Cleaning composition, cleaning material, and method for cleaning mold

Abstract

A cleaning composition containing: a main material of a cleaning composition; and an amine compound which does not contain an amino group at the terminal of the molecular chain and does contain an amino group at a position other than the terminal of the molecular chain.

Description

Detergent composition, cleaning material, and method for cleaning molding dies

[0001] The present disclosure relates to a cleaning composition, a cleaning material, and a method for cleaning a molding mold.

[0002] In the field of plastic molding, such as injection molding, transfer molding, and compression molding, molding is typically performed repeatedly using a mold. As molding operations are repeated, molding materials or components derived from them accumulate inside the mold, causing mold contamination. Such mold contamination can reduce the releasability of molded products and result in poor appearance. Furthermore, further accumulation of contamination can cause dimensional abnormalities in molded products.

[0003] Therefore, in order to prevent the adverse effects of contaminated molds, the molds must be periodically cleaned to remove contaminants adhering to the mold surface.

[0004] Known mold cleaner compositions that exhibit excellent cleaning effects on molds contaminated by repeated molding operations include those containing at least one of synthetic rubber and synthetic resin as a base material, at least one of alkali metal salt and alkali metal hydroxide, and an organic solvent or water (see, for example, Patent Documents 1 and 2). A mold cleaning material comprising such a mold cleaning composition is placed in an open mold, and the mold is then closed and heated and pressurized with the mold cleaning material sandwiched between them. This causes contaminants formed on the mold surface to become integrated into the mold cleaning material, and the mold cleaning material with the integrated contaminants can be peeled off from the mold, thereby cleaning the mold surface.

[0005] JP 2011-021156 A JP 2011-020416 A

[0006] In addition to the mold cleaning methods described in Patent Documents 1 and 2, there is also a method of cleaning a mold by removing contaminants adhering to the mold surface using a mold cleaning material formed from a mold cleaner composition containing an amine compound. However, although a detergent composition containing an amine compound is effective in cleaning the inside of a mold, repeated cleaning of the mold with this detergent composition can sometimes result in contamination on the periphery of the mold.

[0007] An object of the present disclosure is to provide a detergent composition that can suppress contamination of the outer periphery of a molding die, a cleaning material obtained by molding the detergent composition, and a method for cleaning a molding die in which the detergent composition is used to clean the molding die.

[0008] Means for solving the above problems include the following aspects. <1> A detergent composition comprising: a main material for the detergent composition; and an amine compound that does not have an amino group at the molecular chain terminal, but does have an amino group at a position other than the molecular chain terminal. <2> A detergent composition comprising: a reinforcing material for the detergent composition; and an amine compound that does not have an amino group at the molecular chain terminal, but does have an amino group at a position other than the molecular chain terminal. <3> A detergent composition used for cleaning a mold for molding thermosetting resin, comprising an amine compound that does not have an amino group at the molecular chain terminal, but does have an amino group at a position other than the molecular chain terminal. <4> The detergent composition according to any one of <1> to <3>, wherein the amine compound comprises at least one compound selected from the group consisting of secondary amine compounds and tertiary amine compounds. <5> The cleaning composition according to <4>, wherein the amine compound includes a secondary amine compound, and the secondary amine compound is at least one selected from the group consisting of methylethanolamine, ethylethanolamine, propylethanolamine, butylethanolamine, dimethylamine, diisopropanolamine, and diethanolamine. <6> The cleaning composition according to any one of <1> to <3>, wherein the amine compound includes only one hydroxy group. <7> The cleaning composition according to any one of <1> to <6>, wherein the content of the amine compound is less than 20 parts by mass per 100 parts by mass of the main material. <8> A cleaning material obtained by molding the cleaning composition according to any one of <1> to <7>. <9> A method for cleaning a molding die, comprising the steps of: placing the cleaning material according to <8> in an open molding die; clamping the molding die to sandwich the cleaning material between the molding dies, and applying heat and pressure; and peeling the cleaning material from the molding die.

[0009] The present disclosure provides a detergent composition that can suppress contamination of the outer periphery of a molding die, a cleaning material obtained by molding the detergent composition, and a method for cleaning a molding die in which the detergent composition is used to clean the molding die.

