WO2024062659A1 - 離型剤兼潤滑剤組成物、被膜の成形方法および乾性被膜 - Google Patents

離型剤兼潤滑剤組成物、被膜の成形方法および乾性被膜 Download PDF

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WO2024062659A1
WO2024062659A1 PCT/JP2023/010640 JP2023010640W WO2024062659A1 WO 2024062659 A1 WO2024062659 A1 WO 2024062659A1 JP 2023010640 W JP2023010640 W JP 2023010640W WO 2024062659 A1 WO2024062659 A1 WO 2024062659A1
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Prior art keywords
release agent
lubricant composition
mold release
mold
polybutadiene
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English (en)
French (fr)
Japanese (ja)
Inventor
幹典 鈴木
圭司 伊澤
真 石川
宏和 高木
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Yushiro Inc
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Yushiro Chemical Industry Co Ltd
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Priority to CN202380067839.4A priority Critical patent/CN119907739A/zh
Priority to US19/113,516 priority patent/US20260098183A1/en
Priority to KR1020257012897A priority patent/KR20250073276A/ko
Priority to JP2024548069A priority patent/JPWO2024062659A1/ja
Publication of WO2024062659A1 publication Critical patent/WO2024062659A1/ja
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
    • B29C33/60—Releasing, lubricating or separating agents
    • B29C33/62—Releasing, lubricating or separating agents based on polymers or oligomers
    • B29C33/64—Silicone
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
    • B29C33/58—Applying the releasing agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/06—Fibrous reinforcements only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/08—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of continuous length, e.g. cords, rovings, mats, fabrics, strands or yarns
    • B29K2105/0872—Prepregs

Definitions

  • the present invention relates to a mold release agent and lubricant composition suitable for molding of fiber reinforced plastics (FRP) and the like.
  • mold release agent In molding, a mold release agent is used to prevent the workpiece from sticking to the tool or mold.
  • Conventionally used mold release agents include silicone oil, perfluoropolyether, and fluororesin (polytetrafluoroethylene) powder dissolved or dispersed in a solvent alone or in combination; Some compounds are emulsified or dispersed in water by adding a surfactant to the compound.
  • thermosetting resins have traditionally been mainly used, but thermoplastic resins are now being used as the application expands to automobiles, which require mass production. , the speed of molding processing is progressing (Patent Document 1).
  • Patent Document 2 As a release agent/lubricant having excellent heat resistance and repetitive molding processability, there is a release agent composition containing a styrene-diene block copolymer, a functional silicone, a solvent, and optionally one or both of a catalyst and a crosslinking agent (Patent Document 2).
  • Patent Document 2 in order to increase the resistance of the formed coating and improve the repetitive molding processability, a functional silicone is applied and a crosslinking reaction is promoted by a catalyst or a crosslinking agent.
  • the release agent composition of Patent Document 2 improves heat resistance, lubricity, and release property in a one-time use, it is not sufficient to improve the repetitive molding processability.
  • a functional silicone and the crosslinking reaction by a catalyst or a crosslinking agent contribute to the hardening of the formed coating made of the release agent composition, they are not synonymous with the improvement of the adhesion of the release agent coating to the tool or die required in repetitive molding, and there is a limit to repetitive molding.
  • a mold baking release agent in which amino-modified silicone, blocked polyisocyanate, and polyol are dissolved or dispersed in a liquid can form a coating with excellent releasability and adhesion in a short time at a low baking temperature of 150°C or less (Patent Document 3).
  • the coating contains urethane bonds with low heat resistance, there are issues with heat resistance during repeated molding.
  • the purpose of the present invention is to have excellent lubricity and mold release properties, high heat resistance, prevent seizure between the workpiece and the mold, and maintain good contact between the workpiece and the mold even after repeated molding.
  • An object of the present invention is to provide a mold release agent/lubricant composition having good mold release properties.
  • the adhesion of the mold release agent coating is improved, they have discovered that it functions as a mold release agent and lubricant composition, and have completed the present invention.
