JPH0514749B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides an abrasive material that can remove resin burrs and the like generated during molding of synthetic resin molded articles over a long period of time without causing damage to the molded articles. Synthetic resin abrasives can remove burrs by spraying them alone or in the form of a water slurry under pressure.
For example, thermosetting resins such as urea resin, melamine resin, unsaturated polyester resin, alkyd resin, epoxy resin, polyamide, polycarbonate,
Thermoplastic resins such as polystyrene have been used, but unsaturated polyester resins are used for deburring epoxy molding materials used in the manufacture of ICs or LSIs due to the hardening of the molding material and the polishing power. It has been. However, as molding materials have become more sophisticated and of higher quality in recent years, it has become difficult to remove burrs, and there is a demand for abrasives with higher abrasive power. Examples of abrasive materials with high abrasive power include inorganic materials such as glass beads and alumina, but when such abrasive materials are used, they damage the surface of the molded product, impairing its aesthetic appearance, and allow moisture to penetrate through the damaged area, causing damage to the semiconductor. There are serious problems that adversely affect device reliability. On the other hand, when a synthetic resin abrasive material is used, damage to the surface of the molded product can be reduced, but the problem arises that the abrasive particles are quickly destroyed and the abrasive force is quickly reduced. As a result of intensive studies to solve the above problems, the present inventor found that when producing a cured unsaturated polyester resin, a polyvalent isocyanate compound is added to and mixed with the unsaturated polyester and styrene, which are the main raw materials, and then cured. The present invention has been completed based on the discovery that the pot life of the synthetic resin abrasive material obtained can be significantly improved by this method. That is, the present invention is a synthetic resin abrasive material comprising a reaction cured product obtained by reacting unsaturated polyester, styrene, and a polyvalent isocyanate compound. Examples of the unsaturated polyester used in the present invention include esterified polycondensates of dibasic acids and glycol components, and examples of these dibasic acid components include maleic anhydride, itaconic acid, citraconic acid, and isaconic acid. , chlorinated maleic acid, and, if necessary, phthalic anhydride, isophthalic acid, terephthalic acid, monochlorophthalic acid, dichlorophthalic acid, trichlorophthalic acid, Hedd's acid, and tetrachlorophthalic anhydride. acids, tetrabromophthalic anhydride, endomethylenetetrahydrophthalic anhydride, adipic acid,
Saturated dibasic acids such as succinic acid, sebacic acid, glutaric acid, pimelic acid, etc. may also be added. On the other hand, the glycol component includes, for example, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, 1,3-butylene glycol,
2,3-butylene glycol, 1,4-butylene glycol, neopentyl glycol, hexylene glycol, octylene glycol, bisphenol A dioxyethyl ether adduct, bisphenol A dioxypropyl ether adduct, hydrogenated bisphenol A or ethylene oxide,
It is selected from alkylene oxides such as propylene oxide and butylene oxide, and polyhydric alcohols such as trimethylolpropane and glycerin can be used in combination as necessary. Examples of the polyvalent isocyanate compound referred to in the present invention include (1) trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 1,2-propylene diisocyanate,
1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, ethylidene diisocyanate, butylidene diisocyanate, bis(2-isocyanate-ethyl) fumarate, 2,6-diisocyanate methyl caproate, 2, 2,4(2,
