JPS6312623A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:The titled composition suitable for semiconductor sealing, light emitting diode sealing, etc., having improved curing properties and warm heat resistance, obtained by blending a specific alicyclic epoxy resin having sodium content of <=a specific value with an organoaluminum compound and an organosilicon compound as curing catalysts. CONSTITUTION:(A) An alicyclic epoxy resin shown by the formula having <=2ppm Na content is blended with (B) an organoaluminum compound (e.g. aluminum triethyl acetoacetate, etc.) and (C) an organosilicon compound (e.g. diphenylsilanediol, etc.) containing a hydroxyl group or hydrolyzable group directly bonded to silicon atom to give the aimed composition. The resin A is obtained by an ordinary synthesis method and can be prepared by preventing admixture of high-boiling components caused by entrainment in the final purifica tion process by the use of a distillation column, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION (Technical Background) The present invention relates to an epoxy resin composition that exhibits good storage stability at room temperature, has excellent curability, and becomes a cured product with excellent heat resistance and electrical properties.

(Prior art) When curing an epoxy resin, for example, (A) a curing agent such as a polyamine or an acid anhydride such as phenol, or (B) a curing catalyst such as a BF3 complex or a tertiary amine compound is added to the epoxy resin. Usually, it is added to the resin. However, in case (A), when a polyamine is used, there is the disadvantage that the composition cannot be stored for a long period of time due to its strong reactivity with the epoxy resin, and when an acid anhydride is used, it requires high temperatures for curing. The disadvantage is that it requires long-term heating.

On the other hand, in case (B), when the BFi ii body is used, it is possible to cure at a relatively low temperature, but there is a drawback that the electrical and mechanical properties of the cured resin at high temperatures are poor. Furthermore, when a third-class amine is used, a high temperature is required for the curing reaction, and there are also operational problems such as skin irritation.

Furthermore, when curing epoxy resins, attempts have been made to add and blend metal chelate compounds as latent curing catalysts. However, in this case, the curing reaction takes place at temperatures above 200°C.
In addition, the addition of the metal chelate compound is in a relatively large amount of about 5%, and due to the poor dissolution fraction, it is difficult to form a cured resin layer with good properties. .

From this point of view, it is recommended to use an organic aluminum compound and an organosilicon compound having a hydroxyl group or a hydrolyzable group directly bonded to a silicon atom as an epoxy curing catalyst.
JP-A-56-2319.56-462557-5352
2.57-133122 etc.

However, epoxy resins that can be cured with these catalysts include 3,4-epoxycyclohexylmethyl-3',
4'-Epoxycyclohexanecarboxylate (manufactured by Daicel Chemical Industries, Ltd., hepoxide 2021, UC
The so-called E RL-4221 manufactured by Company C is typified by
A ring type epoxy resin is preferred, and the synthesis of this alicyclic epoxy resin is usually carried out by the following route.

(1) Synthesis of 1-trahydrobenzaldehyde by Diels-Alder reaction of butadiene and acrolein (2) Diene synthesis by Teisienko reaction of tetrahydrobenzaldehyde (3) Epoxidation reaction of diene Epoxidation agent used in the epoxidation reaction of (3) Peracetic acid is commonly used industrially and is manufactured by the following process.

What is the manufacturing process of epoxy resin after epoxidation reaction?

It is as follows.

Epoxidation reaction → Low boiling → High boiling → Product When performing an epoxidation reaction using Bacillus peracetic acid, phosphorus is usually Addition of 10 (1 ppm to 1 Qooppm) of an alkali metal salt of polyphosphoric acid or polyphosphoric acid is carried out.

Representative alkali metal salts of polyphosphoric acid include, for example, sodium trioctyl tripolyphosphate, sodium dioctyl tripolyphosphate, and the like.

These are used by partially alkyl esterifying the alkali metal salt of polyphosphoric acid to increase its solubility in the reaction solution.

These salts are to be removed from the epoxy resin product in a high boiling process.