[0010] Hereinafter, modes for carrying out embodiments of the present disclosure will be described in detail. However, the embodiments of the present disclosure are not limited to the following embodiments. In the following embodiments, components (including element steps, etc.) are not essential unless otherwise specified. The same applies to numerical values ​​and their ranges, and they do not limit the embodiments of the present disclosure.

[0011] In the present disclosure, the term "process" includes not only processes that are independent of other processes, but also processes that cannot be clearly distinguished from other processes as long as the purpose of the process is achieved. In the present disclosure, numerical ranges indicated using "to" include the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In the numerical ranges described in stages in the present disclosure, the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described in stages. Furthermore, in the numerical ranges described in the present disclosure, the upper or lower limit of that numerical range may be replaced with a value shown in the examples. In the present disclosure, each component may contain multiple corresponding substances. When multiple substances corresponding to each component are present in a composition, the content or amount of each component refers to the total content or amount of the multiple substances present in the composition, unless otherwise specified.

[0012] [Cleaning Agent Composition] <First Embodiment> A cleaning agent composition according to a first embodiment of the present disclosure includes a main component of a cleaning agent composition and an amine compound that does not contain an amino group at a terminal of the molecular chain and that contains an amino group at a position other than the terminal of the molecular chain (hereinafter, also referred to as a "specific amine compound").

[0013] The cleaning composition of the first embodiment contains a specific amine compound, which can suppress contamination of the outer periphery of a mold even when the cleaning composition is used to repeatedly clean the mold. The reason for this is presumed to be as follows. Note that the present disclosure is not limited to the following presumption.

[0014] When a cleaning composition containing an amine compound having an amino group at the end of the molecular chain (hereinafter also referred to as a "terminal amino group-containing compound") is used to clean a mold, the terminal amino group-containing compound is likely to deteriorate, change in quality, etc. when a cleaning material obtained by molding the cleaning composition is heated. As a result, repeated cleaning of a mold with a cleaning composition containing a terminal amino group-containing compound tends to cause contaminants to accumulate on the periphery of the mold.

[0015] On the other hand, in the cleaning composition of the present disclosure, the specific amine compound is less likely to change in quality or deteriorate when a cleaning material molded from the cleaning composition is heated, which makes it possible to suppress contamination of the outer periphery of a mold even when the mold is repeatedly cleaned with the cleaning composition.

[0016] The cleaning composition is preferably used for cleaning a mold for molding a thermosetting resin.

[0017] (Main Material) The cleaning agent composition contains a main material. Examples of the main material include a rubber material and a resin material. One main material may be used alone, or two or more main materials may be used in combination.

[0018] Examples of rubber materials include butadiene rubbers such as 1,2-polybutadiene, 1,4-polybutadiene, and mixtures thereof, nitrile rubber, ethylene-α-olefin rubbers such as ethylene-propylene rubber, ethylene-α-olefin-polyene rubber, styrene-butadiene rubber, polyisoprene rubber, butyl rubber, silicone rubber, and fluororubber. One type of rubber material may be used alone, or two or more types may be used in combination. For example, a mixture of butadiene rubber and ethylene-α-olefin rubber such as ethylene-propylene rubber may be used.

[0019] Resin materials include polyamide resins such as nylon 6 and nylon 66, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polycarbonate resin, polyarylate resin, vinyl chloride resin, chlorinated vinyl chloride resin, polyethylene resin, chlorinated polyethylene resin, chlorinated polypropylene resin, polypropylene resin, polystyrene resin, acrylonitrile-styrene resin, vinylidene chloride resin, vinyl acetate resin, polyacrylate resin, polyimide resin, butadiene resin, polyacetal resin, ionomer resin, ethylene-vinyl chloride copolymer resin, ethylene Examples of the resin material include vinyl acetate copolymer resin, ethylene-vinyl acetate-vinyl chloride graft polymerization resin, polyphenylene resin, polysulfone resin, methacrylic resin, acrylic-fluororesin, acrylic-silicone oligomer, silicone resin, epoxy-containing silicone-acrylic resin, vinyl ester resin, furan resin, phenolic resin, melamine resin, guanamine resin, urea resin, polyurethane resin, diacryl phthalate resin, ketone resin, epoxy resin, xylene resin, maleic resin, phenoxy resin, coumarone resin, polyvinyl formal resin, polyvinyl butyral resin, etc. One type of resin material may be used alone, or two or more types may be used in combination.

