WO2002090077A1

WO2002090077A1 - Resin composition for cleaning mold

Info

Publication number: WO2002090077A1
Application number: PCT/JP2002/002600
Authority: WO
Inventors: Kiyohito Hiromitsu; Mitsuyoshi Sasayama; Hiroaki Nomura
Original assignee: Nippon Carbide Kogyo Kabushiki Kaisha
Priority date: 2001-04-25
Filing date: 2002-03-19
Publication date: 2002-11-14
Also published as: CN1462230A; JPWO2002090077A1; TWI271295B; CN100366411C; KR20030022129A; MY134844A; HK1058649A1; KR100818454B1; JP3847259B2

Abstract

A resin composition for cleaning a mold which removes stains adhered on the surface of a mold during the molding of a curable resin material, characterized in that it comprises a melamine resin as a mold cleaning resin, at least one guanamine and/or at least one guanamine resin, and a fibrous inorganic compound having an average fiber length of 5 to 30 νm, an average fiber diameter of 0.1 to 1.0 νm and an aspect ratio of 10 to 60.

Description

Description Resin composition for mold cleaning Technical field

TECHNICAL FIELD The present invention relates to a resin composition for cleaning a mold for cleaning an injection mold for electronic parts and a mold for transfer molding. The resin composition for mold cleaning of the present invention exhibits good fluidity and cleanability for ultra-thin and matrix-type mold contamination, and also shows good cleanability for various contaminants. Background art

Conventionally, if the molding of an integrated circuit such as an integrated circuit (hereinafter abbreviated as IC / LSI) using a thermosetting resin such as an epoxy resin is continued for a long time, the inner surface of the mold becomes dirty, and the molding is continued as it is. In many cases, the surface of the molded product was soiled, or the molded product adhered to the mold, making it impossible to continue the molding operation. Therefore, it is necessary to periodically clean the mold, and a method has been proposed in which the mold cleaning resin is molded at a rate of several shots every several hundred shots of molding material to mold. .

For example, Japanese Patent Publication No. 52-788 discloses that “a curable resin molding material (excluding an amino-based resin molding material) is made of a material mainly composed of an amino-based resin. A method of cleaning by molding ”has been proposed, and a resin composition for mold cleaning comprising an amino resin, an organic base material and / or an inorganic base material, and a release agent has been disclosed. Japanese Patent Publication No. Sho 64-10162 discloses a mold containing a co-condensation resin of an amino resin and a phenol resin and a mineral powder having a new Mohs hardness of 6 to 15. A cleaning resin composition is disclosed.

Further, Japanese Patent Application Laid-Open No. H08-578866 discloses that an amino resin composition for cleaning a mold contains a lubricant having an HLB value of 1.5 to 8 so that a complicated mold and A mold cleaning resin composition capable of filling and cleaning every corner of a large mold is disclosed.

In recent years, with the increasing integration, thinning, and surface mounting of ICs and LSIs, The shape and structure have been diversified, and the gate dimensions are extremely small, about 0.4 x 0.4 mm, and the gate dimensions are 1.2-1.5 mm, but the thickness is 0.03- Most of them are extremely thin, about 0.4 mm, and the above-mentioned resin composition for mold cleaning provided conventionally does not necessarily clean when used in ultra-thin or matrix molds. Sex was not enough.

On the other hand, various types of thermosetting resin molding materials for sealing IC, LSI, etc. are used because their compositions need to be changed according to their required characteristics. Accordingly, there is a wide variety of mold contamination states and contaminant components that occur due to repeated molding of sealed molded articles. Among these, molding materials that use biphenyl-based epoxy resins, polyfunctional epoxy resins, and di-opened pentadiene-based epoxy resins as main components in place of the novolak-based epoxy resins that have been used in the past. The contaminants of the mold when the molding is repeated using the mold are severely baked on the mold surface, and particularly the dirt of the biphenyl-based epoxy resin is severe. However, the number of moldings required to completely remove the dirt from the mold has been significantly increased, causing a problem that productivity of ICs and LSIs is greatly reduced.

In order to spread the resin composition for mold cleaning to every corner of ultra-thin and matrix molds, it is necessary to improve the fluidity, but the performance of the cleaning and mold release properties must be reduced. It is important that there is no

On the other hand, from the viewpoint of the cleaning mechanism, the phenomenon that the dirt on the mold is difficult to remove is considered to be stronger when the dirt and the mold are combined than when the mold cleaning resin composition and the dirt are combined. It means that. That is, the cleaning performance deteriorates due to either the bonding force at the interface between the mold and the dirt being increased or the bonding force at the interface between the die-forming resin molding and the dirt being weakened. I have. By improving at least one of these factors, and preferably both, it is possible to improve the cleaning performance.

