JPS58500898A - molding compound - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] molding compound Background of the invention Many types of solid epoxy molding compounds are commercially available. This compound have been used in many applications including the encapsulation of electrical equipment or components. .

These molding compounds are generally tactile so that they cure rapidly at molding temperatures. Contains a medium. However, the presence of a catalyst can significantly reduce the shelf life of the molding compound. suffers a loss. Even when refrigerated, it hardens and loses its usefulness before use.

Mark M. Artow*ty's U.S. Patent No. 3.812.214 has certain curable epoxy resin compositions are described.

This composition is roughly; a) epoxy resins with more than one 1,2-epoxy group per molecule, b) Metal acetylacetonates with only metal-oxygen bonds optionally C) a phenolic accelerator.

The composition is said to have excellent properties including high cure speed and storage stability. It is being However, this patent does not include the use of these as a molding compound. is not described.

Bon-te-JL-1- This invention relates to an improved epoxy molding compound. These formations Shape pound is for all 1 of the composition, a) about 5 epoxy' resins with more than one 1,2-epoxy group per molecule; ~90% by weight, b) 0.001 to 5 weight of metal acetyl oxide having only metal-oxygen bonds %, C) 0.025-30% phenolic accelerator, and d) about 10-95% filler. weight%, consisting of a mixture of These compositions can be in solid or liquid form and have high curing speeds. and storage stability, as well as strength, shrinkage, and use as a molding composition. The relevant physical properties are excellent.

11 to 11 The epoxy resin used in this invention has more than one epoxy group per molecule. Any 1,2-epoxy resin may be used as long as it does. They include 3.4-E poxycyclohexylmethyl-3(3,4-epoxy)cyclohexanecarboxy Sylate [LJnion Carbide Plastics] Plastics) ERL4221 or Ciba Products (Ciba) Araldite manufactured by products cowlpany ) Commercially available under the trade name CY 179], Bis(3,4-■ Hoxy 6- commercially available under the trade name methylcycloherudite CY17B), vinylcyclo l-xane Dioxide (ERL4206 manufactured by Union Carbide Plastics), bis( 2,3-■Poxycyclopentyl) ether resin (Union Carbide Plasti) commercially available under the trade name ERL4205), 2-(3,4-epoxy) Chlohexyl-5,5spi0(3,4-epoxy)cyclohexane-m-dioxy Sun (ERL4234 or Civapu Oda from Union Carbide Plastics Co., Ltd.) Cycloaliphatic epoxy resins such as cycloaliphatic epoxy resins (commercially available under the trade name 7raldite CY175 from Kutsu Co., Ltd.) fat, liquid or solid bisphenol A diglycidyl ether epoxy resin [e.g. From Shell Chemical Company Epon 826, Epon 828, Epon 830, Epon 1001, Epon Commercially available under trade names such as Epon 1002 and Epon 1004], phenol-formaldehyde ・Tonovolak polyglycidyl ether epoxy resin (DE from Dow Chemical Company) (Commercially available under the trade names N431, DEN43B and DEN439), Hoxifresol Lunovolac (for example, ECN1235, ECN1273 from Ciba Products, commercially available under the trade names ECNI 280 and ECN 1299), resorcinol glycycin Zyl ether (e.g. ERE1359 manufactured by Ciba Products), tetraglyside polyphenyl ethane (Shell Chemical Co., Ltd. Epon 1031) Glycidyl ether of phenol 1 poxy resin, diglycidyl phthalate [Cerani E manufactured by Celanese Re5ins Coll1pany D-5661), diglycidyl tetrahydrophthalate (Ciba Products Co., Ltd.) Lardite CY182) and diglycidyl hexahydrophthalate (Cibabroda Araldite CY183 manufactured by Kutsu Co. or ED-5662 manufactured by Celanese Resins) glycidyl ester epoxy resins such as, and halogen-containing bisphenol A Diglycidyl ether epoxy resins (such as Dow Chemical's bromine content) DER542 and DER511) which are 44-48 and 18-20% respectively There are flame-retardant epoxy resins.