[0020] As will be described later, the main material such as a rubber material or a resin material may be used in combination with a crosslinking agent, a curing agent, etc. In this way, when the cleaning material molded from the cleaning composition is heated, the cleaning material becomes in a cured state, and the cured cleaning material can be removed from the mold. Methods for curing the cleaning material include curing by heating and curing by cooling a thermoplastic resin, etc., and it is preferable to use a crosslinking agent, a curing agent, etc. for curing by heating.

[0021] The content of the main material may be 40% by mass to 95% by mass, 50% by mass to 90% by mass, or 50% by mass to 70% by mass, based on the total amount of the detergent composition.

[0022] (Specific amine compound) The detergent composition contains an amine compound (specific amine compound) that does not contain an amino group at a terminal of the molecular chain and contains an amino group at a position other than the terminal of the molecular chain. The specific amine compound may be used alone or in combination of two or more.

[0023] The specific amine compound preferably includes at least one compound selected from the group consisting of secondary amine compounds and tertiary amine compounds, and more preferably includes a secondary amine compound.

[0024] The specific amine compound (preferably at least one compound selected from the group consisting of secondary amine compounds and tertiary amine compounds) may be a compound containing a hydroxy group or a compound not containing a hydroxy group. When the specific amine compound is a compound containing a hydroxy group, the specific amine compound may contain only one hydroxy group or may contain two or more hydroxy groups. From the viewpoint of more suitably suppressing contamination of the outer periphery of the mold, it is preferable that the specific amine compound contains only one hydroxy group.

[0025] Examples of specific amine compounds include methylethanolamine, ethylethanolamine, propylethanolamine, butylethanolamine, octyldiethanolamine, triethanolamine, dimethylamine, dimethylcyclohexylamine, dimethylhexylamine, cyclohexylamine, diisobutylamine, di-n-butylamine, diisopropanolamine, diethanolamine, etc. Among these, from the viewpoint of mold cleaning properties, methylethanolamine, ethylethanolamine, propylethanolamine, butylethanolamine, dimethylamine, diisopropanolamine, and diethanolamine are preferred, and from the viewpoint of more suitably suppressing contamination of the periphery of the mold, methylethanolamine, ethylethanolamine, propylethanolamine, butylethanolamine, and dimethylamine are preferred.

[0026] The content of the specific amine compound may be 1% by mass to 20% by mass, 2% by mass to 15% by mass, or 3% by mass to 10% by mass, relative to the total amount of the detergent composition.

[0027] The content of the amine compound may be 30 parts by mass or less per 100 parts by mass of the main material, and from the viewpoint of suppressing the phenomenon in which a specific amine compound or other component contained in the detergent composition bleeds out to the surface (blooming phenomenon), the content is preferably less than 20 parts by mass, more preferably 18 parts by mass or less, and even more preferably 16 parts by mass or less. The content of the amine compound may be 1 part by mass or more, 3 parts by mass or more, or 5 parts by mass or more per 100 parts by mass of the main material.

[0028] (Crosslinking Agent) The cleaning agent composition may contain a crosslinking agent. For example, when the cleaning agent composition contains a rubber material, a polyethylene resin, or the like as a main material, the cleaning agent composition may contain a crosslinking agent. The crosslinking agent is not particularly limited as long as it can crosslink the rubber material, and examples thereof include organic peroxides. One type of crosslinking agent may be used alone, or two or more types may be used in combination.

[0029] Examples of organic peroxides include 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, t-butylperoxymaleic acid, t-butylperoxyoleate, t-butylperoxy-3,3,5-trimethylhexanoate, cyclohexanone peroxide, t-butylperoxyarylcarbonate, t-butylperoxyisopropylcarbonate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, 2,2-bis(t-butylperoxy)octane, t-butylperoxyacetate, 2,2 4,4-bis(t-butylperoxy)butane, t-butylperoxybenzoate, n-butyl-4,4-bis(t-butylperoxy)valerate, di-t-butylperoxyisophthalate, methyl ethyl ketone peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, α,α'-bis(t-butylperoxy-m-isopropyl)benzene, t-butylcumyl peroxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, and 2,5-dimethyl-2,5-di(t-butylperoxy)hexane-3.