  • the mold release agent and lubricant composition of the present invention comprises a silicone resin whose main constituent unit is a T unit represented by RSiO 3/2 (R represents an organic functional group), and liquid 1,2-polybutadiene. , and a solvent.
  • the molding method of the present invention is characterized by comprising step 1 of applying a release agent/lubricant composition containing a silicone resin having T units represented by RSiO3 /2 (R represents an organic functional group) as its main constituent unit, liquid 1,2-polybutadiene, and a solvent to a mold to form a coating film, and step 2 of heating and curing the coating film at 100 to 400°C for 3 to 60 minutes to form a dry coating on the surface of the mold.
  • the dry coating of the present invention is characterized by comprising a release agent/lubricant composition containing a silicone resin having T units represented by RSiO3 /2 (R represents an organic functional group) as its main constituent unit, liquid 1,2-polybutadiene, and a solvent.
  • the mold release agent/lubricant composition further contains a drying oil.
  • the content of the drying oil is preferably 20% by weight or less based on the total amount of the drying oil and liquid 1,2-polybutadiene. It is preferable that the mold release agent/lubricant composition further contains a radical polymerization initiator.
  • the workpiece material is plastic, glass, synthetic fiber, wood, rubber, stone, cement, concrete, ceramic, or a composite material of two or more of these materials. The workpiece material is particularly effective for fiber-reinforced plastics.
  • the mold release agent and lubricant composition of the present invention is characterized in that a lubricant containing a silicone resin whose main constituent units are T units and liquid 1,2-polybutadiene undergoes intramolecular and intermolecular radical polymerization reactions. Forms a network structure and has high adhesion. Therefore, a dry film formed in a mold using such a mold release agent/lubricant composition has high heat resistance and strength, and is resistant to deterioration or breakage even during repeated molding. Further, even when the mold release agent and lubricant composition of the present invention is used for molding a workpiece, no toxic gas is generated.
  • the formed dry film has high heat resistance and strength, and does not easily deteriorate even after repeated molding, so it is possible to mold various workpiece materials, such as plastics, glass, synthetic fibers, wood, It is possible to provide a mold release agent/lubricant composition suitable for molding processing of rubber, stone, cement, concrete, ceramic, or composite materials of two or more of these materials, especially fiber-reinforced plastics.
  • FIG. 1 is a diagram showing a method for evaluating the film strength of a mold release agent/lubricant composition by a reciprocating sliding friction test.
  • FIG. 2 is a diagram showing a method of evaluating the heat resistance of a formed film by visually confirming the transfer of a test material to a test plate during repeated molding by a press test.
  • the mold release agent and lubricant composition of the present invention comprises a silicone resin whose main constituent unit is a T unit represented by RSiO 3/2 (R represents an organic functional group), liquid 1,2-polybutadiene, and a solvent. Contains.
  • Silicone resins consist of silicon bonded to organic functional groups, with the basic silicon having four bonds.
  • the skeletal structure of silicone is divided into four basic units according to the number of oxygen atoms bonded to silicon (the number of 4-organic functional groups R): M units (monofunctional; RR'R"SiO 1/2 ), D units (bifunctional; RR'SiO 2/2 ), T units (trifunctional; RSiO 3/2 ), and Q units (tetrafunctional; SiO 4/2 ).
  • R is an organic functional group
  • R' and R" are organic functional groups that contain hydrogen atoms.
  • Silicone resin has a structure in which the above four basic units are combined. Its molecular structure is linear, cyclic, branched, or three-dimensional network, and the T units form a three-dimensional network structure by branching or entanglement. Note that silicone resins containing Q units have a branched structure, and silicone resins containing M units and D units have a linear structure. In the present invention, among these, a silicone resin whose main constituent unit is a T unit in which one organic functional group is attached to silicon (hereinafter also referred to as "T-type silicone resin”) is used.
  • T-type silicone resin a silicone resin whose main constituent unit is a T unit in which one organic functional group is attached to silicon
  • R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms.