Said epoxy resins are well known in the art and are described, for example, in U.S. Pat. No. 4,483, No. 2.444.333, No. 2.494,295 and No. 2.5 No. 11.913. In addition, groups such as Epon 828 Mixture of lysidyl ether epoxy resin and alicyclic epoxy resin such as ERL4221 Using mixtures of these epoxy resins, such as It is often advantageous in terms of adjusting the degree.

The compositions of this invention typically contain about 5 to 90% of the total 1, more preferably about 5 to 50%. Contains epoxy @ fat. Generally, this amount provides the optimum properties of the molding compound. Become.

The metal acetylacetonate of the present invention has the following structural formula (where M is a metal ion). , n is 1 to 4 depending on the valence of the metal ion) These indicate the presence of metal-oxygen bonds. is a feature. Within the scope of the present invention are included one or more hydrogen atoms of a methyl or methylene group. gold substituted with a halogen atom or an alkyl, aryl or alkaryl substituent Includes the genus acetylacetonate. Halogen-substituted metal acetylacetone Examples of salts include metal hexafluoroacetylacetonate or trifluoroacetate. There is tylacetonate. Examples of alkyl-substituted acetylacetonates include each methyl There is dipivaloylethane in which three hydrogen atoms of the ru group are replaced with methyl groups.

The acetylacetonate curing agent of the present invention has similar compositions containing unstable halogen atoms. It should not be confused with things. In the compositions of the invention, if halogen is present, However, it bonds directly to the carbon atom of the methylene or methyl group and is therefore extremely stable. Ru. If there are unstable halogen atoms in the epoxy resin curing agent, it usually forms a halogen acid. The presence of such ionic components in the cured resin results in poor electrical properties and corrosion. Many problems arise, including phagocytosis.

Metal acetylaceto whose metal is aluminum, titanium, zinc or zirconium nates are particularly preferred scales within the scope of the present invention. However, aluminum Barium, beryllium, cadmium, calcium, cerous, nichrome, Cobaltous, cobaltous, cupric, ferric, ferrous, gallium, hafnium , indium, lead, lithium, magnesium, manganese, manganous, mole Liveden, molybdenyl, nickel, palladium, platinum, potassium, rhodium, rubidium, ruthenium, sodium, strontium, thallium, thorium, Titanium, tungsten, uranyl, vanadium, vanadyl, zinc and zirconia Virtually any metal acetylacetonate may be used including metal acetylacetonates. rare earth elements scandium, cerium, yttrium, lanthanum, praseodymium, neo Jim, samarium, europium, gadolinium, terbium, dysprosium , holmium, erbium, thulium, ytterbium and lutetium acetate Ruacetonate is known and useful in the practice of this invention.

The metal acetylacetonate is 0.001-5 based on the weight of the epoxy resin. ．． A small amount of 0% catalyst is used. 0.05-3.0% C optimal The result is obtained. The acetylacetonate of the present invention is a curing catalyst and is Or it may become part of the cured epoxy molecule, such as a curing agent added in approximately stoichiometric amounts. It is important that this is not the case.

The phenolic accelerators effectively used in this invention include bisphenol AC? 2,2-bis(4-hydroxyphenyl)propane], pyrogallol, dihydroxydiphenyl, and other ol-1-1 compounds such as salicylaldehyde. , meta-1 and para-human 1-]xybenzaldehyde, catechol, resorci Knoll These are formaldehyde and resorcinol-formaldehyde condensates. child Examples of other phenolic accelerators suitable for use in this invention include ortho-, meth- -, and halogenated phenols such as para-chlorophenol or bromophenol. and ortho-, meta-, and para-nitrophenol. Phenoh The epoxy resin accelerator has a concentration ranging from 0.025 to 30 percent of the epoxy resin composition. , the optimum curing speed is determined when the phenolic accelerator concentration is 0.5 to 10 percent of the amount of epoxy resin. - cent range.

As with acetylacetonate, phenolic compounds are also added in relatively small amounts. However, this causes a heavy reaction with the epoxy resin, and a large part of the epoxy molecule is This is because it is an accelerator or catalyst rather than a stoichiometric curing agent.

