JPH0426642A - Polyhydric phenol-based compound and curing agent of epoxy resin - Google Patents

Abstract

NEW MATERIAL:A cyclic terpene skeleton-containing polyhydric phenol-based compound prepared by adding about two molecules of a phenol to one molecule of a cyclic terpene compound. EXAMPLE:A compound shown by the formula. USE:A raw material for polyester and polycarbonate and a curing agent for thermosetting resins and epoxy resins. PREPARATION:A cyclic terpene compound is reacted with a phenol in the presence of an acidic catalyst to give a cyclic terpene skeleton-containing polyhydric phenol-based compound.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a polyhydric phenol compound containing a cyclic chi skeleton, and this compound can be used as a raw material for polyester, polycarbonate, etc., or itself as a thermosetting resin. It is useful, and is particularly excellent as a curing agent for epoxy resins.

(Prior art) Polyhydric phenol compounds are used as raw materials for polyesters, polycarbonates, etc., and are themselves used as thermosetting resins in various fields such as lamination, painting, adhesion, sealing, and molding. It is also used as a curing agent for epoxy resins used in the field of

In recent years, as the required properties for polymeric materials have become stricter and the conditions under which they are used have become more severe, the currently commonly used bisphenol compounds produced from phenol and acetone, etc., and phenol produced from phenol and formaldehyde, It is no longer possible to fully satisfy the required properties with resin.

For example, curable epoxy resin compositions using phenolic resin as a curing agent are used for semiconductor encapsulation, but performance requirements are becoming stricter in this field as well. That is, as semiconductor devices become more highly integrated, semiconductor elements become significantly larger, and packages themselves become smaller and thinner.

In addition, the mounting of semiconductor elements has also shifted to the surface mount method, and in surface mount, semiconductor devices are directly immersed in a solder bath and exposed to high temperatures, so moisture absorbed in the encapsulant is removed. It expands and cracks appear in the sealing material. Therefore,
Encapsulants with good solder crack resistance are required to have high heat resistance and low moisture absorption, and epoxy resins using cresol novilac type epoxy resin and phenol novolac resin curing agent, which are currently mainly used, are required for encapsulants with good solder crack resistance. The sealing material is
Both heat resistance and moisture absorption are insufficient.

For these reasons, attempts have been made to use a condensate of phenol and hydroxybenzaldehydes as an epoxy resin curing agent, or to use an epoxidized product of the same condensate as an epoxy resin. Although it can be improved, it increases moisture absorption and is not useful for improving solder crack resistance.

In addition, there is a proposal to improve hygroscopicity by introducing alkyl substituents into epoxy resins and their curing agents, but in this case heat resistance decreases, so it is necessary to achieve both heat resistance and low hygroscopicity. I can't.

(Problems to be solved by the invention) The present invention provides a polyhydric phenol compound that can be used for various purposes, and in particular can provide a cured product with excellent heat resistance and low hygroscopicity when used as a curing agent for epoxy resin. The object of the present invention is to provide an epoxy resin curing agent using the same compound, and to provide a curable epoxy resin composition using the same compound.

(Means for solving the problem) As a result of extensive research in order to solve the above-mentioned problem, the present inventors have found that the object can be achieved by using a specific polyhydric phenol compound containing a cyclic thyl-4-ene skeleton. It was.

That is, the polyhydric phenol compound of the present invention is a polyhydric phenol compound containing a cyclic terpene skeleton obtained by adding about two molecules of phenol to one molecule of a cyclic terpene compound, or a polyhydric phenol compound containing a cyclic terpene skeleton. It is any polyhydric phenol compound containing a high molecular weight cyclic terpene skeleton obtained by a condensation reaction between a polyhydric phenol compound and an aldehyde and/or a ketone.

Further, the epoxy resin curing agent of the present invention mainly contains at least one compound selected from the above-mentioned polyhydric phenol compounds containing a cyclic terpene skeleton and the above-mentioned polyhydric phenol compounds containing a molecular weighted cyclic terpene skeleton. It is a curing agent as an ingredient.

Furthermore, the curable epoxy resin composition of the present invention is a composition containing an epoxy resin and the above-mentioned epoxy resin curing agent.