Methods for improving the above factors that lower the cleaning performance include improving the strength of the mold cleaning resin molded article, improving the modulus of the mold cleaning resin molded article, and mold cleaning resin. Consider methods such as improving the adhesion between the molded product and the stain. available. Disclosure of the invention

The present invention has been made in view of the above points, and a resin composition for mold cleaning capable of improving workability of mold cleaning even in an extremely small and extremely thin shape, and also capable of cleaning a variety of contaminant components. The purpose is to provide.

The inventors of the present invention have formed by repeating molding using a molding material mainly containing a biphenyl-based epoxy resin, a polyfunctional epoxy resin, and a dicyclopentadiene-based epoxy resin, which are frequently used as epoxy resins. As a mold cleaning resin composition that can effectively remove contaminants on the mold surface, the average fiber length is 5 to 30 m, the average fiber diameter is 0.1 to 0, and the aspect ratio is 10 to 60. It can be seen that the resin composition containing the fibrous inorganic compound has a high adhesive force to contaminants, and can remove contaminants without increasing the number of required moldings compared to the conventional resin composition for mold cleaning. It has already been proposed in PCT / JP01 / 08678. Furthermore, as a result of intensive studies, the present inventors have found that by blending a guanamine and / or a guanamine-based resin with a resin composition containing the above-mentioned fibrous inorganic compound, the fluidity is improved, The present inventors have found that the resin composition for mold cleaning can be spread to all corners of the mold of the matrix-matrix mold, and have reached the present invention.

That is, the present invention provides a mold cleaning resin composition for removing dirt on a mold surface during molding of a curable resin molding material, comprising a melamine resin as a mold cleaning resin, and at least one kind of Guanamines and / or at least one kind of guanamine-based resin, and fibers having an average fiber length of 5 to 30 m and an average fiber diameter of 0.1 to 1.0; um and an aspect ratio of 10 to 60 The object has been attained by providing a resin composition for cleaning a mold, characterized by containing a particulate inorganic compound. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, embodiments of the present invention will be described in detail.

As the melamine resin in the present invention, one or more selected from melamine resin, melamine-phenol co-condensate, melamine-urea co-condensate and the like are used. be able to. The melamine-phenol cocondensate is formed by co-condensation of melamine, phenols and aldehydes such as formaldehyde, and the melamine-urea cocondensate is formed of melamine, urea and aldehydes. It is obtained by condensation.

The melamine resin in the present invention can be produced by a known method.

For example, formaldehyde and melamine crystal are reacted in an aqueous solution at a molar ratio of 1: 1-4: 1, advantageously 1.5: 1 to 3: 1 to produce an aqueous precondensate solution. The reaction can be carried out with a melamine crystal concentration of 2 ° to 60%, a reaction temperature of 70 to 100 ° C, and a weak alkaline property, and the reaction is completed in 10 to 100 minutes.

Part of the formaldehyde is an aldehyde component other than paraformaldehyde and formaldehyde, for example, aliphatic aldehydes such as acetoaldehyde; aromatic aldehydes such as benzaldehyde; furfural; and other melamine and formaldehyde Aldehyde compounds capable of reacting with ". The use amount of such a compound is preferably 10 parts by weight or less based on 100 parts by weight of formaldehyde.

In the resin composition for cleaning a mold of the present invention, in addition to the melamine-based resin, the melamine-based resin and a secondary amount of other resins that can be blended with the melamine-based resin may be used in an amount that does not adversely affect the effects of the present invention. Can be blended. Examples of such resins include an alkyd resin, a polyester resin, an acrylic resin, an epoxy resin, and rubbers. The mold cleaning resin composition of the present invention may further comprise at least one kind of guanamines and / or at least one kind of guanamine-based resin (hereinafter, may be abbreviated as G component) in addition to the melamine-based resin. It contains. By containing the G component, fluidity is improved, and it is possible to fill and clean every corner of the ultra-thin mold.

The guanamines (hereinafter sometimes abbreviated as Gs) include benzoguanamine (hereinafter sometimes abbreviated as BG), acetoguanamine (hereinafter sometimes abbreviated as AG), and CTU-guanamine (hereinafter sometimes abbreviated as AG). It may be abbreviated as CTU-G.)