The equipment used in this high boiling process is a forced stirring thin film evaporator such as a gravity flow type thin film evaporator or a Smith type evaporator.

Since it is a high-boiling point substance, it is purified under reduced pressure, but in such an evaporator, components with a higher boiling point than the epoxy resin are inevitably mixed into the product due to droplet entrainment.

Therefore, the phosphate added during the reaction is also inevitably mixed.

Currently, the 3,4-
Epoxycyclohexylmethyl-3'.

The 4'-epoxycyclohexane carboxylates are ERL-4221 from Union Carbide and Seroxide 2021 from Daicel Chemical 12111.

These epoxy resins also contain sodium salt of tripolyphosphoric acid added during the reaction.

When the content of sodium was quantified, both URL-4221 and Celoxide 2021 contained 5 to 50 ppm.

In this way, 3゜4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate containing 5 to 50 ppm of sodium is mixed with the above-mentioned specific aluminum compound and a compound having a hydroxyl group or a hydrolyzable group directly bonded to a silicon atom. When curing by mixing with a silicon compound, a large amount of catalyst is required, and a small amount of catalyst may take a long time to cure or may not cure at all.

It goes without saying that from an industrial perspective, it is better to use as little m as possible since the silicon compound is expensive.

Also, regarding the physical properties of the cured product, it is not preferable that a large amount of aluminum aerobic compounds remain.

(Problems to be Solved by the Invention) In view of this situation, the inventors of the present invention have conducted intensive studies and found that the catalytic activity of silicon compounds is reduced by Na ions. Gansho 61-4358
It was discovered that this problem could be solved by using an alicyclic epoxy resin that contains very little Na pigment, as proposed in the above, and led to the present invention.

[Structure of the Invention] That is, the present invention is based on the formula (1) in which r (a) Na content is 2 ppn+ or less.
Thermosetting alicyclic epoxy resin represented by (I) (b) an organic aluminum compound (C) a silicon compound having a hydroxyl group or a hydrolyzable group directly bonded to a silicon atom "resin composition".

The 3,4-epoxycyclohexylmethyl-3',4-1-epoxycyclohexane lupoxylate represented by the formula (D), which is the component (a) serving as the backbone of the resin composition of the present invention, is produced by a process similar to the above-mentioned process. That is, it is produced by (1) synthesis of tetrahydrobenzaldehyde by Diels-Alder reaction of butadiene and acrolein, (2) synthesis of diene by Tischenko reaction, and (3) epoxidation reaction of diene with peracetic acid.

A feature of the production of the compound of formula (1), which forms the backbone of the thermosetting resin composition of the present invention, is that in the final purification step, a distillation column or a device having similar distillation efficiency is used to entrain the compound by droplet entrainment, etc. This is to prevent contamination with high boiling point components.

Here, the distillation column is a device consisting of a packed column, a scouring column, and a capping column used in ordinary chemical industry processes.
As for the number of stages, one or two stages that exhibit efficiency are sufficient.

Further, as a device having a distillation efficiency similar to that of a distillation column, a device for preventing entrainment of droplets or a device simply made by elongating the upper pipe portion of the distillation line may be used.

Usually, Smith type evaporators, which are often used as forced Wl stirring thin film evaporators, often have a cooling device inside the evaporator, but this type causes a lot of droplet entrainment.

Therefore, a cooling device can be installed outside to improve separation efficiency.

During distillation, heating can be performed using high-pressure steam or a heating medium, but heating is performed at about 160°C to 220°C.

The degree of vacuum is 0. It is preferable to carry out the process in a high vacuum of about 3 Torr to 3 Torr.

By performing distillation purification using these devices, the epoxy resin represented by formula (I) used in the thermosetting resin assembly of the present invention becomes extremely pure.

In other words, the sodium salt of polyphosphoric acid added in the peracetic acid epoxidation step is not added.

When a low Ha product is obtained by distillation purification, the yield of the distilled product based on the reaction crude liquid is 80 to 95%, preferably 80 to 85%.

If it exceeds 95%, not only will the distillation efficiency decrease, but also Ha
The content of iron and the degree of coloring increase.