[0030] When the detergent composition contains a crosslinking agent, the content of the crosslinking agent may be 0.1 to 5% by mass, 0.5 to 4% by mass, or 1 to 3% by mass, relative to the total amount of the detergent composition.

[0031] (Curing Agent) The cleaning composition may contain a curing agent. For example, when the cleaning composition contains an epoxy resin as a main component, the cleaning composition may contain a curing agent. The curing agent is not particularly limited as long as it can cure the epoxy resin, and examples thereof include phenol compounds, amine compounds, imidazole compounds, acid anhydrides, and organic phosphoric acid compounds. One type of curing agent may be used alone, or two or more types may be used in combination.

[0032] Examples of phenol compounds include monocyclic bifunctional phenols such as hydroquinone, resorcinol, and catechol; polycyclic bifunctional phenols such as bisphenol A, bisphenol F, naphthalenediols, and biphenols; and polyfunctional phenols such as halides and alkyl group-substituted derivatives thereof.

[0033] Examples of amine compounds include N,N-benzyldimethylamine, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol, tetramethylguanidine, triethanolamine, N,N'-dimethylpiperazine, 1,4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.4.0]-5-nonene, hexamethylenetetramine, pyridine, picoline, piperidine, pyrrolidine, dimethylcyclohexylamine, diamine, Examples include methylhexylamine, cyclohexylamine, diisobutylamine, di-n-butylamine, diphenylamine, N-methylaniline, tri-n-propylamine, tri-n-octylamine, tri-n-butylamine, triphenylamine, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, triethylenetetramine, diaminodiphenylmethane, diaminodiphenyl ether, dicyaminediamide, tolylbiguanide, guanylurea, and dimethylurea.

[0034] Examples of imidazole compounds include imidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 4,5-diphenylimidazole, 2-methylimidazoline, 2-phenylimidazoline, 2-undecylimidazol- ine, 2-heptadecylimidazol- ine, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-phenyl-4-methylimidazole, 2-ethylimidazoline, 2-phenyl-4-methylimidazoline, benzimidazole, 1-cyanoethylimidazole, and 2,4-diamino-6-[2'-methylimidazolyl-(1')]ethyl-s-triazine.

[0035] Examples of acid anhydrides include phthalic anhydride, hexahydrophthalic anhydride, pyromellitic dianhydride, and benzophenonetetracarboxylic dianhydride.

[0036] Examples of the organic phosphoric acid compound include hexamethylphosphoric acid triamide, tri(dichloropropyl) phosphate, tri(chloropropyl) phosphate, triphenyl phosphite, trimethyl phosphate, phenylphosphonic acid, triphenylphosphine, tri-n-butylphosphine, diphenylphosphine organic phosphoric acid compounds, and halides thereof.

[0037] When the detergent composition contains a crosslinking agent, the content of the crosslinking agent may be 0.1 to 5% by mass, 0.5 to 4% by mass, or 1 to 3% by mass, relative to the total amount of the detergent composition.

[0038] (Reinforcing Material) The detergent composition may contain a reinforcing material. Examples of the reinforcing material include inorganic fillers such as silica such as amorphous silica, talc, alumina, calcium carbonate, and aluminum hydroxide. One type of reinforcing material may be used alone, or two or more types may be used in combination.

[0039] When the detergent composition contains a reinforcing material, the content of the reinforcing material may be 10% by mass to 50% by mass, 15% by mass to 40% by mass, or 20% by mass to 30% by mass, relative to the total amount of the detergent composition.

[0040] The content of the reinforcing material may be 20 parts by mass to 55 parts by mass, 25 parts by mass to 50 parts by mass, or 30 parts by mass to 45 parts by mass, relative to 100 parts by mass of the main material. When the content of the reinforcing material is 55 parts by mass or less, an increase in viscosity of the cleaning composition can be suppressed, and the cleaning composition tends to have excellent mold followability.

