Classifications

• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/15—Heterocyclic compounds having oxygen in the ring
  • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
  • C08K5/1545—Six-membered rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
  • C08L71/02—Polyalkylene oxides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
  • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
• • 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
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
  • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxy groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
  • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2483/00—Characterised by the use 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; Derivatives of such polymers
  • C08J2483/04—Polysiloxanes

Definitions

• the present invention relates to a mold release agent for plastics, which is an emulsion composition of organopolysiloxane.
• plastics for food containers and packaging such as PET, PP, and PS are used depending on the type of food and the storage temperature.
• Plastic for food containers and packaging is molded into a sheet or film in the manufacturing process and then wound into a roll. Normally, when winding on a roll, a mold release agent is applied to the surface of the sheet or film to prevent the sheets or films from adhering to each other.
• molded products such as cases, trays, and cups in which sheets and films are molded are stored in layers, but if a mold release agent is applied to them, they can be removed one by one smoothly without blocking.
• an emulsion composition of an organopolysiloxane having a viscosity of 100 to 100,000 mm 2 / s is suitable as a mold release agent for synthetic resins for food containers and packaging.
• an organopolysiloxane emulsion composition to plastic as a mold release agent, dilute the organopolysiloxane concentration with water to 0.1-5.0% and use rotary dampening, gravure method or spray. Apply by the method.
• the emulsion itself may be destroyed, causing gel or oil floating.
• an emulsion is applied to plastics in a state where gel or oil floats, uneven wetting occurs, and problems such as adhesion between plastics and uneven appearance occur.
• the Sanitary Council for Polyethylene, etc. has established raw materials that can be used for plastics such as containers and packaging that come into direct contact with food (positive list system), and safety has been confirmed for the use of containers and packaging that come into direct contact with food. It is recommended to use raw materials. Therefore, an emulsion of organopolysiloxane that can use the raw materials listed on the positive list of the Sanitary Council for Polyethylene and the like and can solve the above-mentioned objective problems is desired as a mold release agent for plastics for food containers and packaging.
• Patent Document 1 is an organopolysiloxane emulsion release agent composition having excellent wettability and good transparency.
• the average particle size is as large as 200 nm or more, the dilution stability and the mechanical stability may be inferior.
• polyoxyethylene nonylphenyl ether sodium sulfate is used as an anionic surfactant, but since it is a concern as an environmentally hazardous substance, it should not be used as a mold release agent for plastics used for food containers and packaging. Not recommended.
• Patent Document 2 is a silicone release agent composition with less whitening of the film.
• the composition of Patent Document 2 includes propylene glycol.
• polyoxyethylene lauryl ether is used alone as the nonionic emulsifier, but when the nonionic emulsifier is used alone, the average particle size may not be fine and the stability may be poor.
• those having a polyoxyethylene chain of 1 to 6 may cause cracks in the synthetic resin, particularly PS and OPS, and therefore, even in the emulsion of the example of Patent Document 2. When used as a release agent for PS or OPS, cracks may occur.
• Patent Document 3 is an emulsion containing phenoxyethanols when emulsified, which has a narrow particle size distribution and excellent stability. However, the average particle size of all the examples is as large as 1 ⁇ m or more, and the dilution stability and mechanical stability are excellent. Expected to be low.
• Patent Document 4 is an alkyl aralkyl co-modified silicone emulsion release agent for aluminum die casting.
• Alkyl aralkyl covariant silicone has a lower mold release property with respect to plastic than dimethylpolysiloxane, and is not suitable as a mold release agent for plastics.
• Patent Document 5 is a silicone water-dispersed mold release agent composition in which a sorbitan higher alkyl ester and other nonionic surfactant, which are preferably used during vulcanization molding of acrylic rubber, are used in combination. It is said that when an anionic surfactant is added to a silicone emulsion, the negative value of the zeta potential of the emulsion becomes large and the electron repulsion between the emulsion particles becomes strong, so that it is difficult to aggregate and the mechanical stability is improved. Patent Document 5 does not contain an anionic surfactant, and it is expected that the mechanical stability is low.
• Patent Document 6 is an emulsion obtained by emulsifying an organopolysiloxane with a polyoxyethylene alkyl ether having an HLB of 10 or higher. Similar to Patent Document 5, there is no anionic surfactant compounded, and it is expected that the mechanical stability is low.
• Patent Document 7 is a silicone emulsion composition containing an organopolysiloxane, a polyoxyethylene alkyl ether having an alkyl chain having 8 to 11 carbon atoms, and an anionic surfactant. Emulsions containing polyoxyethylene alkyl ethers having 8 to 11 carbon atoms may crack when applied to plastics.
• Patent Document 8 is a silicone emulsion composition obtained by emulsifying organopolysiloxane with polyoxyethylene alkyl ether and sucrose fatty acid ester.