  • the hydrocarbon group includes linear hydrocarbon groups and cyclic hydrocarbon groups.
  • the linear hydrocarbon groups are alkyl groups and alkenyl groups, and the cyclic hydrocarbon groups are phenyl groups. Of these, alkyl groups that do not have unsaturated bonds, specifically methyl groups, are preferred.
  • Some of the hydrogen atoms of the hydrocarbon group may be substituted with nitro groups, sulfo groups, or amino groups, as long as the effect of the present invention is not impaired.
  • T-type silicone resin is a copolymer consisting of (CH 3 ) 2 HSiO 1/2 units, (CH 3 ) 3 SiO 1/2 units, and (CH 3 )SiO 3/2 units, (CH 3 ) 2 HSiO Copolymer consisting of 1/2 units and (CH 3 )SiO 3/2 units, (CH 3 ) 2 HSiO 1/2 units, (CH 3 )SiO 3/2 units, and (C 6 H 5 ) 3 SiO Examples include copolymers consisting of 1/2 units.
  • Liquid 1,2-polybutadiene is a polybutadiene with vinyl-type double bonds. Liquid 1,2-polybutadiene is preferably composed only of monomer units with vinyl-type double bonds. Because liquid 1,2-polybutadiene has many double bonds in its side chains, it generates a large amount of radicals, and a network structure can be formed by the polymerization reaction between silicone resin and 1,2-polybutadiene.
  • liquid 1,2-polybutadiene as used herein includes 1,2-polybutadiene glycol having a hydrogen (-H) or hydroxyl group (-OH) at the end.
  • the number average molecular weight (Mn) of liquid 1,2-polybutadiene is usually 500 to 100,000, preferably 500 to 10,000, more preferably 500 to 5,000, and particularly preferably 500 to 3,000.
  • B-1000 terminal structure H, number average molecular weight (Mn) 1200, viscosity (45°C) 1000 mPa ⁇ s
  • B-3000 terminal structure H, number average molecular weight (Mn) 3200, viscosity (45 °C) 21,000 mPa ⁇ s
  • G-3000 terminal structure OH, number average molecular weight (Mn) 3,000, viscosity (45°C) 31,000 mPa ⁇ s)
  • polybutadiene A to C are all Nippon Soda ( Co., Ltd.).
  • the content ratio of the T-type silicone resin and liquid 1,2-polybutadiene is usually 0.2 to 5 parts by weight of the T-type silicone resin. 2 parts by weight, preferably 0.3 to 1 part by weight.
  • the solvent for dissolving the T-type silicone resin and liquid 1,2-polybutadiene is not limited as long as these compounds can be dissolved, but examples include propylene glycol monomethyl ether acetate (PGMAC), isohexane, and dipropylene glycol.
  • PGMAC propylene glycol monomethyl ether acetate
  • Commercially available solvents such as dimethyl ether, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane and 2,3-dimethylbutane, toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, solvent naphtha, etc. It can be used as is.
  • the amount of dilution with the solvent is appropriately determined depending on the film thickness (thickness of the dry film) and coating method.
  • the film thickness is usually 1 to 10 ⁇ m, preferably 2 to 5 ⁇ m.
  • the T-type silicone resin and liquid 1,2-polybutadiene react, specifically, undergo a radical polymerization reaction to form a strong network structure between and within molecules, The adhesion of the release agent coating can be improved.
  • the mold release agent/lubricant composition further contains a drying oil in addition to the T-type silicone resin and liquid 1,2-polybutadiene.
  • the drying oil has an iodine value (IV) of 130 or more, and is an oil that forms a film and solidifies by taking in oxygen from the air and reacting with it.
  • the iodine value is the number of grams of iodine that can be added to 100 g of fats and oils, and a large value indicates a high content of unsaturated fatty acids.
  • Drying oils are, for example, linseed oil (IV 170-204) and tung oil (IV 155-175). Drying oils can generate radicals at lower temperatures than liquid 1,2-polybutadiene. Since this drying oil promotes the generation of radicals in liquid 1,2-polybutadiene, a dry film can be formed even at lower temperatures.