[0041] (Release Agent) The cleaning composition may contain a release agent. Examples of the release agent include fatty acid-based release agents, silicone oil, polyethylene, etc. One type of release agent may be used alone, or two or more types may be used in combination.

[0042] Examples of fatty acid-based release agents include aliphatic carboxylic acids, aliphatic carboxylic acid esters, and fatty acid amides, such as palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachic acid, behenic acid, lignoceric acid, cerotic acid, melissic acid, tetraacontanoic acid, montanic acid, adipic acid, and azelaic acid; esters of these aliphatic carboxylic acids with alcohols having 30 or less carbon atoms; metal salts of these aliphatic carboxylic acids (e.g., calcium salts and zinc salts); fatty acid amides such as oleic acid amide and stearic acid amide; carnauba wax, montan wax, and the like. Examples of silicone oils include dimethyl silicone oil, methylphenyl silicone oil, and methylhydrogen silicone oil. Among these, montanic acid esters and polyethylene are preferred as release agents from the viewpoint of releasability.

[0043] When the detergent composition contains a release agent, the content of the release agent may be 1 to 15% by mass, 2 to 10% by mass, or 3 to 5% by mass, relative to the total amount of the detergent composition.

[0044] (Other Components) The detergent composition may or may not contain other components in addition to the above-mentioned components, such as a detergent, an organic solvent, water, a softener such as aromatic oil or naphthenic oil, a vulcanizing agent such as sulfur, a vulcanization accelerator, an antioxidant, and zinc oxide.

[0045] The detergent may be any detergent other than the specific amine compounds described above, such as alkali metal salts, alkali metal hydroxides such as potassium hydroxide, amide group-containing compounds such as propionic acid amide, and primary amine compounds.

[0046] From the viewpoint of suppressing contamination of the outer periphery of the mold, the content of the primary amine is preferably 1 mass % or less, more preferably 0.5 mass % or less, and even more preferably 0 mass %, based on the total amount of the detergent composition.

[0047] Examples of organic solvents include amide-based solvents, alcohol-based solvents, ketone-based solvents, ether-based solvents, hydrocarbon-based solvents, halogenated hydrocarbon-based solvents, phenol-based solvents, ester-based solvents, and sulfur-based solvents (such as dimethyl sulfoxide).

[0048] In order to maintain detergency, organic solvents or water are sometimes used in cleaning compositions. However, the cleaning composition of the first embodiment contains a specific amine compound, which allows the cleaning composition to maintain detergency without using organic solvents or water. Furthermore, the absence of organic solvents and water prevents their volatilization, and the cleaning composition of the first embodiment has excellent storage stability.

[0049] The detergent composition can be produced by mechanically kneading the components using a Banbury mixer, a kneader, a roll mixer, an extruder, or the like.

[0050] Second Embodiment A cleaning composition according to a second embodiment of the present disclosure includes a reinforcing material for a cleaning composition and an amine compound (specific amine compound) that does not include an amino group at the terminal of the molecular chain and includes an amino group at a position other than the terminal of the molecular chain. The cleaning composition of the second embodiment differs from the first embodiment in that the reinforcing material is an essential component instead of a main component. The cleaning composition of the second embodiment includes the specific amine compound, which makes it possible to suppress contamination of the outer periphery of a mold even when the mold is repeatedly cleaned using the cleaning composition. A description of preferred configurations common to the first embodiment will be omitted.

[0051] As in the first embodiment, examples of the reinforcing material used in the second embodiment include inorganic fillers such as silica such as amorphous silica, talc, alumina, calcium carbonate, and aluminum hydroxide.

[0052] The content of the reinforcing material may be 40% by mass to 95% by mass, 50% by mass to 90% by mass, or 50% by mass to 70% by mass, based on the total amount of the detergent composition.

[0053] The cleaning composition of the second embodiment may contain other components in addition to the reinforcing material and the specific amine compound. Examples of such components include the materials exemplified above as the main material, a crosslinking agent, a curing agent, a release agent, and other components.