• polyoxyethylene (3) decyl ether is used as the polyoxyethylene alkyl ether, but the polyoxyethylene alkyl ether having 10 or less carbon atoms in the alkyl group may cause cracks in the plastic. is there.
• Patent Document 9 is a silicone emulsion obtained by emulsifying organopolysiloxane with polyoxyethylene hexyl decyl ether or polyoxyethylene isostearyl ether.
• the average particle size is about 400 nm, which is relatively large, and there is a risk that dilution stability and mechanical stability may be poor.
• Patent Document 10 is an emulsion obtained by emulsifying organopolysiloxane with an anionic surfactant and a polyhydric alcohol.
• anionic surfactants and polyhydric alcohols have a lower function of lowering surface tension than nonionic surfactants such as polyoxyethylene alkyl ethers.
• the emulsion of Patent Document 10 is diluted 50 times with water, the surface tension (25 ° C.) is as high as 45 dyne / cm or more, and since it does not contain a nonionic surfactant, it has poor wettability when applied to plastic. May occur.
• the present invention has been made in view of the above circumstances, and is a mold release agent for plastics, which is an emulsion of an organopolysiloxane that has excellent dilution stability, mechanical stability, good wettability, and is less likely to crack the plastic.
• the purpose is to provide.
• the present invention provides a mold release agent for plastics, which contains the following components (A) to (E) and has an average particle size of 200 nm or less.
• (A) Organopolysiloxane having a viscosity at 25 ° C. of 100 to 100,000 mm 2 / s, represented by the following general formula (1): 100 parts by mass,
• R 1 may be the same or different, and is any of a hydroxy group, a hydrogen atom, a linear unsubstituted alkyl group having 1 to 32 carbon atoms, and a phenyl group, and L is an integer of 60 to 1500.
• each of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane is less than 3% in (A) organopolysiloxane.)
• the mold release agent for plastics of the present invention is an emulsion of an organopolysiloxane that has excellent dilution stability, mechanical stability, good wettability, and is less likely to crack the plastic. It will be possible to provide.
• the mold release agent for plastics of the present invention further contains (F) a sorbitan fatty acid ester represented by the following general formula (4) in an amount of 5.0 parts by mass or less with respect to 100 parts by mass of the (A) organopolysiloxane. It is preferable to do so.
• R 3 is an alkyl group having 12 to 22 carbon atoms.
• the content of the (F) sorbitan fatty acid ester is preferably 0.1 to 5.0 parts by mass. When the content of the (F) sorbitan fatty acid ester is within this range, cracks are less likely to occur when the mold release agent for plastics of the present invention is applied.
• the content of the (B) anionic surfactant is preferably 0.1 to 10.0 parts by mass.
• the content of the anionic surfactant (B) is within this range, the mechanical stability and releasability of the mold release agent for plastics of the present invention tend to be higher.
• the average particle size of the mold release agent for plastics is 100 nm or less.
• both dilution stability and mechanical stability tend to be good, and oil floating and the like are less likely to occur during dilution and stirring.
• the mold release agent for plastics preferably has a pH at 25 ° C. of 4.0 to 10.0. This is because such a mold release agent for plastics changes the structure of the component (A) even when stored at a high temperature, and has little effect on the mold release property for plastics.
• the mold release agent for plastics can be particularly preferably used for plastics for food containers and packaging.
• the mold release agent for plastics of the present invention does not contain environmentally hazardous substances such as nonylphenol and octylphenol, and only the raw materials approved in the "Voluntary Standards for Food Containers and Packaging Made of Synthetic Resins such as Polyolefins" for plastics of the present invention This is because the composition of the release agent can be configured, and such a release agent for plastics is suitable as a release agent for food trays and egg packs.
• the plastic since the particle size of the emulsion is fine, the plastic has good dilution stability, mechanical stability, and storage stability, has excellent wettability to the plastic, and is less likely to cause stress cracks to the plastic.
• a mold release agent can be provided. Further, the mold release agent for plastics of the present invention can be composed of the raw materials listed in the positive list provided by the Sanitary Council for Polyethylene, etc., and is suitable for food containers and packaging.
• an emulsion type release agent of organopolysiloxane which is excellent in dilution stability, mechanical stability and storage stability, has good wettability, and does not cause cracks in plastics.
• the present inventors have obtained an organopolysiloxane having a viscosity at 25 ° C. of 100 to 100,000 mm 2 / s as an anionic surfactant, polyoxyethylene alkyl ether, and the like.
• an emulsion type mold release agent having an average particle size of 200 nm or less, and the obtained release agent is diluted and stable.
• the present invention has been completed by finding that it has excellent properties, mechanical stability, storage stability, good wettability to plastics, and is less likely to cause stress cracks.
• the mold release agent for plastics of the present invention can be composed of raw materials listed on the positive list of the Sanitary Council for Polyethylene, etc., and can be safely used for containers and packaging that come into direct contact with food. It is a thing.