If it is less than 80%, the distillation efficiency and the purity of the distillate amount will be high, but the economy will be poor.

Component (a) serving as the skeleton of the thermosetting resin assembly of the present invention,
That is, Na in the epoxy compound represented by formula (1)
For example, sample 1 to 1 in a platinum crucible is
Accurately weigh 2g (6), burn the organic matter in an electric furnace at 500-600°C, dissolve the residue in nitric acid aqueous solution, dilute it to an appropriate concentration, and analyze it using atomic absorption spectrometry. Analysis shows it to be less than 2 ppm.

The aluminum compound which is the component (b) of the thermosetting resin composition of the present invention has an alkoxy group, phenoxy group, acyloxy group, β-diketonate group, 〇-levonylphenolate group, etc. bonded to the aluminum atom. Preferably, it is a lead compound of organoaluminium.

Here, the alkoxy group preferably has 1 to 10 carbon atoms, and examples thereof include methoxy, ethoxy, isopropoxy, butoxy, bentoxy, etc.; examples of the phenoxy group include phenoxy group, 〇-methylphenoxy group, 0-methoxyphenoxy group, etc. group, p-itrophenoxy group, 2.6
-dimethylphenoxy groups, etc. Niacyloxy groups include acetate, propionate, isopropionate, butylade, stearard, ethylacetoacetate, propylacetoacetate, butylacetoacetate diethylmalate, dipivaloyl Examples of the β-diketonate group include acetylacetonate, trifluoroacetylacetonate, hexafluoroacetylacetonate, O OCH30 CH3-C-CH-C-CH3, ○ ○ Examples of the 20-carbonylphenolate group include salicylaldehydate.

Specific examples of such aluminum compounds include trismethoxyaluminum, trisethoxyaluminum, trisisopropoxyaluminum, trisphenoxyaluminum, trisparamethylphenoxyaluminum, isopropoxyjethoxyaluminum, trisbutoxyaluminum, trisacetoxyaluminum, trissteer. Lard aluminum, tris butylade aluminum, tris propionate aluminum, tris isopropionate aluminum, tris acetylacetonate aluminum, tris trifluoroacetylacetonate aluminum, tris hexafluoroacetylacetonate aluminum, tris ethyl acetoacetate aluminum, tris These aluminum compounds are salicylaldehydate aluminum, tris-diethylmalorade aluminum, trispropylacedoate aluminum, tris-butylacetoacetate aluminum, tris-dipivaloylmethanato aluminum, diacetylacetonate dipipalmethanato aluminum. They may be used alone or in a mixed system of two or more, and the amount added is in the range of 0.0001 to 1%, preferably 0.001 to 0.1%, based on the weight a ratio of the epoxy resin. be.

If the blend M is less than 0.001171%, sufficient properties of the cured product cannot be obtained, and if it exceeds 1%,
This is not preferable because it not only increases cost but also tends to reduce moisture resistance.

Examples of the organosilicon compound as component (C) used in the thermosetting resin composition of the present invention include organosilanes and organosiloxanes described below.

Organo used in the thermosetting resin composition of the present invention (in the above formula, Hydr means an OH group or generating OHM by hydrolysis, X, x and x3 may be the same or different, carbon Alkyl group having 1 to 5 atoms: phenyl group, tolyl group.

Paramethoxyphenyl group: parachlorophenyl group.

Aryl groups such as para-nitrophenyl group: 7ralkyl such as benzyl group, phenethyl group, para-methoxybenzyl group, para-methylbenzyl group! l! : Vinyl group.

It represents an alkenyl group such as an allyl group, a propenyl group, or a phthynyl group, or an acyl group such as an acetyl group, a benzoyl group, or a trifluoroacetyl group.

p, q and r are integers from 0 to 3, and D+Q+r is 3 or less.