  • the content of the drying oil is preferably 20% by weight or less, more preferably 5 to 20% by weight, based on the total amount of the drying oil and liquid 1,2-polybutadiene.
  • the mold release agent/lubricant composition has excellent heat resistance, lubricity, and mold release properties, and its dry film does not deteriorate or break even after repeated molding. becomes less likely to occur. If the content of drying oil is too large relative to the total amount of drying oil and liquid 1,2-polybutadiene, the required film strength may not be obtained.
  • the mold release agent/lubricant composition further contains a radical polymerization initiator.
  • a radical polymerization initiator either a photopolymerization initiator or a thermal polymerization initiator can be used.
  • Photopolymerization initiators include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, benzyl and thioxanthone.
  • Specific examples include benzophenone, benzyl dimethyl ketal, 2,2-diethoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 3,3-dimethyl-4-methoxy-benzophenone, p- Isoamyl dimethylaminobenzoate, ethyl p-dimethylaminobenzoate, p-methoxybenzophenone, 1-hydroxycyclohexylphenyl ketone, methylphenylglyoxylate, ethylphenylglyoxylate, 2-hydroxy-2-methyl-1-phenylpropane -1-one and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide.
  • Thermal polymerization initiators include azo compounds and organic peroxides.
  • Azo compounds include azobisisobutyronitrile, dimethyl 2,2'-azobis(2-methylpropionate), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis( isobutyronitrile), 2,2'-azobis-2-methylbutyronitrile, 1,1'-azobis(1-cyclohexanecarbonitrile), 2,2'-azobis(methylisobutyrate) and 2,2 Examples include '-azobis(2-amidinopropane) dihydrochloride.
  • Organic peroxides include dicumyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, t-butyl hydroperoxide, benzoyl peroxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, p -Menthane hydroperoxide, di-t-butyl peroxide and the like.
  • the content of the radical polymerization initiator is not particularly limited, but is approximately 0.01 to 0.5% by weight, preferably 0.01 to 0.1% by weight, based on the total weight of the mold release agent and lubricant composition. Weight%. Within this range, both the curing speed of the release agent and lubricant composition and the strength of the film are excellent. If the content of the radical polymerization initiator is too small, a sufficient effect of lowering the film formation temperature and shortening the reaction time cannot be exhibited, and if the content is too large, the reaction is not promoted, so there is no cost advantage.
  • the release agent/lubricant composition of the present invention is applied to the necessary parts of a mold, heated and cured to form a dry film, and used in molding of plastic, glass, synthetic fiber, wood, rubber, stone, cement, concrete, ceramic, or a composite material of two or more of these materials as the workpiece (target material).
  • the release agent/lubricant composition is particularly suitable for molding composite materials in which fibers such as carbon fiber or glass fiber are added to plastic to improve their strength, so-called fiber-reinforced plastics (FRP).
  • the method for forming the dry coating includes step 1 of applying the release agent/lubricant composition to a mold to form a coating film, and step 2 of heating and curing the coating film at 100 to 400°C for 3 to 60 minutes to form a dry coating on the surface of the mold.
  • RTM resin transfer molding
  • FRP fiber reinforced plastic
  • RTM is a molding method in which the above-described FRP base material such as carbon fiber or glass fiber is placed in a mold, and then resin is injected and cured, and it consists of a shaping process 1 and a molding process 2.
  • process 1 a fabric made of carbon fiber or glass fiber is cut into a predetermined shape, arranged in the same position and direction, and the preform shaped into the product shape is passed through the cavity (female mold) and core (male mold). Place it in a mold.
  • a mold release agent/lubricant composition is applied to the surfaces of the mold cavity and core, and heated and cured in a drying oven or direct flame to form a dry film inside the mold.
  • the resin and curing agent are mixed and injected into the mold at high pressure, and the resin is poured between the fibers of the preform to fill the mold with the resin while heating and curing to obtain a molded product.
