JPS59189158A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. which has excellent mold release characteristics and imprintablility and scarcely stains molds, composed of a mixture obtd. by melt-mixing a phenolic novolak, an epoxy resin and a silicone compd. by heating. CONSTITUTION:A phenolic novolak having an MW of 500 or below, an epoxy resin (e.g. bisphenol type epoxy resin) in an equivalent ratio of the phenolic hydroxyl group to the epoxy group of 2 or above, and a silicone compd. (e.g. organosiloxane) in a molar ratio of Si of the silicone compd. to the OH group of the phenolic novolak of 1/10-10/10 and in a quantity of 0.5-5wt% based on the combined quantity of the three ingredients, are melt-mixed together in the presence of at least one compd. selected from among a tert. amine or its derivative (e.g. triethylamine), an organophosphine (e.g. octylphosphine), an org. Al compd. (e.g. aluminum isopropoxide), a Ti compd.(e.g. titanium white) and an acid (e.g. p-toluene-sulfonic acid) by heating.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a mold releasable resin composition that has excellent mold releasability and imprinting properties and is free from mold stains. It is fixed by reacting with the resin component.

Recently, the field of electrical and electronic equipment has made remarkable progress, and the use of plastic parts has become commonplace. In the case of molded products, these plastic parts are obtained by compression molding, transfer molding, or injection molding of phenolic resins, epoxy resins, etc., and then curing them in a metal pot (thermosetting) or cooling them (thermoplastics). ing. What is required in this molding process, particularly in the process of molding thermosetting resins, is good mold release properties and no staining of the mold. Generally, mold release is for molded products)
By forming a release agent film between the molded product and the mold, the adhesive force between the mold and the molded product is eliminated and the two can be easily separated. Therefore, the amount of mold release agent that migrates and orients to the mold increases in proportion to the number of molding shots, and when this is subjected to thermal history, it is baked into the mold, causing mold fogging and mold staining. A good mold and less mold staining are contradictory to each other. Also, IC
For parts, etc., molded products are marked (stamped) to distinguish between good and bad products. At this time, if the release agent forms a film on the surface of the molded product, problems such as poor ink adhesion and easy peeling of the mark may occur. For this reason, molding and assembling manufacturers are dealing with this by incorporating a degreasing process using a solvent or the like into the post-molding process.

However, if the mold release agent deteriorates due to oxidation or the like, degreasing will be incomplete, so a molding material with good marking properties is desired, and this marking property is also a property that contradicts the mold release property. Therefore, a molding material with good mold releasability and imprintability and with little mold staining has not become a reality.

The present invention provides a resin composition that has good mold releasability and imprinting properties and has little mold staining.

The gist of the present invention is (1) a releasable resin composition comprising a heat-melted mixture of phenol novolacs, epoxy resins, and silicone compounds (however, the vortex ratio of phenolic hydroxyl groups/epoxy groups is 2 or more); .

(2) Phenol novolaks, epoxy resins, and silicone compounds (however, the equivalent ratio of phenolic hydroxyl groups/epoxy groups is 2 or more) are combined with tertiary amines or derivatives thereof, organic phosphine compounds, organic aluminum compounds,
A releasable resin composition comprising a mixture heated and melted in the presence of one or more selected from titanium compounds or acids, the releasable resin composition can be used alone, or Furthermore, it can be blended with other phenolic resins or epoxy resins and used as part or all of a curing agent or mold release agent. Furthermore, fillers, curing agents, mold release agents, etc. can be added. The term phenol novolacs as used herein refers to all compounds containing a phenolic hydroxyl group or a derivative thereof in the novolak skeleton.