Aliphatic diisocyanates such as 4,4)-trimethylhexamethylene diisocyanate and dimer acid diisocyanate, (2) 1,3-cyclopentane diisocyanate, 1,4-cyclopentane diisocyanate, 1,3-cyclopentane diisocyanate and methyl cycloaliphatic diisocyanates, such as cyclohexylene diisocyanate,
(3) Aromatic diisocyanates such as m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-methylene diisocyanate, 1,4-naphthalene diisocyanate, (4) 4,4 aliphatic/aromatic diisocyanates such as '-diphenylene-methane diisocyanate, 2,4- or 2,6-tolylene diisocyanate, 4,4'-toluidene diisocyanate, 1,4-xylylene diisocyanate; cydine diisocyanate,
4,4'-diphenyl ether diisocyanate,
Nuclear substituted aromatic compounds such as chlorodiphenylene diisocyanate, (6) triphenylmethane-4,
Tolylene isocyanates such as 4',4''-triisocyanate, 1,3,5-triisocyanatebenzene, 2,4,6-triisocyanatetoluene, (7)4,4'-diphenyldimethylmethane-
(8) Polymeric isocyanates such as tolylene diisocyanate dimers and trimers. Examples of diols or polyols include the following. Diol: Nitylene glycol, propylene glycol,
β, β'-dihydroxy diethyl ether (diethylene glycol), dipropylene glycol, 1,
4-butylene glycol, 1,3-butylene glycol, polyethylene glycol, polypropylene glycol, polypropylene, -polyethylene glycol, polybutylene glycol. Polyol: A compound having two or more types of hydroxyl groups in one molecule, such as glycerin, trimethylolpropane, pentaerythritol, sorbitol, 2-methylglucoside, and 1,2,6-hexanetriol. Polyether polyol: Prepared by adding propylene oxide, ethylene oxide, etc. to a polyhydric alcohol such as glycerin or propylene glycol. It also includes polyether polyols rich in hydroxyl groups, which are obtained by reacting ethylene oxide or propylene oxide with various functional compounds such as ethylenediamine or ethanolamine. Polyester polyol: Synthesized by a condensation reaction between carboxylic acids such as adipic acid, dimer acid, phthalic anhydride, and isophthalic acid, and diols and triols such as ethylene glycol, diethylene glycol, propylene glycol, trimethylolpropane, and glycerin. . Polymer polyol: It can be prepared by copolymerizing a polymerizable monomer having one or more hydroxyl groups in one molecule and another monomer copolymerizable therewith. A polymerizable monomer having one or more hydroxyl groups in one molecule is represented by the following general formula. (In this formula, n=1,2, m=1,2,3 R: Alkylene group having 2 to 12 carbon atoms, which may be substituted with other atoms such as halogen.) For example, acrylic acid-2 -hydroxyethyl,
2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 2-methacrylate
Hydroxyethyl, 2-hydroxypropyl methacrylate, and the like. The mixing ratio of the unsaturated polyester, styrene, and polyvalent isocyanate compound used in the present invention is not particularly limited as it varies greatly depending on the type or desired performance of each, but is usually 40 to 80% by weight of the unsaturated polyester. Department,
Preferably 60 to 70 parts by weight, 10 to 40 parts by weight of styrene, preferably 30 to 40 parts by weight, and 20 parts by weight or less of the polyvalent isocyanate compound, preferably 3 to 10 parts by weight. In the above formulation, if necessary, a suitable amount of a known curing accelerator such as cobalt naphthenate, N,N'-dimethylaniline, cobalt octenoate, etc.
There is no problem in adding preferably 0.1 to 2 parts by weight. Further, if necessary, a suitable amount of a surfactant may be added, preferably in a range of 5 parts by weight or less.
Further, an antistatic agent, a thixotropic agent, etc. may be added, or other components such as glass beads, alumina, melamine resin, polystyrene resin, etc. may be mixed. The resin according to the present invention may be cured by any known method. That is, an appropriate amount of a known catalyst such as methyl ethyl ketone peroxide, dicumyl peroxide, cyclohexanone peroxide, or t-butyl peroxide is preferably added.