Examples of the guanamine-based resin include a methylolated benzoguanamine resin (hereinafter may be abbreviated as F—BG), a methylolated acetoguanamine resin (hereinafter referred to as F-BG). Sometimes abbreviated as one AG. ), Methylolated CTU-guanamine resin (hereinafter may be abbreviated as F-CTU-G), methamine mono-guanamine resin (hereinafter sometimes abbreviated as F-G), and melamine-benzoguanamine Condensation resin (hereinafter sometimes abbreviated as M / BG-F), melamine-acetoguanamine co-condensation resin (hereinafter sometimes abbreviated as M / AG-F), and melamine-CTU-guanamine co-condensation resin (Hereinafter sometimes abbreviated as M / CTU-GF). And melamine-guanamine co-condensation resin (hereinafter sometimes abbreviated as M / G-F).

As the FG, for example, about 1 to 12 moles of formaldehyde are reacted with 1 mole of guanamines by a known method to obtain a monomethyl guanamine resin, a dimethyl guanamine resin, Methylolated guanamine resin and tetramethyl monoguanamine resin can be obtained. These FG may be a mixture of FG such as mono, di, tri and tetra. In addition, these FGs do not necessarily need to be mononuclear, for example, dinuclear, trinuclear, or tetranuclear formed by condensing a part of a methylol group with a methylene group. May be mixed.

Further, the ratio of melamine to guanamine is not particularly limited in the M / GF, but guanamine is preferably used in an amount of 10 to 200 parts by weight with respect to 100 parts by weight of melamine. More preferably, it is used in an amount of 30 to 100 parts by weight, and is obtained by methylolation with an aldehyde such as formaldehyde. The amount of formaldehyde used for methylolation is preferably about 1 to 10 mol, more preferably 1.5 to 4 mol, per 1 mol of the total of melamine and guanamines.

These G components are blended with 100 parts by weight of the melamine resin and 3 to 65 parts by weight of at least one guanamine and / or 5 to 200 parts by weight of at least one guanamine resin. Is preferred. If the content of the G component is less than the lower limit, the effect of improving the fluidity is small, and if it is more than the upper limit, it adheres to the inside of the mold, making it difficult to remove the cured product.

Here, 100 parts by weight of the melamine-based resin means the total amount of the melamine-based resin and the melamine-based resin in the melamine-based resin-impregnated pulp described later.

The resin composition for mold cleaning of the present invention, in addition to the melamine resin and the G component described above, It contains a fibrous inorganic compound having an average fiber length of 5 to 30 m, an average fiber diameter of 0.1 to 1.0 m, and an aspect ratio of 10 to 60 (hereinafter sometimes abbreviated as W component). By containing the W component, the adhesive strength to a dirt component and the like is improved, and an excellent cleaning effect is exhibited.

Examples of the fibrous inorganic compound include Albolex Y, Albolex Μ20 (all, manufactured by Shikoku Chemicals), Tismo-D, Tastemoshi (all, manufactured by Otsuka Chemical Co., Ltd.), USB-S N_WA, Moss Heidi (above, manufactured by Ube Industries, Ltd.) and the like. Among these, Albolex Y is preferably used, but the average fiber length is 5 to 30 / im and the average fiber diameter is 0.1 to 1. Any fibrous inorganic compound having an aspect ratio of 0 and an aspect ratio of 10 to 60 can be used.

In addition, these effects can be further enhanced by subjecting the fibrous inorganic compound to a surface treatment with an epoxysilane-based, aminosilane-based, methacryloxysilane-based, or other resin. Examples of the fibrous inorganic compound subjected to the surface treatment include Arbolex YS3A, Alporex YS2B, Arbolex YS4 (all manufactured by Shikoku Chemicals Co., Ltd.), Teismo D101, and Tismo_D1. 0 2 (all, manufactured by Otsuka Chemical Co., Ltd.).

The content of the W component is preferably 1 to 30 parts by weight, more preferably 5 to 20 parts by weight, and particularly preferably 5 to 10 parts by weight, based on 100 parts by weight of the melamine resin. . When the content of the W component is less than 1 part by weight, the cleaning effect is poor. When the content is more than 30 parts by weight, the fluidity of the resin composition for mold cleaning deteriorates, and the W component is expensive, so that it is economical. Is not a good idea either.

The resin composition for cleaning a mold of the present invention may contain pulp.

As the pulp, straw pulp, bamboo pulp, wood pulp (conifer pulp, hardwood pulp) and the like may be used, and any of chemical pulp and mechanical pulp may be used.

Further, pulp impregnated with a melamine resin and / or a guanamine resin (resin impregnated pulp) may be used as the pulp. The resin-impregnated pulp is prepared by impregnating and drying a melamine-based resin aqueous solution such as a melamine-formaldehyde resin aqueous solution or a melamine-phenol-formaldehyde resin aqueous solution. Further, a part or all of the pulp may be replaced with powder pulp, whereby the fluidity can be further improved.

Although the size of the pulp is not particularly limited, it is generally 5 to 1000 μm, preferably about 10 to 200 μm.