The fillers of this invention are generally chemically inert. These are usually epoxy resin, gold Does not react with any of the genus acetylacetonates or promoters. Instead, they are The ability to stabilize the physical properties of the molding compound, especially during and after resin curing have.

Any conventional filler can be utilized in the compositions of the present invention. Kaori is a typical filler. porcelain, fired clay, novakicolite, crushed sand, amorphous glass. silica, mica, talc, carbon black, alumina and Ru. Alternatively or additionally, filler fillers can be used for IfI construction. These fillers contain products There are fibrous materials such as glass fiber, mineral wool, and others that increase the strength of the material.

The molding compound should contain about 10-95% of the total filler. better Preferably for about 50-95% filler materials, the liquid resin is divided into two parts. is preferable. These parts are aceticated at high temperatures to make them easier to melt separately. Mixed with tylacetonate metal and promoter.

Mix them after cooling. In this two-part method, the filler is You can also add .

In utilizing this composition, conventional techniques may be used.

For example, solid compositions are compressed, I-transfer or injection molded, whereas liquid compositions are are usually injection molded or extruded. The composition is generally heated to about 150-200°C under molding pressure. is heated to.

Under these conditions, curing occurs within a few minutes. virtually any shape or size A molded article is formed.

In a preferred embodiment of the invention, the molding compound contains one or more Includes subsidies. For example, up to about 10% by weight, preferably 1 to 5% by weight of flame retardant. included.

Most combustion agents can be used, including antimony oxide and halogenated hydrocarbons. General A molding agent such as a wax, usually in an amount of 0.2 to 4% by weight, is also highly desirable. this and other ingredients may be mixed with the composition prior to molding to achieve known benefits. .

The following examples are presented for illustrative purposes only and are not intended to limit the scope of the invention. It's not. Many changes are possible without departing from its spirit and scope. especially Unless otherwise stated, all percentages are by weight.

Support - [ For comparison, molding compounds with different filler compositions are prepared and tested. on each side A molding compound is produced as follows. 13 by mechanical stirring Dissolve the accelerator in half the amount of epoxy resin at 0°C. 11 by similar stirring Dissolve the acetylacetonate metal in the remaining half at 0°C. Next, put these two in the room Cool to room temperature and fill as directed in a Ross (R03S) planetary mixer under reduced pressure. Mix with filler.

It is shown in the table below.

Assembling A B C Alicyclic 1 boxy resin 95 95 95 (ERL4221> ) 1-nol resin accelerator 5 5 5 Aluminum acetyl acetyl 1 1 1 Cetonate Silica filler -0-2501500 main ' Gluing time (min, 150 0.55 0.50 at 0.34°C) Goyu I" LL A B C Stiff mill, set at 175℃ 262 165 55) Linear shrinkage (mil/inch > 34 32 18 bending strength 1) six 103) 6 ．． 3 10.2 11.4 Bending modulus (tlsiX O, 250, 690, 86106) Comparative sample Δ is a very poor molding compound. In addition to the differences in properties shown , cracks and hardening due to high curing heat are obvious. Improved properties in other two samples The increase is remarkable and is directly related to the increase in filler composition.

As the gelation time of each sample increases, the reaction rate decreases slightly as the filler density increases. shows an increase in 30 seconds after removing the rigid molded product from the sample, suspend the end. (measured as the bending deflection that occurs when a weight is placed on a flat disc) is due to the difference in the filler. This shows that the resistance to deformation after the molded product is removed is improved.

The difference in yield (measured on the molded part after cooling) is due to the stability of the highly filled molding compound. shows an increase and uniformity of Finally, the bending properties of the molded samples were determined by the filler intensity. It improves as it gets higher.

Husband-"L-Koiichi"ichi Comparative molding compounds are prepared and tested as described in Example 1. So The composition and results are as follows.