The cyclic terpene skeleton-containing polyhydric phenol compound in the present invention can be produced by reacting a cyclic terpene compound and a phenol in the presence of an acidic catalyst.

Furthermore, the polymeric Europeanized cyclic chirupone skeleton-containing polyhydric phenol compound of the present invention is obtained by combining the cyclic terpene skeleton-containing polyhydric phenol compound produced as described above with aldehydes and/or ketones. It can be produced by a condensation reaction.

The cyclic terpene compound as a raw material for producing the cyclic terpene skeleton-containing polyhydric phenol compound of the present invention may be a monocyclic terpene compound or a bicyclic terpene compound. Specific examples include the following:

Limonenni Nopentin: It is an optical isomer of limonene.

Terbinolene: Binene: α-type β-type Terbinene: α-type β-type γ-type Metadiene: 3.8-type 2.4-type In addition, the cyclic terpene skeleton-containing polyhydric phenol compound of the present invention Examples of phenols that are the other raw materials for production include phenol, cresol, xylenol, propylphenol, nonylphenol, hydroquinone, resorcinol, methoxyphenol, bromophenol, bisphenol A, bisphenol F, and the like.

In the addition reaction between the cyclic terpene compound and phenols, 1 phenol is added to 1 mole of the cyclic terpene compound.
~12 mol, preferably 2 to 8 mol, are used and the process is carried out in the presence of an acid catalyst at a temperature of 40 DEG to 160 DEG C. for 1 to 10 hours. Examples of the acidic catalyst include hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, boron trifluoride or its complex, and activated clay. Although the reaction solvent does not have to be used, solvents such as aromatic hydrocarbons, alcohols, and ethers are usually used.

The cyclic terpene skeleton-containing polyhydric phenol compound of the present invention produced in this manner, for example, produced from limonene and phenol is a compound represented by the following structural formula (I), and α-terpinene and phenol is a compound represented by the following structural formula (■).

The cyclic terpene skeleton-containing polyhydric phenol compound of the present invention can be used as a raw material for producing polyester, polycarbonate, etc., and can be cured with, for example, hexamethylene diamine, or as a curing agent for epoxy resin. If used as a compound, a cured product with high heat resistance and low hygroscopicity can be obtained. Furthermore, if this is subjected to a condensation reaction with aldehydes and/or ketones, the high molecular weight cyclic chiluine skeleton-containing product of the present invention can be obtained. A polyhydric phenol compound is obtained.

Examples of aldehydes and acetones to be subjected to a condensation reaction with the above-mentioned cyclic chillin skeleton-containing polyhydric phenol compound to produce the high molecular weight cyclic chillin skeleton-containing polyhydric phenol compound of the present invention include formaldehyde,
NOYA formaldehyde, acetaldehyde, penzaydehyde, hydroxyben X'fuldehyde, acetone,
Examples include cyclohexanone.

In the condensation reaction, the polyhydric phenol compound containing a cyclic terpene skeleton can be reacted with other phenols, but in this case, the proportion of the polyhydric phenol compound containing a cyclic terpene skeleton is at least 20% by weight, preferably at least 40% by weight, based on the total amount with other phenols. If the proportion of the cyclic terpene skeleton-containing polyhydric phenol compound is small, a high molecular weight product with satisfactory physical properties cannot be obtained.

In the condensation reaction, the reaction ratio of phenols and aldehydes and/or ketones is 0.1 to 1.0 to 1 mole of phenols.
0 mol, preferably 0.2 to 0.7 mol, and the reaction is carried out at a temperature of 40 to 200° C. for 1 to 12 hours in the presence of an acidic catalyst. If the reaction ratio of aldehydes and/or ketones increases too much, the molecular weight will increase significantly,
It improves heat resistance, but its high viscosity makes it difficult to handle during molding.

Examples of acidic catalysts for the condensation reaction include mineral acids such as hydrochloric acid and sulfuric acid, organic acids such as uric acid and toluenesulfonic acid, and other organic acid salts that exhibit acidity. Catalysts can be used. The amount of acidic catalyst used is 0.1 to 5 parts by weight per 100 parts by weight of phenol. In the condensation reaction, inert solvents such as aromatic hydrocarbons, alcohols, and ethers can be used.