  • molding processes for fiber-reinforced plastics include autoclave molding, press molding, sheet winding molding, filament winding molding, continuous pultrusion molding, and injection molding, and the release agent/lubricant composition of the present invention can be suitably used in any of these molding processes.
  • the test was repeated until peeling was observed, and the heat resistance was evaluated.
  • the heat resistance was evaluated as A when the number of molding was 8 times, B when it was molded 4 to 7 times, and C when it was molded 3 times or less.
  • Example 1 A release agent and lubricant composition was prepared by mixing 10 parts by weight of X-48-1030 (T-type silicone resin, manufactured by Shin-Etsu Chemical Co., Ltd.), 0.25 parts by weight of B-1000 (liquid 1,2-polybutadiene, manufactured by Nippon Soda Co., Ltd.), and 89.75 parts by weight of propylene glycol monomethyl ether acetate.
  • the release agent/lubricant composition was applied to a mold and heated at 200° C. for 20 minutes to form a dry coating, and the coating strength, heat resistance and transferability were evaluated.
  • the amounts of each component of the release agent/lubricant composition and the evaluation results are shown in Table 2.
  • Examples 2 to 8 A mold release agent and lubricant composition was prepared in the same manner as in Example 1 by mixing T-type silicone resin, liquid 1,2-polybutadiene, solvent, and other components in the types and amounts shown in Tables 2 and 3. did. A dry film of the release agent/lubricant composition was formed under the same conditions as in Example 1, and the film strength, heat resistance, and transferability were evaluated.
  • Example 6 X-48-5030 (T-type silicone resin, Shin-Etsu Chemical Co., Ltd.) was irradiated with UV light because UV irradiation is recommended.
  • the release agent and lubricant composition was applied to a mold and heated at 200°C for 20 minutes, and at the same time, a black light (MidBeam 2.0) was used to irradiate with UV light (accumulated light amount 2824 (mJ/ cm2 )) to form a dry coating.
  • Example 9 to 11 In the amounts shown in Tables 2 and 3, , and propylene glycol monomethyl ether acetate were mixed to prepare a mold release agent/lubricant composition.
  • the mold release agent and lubricant composition was applied to a mold, and heated at 150 ° C. for 20 minutes in Example 9, 100 ° C. for 60 minutes in Example 10, and 180 ° C. for 20 minutes in Example 11, A dry film was formed, and film strength, heat resistance, and transferability were evaluated.
  • Table 2 or Table 3 shows the amount of each component in the mold release agent/lubricant composition and the evaluation results.
  • Example 12 10 parts by weight of X-48-1030 (manufactured by Shin-Etsu Chemical Co., Ltd.), 0.7 parts by weight of B-1000 (liquid 1,2-polybutadiene, manufactured by Nippon Soda Co., Ltd.), 0.3 parts by weight of linseed oil, and 89 parts by weight of propylene glycol monomethyl ether acetate were mixed to prepare a release agent/lubricant composition.
  • the mold release agent/lubricant composition was applied to a mold and heated at 150° C. for 20 minutes to form a dry film, and the film strength, heat resistance, and transferability were evaluated. Table 3 shows the amount of each component in the mold release agent/lubricant composition and the evaluation results.
  • X-48-1030 T-type silicone resin, manufactured by Shin-Etsu Chemical Co., Ltd. 10 parts by weight, B-1000 (liquid 1,2-polybutadiene, manufactured by Nippon Soda Co., Ltd.) 1 part by weight, 2,2'- A release agent and lubricant composition was prepared by mixing 0.05 parts by weight of dimethyl azobis(2-methylpropionate) (manufactured by Tokyo Chemical Industry Co., Ltd.) and 88.95 parts by weight of propylene glycol monomethyl ether acetate. .
  • the mold release agent/lubricant composition was applied to a mold and heated at 200° C. for 5 minutes to form a dry film, and the film strength, heat resistance, and transferability were evaluated. Table 3 shows the amount of each component in the mold release agent/lubricant composition and the evaluation results.
