JPS59172541A - Mold-releasable resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. which has excellent mold release characteristics and imprintability and does not stain molds, by using a heated molten mixture of a phenolic novolak and a silicone compd. CONSTITUTION:The titled resin compsn. contains, as part or the whole of a principal resin, a hardener or a parting agent, a mixture obtd. by melting a phenolic novolack and a silicone compd. (e.g., a hydroxyl or epoxy group-contg. organopolysiloxane compd.) in the presence of, if necessary, at least one member selected from among a tert. amine (derivative) (e.g. trimethylamine), an organophosphine compd. (e.g. octylphosphine), an organoaluminum compd. (e.g. aluminum isopropoxide), a titanium compd. (e.g. butyl titanate) and an acid (e.g. p-toluenesulfonic acid) by heating. The compsn. is characterized in that it has excellent mold release characteristics and imprintability and does not stain molds.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is made of aluminum that has excellent mold releasability and imprinting properties and is free from mold stains.
This relates to a moldable resin composition, and its feature is that the silicone compound is uniformly dispersed in the resin component or 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. When these plastic parts are molded products, phenolic resin, epoxy resin, etc. are cured in a mold by compression molding, transfer molding, or injection molding.

Molded products are obtained by thermosetting (4) or cooling (thermoplastic). What is required in this molding process, particularly in the process of molding thermosetting resins, is good mold releasability and no staining of the mold. Generally speaking, mold release is done by oozing out the release agent from the molded product and forming a film of release agent between the molded product and the mold, thereby reducing the adhesion between the mold and the molded product (and making it easy for both to be released). Therefore, the mold release agent that migrates and orients to the mold increases in proportion to the number of molding shots, and this absorbs thermal history and is baked into the mold (by ℃ mold rest and mold In other words, good mold release and less mold contamination are contradictory to each other.In addition, for IC parts, etc., molded products are marked to distinguish between good and bad products. At this time, if the mold release agent forms a film on the surface of the molded product, problems such as poor ink adhesion or easy peeling of the mark may occur.For this reason, mold assembly manufacturers do not perform a degreasing process using a solvent, etc. This is being addressed by incorporating it into the post-molding process.

However, if the mold release agent deteriorates due to oxidation or the like, degreasing will not be complete, so a molding material with good marking properties is desired.

This imprinting property is also a property that is separate from mold releasability. Therefore,
A molding material with good mold releasability and imprintability (and less mold staining) has not yet 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 resin composition comprising a heated and melted mixture of a phenol novolac and a silicone compound as the main resin, curing agent, or mold release agent in whole or in part.

(2) A mixture obtained by heating and melting a phenol novolac and a silicone compound in the presence of one or more selected from tertiary amines and their derivatives, organic hofufine compounds, organic aluminum compounds, titanium compounds, or acids. This is a resin composition using as all or a part of the main resin, curing agent, or mold release agent.

Phenol novolacs here refer to all those containing a phenolic hydroxyl group or its derivatives in the novolak skeleton, and are not limited to single-component novolacs of phenols (phenol, alkylphenol, resorcinol, etc.), but also any combination of phenols. It also includes co-condensed (multi-component) novolaks and co-condensed novolaks of phenols and other resins. In addition, the silicone compound refers to all organosilanes and organopolysiloxanes, such as (+) general formula (R') mS i (0R2) nR1:
Alkyl group or vinylated alkyl group or epoxidized alkyl group R2H, alkyl group (-CH,, -C,H,, etc.)
However, it refers to organopolysiloxane compounds having at least one OR2 group or epoxy group in the organosilane (11) molecule represented by m+n=4 (m% n≧1).

Furthermore, as examples of reaction catalysts, ■ tertiary amine and its derivatives trimethylamine, triethylamine, 2, 3.4.6
．． 7.8.9.10. -octahydro-viramide (1
, 2-a) Azepine, etc. and their quaternary ammonium salts (a) ml, secondary and tertiary phosphine: octylphosphine, methylphenylphosphine/tricyclohexylphosphine, triphenylphosphine, etc. (b) ) Available
fl Betaine-type adducts of compounds having a tertiary phosphine and a π bond: maleic anhydride-triphenylphosphine adduct, thioisocyanate-triphenylphosphine adduct, diazodiphenylmethane-triphenylphosphine adduct, etc. (C) Organic phosphonium salt ■ 0 Cfs PCH2Cl, [/sl'Etl) (i) I
"[/, PEt)OBretc ■ Organoaluminium compound (a) Al(OR)3R: H, alkyl group, aryl group, aryl group-containing hydrocarbon group, aluminum isopropoxide, aluminum n-butoxide, aluminum tert-butoxide, Aluminum pec-butyrate, aluminum benzoate, etc. (b) Aluminum β-diketone complex (aluminum chelate) Aluminum acetylacetonate, aluminum trifluoroacetylacetonato, aluminum pentafluoroacetylacetonate, etc. ■Titanium compounds butyl titanate, titanium white, etc. ■Acids Examples include para-toluenesulfonic acid.