The pulp content is generally 5 to 70 parts by weight, preferably 20 to 60 parts by weight, based on 100 parts by weight of the melamine resin. If the pulp content is less than 5 parts by weight, there is no effect of addition, and if it is more than 70 parts by weight, the fluidity deteriorates, and the mold is not filled to every corner, and the contaminants of the mold remain, which is preferable. Absent.

Further, the resin composition for cleaning a mold of the present invention may contain a mineral powder. Examples of the mineral powder include natural materials such as corundum, emery, garnet, and gay stone, and oxides such as iron, titanium, sodium, calcium, magnesium, aluminum, chromium, and boron. Carbides are preferable, and examples of these oxides or carbides include gay oxide, magnesium oxide, aluminum oxide, gay carbide, and boron carbide. The mineral powder preferably has a new Mohs hardness of 6 to 15 in hardness.

The particle size of the minerals powder is not particularly limited, but is generally # 100 to # 400, preferably # 100 to 200, more preferably # 100 to # 1 0 0 0 is good. If the particle size is smaller than # 400, the cleaning effect will be worse, dust will be generated during handling and the working environment will deteriorate, and if the particle size is larger than # 100, the mold will be damaged and cleaning will not be possible. It is likely to cause defects such as unevenness and insufficient filling of the mold.

The content of the mineral powder is not particularly limited, but is preferably 10 to 90 parts by weight, more preferably 10 to 100 parts by weight of the melamine resin. To 30 parts by weight.

Further, the resin composition for cleaning a mold of the present invention may contain a lubricant. Examples of the lubricant include metal stones such as zinc stearate, calcium stearate, and zinc myristate; fatty acids such as stearic acid, oleic acid, and behenic acid; and fatty acid esters such as butyl stearate and dodecyl stearate. , Stearic acid monoglyceride, oleic acid monoglyceride, hydroxystearin Fatty acid partial esters such as acid monoglyceride, pentaerythritol monostearate, polyglycerin stearate, sorbitan triolate, lauric acid amide, myristic acid amide, erlic acid amide, oleic acid amide, Fatty acid amides such as stearic acid amide, and fatty acid bisamides such as methylene bisstearic acid amide, ethylene bisstearic acid amide, and ethylene bisoleic acid amide. The content of the lubricant is preferably not more than 1.5 parts by weight, and more preferably not more than 1 part by weight, based on 100 parts by weight of the melamine resin in order to maintain good mold cleaning properties.

The mold cleaning resin composition of the present invention may further include other additives such as an inorganic or organic filler other than the mineral powder, a coloring agent, a curing catalyst, a lubricant other than the lubricant, and an antioxidant. May be contained. Specific examples of such additives include, for example, inorganic or organic substances such as wood powder, vinylon fiber, glass powder, glass fiber, untreated calcium carbonate, talc, aluminum hydroxide, barium sulfate, and zinc sulfide. Fillers: for example, inorganic pigments such as titanium oxide, carbon black, zinc white, cadmium yellow, and bengalara; organic pigments such as phthalocyanine, azo, and diazo; benzoxazole-based, naphthotriazole-based; Coloring agents such as fluorescent pigments such as comarines, and dyes such as anthraquinones, indicos, and azos; organic acids such as phthalic anhydride, oxalic acid, sulfamic acid, and paratoluenesulfonic acid, and hydrochloric acid , Sulfuric acid and other inorganic acids, these acids and triethylamine, triethanolamine, | 3-dimethylaminoethanol, 2-medium Rue 2-Amino-1 Curing catalyst such as salts with monopropanol; for example, stear amide, methylol stear amide, methylene bis stear amide, paratoluenesulfonic acid amide, cetyl alcohol, paraffin, silicone oil And lubricating agents such as naphthylamine-based antioxidants, p-phenylenediamine-based antioxidants, and thiobisphenol-based antioxidants.

The resin composition for cleaning a mold of the present invention preferably contains at least one selected from the pulp, mineral powder, curing catalyst and lubricant.

An example of a preferable compounding example of the resin composition for cleaning a mold of the present invention is shown below.

(A) Melamine resin 100 parts by weight (B) at least one type of guanamines 3 to 65 parts by weight and / or at least one type of guanamine-based resin 5 to 200 parts by weight

(C) Pulp 5 to 70 parts by weight

(D) Mineral powder having a particle size of # 100 to # 400000 10 to 90 parts by weight

(B) 1 to 30 parts by weight of a fibrous inorganic compound having an average fiber length of 5 to 30 and an average fiber diameter of 0.1 to 1.0 m and an aspect ratio of 10 to 60.