The high molecular weight cyclic terpene skeleton-containing polyhydric phenol compound of the present invention thus obtained can be used as a resin material for molding using hexamethylenetetramine or the like as a curing agent, and especially as a curing agent for epoxy resins. It is excellent as such.

Next, the epoxy resin curing agent of the present invention mainly contains at least one compound selected from the cyclic terpene skeleton-containing polyhydric phenol compound and the polymerized cyclic terpene skeleton-containing polyhydric phenol compound of the present invention. It is a curing agent as an ingredient. That is, the epoxy resin curing agent of the present invention may consist only of a polyhydric phenol compound containing a cyclic terpene skeleton, or may consist only of a polyhydric phenol compound containing a high molecular weight cyclic terpene skeleton. Alternatively, it may be a mixture of the two, or it may be a combination of these and other epoxy resin curing agents.

Other epoxy resin curing agents that can be used in combination include, for example, phenolic resins such as Nogelac-type phenolic resin and Nogelac-type cresol resin, acid anhydrides such as tetrahydrophthalic anhydride and pyromellitic anhydride, noaminodiphenylmethane, and diaminodiphenylmethane. Examples include amines such as nophenylsulfone. The amount of these other curing agents used in combination is desirably 50% by weight or less based on the total amount of curing agents. If the amount of other epoxy resin curing agents becomes too large,
The excellent effects of the curing agent of the present invention cannot be fully exhibited.

Next, the curable resin composition of the present invention is a composition containing an epoxy resin and the epoxy resin curing agent of the present invention described above.

There are no particular restrictions on the epoxy resin, and those used in ordinary epoxy resins can be used.
For example, bisphenol A1 bispheno (J3), resorcinol, hydroquinone, bifu, nor,
Tetramethylbif□nol, phenols are lac, cresol + l? Lac, various phenols such as bisphenol A novolac, these phenols,
Epoxy resins manufactured from various phenolic resins such as polyhydric phenol resins obtained by condensation reactions with various aldehydes such as oxybenzaldehyde, crotonaldehyde, and glyoxol, and shrimp halohydrin, noaminodiphenylmethane, amino Examples include epoxy resins produced from various amines such as phenol and quizyrenzamine and epichlorohydrin.

The curable epoxy resin 1 composition of the present invention may contain a curing accelerator, filler, coupling agent, flame retardant, plasticizer, solvent, reactive diluent, pigment, etc. as necessary. I can do it.

Examples of the curing accelerator include imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole, 2,4. ．． Examples include amines such as 6-) lith(-/(]4) methylaminomethyl)phenol and benzyltmethylamine, and organic phosphorus compounds such as tributylphosphine and triphenylphosphine.

Examples of inorganic fillers include fused silica, crystalline silica, glass powder, alumina, and zircon; examples of flame retardants include antimony trioxide and phosphoric acid; It is also possible to make part of the resin flame retardant by using a brominated epoxy resin.

The curable epoxy resin composition of the present invention, that is, the curable epoxy resin using the cyclic terpene skeleton-containing polyhydric phenol compound of the present invention or the polymeric eyelid cyclic terpene skeleton-containing polyhydric phenol compound as the main component of the curing agent. provides a cured product with higher heat resistance and lower hygroscopicity than conventional curable epoxy resin compositions, so it can be advantageously used in fields such as sealing, lamination, and painting.

(J5) (Examples, etc.) Further details will be given below with reference to Examples and Comparative Examples.

Note that Example 1 is an example of a polyhydric phenol compound containing a cyclic terpene skeleton, Example 2 and Example 3 are examples of a polyhydric phenol compound containing a high molecular weight cyclic terpene skeleton, and Example 4 is an example of a polyhydric phenol compound containing a cyclic terpene skeleton. -6 are examples of curable epoxy resin compositions using the cyclic terpene skeleton-containing polyhydric phenol compounds of Examples 1-3 as epoxy resin curing agents.

Example 1 Phenol 3381.1.1.3 was placed in a three-necked flask with an internal volume of 51 mm equipped with a thermometer, a stirrer, and a condenser. Charge 34.9' of tri-boron nitride diethyl ether complex and heat to 70-80C.
At this temperature, 816 g of limonene was added dropwise over 3 hours, and the mixture was further stirred at the same temperature for 2 hours to allow the reaction to occur.