The present invention involves heating and melting mixing phenol novolaks and silicone compounds in the presence or absence of a catalyst, thereby uniformly dispersing a silicone compound with excellent mold release properties into a resin component (phenol novolacs). It has been discovered that mold releasable resins can be obtained by reacting with resin components, and that resin compositions using these resins have excellent mold releasability, imprintability, and mold stain resistance properties.

By uniformly dispersing or fixing a silicone compound, which is a mold release compound, in phenol novolacs that can react with various substances, a mold release resin that is effective in mold release and does not easily dissolve out of the resin can be obtained. By using this, it has become possible to create a resin composition that has excellent mold releasability, imprinting properties, and mold stain resistance.

The present invention uses phenol novolaks, which are the main raw materials for thermosetting molding materials (main resins for phenolic resin molding materials, curing agents for epoxy resin molding materials, etc.) and general-purpose silicone compounds, and is completely new, versatile and industrial. The present invention provides a mold-releasing resin composition with high properties.

Incidentally, as the ratio of silicone compound/phenol novolak increases, the mold release effect increases, but the reactivity of the phenol novolak decreases. Moreover, the higher the ratio of the silicone compound-phenol novolak heat-melted mixture (hereinafter referred to as a release material), the better the release properties of the release resin composition. Further, it is preferable that the molecular weight of the releasable substance 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 C% length 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 novolak ratio is 5i10.
It is desirable that the H group molar ratio is 1/10 to 10/10, the usage ratio in the molding material is 0.5 to 5 NftK%, and the molecular weight of the phenol novolak is 250 to 600.

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. This is due to the 4i1 structure and water repellency of silicone.

Examples will be explained below.

Moreover, the raw materials of the mold release resin used in the examples are as follows.

Phenol novolac 2: Number average molecular weight 450 Phenol novolac B: 200 Phenol novolac C: 700 Silicone ■:
Methyltriethoxysilane Silicone ■: 1aJ (4(0(-Hsfil)) silicone among silicone compounds ■: Silicone resin (OHz) catalyst α nitriphenylphosphine catalyst β Nialuminum acetylacetonato catalyst γ: 2
．． 3.4.6.7.8.9.10. -Octano-1-hydropyramide (1,2-a) acepine basic manufacturing method I 28 parts of phenol noboraf, 18 parts of hexypmethylenetetramine per part of mold release resin, 65 parts of wood flour, 25 parts of calcium carbonate, star') ZeC of the mixture and stirred for 5 minutes with a heated roll at 80°C.

Basic manufacturing method■ Add 20 parts of ortho-cresol novolac type epoxy resin, 28 parts of phenol novolaf, part of mold release resin, 70 parts of crystalline silica, 0.2 parts of silica modifier, and 6 parts of carnauba socks and heat at 90°C. Knead on a roll for 5 minutes.

(Note) The number average molecular weight of the phenol novolac used in the basic manufacturing method is 600. Application examples Phenol novolac A-B-C and silicone Φ■・■
Several releasable resins were prototyped by combining and heating and melting and mixing catalysts α, β, and γ. This resin was made into materials using basic production methods (1) and (K) to obtain various phenolic 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 release properties and mold staining properties were evaluated. In addition, the stampability was evaluated using the molded product. The results are shown in the attached table, and the product using the phenol novolac/silicone heat-melted mixture according to the present invention not only has excellent mold releasability and mold staining, but also has excellent stamping performance.

・Mold releasability: The molded product is molded using a releasability evaluation mold (a mold without dowel pins) and determined by the number of molds removed.

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

- Stampability: After stamping the molded product, apply cellophane tape. Judgment is based on the number of molded products whose stamps are removed when the cellophane tape is removed.

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

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

Claims (2)

[Claims] (1) A resin composition comprising a heat-melted mixture of phenol novolacs and siliconized 121 as the main resin, curing agent, or mold release agent in whole or in part. (2) A mixture obtained by heating and melting a phenol novolac and a silicone compound in the presence of one or more selected from tertiary amines or derivatives thereof, organic phosphine compounds, organic aluminum compounds, titanium compounds, or acids. A resin composition using as all or a part of the main resin, curing agent, or mold release agent.