In preparing the resin composition for cleaning a mold of the present invention, the melamine resin, the G component and the W component, and optionally, other secondary amounts of resin, pulp, minerals, powder, etc. Any means capable of uniformly mixing the additives can be adopted. For example, 210, a ribbon blender, a hensyl mixer, a ball mill, a roll kneader, a grinder, an evening tumbler and the like can be exemplified.

Examples of the curable resin molding material capable of cleaning a mold using the resin composition for cleaning a mold of the present invention include an epoxy resin molding material and a fuanol resin molding material, and preferably an epoxy resin molding material. Yes, especially epoxy resin molding materials for semiconductor encapsulation. Further, the mold cleaning resin composition of the present invention can be used for any mold as long as the mold is used for automatically molding the curable resin molding material. Generally, a mold made of iron, chromium, or the like is used. It can be suitably applied to Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples.

Production Example 1

Benzoguanamine (BG) 374 parts by weight and formalin (37% aqueous solution) 243 parts by weight (1.5 moles of formaldehyde to 1 mole of BG) at 90 ° C, pH 7.4 to 7 The reaction was carried out by heating in step 6. When the reaction system became a transparent solution, the reaction was immediately stopped, and the solution was poured directly into a batt-shaped vessel, and allowed to cool, thereby precipitating F-BG crystals. The reaction system gels white as a whole without separation into F-BG and water. The plate-like gel was crushed and dried at 80 ° C. for 2 hours in a hot air drier to remove water, thereby obtaining a white methylol benzoguanamine (a). Production Example 2

Melamine 12.6 parts by weight, BG 126 parts by weight and formalin (37% aqueous solution) 271 parts by weight (formaldehyde 1 mol per 1 mol of melamine and BG) at 85-90 ° C The reaction was heated at pH 9.5 to 10 and when the reaction system became a clear solution, the reaction was stopped immediately, poured directly into a batch-shaped vessel, and allowed to cool to precipitate M / BG-F crystals. Let it. The reaction system gels white as a whole without separation into M / BG-F and water. The gel was crushed and dried in a hot air drier at 80 ° C. for 2 hours to remove water to obtain white M / BG-F ¹ (b). Production Example 3

Melamine 346 parts by weight, formalin (37% aqueous solution) 522 parts by weight and phenol (85% aqueous solution) 131 part by weight were heated and reacted, and melamine-phenol-formaldehyde resin was obtained by a known method. After adding 248 parts by weight of pulp to the obtained resin solution and kneading the mixture, the mixture was dried under reduced pressure to obtain a melamine-phenol-formaldehyde resin powder mixed with pulp having a pulp content of 15% (melamine resin-impregnated pulp). . Example 1

30 parts by weight of melamine-phenol-formaldehyde resin powder (melamine-based resin-impregnated pulp) obtained in Production Example 3; commercially available melamine resin (Nikaresin S—176) manufactured by Nippon Rikiichi Baidoe Industry Co., Ltd. 50 parts by weight, CTU-guanamine 30 parts by weight, aluminum borate (Albolex YS 4 manufactured by Shikoku Chemicals Co., Ltd.) 5 parts by weight, silica powder of particle size # 200 0 parts by weight, benzoic acid 0.1 Parts by weight and 0.5 parts by weight of zinc stearate were pulverized with a ball mill, and 0.3 parts by weight of ethylenebisstearic acid amide was added with a Nauter mixer to obtain a resin composition A for mold cleaning. Obtained.

Table 1 shows the characteristic values and the cleaning effect test results of the obtained resin composition for cleaning a mold. As can be seen from the test results, the resin composition for mold cleaning A exhibited good fluidity and a good cleaning effect. Example 2

Melamine monophenol formaldehyde resin powder obtained in Production Example 3 (melamine resin impregnated pulp) 30 parts by weight, commercially available melamine resin (Nikaresin S-176, Nippon Carbide Co., Ltd.) 25 25 parts by weight, 25 parts by weight of methylol lupenzoguanamine (a) obtained in Production Example 1, 5 parts by weight of aluminum borate (Arborex YS 4 manufactured by Shikoku Chemicals Co., Ltd.), silica powder of particle size # 200 20 Parts by weight, 0.2 parts by weight of benzoic acid and 0.5 parts by weight of zinc stearate were pulverized with a ball mill, and 0.3 parts by weight of ethylenebisstearic acid amide was added with a Now Yuichi mixer. A cleaning resin composition B was obtained.