  • Example 14 to 16 A mold release agent and lubricant composition was prepared in the same manner as in Example 13, except that the radical polymerization initiator and propylene glycol monomethyl ether acetate were changed to the types and amounts shown in Table 3.
  • the mold release agent and lubricant composition was applied to a mold, and heated at 300°C for 5 minutes in Example 14, 400°C for 3 minutes in Example 15, and 150°C for 10 minutes in Example 16, A dry film was formed, and film strength, heat resistance, and transferability were evaluated.
  • UV irradiation was applied using a black light (MidBeam 2.0) with an integrated light amount of 9414 (mJ/cm 2 ). Table 3 shows the amount of each component in the mold release agent/lubricant composition and the evaluation results.
  • Example 17 X-48-1030 (T-type silicone resin, manufactured by Shin-Etsu Chemical Co., Ltd.) 10 parts by weight, B-1000 (liquid 1,2-polybutadiene, manufactured by Nippon Soda Co., Ltd.) 0.9 parts by weight, linseed oil 0 .1 part by weight, 0.05 part by weight of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (manufactured by Tokyo Chemical Industry Co., Ltd.), and 88.95 parts by weight of propylene glycol monomethyl ether acetate were mixed and separated. A mold agent and lubricant composition was prepared. The mold release agent/lubricant composition was applied to the mold and heated at 150° C.
  • UV irradiation was performed using a black light (MidBeam 2.0) [total light amount 4707 (mJ/cm 2 )].
  • a dry film was formed and the film strength, heat resistance and transferability were evaluated.
  • Table 3 shows the amount of each component in the mold release agent/lubricant composition and the evaluation results.
  • Example 18 A mold release agent/lubricant composition was prepared in the same manner as in Example 2, except that isohexane was used instead of propylene glycol monomethyl ether acetate. A dry film of the release agent/lubricant composition was formed under the same conditions as in Example 1, and the film strength, heat resistance, and transferability were evaluated. The results are shown in Table 3.
  • Tables 2 and 3 show the amount of each component in the mold release agent/lubricant composition and the evaluation results.
  • the release agent and lubricant compositions of Examples 1 to 18 exhibited sufficient performance in terms of film strength, transferability, and heat resistance.
  • Test example 1 The mold release agent/lubricant composition of Example 2 was applied to a mold made of S55C (carbon steel), dried, and heat-treated at 200° C. for 20 minutes. A mixture of Home Jaricon (Kashima Concrete Transportation Co., Ltd.) and water was poured into the formwork in advance to a thickness of 5 mm, and the mold was dried at 70°C for 24 hours. After cooling, the concrete was removed from the formwork, and the state of transfer of the mold release agent/lubricant composition to the concrete was visually confirmed to evaluate the durability of the film (repeated molding). The mold release agent/lubricant composition of Example 2 withstood eight uses and had sufficient resistance to repeated molding operations.
  • Test Example 2 As in Test Example 1, the mold release agent/lubricant composition of Example 2 was applied to a mold made of S55C, dried, and heat-treated at 200° C. for 20 minutes.
  • General-purpose polystyrene (GPPS) manufactured by PS Japan Co., Ltd.
  • GPPS General-purpose polystyrene
  • the resin molded product was removed from the mold, and the state of transfer of the mold release agent/lubricant composition to the resin molded product was visually confirmed to evaluate the durability of the film (repeated molding).
  • the mold release agent/lubricant composition of Example 2 withstood eight uses and had sufficient resistance to repeated molding operations.
  • a mold release agent composition was prepared by mixing 10 parts by weight of X-48-1030 (manufactured by Shin-Etsu Chemical Co., Ltd.) and 90 parts by weight of propylene glycol monomethyl ether acetate. The mold release agent composition was applied to a mold and heated at 200° C. for 20 minutes to form a film, and the film strength, heat resistance, and transferability were evaluated. In the mold release agent composition of Comparative Example 1 in which liquid 1,2-polybutadiene was not added, the film did not form a network structure and did not maintain sufficient film strength.