It includes not only single-component novolaks such as phenol (phenol ψ alkylphenol resorcinol, etc.) but also co-condensed novolacs with any combination of phenols and co-condensed novolacs with phenols and other resins. Epoxy resins also include: Refers to all substances having an epoxy group. For example, it refers to bisphenol type epoxy resin, novolac type epoxy resin, triazine nucleus-containing epoxy resin, etc. In addition, the silicone compound refers to organosilanes and organopolysiloxanes in general, such as (1) general formula (R1) mSt (OR2) HRl: alkyl group, vinylated alkyl group, or epoxidized alkyl group (for example, m+n= Organosilane (11) represented by 4 (Is n≧1) - refers to organopolysiloxane compounds having at least one OR2 group or epoxy group in the molecule.

Furthermore, as examples of reaction catalysts, ■ tertiary amine or its derivatives trimethylamine, triethylamine, 2.3.4.6
．． 7.8.9.10-octahydro-viramide (1,
2-a) Azepine, etc. or quaternary ammonium salts thereof ■Organophosphine compounds (a) First and second tertiary phosphine: octylphosphine, diphenylphosphine, butylphenylphosphine, tricyclohexylphosphine, triphenylphosphine, etc. b) Bemain-type adducts of organic tertiary phosphine and compounds having a π bond: maleic anhydride-triphenylphosphine adduct, thioisocyanate-triphenylphosphine adduct, diazodiphenylmethane-triphenylphosphine adduct, etc. (c) Organic Phosphonium salt (53PCH2s Pcte, (g3pEt)e
Iθ, Ca3PEt 'PBrel etc■ Organoaluminum compound (a) AI! , (OR)3. RjH, alkyl group,
Aryl group, aryl group-containing hydrocarbon group, aluminum isopropoxide, aluminum n-butoxide, aluminum tert-butoxide, aluminum 5ee-
Butyrate, allumilam benzoate, etc. (b) 7
v Miniram β-diketone complex (aluminum chelate) Aluminum acetylacetonate, aluminum driblioroacetylacetonato, aluminum pentafluoroacetylacetonate, etc.■Titanium compounds phytyl titanate, titanium white, etc.■Acids such as paratoluenesulfonic acid, etc. .

The present invention involves uniformly dispersing a material obtained by heating and melting mixing a phenol novolac, an epoxy resin, and a silicone compound in the absence or presence of a catalyst, that is, a silicone compound with excellent mold release properties, into a resin component or in combination with a resin component. It has been discovered that a resin composition using the reacted substance has outstanding properties in terms of mold releasability, imprintability, and mold stain resistance. By uniformly dispersing or fixing silicone compounds, which are P-type compounds, such as phenol novolaks and epoxy resins that can react with various substances, they are effective in release and do not easily elute to the outside of the resin. A releasable resin was obtained, and by using this resin, a resin composition with excellent mold releasability, imprintability, and mold stain resistance was made possible.

Epoxy resins are used to reduce the elution of silicone compounds to the outside. That is, it is used because it has the effect of increasing the viscosity of the mold release resin and the effect of improving compatibility. Further, the ratio used must be an equivalent ratio of phenolic hydroxyl group/epoxy group of 2 or more. If it is less than 2, the releasing resin may gel.

Incidentally, as the ratio of silicone compound/phenol novolak increases, the mold release effect increases, but the reactivity of the phenol novolak decreases. The higher the ratio of the releasable resin used, the better the releasability of the releasable resin composition. Furthermore, it is preferable that the molecular weight of the releasable resin decreases as the process progresses from compression molding to transfer molding to injection molding, and as the process progresses from high pressure molding to low pressure molding. The characteristics can be maximized by selecting the mixing ratio of silicone compound/phenol novolak, molecular weight, usage ratio in the composition, etc. depending on the purpose. Especially for epoxy resin low-pressure encapsulation molding materials, the silicone compound/phenol novolacs molar ratio is 5t10H group molar ratio. ~1 岑. , the usage ratio in the molding material is 0.5~
It is desirable that the molecular weight of the phenol novolak is 500 or less. In a range other than the above, disadvantages such as poor moldability may occur. Further, by using the resin composition according to the present invention, features such as a reduction in the internal stress of a molded article and an improvement in moisture resistance can be obtained. Furthermore, it has become possible to obtain a phenolic resin low-pressure encapsulation molding material with good moisture resistance.