Next, the product was washed three times with distilled water, heated under reduced pressure to distill off phenol and by-products, and finally 16
A polyhydric phenol-based compound 152 (l) containing a cyclic cyclothylene skeleton was obtained at a temperature of 82°C and softened by holding at 0°C and 5 wHg for 1 hour. The purity was 89.

Example 2 A three-necked flask with an internal volume of 31 and equipped with a thermometer, a stirrer, and a cooling tube was charged with the polyhydric phenol compound 109219 produced in Example 1, toluene 1000J9, and 5 g of oxalic acid, and the temperature was raised to 80°C. Dissolved uniformly by heating. Next, 75 g of 36 thiformaldehyde aqueous solution was added to the internal temperature 'f
, while maintaining the temperature at 80°C, dripping for 1 hour, then 80°C.
The mixture was kept at 0°C for 1 hour to react.

Next, water and toluene were distilled off while increasing the temperature, and finally the mixture was maintained at 160° C. under a reduced pressure of 5 s+Hg for 1 hour to completely remove water and toluene. The obtained high molecular weight polyhydric phenol compound was a yellow solid with a softening point of 126°C.

Example 3 80 g of benzaldehyde was used in place of 75 g of the 36 thiformaldehyde aqueous solution (]7) used in Example 2, and the reaction was otherwise carried out in the same manner as in Example 2. Post-treatment was carried out in the same manner, and the softening point was 132°C. A yellow-red high molecular weight polyhydric phenol compound was obtained.

Examples 4 to 6 Comparative Examples 1 to 2 Polyhydric phenol compounds obtained in Examples 1 to 3 and phenol nogelac resin as curing agents (for Comparative Example 1)
, or a phenol resin obtained by a condensation reaction of phenol and salicylaldehyde (in the case of Comparative Example 2), an orthocresol type epoxy resin as an epoxy resin, a flame-retardant brominated epoxy resin, antimony trioxide as a flame retardant,
Triphenylphosphine was used as a curing accelerator, silica powder was used as a filler, epoxysilane was used as a surface treatment agent, and carnauba wax was used as a mold release agent, as shown in Table 1.

Each of the formulations was then mixed using a mixing roll for 90 minutes.
Each melted image mixture obtained by melt-kneading at a temperature of ~120° C. for 5 minutes was taken out in the form of a sheet, cooled and pulverized to obtain each molding material (curable epoxy resin composition). Each of the molding materials was molded using a low-pressure transfer molding machine at a mold temperature of 180°C for a molding time of 180 seconds to seal test pieces for glass transition temperature, moisture absorption, and bending test measurements, as well as simulated elements. A 44-pin PPP (Flat Plastinokunoya Tsukei) was obtained and post-cured by heating at 180° C. for 8 hours. After post-cure, glass turning $
6.Temperature, water absorption, bending test, solder heat resistance, etc. were tested.

The results are shown in Table 1, and the cured products of each of the epoxy resin compositions of Examples 4 to 6 had high glass transition temperatures and low moisture absorption rates, so they had excellent nozzle crack resistance. Therefore, it was excellent for semiconductor encapsulation.

Notes to Table 1 *1... Yuka L Eboxy Co., Ltd. Product name: Ebiko
) 180H65, epoxy equivalent weight 201. li'/eq
, Softening point 670℃ *2...Yuka Shell Epoxy Co., Ltd. (trade name: Epicor) 5050. Epoxy weight: 9385g/eQ, bromine content: 49t*3...manufactured by Gunei Chemical Co., Ltd., softening point: 85°C*4: softening point: 108°C, hydroxyl equivalent: gsg/eq-*5...Ryusei Company product name RD-8 *6...Shin-Etsu Chemical Company product name KBM-403*7...
It was determined from the transition point of the thermal expansion curve using TMA.

*8... Moisture absorption rate after 200 hours at 120°C, 100% RH *9... 44 bottles FPP] After absorbing moisture for 168 hours at 85°C and 85° RH, 6 pieces were placed in a 260°C/% under bath for 10 minutes. The samples were immersed for a second and the number of cracks generated was determined.