Table 1 shows the characteristic values and the cleaning effect test results of the obtained resin composition for cleaning a mold. As can be seen from the test results, the resin composition B for mold cleaning showed good fluidity and a good cleaning effect. Example 3

30 parts by weight of melamine-phenol-formaldehyde resin powder (melamine-based resin-impregnated pulp) obtained in Production Example 3, commercially available melamine resin (Nicarezin S-176 manufactured by Nippon Carbide Co., Ltd.) 25 parts by weight, 25 parts by weight of M / BG-F (b) obtained in Production Example 2, 5 parts by weight of aluminum borate (Alvolex YS4 manufactured by Shikoku Chemicals Co., Ltd.), 5 parts by weight, particle size # 200 20 parts by weight of silica powder, 0.2 parts by weight of benzoic acid and 0.5 parts by weight of zinc stearate are crushed by a ball mill, and 0.3 parts by weight of ethylenebisstearic acid amide are used in a Nauta mixer. In addition, a mold cleaning resin composition C was obtained.

Table 1 shows the characteristic values and the cleaning effect test results of the obtained resin composition for cleaning a mold. As can be seen from the test results, the resin composition C for mold cleaning showed good fluidity and a good cleaning effect. Example 4

30 parts by weight of melamine-phenol-formaldehyde resin powder (melamine-based resin-impregnated pulp) obtained in Production Example 3; commercially available melamine resin Nicarezin S-176 6) 40 parts by weight, benzoguanamine 5 parts by weight, methylol benzoguanamine obtained in Production Example 1 (a) 10 parts by weight, aluminum borate (Shikoku Chemical Industry Co., Ltd.) Albolex YS 4) 5 parts by weight, 20 parts by weight of silica powder having a particle size of # 200, 0.2 parts by weight of benzoic acid and 0.5 parts by weight of zinc stearate 0.3 parts by weight of the acid amide was added using a Nauta mixer to obtain a resin composition D for cleaning a mold.

Table 1 shows the characteristic values and the cleaning effect test results of the obtained resin composition for cleaning a mold. As can be seen from the test results, the resin composition D for mold cleaning showed good fluidity and a good cleaning effect. Comparative Example 1

In Example 1, the amount of CTU guanamine and aluminum borate (Alporex Y S4 manufactured by Shikoku Chemicals Co., Ltd.) was set to 0 parts by weight, and this was used as a resin composition E for cleaning a mold. Comparative Example 2

In Example 1, a resin composition F in which the amount of CTU guanamine was 50 parts by weight was used. Comparative Example 3

In Example 1, the amount of the commercially available melamine resin was changed to 0 parts by weight, and the methylolbenzoguanamine (a) obtained in Production Example 1 was changed to 50 parts by weight instead of 30 parts by weight of CTU-guanamine. The resin composition G for cleaning a mold was used.

Table 11 shows the results of a mold cleaning test performed using the mold cleaning resin compositions A to G by the following test method.

Test method

Using a commercially available biphenyl-based epoxy resin molding material (CEL-900 XU, manufactured by Hitachi Chemical Co., Ltd.), the mold is stained by molding 500 shots using a TQFP mold. Was realized. The evaluation was performed by repeatedly molding the mold cleaning resin composition using the dirty mold until the mold surface was cleanly cleaned.

Table 1

Production Example 4

375 parts by weight of acetoguanamine (AG) and 73 parts by weight of formalin (37% aqueous solution) (3 moles of formaldehyde with respect to 1 mole of AG) are heated and reacted at 65-70ΐ; ρΗ9. When the reaction system becomes a nearly transparent solution, the reaction is stopped immediately, and the mixture is poured into a batt-shaped vessel as it is, and is allowed to cool to precipitate F-AG crystals. The reaction system gels white as a whole without separation into FAG and water. The plate-like gel was crushed and dried with a hot air drier at 80 ° C. for 2 hours to remove water to obtain white methylolacetoguanamine (c). Production Example 5

CTU guanamine (11.6 parts by weight) and formalin (350 parts by weight) (formaldehyde (3.3 mol) per 1 mol of melamine and CTU-G) were heated and reacted at 90-95 ° C and pH9. After the reaction system became a clear solution, methylolation was performed for 30 minutes. Next, add 126 parts by weight of melamine, and react by heating at 70 to 8 (TC) .When the reaction system becomes a clear solution, immediately stop the reaction, pour it into a bag-like container, and heat with hot air. It was dried at 80 ° C for 5 hours in a drier to remove water, and white M / CTU-G-F (d) was obtained. Production Example 6

Melamine 346 parts by weight, formalin (37% aqueous solution) 52 parts by weight, and phenol 131 parts by weight were heated and reacted to produce melamine formaldehyde monophenol resin by a known method, and obtained. The resin solution was mixed with 248 parts by weight of pulp, kneaded, and dried under reduced pressure to obtain melamine formaldehyde-phenol resin powder (melamine resin impregnated pulp) mixed with pulp having a pulp content of 27%. Production Example 7