  • a mold release agent composition was prepared by mixing silicone resin, polybutadiene, and propylene glycol monomethyl ether acetate in the types and amounts shown in Table 4.
  • a film was formed in the same manner as in Comparative Example 1, and the film strength, heat resistance, and transferability were evaluated.
  • Comparative Example 2 which used MQ-type silicone resin instead of T-type silicone resin, did not exhibit any effect.
  • Comparative Example 3 in which 1,4-polybutadiene was used instead of liquid 1,2-polybutadiene, the radical polymerization reaction did not proceed and the film was insufficiently cured, so the film strength and heat resistance were rated B.
  • a mold release agent composition was prepared by mixing the following parts. A film was formed in the same manner as in Comparative Example 1, and the film strength, heat resistance, and transferability were evaluated. In Comparative Example 4 in which modified silicone oil was used instead of silicone resin, the release agent was transferred to the test material due to an oily film, and the heat resistance was poor.
  • VISPAC 1210 polyisobutylene, manufactured by Souken Co., Ltd.
  • paraffinic mineral oil kinematic viscosity 46 mm 2 /s, 40°C
  • solvent naphtha 80.0 parts by weight X-48-
  • a mold release agent composition was prepared by mixing 10 parts by weight of 1030 (T-type silicone resin, manufactured by Shin-Etsu Chemical Co., Ltd.).
  • a film was formed in the same manner as in Comparative Example 1, and the film strength, heat resistance, and transferability were evaluated.
  • Comparative Example 5 in which the same thermoplastic polymer polyisobutylene was used instead of liquid 1,2-polybutadiene, the curing of the molded film was not promoted, resulting in poor heat resistance and poor transferability.
  • a mold release agent composition was prepared by mixing the components shown in Table 5. A film was formed using the obtained mold release agent composition under the conditions shown in Table 5, and the film strength, heat resistance, and transferability were evaluated.
  • the composition of Patent Document 1 Japanese Unexamined Patent Publication No. 2014-70080
  • a mold release agent composition was prepared by mixing .2 parts by weight.
  • a film was formed using the obtained mold release agent composition under the conditions shown in Table 5, and the film strength, heat resistance, and transferability were evaluated.
  • the composition of Patent Document 2 Japanese Patent Publication No. 2009-519849 was inferior in transferability and heat resistance.
  • Comparative Examples 9 to 11 In Comparative Example 9, DRYFILM RA (PTFE + HFC alternative, manufactured by DuPont, USA), in Comparative Example 10, Chemlease AF-7EZ (fluorine + silicone, manufactured by Chemtrend Japan, Inc.), and in Comparative Example 11, Chemlease HT-S (fluorine + silicone, manufactured by Chemtrend Japan, Inc.) were used to form a coating under the conditions shown in Table 5, and the coating strength, heat resistance, and transferability were evaluated.
  • DRYFILM RA PTFE + HFC alternative, manufactured by DuPont, USA
  • Chemlease AF-7EZ fluorine + silicone, manufactured by Chemtrend Japan, Inc.
  • Chemlease HT-S fluorine + silicone, manufactured by Chemtrend Japan, Inc.
  • the commercially available mold release agent compositions of Comparative Examples 9 to 11 cannot be repeatedly molded.
  • the mold release agent/lubricant composition of the present invention has excellent repeatable moldability.
  • Tables 4 and 5 show the amount of each component in the mold release agent composition and the evaluation results.
  • Silicone resin A X-48-1030 (Shin-Etsu Chemical Co., Ltd., active ingredient: approx. 50%)
  • Silicone resin B X-40-2756 (Shin-Etsu Chemical Co., Ltd.), active ingredient: 100%)
  • Silicone resin C X-48-5030 (Shin-Etsu Chemical Co., Ltd.), active ingredient: 100%)
  • Silicone resin D WACHER 1038 (manufactured by Wacker Asahi Kasei Silicone Co., Ltd.)
  • Silicone resin E DOWSIL RSN-6018 (Resin Intermediate, manufactured by Dow Toray Co., Ltd.)