[0054] <Third Embodiment> A cleaning composition according to a third embodiment of the present disclosure is a composition used for cleaning molds for molding thermosetting resins, which contains an amine compound (specific amine compound) that does not contain an amino group at the end of the molecular chain and that contains an amino group at a position other than the end of the molecular chain. The cleaning composition of the third embodiment differs from the first and second embodiments in that the main material and the reinforcing material are not essential components and in that the cleaning composition is used exclusively for cleaning molds for molding thermosetting resins. Since the cleaning composition of the third embodiment contains the specific amine compound, contamination of the outer periphery of the mold can be suppressed even when the mold is repeatedly cleaned using the cleaning composition. Description of preferred configurations common to the first and second embodiments will be omitted.

[0055] The cleaning agent composition of the third embodiment may be used without being combined with a main material or a reinforcing material, as long as it is used to clean a mold for molding a thermosetting resin.

[0056] [Cleaning Material] The cleaning material of the present disclosure is a cleaning material obtained by molding any one of the cleaning agent compositions according to the first to third embodiments of the present disclosure described above.

[0057] The cleaning material of the present disclosure is, for example, a member in which the aforementioned cleaning composition is formed into a powder, tablet, sheet, small piece, film, or strip shape. The cleaning material of the present disclosure may be a member in which the cleaning composition formed into a film, sheet, or the like is laminated, or a member in which the cleaning composition formed into a film, sheet, or the like is laminated or attached to a film, sheet, or other member with different properties. The cleaning material is used, for example, for cleaning molds. When the cleaning material is a sheet-shaped member, the thickness of the cleaning material may be 3 mm to 10 mm.

[0058] [Method for cleaning a molding die] The method for cleaning a molding die of the present disclosure includes the steps of placing the cleaning material of the present disclosure inside an open molding die, clamping the molding die to sandwich the cleaning material between the molding dies and applying heat and pressure, and peeling the cleaning material from the molding die.

[0059] The method for cleaning a molding die includes placing the cleaning material of the present disclosure into an open molding die. For example, the cleaning material may be in the form of a powder, tablet, sheet, or strip and placed into the open molding die. As an example, a sheet-like cleaning material may be placed between an upper mold and a lower mold, each of which has a recess formed therein.

[0060] The method for cleaning molding dies includes the steps of clamping the cleaning material between the molding dies by closing the molding dies, and then applying heat and pressure. The cleaning material is placed inside the open molding dies, and then the molding dies are closed to sandwich the cleaning material between the molding dies, followed by heating and pressure. By applying pressure, the cleaning material placed inside the molding dies is filled into the cavity formed by the recesses formed in the upper die and the recesses formed in the lower die, and is pressed against the mold surface. Furthermore, by heating, contaminants adhering to the inside of the mold are integrated with the cleaning material. In some cases, burrs formed around the cavity are also integrated during this process.

[0061] The method for cleaning a molding die includes a step of peeling the cleaning material from the molding die. For example, after performing the above-mentioned heating and pressurizing for a predetermined time, the upper and lower dies are opened and the cleaning material is peeled from both the upper and lower dies. In this way, the mold is cleaned.

[0062] The conditions for sandwiching the cleaning material between molds, compression molding, and heating are set appropriately depending on the composition, type, etc. of the cleaning material. For example, when a rubber material or a resin material is used as the main material, it is preferable to heat it at 160°C to 190°C for 1 minute to 5 minutes.

[0063] Examples of molds to be cleaned using the molding die cleaning method of the present disclosure include molds for molding thermosetting resins. More specifically, the molds to be cleaned may be molds for molding semiconductor devices that are repeatedly molded using thermosetting resins.

[0064] The thermosetting resin may be, for example, an epoxy resin. The mold to be cleaned may be a molding mold for sealing a semiconductor device, which is repeatedly molded using a resin composition containing an epoxy resin.

[0065] The resin composition may contain, in addition to the epoxy resin, a curing agent, and, if necessary, additives such as an inorganic filler and a curing accelerator.