What is necessary is to add and mix 0.1 to 4 parts by weight and cure. Furthermore, if necessary, after curing, 1
A ~5 hour after cure can also be performed. The resulting cured product is then pulverized using a crusher, hammer, ball mill, roll mill, impact pulverizer, etc., and if necessary, the particle size is made uniform by classification to obtain the abrasive material according to the present invention. The abrasive material obtained by the above method may be further mixed with other abrasive materials, such as urea resin, melamine resin, alkyd resin, epoxy resin, polyamide resin, polycarbonate resin, polystyrene resin, glass beads, alumina, walnut powder, etc., as necessary. Can be used in combination. According to the method of the present invention, the pot life can be extended without reducing the polishing force, which was not achieved with the prior art. This effect was obtained by adding a polyvalent isocyanate compound to the conventionally used resin consisting of unsaturated polyester and styrene. Furthermore, the present invention has the following effects. In other words, when conventional abrasive materials made of unsaturated polyester resin and styrene are used as an aqueous slurry, low-molecular substances are extracted into the aqueous phase and the slurry becomes acidic. Although it causes problems such as corrosion, this phenomenon can be easily prevented with the abrasive material according to the present invention. Further, since the abrasive material according to the present invention has good sedimentation properties in water, the slurry concentration during use is stabilized, and as a result, the effect of stabilizing the abrasive power is obtained. Next, the present invention will be further explained with reference to Examples and Comparative Examples. In the following, parts mean parts by weight. Comparative Example 1 1.5 mol of isophthalic acid, 3.0 mol of maleic anhydride, and 4.95 mol of propylene glycol were added, and 180
The temperature was maintained at ~210°C and the reaction was allowed to occur until the acid value reached 35.
This is referred to as unsaturated polyester 1. These were mixed at the following blending ratio. Unsaturated polyester 1 70 parts Styrene 30 parts 6% Cobalt naphthenate 0.25 parts Methyl ethyl ketone peroxide 1 part After mixing, the mixture was left at room temperature for 20 hours, and then heated at 80° C. for 3 hours. The obtained cured product was pulverized using a crusher, and then further pulverized using an impact pulverizer. By classification, 60 mesh passes and 80 mesh passes were separated to obtain abrasive material. Example 1 NP-1100 (trade name) manufactured by Mitsui Toatsu Chemical Co., Ltd., which is a hexamethylene diisocyanate water adduct, was used as a polyvalent isocyanate compound and mixed in the following formulation. An abrasive was obtained in the same manner as in Comparative Example 1. Unsaturated polyester 1 70 parts Styrene 30 parts NP-1100 5 parts 6% Cobalt naphthenate 0.25 parts Methyl ethyl ketone peroxide 1 part Example 2 An abrasive material was obtained in the same manner as in Example 1 except that NP-1100 was 10 parts. Example 3 An abrasive was obtained in the same manner as in Example 1 except that 20 parts of NP-1100 was used. Example 4 An abrasive was obtained in the same manner as in Example 1 except that 30 parts of NP-1100 was used. Example 5 In Example 1, instead of NP-1100, 4,
4′-diphenylmethane diisocyanate (hereinafter
An abrasive material was obtained in the same manner using 5 parts of MDI (abbreviated as MDI). Example 6 An abrasive was obtained in the same manner as in Example 5 except that MDI was changed to 10 parts. Example 7 An abrasive was obtained in the same manner as in Example 5 except that MDI was changed to 20 parts. Example 8 An abrasive material was obtained in the same manner as in Example 5 except that MDI was changed to 30 parts. Evaluation of Abrasive Material The characteristics of the obtained abrasive material were evaluated by the following method. Surface hardness: The surface hardness of the molded plate before pulverization was measured using a Barcol hardness meter 934-1. PH: Measured using a PH meter 24 hours after preparing the 10% water slurry. Hydrophilicity: A 20% slurry was prepared, and the sedimentation rate and sedimentation volume of the abrasive were measured. Pot life: A 40% water slurry was prepared and projected onto a tin plate at a projection pressure of 4 kg/cm ² and a projection distance of 5 cm. The ABS plate was polished for 30 seconds under the same conditions every hour, and the weight loss was measured. The pot life was defined as the time until the weight decreased to 1/2 of the initial weight loss. The results are shown in Table-1.

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Claims (1)

[Claims] 1. A synthetic resin abrasive material comprising a reaction cured product obtained by reacting unsaturated polyester, styrene, and a polyvalent isocyanate compound.