Melamine (480 parts by weight) and formalin (37% aqueous solution) (522 parts by weight) were heated and reacted to form a melamine formaldehyde resin by a known method. Then, the mixture was kneaded and dried under reduced pressure to obtain a melamine-formaldehyde resin powder mixed with pulp having a pulp content of 27% (melamine resin impregnated pulp). Example 5

Melamine formaldehyde monophenol resin powder obtained in Production Example 6 (melamine resin impregnated pulp) 30 parts by weight, commercially available melamine resin (Nicarezin S-176 from Nippon Carbide Co., Ltd.) 5 0 parts by weight, 5 parts by weight of acetoguanamine, 5 parts by weight of aluminum borate (Alborex YS4 manufactured by Shikoku Chemicals Co., Ltd.), 20 parts by weight of silica powder having a particle size of # 0, 20 parts by weight, 0.1 part by weight of benzoic acid Parts and 0.5 parts by weight of zinc stearate were pulverized with a ball mill, and 0.3 parts by weight of ethylenebisstearic acid amide was added by a Nauta mixer to obtain a resin composition H for mold cleaning. .

Table 12 shows the characteristic values and the cleaning effect test results of the obtained resin composition for mold cleaning. As can be seen from the test results, the resin composition H for cleaning a mold showed good fluidity and a good cleaning effect. Example 6

30 parts by weight of the melamine formaldehyde-phenol resin powder (melamine resin impregnated pulp) obtained in Production Example 6, 10 parts by weight of methylolacetoguanamine (c) obtained in Production Example 4, Melamine resin (Nicarbe Dye Co., Ltd. Nicarezin S_176), 40 parts by weight, aluminum borate (Shikoku Chemicals Co., Ltd., Arbolex YS4) 5 parts by weight, particle size # 200 silica powder 20 parts by weight, 0.1 part by weight of benzoic acid and 0.5 part by weight of zinc stearate were pulverized by a ball mill, and 0.3 part by weight of ethylenebisstearic acid amide was used with a Nauta mixer. In addition, a mold cleaning resin composition I was obtained.

Table 12 shows the characteristic values and the cleaning effect test results of the obtained resin composition for mold cleaning. As can be seen from the test results, the resin composition for mold cleaning I exhibited good fluidity and a good cleaning effect. Example 7

30 parts by weight of melamine formaldehyde monophenol resin powder (melamine resin impregnated pulp) obtained in Production Example 6, 10 parts by weight of M / CTU-G-F (d) obtained in Production Example 5, 40 parts by weight of commercially available melamine resin (Nikaresin S-176, manufactured by Nippon Rikaichi Bay Die Co., Ltd.), 5 parts by weight of aluminum borate (Albolex YS4, manufactured by Shikoku Chemicals, Ltd.), particle size # 20 0.2 part by weight of silica powder, 0.1 part by weight of benzoic acid and 0.5 part by weight of zinc stearate are ground with a ball mill, and 0.3 part by weight of ethylene bis stearic acid amide is mixed with Nauta mixer. In addition, a mold cleaning resin composition J was obtained.

Table 12 shows the characteristic values and the cleaning effect test results of the obtained resin composition for mold cleaning. As can be seen from the test results, the resin composition J for mold cleaning exhibited good fluidity and a good cleaning effect. Example 8

Melamine formaldehyde-phenol resin powder obtained in Production Example 6 (melamine resin impregnated pulp) 30 parts by weight, methylol benzoguana obtained in Production Example 1 Min (a) 10 parts by weight, a commercially available melamine resin (Nikkaresin Sangyo Co., Ltd. Nikkaresin S-176) 40 parts by weight, acetguanamine powder 5 parts by weight, boric acid aluminum (Shikoku Chemical Industry Co., Ltd.) Alvolex YS 4) 5 parts by weight, 20 parts by weight of silica powder having a particle size of # 200, 0.1 parts by weight of benzoic acid and 0.5 parts by weight of zinc stearate 0.3 parts by weight of stearic acid amide was added using a Nauta mixer to obtain a mold cleaning resin composition K.

Table 12 shows the characteristic values and the cleaning effect test results of the obtained resin composition for mold cleaning. As can be seen from the test results, the resin composition K for mold cleaning exhibited good flowability and a good cleaning effect. Example 9

30 parts by weight of melamine formaldehyde-phenol resin powder (melamine resin impregnated pulp) obtained in Production Example 6, 10 parts by weight of M / CTU-GF (d) obtained in Production Example 5, commercially available Melamine resin (Nicarbe Dye Co., Ltd. Nicarezin S-176) 40 parts by weight, Acetguanamine powder 5 parts by weight, CTU Guanamine powder 5 parts by weight, Aluminum borate (Shikoku Chemicals Co., Ltd. Albolex YS 4) 5 parts by weight, 20 parts by weight of silica powder having a particle size of # 200, 0.1 parts by weight of benzoic acid, and 0.5 parts by weight of zinc stearate are crushed by a ball mill into ethylenebisstearic acid amide. 0.3 parts by weight was added using a Nauta mixer to obtain a mold cleaning resin composition L.