Examples will be explained below. In addition, the raw materials for the mold release resin used in the examples are as follows.

Phenol novolac A: Number average molecular weight 400B:
200 C: '700 Epoxy resin ■: Bisphenol type epoxy (Shell 828) ■: Cresol Novosic type epoxy (Inu Nippon Ink N-660) Epoxy resin ■: Triglycidyl isocyanurate (TGIC) Silicone X: Methyltriethoxine-poor Y: silicone face intermediate (OCH3 type) Z, silicone resin (OH type) Catalyst α nitriphenylphosphine I β Nialuminum acetylacetonato γ: 2.
3.4.6.7.8.9.10-octahydropyramide (1,2-a) azepine Basic production method I 2228 parts by weight of phenol novo, 18 parts by weight of hexamethylenetetramine based on part by weight of mold release resin, 65 parts by weight of wood flour, 25 parts by weight of calcium carbonate, and parts by weight of stearic acid C are added and kneaded for 5 minutes using heated rolls at 80°C.

Basic production rate ■ 20 parts by weight of ortho-cresol novolac type epoxy resin, 2228 parts by weight of phenol novo, 1 part by weight of mold release resin, 70 parts by weight of crystalline silica, 0.2 parts by weight of silica modifier,
0.2 parts by weight of a hardening accelerator and 6 parts by weight of carnauba wax are added and kneaded for 5 minutes using heated rolls at 90°C.

(Note) The number average molecular weight of the phenol novolak used in the basic manufacturing method is 550°.Application example: Phenol novolak A/B@C and epoxy resin
Several mold releasable resins were experimentally produced by heating, melting, and mixing ① and ②, silicone xyz, and catalysts α, β, and γ. This resin was processed into materials using Basic Production Methods I and (2) to obtain various phenol resin molding materials and epoxy resin molding materials. These materials were molded using a small molding machine or a transfer molding machine, and their mold releasability and mold staining property were evaluated. In addition, the stampability was evaluated using molded products. The results shown in Tables 1 and 2 show that the products using the phenol novolacs/epoxy resins/silicone compound heat-melted mixture according to the present invention had good mold releasability. It not only has excellent resistance to stains and mold stains, but also has excellent imprintability.

The numerical value is a relative value when the comparative example is taken as 100. The higher the numerical value, the better: Mold stain, crack resistance, moisture resistance. The smaller: Mold releasability, stamping property. The symbol indicates the tendency of the characteristics.

Good←◎・○・△・×→Bad・Mold releasability: Molded with a releasability evaluation mold (mold without knock bottle) and judged by the number of molds removed.

・Mold contamination: Determined by the number of molding shots until W clouding or mold release failure occurs.

- Stampability: After stamping, sellotape is applied to the molded product. Judgment is made by the number of molded products that have the stamp removed when the sellotape is removed.

・Crack resistance: A molded product with a large insert is subjected to a temperature cycle test (high and low temperatures), and the molded product is judged by the number of grooves in which cracks occur.

・Moisture resistance: Determined by the time it takes for a molded product with a humidity sensing element inserted into a pressurized humidifier to sense humidity.

Claims (2)

[Claims] (1) A thermosetting resin composition comprising a heat-melted mixture of phenol novolaks, epoxy resins, and silicone compounds (provided that the equivalent ratio of phenolic hydroxyl groups to epoxy groups is 2 or more) as the main resin. (2) Phenol novolacs, epoxy resins, and silicone compounds (however, the equivalent ratio of phenolic hydroxyl groups/epoxy groups is 2 or more), tertiary amines or derivatives thereof, organic phosphine compounds, organic aluminum compounds,
A thermosetting resin composition whose main resin is a mixture heated and melted in the presence of one or more selected from titanium compounds or acids.