2 Comparing Samples I and J without filler and metal acetylacetonate with other samples. The advantages of the present invention can be seen by looking at it. Samples D to H have excellent stability and hardening/forming. Properties after shaping: 95 parts of Epon 828 poxy resin, 5 parts of Epon 871 poxy resin, 2 parts zirconium acetylacetonate catalyst, 0CF4058B1/8 focused glass A molding composition consisting of 25 parts of fibers is prepared by the method of Example 1. Composition compression molded to make excellent parts. Molded parts have a bending strength of 10.6 oopsi , 5 parts of Si Epon 1004 epoxy resin with a bending modulus of 1.2 x 106cl and 7.5 parts of plastic resin at 120°C, 42.5 parts of ERL422 On the other hand, separately, 1 part of aluminum acetylacetonate was dissolved in 42.5 parts of aluminum acetylacetonate. Does not dissolve in ERL4221. After cooling, these resins were mixed in a planetary mixer under reduced pressure for several minutes. 108 grams of crystalline silica, 54 parts of milled glass, and Candelilla mold release agent. Mix with 0.33 parts of powder.

This composition was compression molded at 350°F for 3 minutes into 1/8 x 4" flat discs. This results in an excellent part that easily separates from the mold. Parts have an average heating agent of 96 mils It has its own characteristics.

Large-] L two mackerel-j- 13 Three molding compounds are prepared from solid epoxy resin. For each item, add all ingredients. Grind to a fine powder and dry mix for 5 minutes on a paint shaker. Next, add this to 150~ Melt on a two roll machine at 155°F for 2-3 minutes. The molten sheet is re-pulverized. A 4″ diameter part was formed by transfer molding at 175°C for 3 minutes.

The composition and test results are as follows.

Borac (Dow XD7 L Epon 1004) Catechol 9.0 9.0 9.0 Aluminum acetyl 2.0 2.0 2.0 Silane-covered amorphous silica 300 300 300 power Table ``Circle 1''- Gel time 28 41 31 150℃ (seconds) Heating side 66 (Mill, at 175°C) Linear contraction 6 Molding composition samples with flame retardant added are prepared and tested as in Example 1. composition and conclusion The results are as follows.

(1 part heavy) N O Alicyclic epoxy resin (ERL 95 954221) Phenolic resin accelerator 55 Aluminum azetylacetate 11 Nate Synthetic ester internal lubricant 0.63 0.63 female fuel agent Antimony oxide 5 Decabromodiphenyle \Q +.

-chill 5 filler Surface modification with epoxy silane 100 aluminum trihydrate Crystalline silica filler, 32 85 5 meshes 0CF739BB1/8 molten 50 50 molten glass Heating stiffness 44 35 Linear contraction　10　10 1JL9/l V-OV-1 This data makes it possible to mold the molded product of the present invention without compromising any of its other desirable physical properties. It can be seen that flame retardancy can be imparted to the compound.

The patents and/or publications mentioned above are cited as references. See above Obviously, other modifications and variations of the invention are possible. Therefore the book In embodiments of the above aspects of the invention, the invention as defined in the appended claims It goes without saying that within limits, changes can be made.

Claims (1)

[Claims] 1. Based on the total amount of the composition a) an epoxy resin having more than one 1,2-epoxy group per molecule from about 5 to 90% by weight, b) Metal acetylacetone with only metal-oxygen bonds C) Phenolic accelerator 0.025-30% by weight, and d) about 10-95% filler. A molding compound consisting of a mixture of. 2. The molding compound according to claim 1, wherein the filler comprises a fibrous material. 3. The molding compound according to claim 1, wherein the mixture is in the form of solid particles. 4. The molding compound according to claim 1, wherein the mixture is liquid. 5. The molded compound according to claim 1, wherein the filler is about 50 to 95% of the total amount. Wound. 6. The molded cod according to claim 5, wherein the epoxy resin accounts for about 5 to 50% of the total amount. Unpounded. 7. Claim 6, wherein the metal acetylacetonate' is 0.5 to 3% of the total 1. Molding compound as described in. 8. According to claim 7, the phenolic accelerator is 0.5 to 10% of the total amount. molding compound. 9. The metal of acetylacetonate is aluminum, titanium, zinc and zirconium. Claim 10 selected from the group consisting of Molding compound as described in Section. 11. The molding compound according to claim 1, further comprising a mold release agent.