  • Polybutadiene D POLYVEST 130 (1,4-polybutadiene, manufactured by Evonik Japan Co., Ltd., viscosity 3000 mPa ⁇ s, 20° C.)
  • Radical polymerization initiator A dimethyl 2,2'-azobis(2-methylpropionic acid) (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • Radical polymerization initiator B di-tert-butyl peroxide (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • Radical polymerization initiator C phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide) (manufactured by Tokyo Kasei Kogyo Co., Ltd.)
  • Silicone oil A TSF4421 (modified silicone oil, manufactured by Momentive Performance Materials Japan)
  • Silicone oil B XIAMETER SH203 (alkyl modified silicone oil, manufactured by Dow Toray Industries, Inc.)
  • Polyisobutylene VISPAC 1210 (adhesion improver, manufactured by Souken Co., Ltd.)
  • Mineral oil A Paraffinic mineral oil, equivalent to ISO VG46
  • Mineral oil B Paraffinic mineral oil, equivalent to ISO VG460
  • Styrene-diene block copolymer (G-1651EU, manufactured by Clayton Corporation)
  • Silane coupling agent SILQUEST A-1122 SILANE (manufactured by Nisso Sangyo Co., Ltd.)
  • Tetrabutyl orthotitanate manufactured by Tokyo Chemical Industry Co., Ltd.
  • DRYFILM RA PTFE + CFC substitute HFC, manufactured by DuPont, USA
  • Chemlease AF-7EZ fluorine + silicone, Chem Trend Japan Co., Ltd.
  • Chemlease HT-S fluorine + silicone, Chem Trend Japan Co., Ltd.

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PCT/JP2023/010640 2022-09-21 2023-03-17 離型剤兼潤滑剤組成物、被膜の成形方法および乾性被膜 Ceased WO2024062659A1 (ja)

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US19/113,516 US20260098183A1 (en) 2022-09-21 2023-03-17 Release agent and lubricant composition, method for forming coating film, and dry coating film
KR1020257012897A KR20250073276A (ko) 2022-09-21 2023-03-17 이형제 겸 윤활제 조성물, 피막의 성형 방법 및 건성 피막
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4843378B1 (https=) * 1970-12-29 1973-12-18
JPS62149193A (ja) * 1985-09-27 1987-07-03 宇部興産株式会社 スル−ホ−ルメツキ配線板の製法
JPH0516146A (ja) * 1991-07-16 1993-01-26 Olympus Optical Co Ltd プラスチツク成形用金型の製造方法
JP2001200114A (ja) * 2000-01-17 2001-07-24 Japan Polyolefins Co Ltd ラミネート用樹脂組成物および積層体並びにその製造方法
JP2022096673A (ja) * 2020-12-18 2022-06-30 松本油脂製薬株式会社 ゴム製品の成型加硫用離型剤組成物及びその利用

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US20070141362A1 (en) 2005-12-19 2007-06-21 Elkins Casey L Composition for coating substrate to prevent sticking
JP6002523B2 (ja) 2012-09-27 2016-10-05 Ｊｘエネルギー株式会社 潤滑剤組成物およびそれを用いた成形方法
JP6869480B2 (ja) 2018-08-31 2021-05-12 複合資材株式会社 焼付型離型剤

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4843378B1 (https=) * 1970-12-29 1973-12-18
JPS62149193A (ja) * 1985-09-27 1987-07-03 宇部興産株式会社 スル−ホ−ルメツキ配線板の製法
JPH0516146A (ja) * 1991-07-16 1993-01-26 Olympus Optical Co Ltd プラスチツク成形用金型の製造方法
JP2001200114A (ja) * 2000-01-17 2001-07-24 Japan Polyolefins Co Ltd ラミネート用樹脂組成物および積層体並びにその製造方法
JP2022096673A (ja) * 2020-12-18 2022-06-30 松本油脂製薬株式会社 ゴム製品の成型加硫用離型剤組成物及びその利用

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