was obtained by the method of (2) of Example 1. This glycidyl ether of polyhydric phenol was semi-solid at room temperature, had an epoxy equivalent of 203 and hydrolyzable chlorine of 0.09 wt.

Using this glycidyl ether of a polyhydric phenol as the main ingredient, a cured molded article was prepared with the same formulation as in (3) of Example 1. The viscoelasticity measurement result of this molded product is shown in FIG. The glass transition temperature was 168 ° C.

To explain FIG. 3 in detail, the abscissa indicates the temperature at the time of viscoelasticity measurement, the ordinate indicates the dynamic elastic modulus, and the ordinate indicates the tan δ. The solid line is the measurement result for the cured molded article of Example 1, the dotted line is for Comparative Example 1, and the alternate long and short dash line is for the cured molded article of Comparative Example 2. The upper solid line 1, the dotted line 2, and the alternate long and short dash line 3 indicate the dynamic elastic modulus, which is simply expressed as the elastic modulus in the text. The lower solid line 1 ', the dotted line 2', and the alternate long and short dash line 3'indicate tan δ.

The peak of tan δ near −70 ° C. is called secondary dispersion and is attributed to the micro Brownian motion of the molecule. The peaks of tan δ near 160 ° C. and around 200 ° C. are called main dispersion and are attributed to the motion of the entire molecule, and the temperature at the peak point of tan δ is the glass transition temperature.

EFFECT OF THE INVENTION At present, glycidyl ether of cresol novolac as shown in Comparative Example 1 is mainly used for semiconductor encapsulation. On the other hand, there is a demand for a glycidyl ether having a lower elastic modulus and a higher glass transition temperature.

The polyhydric phenol novolac glycidyl ether of the present invention has a high glass transition temperature with respect to the conventional cresol novolac glycidyl ether and heat-resistant glycidyl ether, and has the same elastic modulus and hydrolyzable chlorine content. It has excellent properties as a main ingredient of a semiconductor encapsulating composition.

[Brief description of drawings]

FIG. 1 is a ¹³ C-NMR chart of the polyhydric phenol novolac obtained in (1) of Example 1. FIG. 2 is a ¹³ C-NMR chart of the glycidyl ether of polyhydric phenol novolac obtained in (2) of Example 1. FIG. 3 is a viscoelasticity measurement result (dynamic elastic modulus or tan δ-temperature relationship diagram) of the cured molded articles of Example 1 and Comparative Examples 1 and 2. In FIG. 3, 1, 2 and 3 show the dynamic elastic modulus-temperature relationship of the cured molded articles of Example 1 and Comparative Examples 1 and 2, respectively. Further, 1 ', 2', 3'indicate the tan δ-temperature relationship of the cured molded articles of Example 1 and Comparative Examples 1 and 2, respectively.

 ─────────────────────────────────────────────────── ─── Continuation of front page (56) Reference JP-A-59-133218 (JP, A) JP-A-59-36123 (JP, A) JP-A-59-109514 (JP, A) JP-A-59- 147015 (JP, A)

Claims (3)

[Claims] 1. A general formula (In the formula, R is a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and an aromatic group, and n is 1.
It is a number from 5 to 25. ) A glycidyl ether of a polyhydric phenol novolac represented by. 2. A formula The bisphenol (1,3,3-trimethyl-1, p-hydroxyphenyl-indan-6-ol) represented by the general formula RCHO (III) (in the formula, R is a hydrogen atom, alkyl having 1 to 4 carbon atoms) Group and a group selected from the group consisting of aromatic groups.) Polycondensation with an aldehyde represented by the formula) to give a polyhydric phenol, and then the polyhydric phenol is glycidyl etherified with epihalohydrin. Yes, general formula (In the formula, R is a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and an aromatic group, and n is 1.
It is a number from 5 to 25. The manufacturing method of the glycidyl ether of the polyhydric phenol novolak represented by these. 3. General formula (In the formula, R is a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and an aromatic group, and n is 1.
It is a number from 5 to 25. ) A semiconductor integrated circuit sealant comprising a glycidyl ether of a polyhydric phenol novolac represented by