[0066] A molding mold cleaned by the cleaning method of the present disclosure has contaminants removed, returning the mold surface to its original state. Therefore, when molding using a thermosetting resin, it is preferable to apply a release agent to the mold surface beforehand. For example, when molding a molding material containing Montan acid wax as a release agent, it is preferable to apply the same Montan acid wax, and when molding a molding material containing carnauba wax, it is preferable to apply the same carnauba wax. A preferred method for applying a release agent to the mold surface is to prepare an unvulcanized rubber composition containing the release agent and form it into a sheet. For example, a sheet obtained by blending a release agent with unvulcanized rubber, as described in JP 2011-020416 A, can be mentioned. Then, a sheet made of the unvulcanized rubber composition containing the release agent is loaded into a mold and heated, whereby the contained release agent is applied to the mold surface. This is thought to be because the release agent in the unvulcanized rubber composition melts during heat vulcanization and seeps onto the mold surface, forming a uniform release agent film on the surface.

[0067] Next, embodiments of the present disclosure will be described in detail using examples, but the embodiments of the present disclosure are not limited to these examples.

[0068] First, the components constituting the detergent composition were prepared. 1) EPR (main material): ethylene-propylene-diene rubber, manufactured by Mitsui Chemicals, Inc., EPT4045 (ethylene content: 54 mol%, diene component content: 8.1 mol%) 2) BR (main material): butadiene rubber, manufactured by JSR Corporation, BR-01 (cis-1,4 bond: 95%) 3) amorphous silica particles (reinforcing material): BET specific surface area 200 m ２ / g, bulk density 140g / L 4) Titanium oxide: average particle size 0.25μm 5) Amide wax: release agent 6) Organic peroxide: crosslinking agent 7) AEE: 2-(2-aminoethoxy)ethanol, boiling point 222°C, primary amine compound 8) NMEOA: methylethanolamine, boiling point 159°C, secondary amine compound 9) BEOA: butylethanolamine, boiling point 198°C, secondary amine compound 10) DIPOA: diisopropanolamine, boiling point 249°C, secondary amine compound 11) DEOA: diethanolamine, boiling point 269°C, secondary amine compound 12) ODEOA: octyldiethanolamine, boiling point 319°C, tertiary amine compound 13) 2-amino-2-methyl-1-propanol, boiling point 165°C, primary amine compound

[0069] [Examples 1 to 8 and Comparative Examples 1 and 2] The components constituting the cleaning composition were blended in the ratios shown in Table 1, and the blend was kneaded using a kneading roll. The blend was then formed into a sheet (5 mm thick) using a rolling roll to produce the desired sheet-shaped cleaning material. The numerical values ​​for each component in Tables 1 and 2 are in parts by mass, and blank spaces in Tables 1 and 2 indicate that the component was not blended.

[0070]

[0071]

[0072] [Evaluation 1 of Contamination on the Outer Surface of a Molding Mold] Using each of the cleaning materials obtained in Examples 1 and 2 and Comparative Example 1 as described above, contamination on the outer surface of a molding mold was evaluated as follows. 1.0 g of each cleaning material was sandwiched between the upper and lower molds at 175°C, heated and cured for 5 minutes, and then removed from the upper and lower molds. This process was repeated 50 times. The presence of contaminants on the outer surfaces of the upper and lower molds was then evaluated. In this evaluation, gas contamination was significantly observed in Comparative Example 1, which used AEE, while the occurrence of gas contamination was suppressed in the other Examples 1 and 2.

[0073] [Cleaning Evaluation 1 of Cleaning Materials] An iron plate was prepared by applying an epoxy resin molding material, a semiconductor encapsulating resin, at high temperature and curing it at 175°C for 24 hours to prepare a surface-treated iron plate. Next, each of the cleaning materials obtained in Examples 1 and 2 and Comparative Example 1 was placed on the surface-treated iron plate, and each cleaning material was heated and pressurized at 175°C for 5 minutes. Each cleaning material was then peeled from the iron plate, and the degree of removal of the epoxy resin molding material (i.e., the cleaning effect of the cleaning material) was evaluated. In all of Examples 1 and 2 and Comparative Example 1, the degree of removal of the epoxy resin molding material was excellent, confirming the cleaning effect of the cleaning material. The epoxy resin molding material used was a material containing an epoxy resin, a phenolic compound as a curing agent, and silica particles as an inorganic filler, with an epoxy group:phenolic hydroxyl group equivalent ratio of 1:1 and an inorganic filler content of 78% by volume.