Among the above organosilanes, those more preferable for the thermosetting resin composition of the present invention include, for example, triphenylmethoxysilane, diphenyldimethoxysilane,
Triphenylethoxysilane.

diphenylmethylmethoxysilane, phenylvinylmethylmethoxysilane, diphenyljethoxysilane, tri(paramethoxyphenyl)methoxysilane, triacetylmethoxysilane, diphenylethylethoxysilane,
Diphenylethyl ethoxysilane, diphenylmethylacetoxysilane, diphenyldibuO pionyloxysilane, diphenylmethyltriphenylacetoxysilane.

Tri(paranitrophenyl)methoxysilane, triacetylmethoxysilane, phenyldihynylbroboxysilane, 2-phanyldiphenylmethoxysilane, di(2-
hentenyl) phenylethoxysilane, phenylcinlopyrmeth 4; disilane.

Tri(paramethoxyphenyl)ethoxysilane.

Paramethylbenzyltrimethoxysilane, trifluoroacetyltrimethoxysilane, di(parachlorophenyl)jethoxysilane, triethylmethoxysilane, trimethylmethoxysilane, tripropylmethoxysilane,
Tributyl ethoxysilane, triisobutylacetoxysilane.

(φ: phenyl) and their hydrolysis products.

Furthermore, the organosiloxane used in the thermosetting resin composition of the present invention is composed of a bifunctional unit represented by the following formula (Vl) and/or a trifunctional unit represented by the following formula (Vl). The terminal of the siloxane group has the following formula (Vl
'), which is sealed by the Ichinomiya functional unit represented by T( (in the above formula, Y
6 may be the same or different, -1 group: hydrolyzable group: alkyl group having 1 to 5 carbon atoms: phenyl group, tolyl group, paramethoxyphenyl.

7-aryl groups such as parachlorophenyl and paracyanophenyl; aralkyl groups such as benzyl group, phenethyl group, paramethoxybenzyl group, and paramethylbenzyl; vinyl group;
Alkenyl groups such as allyl group, propenyl group, butenyl,
In particular, at least one of the structural units (representing an acyl group such as an acetyl group, a benzoyl group, a trifluoroacetyl group, etc.) contains at least one of an -0H group and a hydrolyzable group.

Among the organosiloxanes mentioned above, the degree of polymerization is 50 or less,
OHH base or hydrolyzable base? is 1,000 or less, suitable for the present invention, and furthermore, those with the above equivalent weight of 50 to 500.
It is preferable that

Specific examples of such preferred organosiloxane include 1,3-dimethoxy-1,3-dimethyl-1,3-
diphenyldisiloxane, 1,5-jethoxy-1,3
, 5-trimethyl-1,3゜5-triphenyltrisiloxane, 1.7-simethoxy1,3.5.7-titramethyl-1.3゜5.7-tetraphenyltetrasiloxane, 1゜3-dimethoxy Sidetraphenyldisiloxane, 1.5-dimethoxy-3,3-dimethyl-1,5-tetraphenyltrisiloxane, 1.3.5-trimethoxypentaphenyltrisiloxane, 1.5-dimethoxyhex(p-methoxy (phenyl) triquiloxane, φ (φ: phenyl group) (φ: phenyl group) and their hydrolysis products, and Q 1
-3037 (methoxy fund 118 fift%, Toshiba Silicone Co., Ltd. product name) and 5H6018 (Q) l equivalent approximately 4
This also applies to silicone resins available under trade names such as 00° Higashi Silicone Co., Ltd. (trade name).

However, the above organosilane and organoborisiloxane compounds may be used alone or in a mixed system of two or more, and the amount added is determined by the weight ratio of 0 to epoxy resin.
, ooi ~1 preferably o, oos ~0.05 is sufficient.

In the thermosetting resin composition of the present invention, in addition to the above-mentioned curing catalyst, a commonly used acid anhydride curing agent may be blended, if necessary.

Examples of such acid anhydride curing agents include phthalic anhydride, maleic anhydride, hexahydrophthalic anhydride,
Tetrahydrophthalic anhydride, methylhimic anhydride,
Examples include biOmellitic anhydride, benzophenonetetracarboxylic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, and dodecenylsuccinic anhydride.