Table 12 shows the characteristic values and the cleaning effect test results of the obtained resin composition for mold cleaning. As can be seen from the test results, the resin composition L for mold cleaning showed good fluidity and a good cleaning effect. Example 10

30 parts by weight of melamine monoformaldehyde resin powder (melamine resin impregnated pulp) obtained in Production Example 7, 10 parts by weight of methylolacetoguanamine (c) obtained in Production Example 4, commercially available melamine resin (Japan Nikkaresin S—176 6) 40 parts by weight, aluminum borate (Shikoku Chemical Industry Co., Ltd. Volex YS 4) 5 parts by weight, 20 parts by weight of silica powder of particle size # 200, 0.1 parts by weight of benzoic acid and 0.5 parts by weight of zinc stearate 0.3 parts by weight of the amide was added using a Nauta mixer to obtain a resin composition M for cleaning a mold.

Table 12 shows the characteristic values and the cleaning effect test results of the obtained resin composition for mold cleaning. As can be seen from the test results, the mold cleaning resin composition M exhibited good fluidity and a good cleaning effect.

Table 12 shows the results of a mold cleaning test performed using the mold cleaning resin compositions H to M according to the same test method as that for the mold cleaning resin compositions A to G described above. . Table 1 2

Industrial applicability

The mold cleaning resin composition of the present invention exhibits excellent fluidity and cleanability with respect to ultra-thin and matrix-type mold contamination, and is suitable for molding a curable resin molding material such as a bifuunyl epoxy resin. Excellent cleaning effect is also observed for generated mold contamination.

Claims

The scope of the claims

1. When molding a curable resin molding material, a mold cleaning resin composition that removes stains on a mold surface contains a melamine resin as a mold cleaning resin, and at least one kind of guanamines and Contains at least one guanamine-based resin and a fibrous inorganic compound having an average fiber length of 5 to 30 μm, an average fiber diameter of 0.1 to 1.0 μm, and an aspect ratio of 10 to 60. A resin composition for cleaning a mold.

2. The resin composition according to claim 1, wherein said guanamine is benzoguanamine, acetoguanamine or CTU-guanamine.

3. The resin composition for cleaning a mold according to claim 1, wherein the guanamine-based resin is a methylolated guanamine resin or a melamine-guanamine co-condensation resin.

4. The resin composition for cleaning a mold according to claim 1, wherein the content of the guanamine is 3 to 65 parts by weight based on 100 parts by weight of the melamine resin.

5. The resin composition for cleaning a mold according to claim 1, wherein the content of the guanamine-based resin is 5 to 200 parts by weight based on 100 parts by weight of the melamine-based resin.

6. The resin composition for cleaning a mold according to claim 1, wherein the content of the fibrous inorganic compound is 1 to 30 parts by weight based on 100 parts by weight of the melamine-based resin.

7. The resin composition for cleaning a mold according to claim 1, wherein the fibrous inorganic compound is surface-treated.

8. The resin composition for mold cleaning according to claim 1, further comprising at least one selected from pulp, mineral powder, curing catalyst and lubricant.

9. A mold cleaning resin composition for removing a stain on a mold surface during molding of a curable resin molding material, the composition comprising the following (A) to (E). object.

(A) Melamine resin 100 parts by weight

(B) 3 to 65 parts by weight of at least one guanamine and / or 5 to 200 parts by weight of at least one guanamine-based resin

(C) Pulp 5 to 70 parts by weight

(B) 1 to 30 parts by weight of a fibrous inorganic compound having an average fiber length of 5 to 30 m, an average fiber diameter of 0.1 to 1.0 m and an aspect ratio of 10 to 60.

10. The mold cleaning resin composition according to claim 9, wherein the guanamine is benzoguanamine, acetoguanamine or CTU-guanamine.

11. The resin composition according to claim 9, wherein the guanamine-based resin is a methylolated guanamine resin or a melamine-guanamine co-condensation resin.

12. The resin composition for cleaning a mold according to claim 9, wherein the fibrous inorganic compound has been subjected to a surface treatment.

13. The mold cleaning resin composition according to claim 9, wherein a part or all of the pulp is powder pulp.

14. The mold cleaning resin composition according to claim 9, wherein the pulp contains pulp impregnated with a melamine resin and / or a guanamine resin.