[0074] [Evaluation 2 of Contamination on the Outer Periphery of a Molding Mold] Using the cleaning materials of each Example and Comparative Example obtained as described above, the same procedure as in [Evaluation 1 of Contamination on the Outer Periphery of a Molding Mold] was carried out. Then, the presence or absence of contaminants on the outer peripheries of the upper and lower mold surfaces was evaluated according to the following evaluation criteria. The results are shown in Table 3. (Evaluation criteria) A: The generation of gas contamination was suppressed. B: Gas contamination occurred, but within an acceptable range. C: Significant gas contamination occurred.

[0075] [Cleaning Material Cleaning Evaluation 2] The same procedure as in [Cleaning Material Cleaning Evaluation 1] was carried out using the cleaning materials of each Example and Comparative Example obtained as described above. The degree of removal of epoxy resin molding material (i.e., the cleaning effect of the cleaning material) was evaluated according to the following evaluation criteria. The results are shown in Table 3. (Evaluation Criteria) A: When each cleaning material was peeled from the iron plate, the epoxy resin molding material was sufficiently removed. B: When each cleaning material was peeled from the iron plate, some of the epoxy resin molding material was not removed and remained on the iron plate. C: When each cleaning material was peeled from the iron plate, a large amount of the epoxy resin molding material was not removed and remained on the iron plate.

[0076] [Blooming] The cleaning materials of each Example and Comparative Example obtained as described above were stored at 20°C for 24 hours and then visually inspected. The blooming was evaluated according to the following evaluation criteria. The results are shown in Table 3. (Evaluation criteria) A: No bleeding of the cleaning material. B: Bleeding of the cleaning material was observed.

[0077]

[0078] In each example, the generation of gas stains was suppressed compared to Comparative Examples 1 and 2. In the examples, the use of a secondary amine compound resulted in a favorable evaluation of cleaning performance. Furthermore, in the examples, it was confirmed that excellent blooming resistance was achieved by setting the amount of the amine compound to 15 parts by mass or less per 100 parts by mass of the total of the main materials, EPR and BR.

[0079] The disclosure of PCT / JP2023 / 027450, filed July 26, 2023, is incorporated herein by reference in its entirety. All publications, patent applications, and technical standards mentioned herein are incorporated herein by reference to the same extent as if each individual publication, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A cleaning composition comprising: a main component of the cleaning composition; and an amine compound which does not contain an amino group at the end of the molecular chain, and which contains an amino group at a position other than the end of the molecular chain.

2. A detergent composition comprising: a reinforcing material for a detergent composition; and an amine compound which does not contain an amino group at the end of the molecular chain and contains an amino group at a position other than the end of the molecular chain.

3. A cleaning composition for cleaning a mold for molding a thermosetting resin, which contains an amine compound that does not contain an amino group at the end of the molecular chain and contains an amino group at a position other than the end of the molecular chain.

4. The cleaning composition according to any one of claims 1 to 3, wherein the amine compound comprises at least one compound selected from the group consisting of secondary amine compounds and tertiary amine compounds.

5. The cleaning composition according to claim 4, wherein the amine compound includes a secondary amine compound, and the secondary amine compound is at least one selected from the group consisting of methylethanolamine, ethylethanolamine, propylethanolamine, butylethanolamine, dimethylamine, diisopropanolamine and diethanolamine.

6. The cleaning composition according to any one of claims 1 to 3, wherein the amine compound contains only one hydroxy group.

7. A cleaning composition according to any one of claims 1 to 6, wherein the content of the amine compound is less than 20 parts by mass per 100 parts by mass of the main material.

8. A cleaning material obtained by molding the cleaning composition according to any one of claims 1 to 7.

9. A method for cleaning a molding die, comprising the steps of: placing the cleaning material according to claim 8 into an open molding die; clamping the molding die to sandwich the cleaning material therebetween, and applying heat and pressure; and peeling the cleaning material from the molding die.

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