(Effects of the Invention) The cyclic terpene skeleton-containing polyhydric phenol compound of the present invention exhibits heat resistance when cured with hexamethylene diamine or the like and when cured with an epoxy resin used as a curing agent for epoxy resin. Provides a cured product with high and low hygroscopicity.

Procedural Amendment July 77, 1990 Commissioner of the Japan Patent Office Yoshi 1) Moon Tsuyoshi 1゜2゜3゜ Indication of the case 1998 Patent Application No. 13/G 16 Name of the invention Polyhydric phenol compound and epoxy Relationship with the case of the person who amended the resin “curing agent” Patent applicant name Yuka Shell Epoxy Co., Ltd. and 7 others 4゜Representative person 2゜Subject of amendment (1) “Detailed description of the invention column” in the specification Contents of the amendment Contents of the amendment (1) “Dipentene” in the second line from the bottom of page 2 of the specification:
" is corrected to "dipentene:".

(2) The β-type binene written on the right side of the middle row of page 7 is corrected as follows.

(3) Same page 10, No. I! Correct "acetones" in the / line to "ketones".

(4') Correct "epoxy resin" in the second line from the bottom of page 73 to "epoxy resin composition" (J-)
``Example group Otsu'' on the 7th line of page 1 Otsu of the same page is changed to ``Example 1
1. 〜7'', corrected.

(B) Corrected “Example Hiroshi~Otsu” in line j of page 1♂ to “Example t~7”, and changed “Comparative example/～ノ” in line 6 of the same page to “Comparative example/～ 3,” he corrected.

(7) Next to "cresol type epoxy resin" on page 1g, line 72 of the same page, enter the description "epoxy resin of condensate type of phenol and salicylaldehyde".

(f) "Example G-t" on the 1st page, line 1/~/2 of the same page.
" is corrected to "Example t-7."

(ri) The table / on page 20 is corrected to the table / on the next page.

(10) The entire text of page 2 will be corrected as follows.

Table / Note 1... Yuka Ciel Epoxy Co., Ltd. (trade name: Epicor)
/IθH Otsu3, epoxy equivalent, 2o/P/e q,,
Softening point Otsu 7C 2... Yuka Shell Epoxy Co., Ltd. Product name Epicoat 1032H Otsu 01 Epoxy equivalent/J9P/eq. , Softening point Otsu 2C 3... Yuka Shell Epoxy Co., Ltd. trade name Epicor)
! ;0!0, epoxy equivalent 31B; P/eq-1
Bromine content t% 4...manufactured by Gunei Chemical Co., Ltd., softening point ♂tC 5...softening point 10g'C, hydroxyl group equivalent 91 P/e
q.

6...Tatsumori company product name R, D-f 7...Shin-Etsu Chemical company product name KBM-11t038...
・Using TMA, the transition point of the thermal expansion curve was determined.

9.../20C, 100%RH, moisture absorption rate after 200 hours Bone 10...t4t bottle PPP/6 pieces gsc, is%
After absorbing moisture for an hour at RH, they were immersed in a 1.2 OC solder bath for 10 seconds, and the number of cracks was determined.

(//) The last line of page 22 has been amended as follows.

(Effect of the invention) The cyclic terpene skeleton-containing polyhydric phenol compound of the present invention has high heat resistance when cured with hexamethylene diamine or the like and when used as a curing agent for epoxy resin to cure the epoxy resin. , and provides a cured product with low hygroscopicity.

Patent applicant Yuka Shell Epoxy Co., Ltd. and 7 others

Claims (4)

[Claims] (1) Approximately 2 phenols per molecule of cyclic terpene compound
A polyhydric phenol compound containing a cyclic terpene skeleton, which is added in proportion to the molecule. (2) A high molecular weight cyclic terpene skeleton-containing polyhydric phenol compound obtained by a condensation reaction between the polyhydric phenol compound according to claim 1 and aldehydes and/or ketones. (3) An epoxy resin curing agent containing at least one compound selected from the polyhydric phenol compound according to claim 1 and the polyhydric phenol compound according to claim 2 as a main component. (4) A curable epoxy resin composition comprising an epoxy resin and the epoxy resin curing agent according to claim 3.