Since both the organic aluminum compound and the organosilicon compound, which are components (b) and (C) of the resin composition of the present invention, begin to show activity at about 80°C, the curing temperature may be 30 to 200°C, and is preferably is 80-180
It is ℃.

Note that this curing reaction does not need to be carried out in a closed system unlike conventional organometallic compound catalysts, and it is sufficient to carry out it in air.

In the present invention, fillers such as silica, pigments, dyes, etc. may be added as necessary.

In addition, in the resin composition of the present invention, other epoxy resins such as shrimp-bis type epoxy resin, limonene dieboxide, vinyl cyclohexene dieboxide, vinyl cyclohexene monoepoxide, etc. may be used as long as the properties thereof are not impaired. A mixture of alicyclic epoxies and the like may be used.

(Effect of the invention) The Na content as the skeleton of the resin composition of the invention is 2 ppm.
The epoxy resin represented by the following formula (I) is the conventional (I
> The resin composition of the present invention exhibits properties completely different from those of the compound represented by the formula, and has excellent curability and electrical properties, especially excellent heat resistance, and is suitable for semiconductor encapsulation, light-emitting diode encapsulation, etc. Are suitable.

The present invention will be explained in detail below with reference to Examples.

Synthesis Example-1 3-Cyclohexenylmethyl-3-cyclohexenecarboxylate 173/(!F, ethyl acetate solution containing 30 wt% peracetic acid 4 S OKg, acetic acid solution containing 20% sodium trioctyl tripolyphosphate 3 Kg to 1
Continuously feed peracetic acid into a complete mixing tank and a piston flow tower for an hour, and while keeping the temperature at 35℃, the conversion rate of peracetic acid is 9.
The reaction was allowed to occur until the concentration reached 0% or more.

Acetic acid, ethyl acetate, and excess peracetic acid were evaporated from the resulting reaction crude liquid using a gravity thin film evaporator.

Thereafter, in order to remove high-boiling components, it was purified using a Smith evaporator.

It was heated under reduced pressure of 0.5 Torr using high-pressure steam at 180°C to 190°C to obtain a distillate at a rate of 167Kg/Hr.

At this time, the amount of bottoms containing high-boiling substances was 36 Kg/Hr.

The hue of the obtained product is APHA 20, epoxy equivalent 13
It was 3.

Comparative Synthesis Example-1 The reaction was carried out under the same conditions as in Synthesis Example-1, and in the final purification step, the same M product was carried out using an internal condenser type Smith evaporator.

The hue of the obtained product is APIIA 40. Epoxy weight (6) was 135.

Example-1 3,4-epoxycyclohexylmethyl-3'',4''-epoxycyclohexanecarboxylate obtained in Synthesis Example-1 and Comparative Synthesis Example-1 and commercially available ERL manufactured by UCC
-4221 was measured for Na content.

2 g of each sample was accurately weighed in a platinum crucible, burned in an electric furnace at 600° C. for 4 hours, and the residue was dissolved with nitric acid, poured into a 50 d volumetric flask, and analyzed by atomic absorption spectrometry.

Table-1 Example-2 Synthesis Example-1, Comparative Synthesis-2 and commercially available ERL manufactured by uCC
-4221 each epoxy resin 100ffifa
per part, diphenylsilanediol (C6H5)S
20.1 parts of i (OH) and 0.05 parts of trisethylacetoacetatoaluminum were mixed, and the gelation time of each composition at 100°C was measured. The results are shown in Table-2.

Table 2 Ha content used in the thermosetting pilgrim composition of the present invention is 2 p
3,4-epoxycyclohexylmethyl below pra
It can be seen that 3-,4-mono-epoxycyclohexane rupoxylate has excellent reactivity.

Claims (1)

[Claims] (a) Alicyclic epoxy resin represented by the formula (I) with a Na content of 2 ppm or less ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (I) (b) Organic aluminum compound (c ) A thermosetting resin composition comprising an organosilicon compound having a hydroxyl group or a hydrolyzable group directly bonded to a silicon atom.