• the mold release agent for plastics of the present invention is a mold release agent for plastics, which contains the following components (A) to (E) and has an average particle size of 200 nm or less.
• (A) Organopolysiloxane having a viscosity at 25 ° C.
• R 1 may be the same or different, and is any of a hydroxy group, a hydrogen atom, a linear unsubstituted alkyl group having 1 to 32 carbon atoms, and a phenyl group, and L is an integer of 60 to 1500.
• each of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane is less than 3% in (A) organopolysiloxane.)
• (A) Organopolysiloxane] (A) Organopolysiloxane having a viscosity at 25 ° C. of 100 to 100,000 mm 2 / s, represented by the following general formula (1): 100 parts by mass.
• R 1 may be the same or different, and is any of a hydroxy group, a hydrogen atom, a linear unsubstituted alkyl group having 1 to 32 carbon atoms, and a phenyl group, and L is an integer of 60 to 1500.
• the content of each of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane is less than 3% in (A) organopolysiloxane.
• R 1 may be the same or different, and is any one of a linear unsubstituted alkyl group, a phenyl group, a hydroxy group, and a hydrogen atom having 1 to 32 carbon atoms.
• L is an integer from 60 to 1500, preferably 150 to 1200.
• the linear unsubstituted alkyl group having 1 to 32 carbon atoms includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, an n-decyl group, an n-dodecyl group and an n-.
• alkyl groups such as a tetradecyl group, an n-hexadecyl group, an n-octadecyl group and an eicosyl group. It is preferably a linear unsubstituted alkyl group or phenyl group having 1 to 20 carbon atoms, and more preferably a methyl group or a phenyl group from the viewpoint of versatility. Further, from the viewpoint of releasability, it is preferable that at least 50 mol% of the organic group bonded to the silicon atom in one molecule is a methyl group.
• the organopolysiloxane contains a large amount of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane, it becomes difficult to emulsify, the average particle size becomes large, or storage stability and dilution are performed. Stability and mechanical stability may decrease.
• the contents of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane in the organopolysiloxane are each less than 3%. It is preferably less than 1% each, and more preferably less than 0.1% each. The lower limit of each content is not limited, but can be, for example, 0.001%.
• the viscosity of the component (A) organopolysiloxane at 25 ° C. is 100 to 100,000 mm 2 / s. If the viscosity is less than 100 mm 2 / s, the resulting composition will not exhibit sufficient releasability.
• the minimum viscosity of dimethylpolysiloxane, methylhydrogenpolysiloxane, and methylphenylpolysiloxane registered on the positive list of the Polysyloxide Hygiene Council is 100 mm 2 / s.
• the viscosity of the organopolysiloxane of the component (A) is larger than 100,000 mm 2 / s, the surface may become sticky when applied to a film or the like. It is preferably 200 to 50,000 mm 2 / s, and more preferably 300 to 10,000 mm 2 / s.
• the organopolysiloxane of the component (A) may have a viscosity at 25 ° C. in the above range, and may be used alone or in combination of two or more.
• (B) Anionic surfactant (B) Alkyl sulfonate, alkyl benzene sulfonate, alpha olefin sulfonate, polyoxyethylene alkyl ether sulfate, alkyl ether sulfate, polyoxyethylene alkyl ether acetate, alkyl acetate, alkyl phosphate, poly One or more anionic surfactants selected from oxyethylene alkyl ether phosphate, alkyl sulfosuccinate, polyoxyethylene alkyl ether sulfosuccinate, methyl tauric acid, alaninate and salts thereof: 0.1- 15.0 parts by mass.
• the alkyl sulfonate has an alkyl group having 10 to 20 carbon atoms, and the salts are sodium, potassium, and ammonium.
• the number of carbon atoms is preferably 10 to 15. When the number of carbon atoms is in the range of 10 to 15, the emulsion which is the mold release agent for plastics of the present invention tends to have a small particle size, and the storage stability is good.
• the alkylbenzene sulfonate has an alkyl group having 9 to 20 carbon atoms, and the salts are sodium, potassium, and ammonium.
• the number of carbon atoms is preferably 9 to 15. When the number of carbon atoms is in the range of 9 to 15, the mold release agent for plastics of the present invention tends to have a small particle size and has good storage stability.
• the alkyl ether sulfate has an alkyl group having 12 to 16 carbon atoms, and the salt is a sodium salt.
• Alkyl sulfosuccinate has an alkyl group having 4 to 16 carbon atoms.
• the polyoxyethylene alkyl ether sulfate has an alkyl group having 12 to 20 carbon atoms, and the salts are sodium and ammonium.
• the number of carbon atoms is preferably 12 to 16. When the number of carbon atoms is in the range of 12 to 16, the mold release agent for plastics of the present invention tends to have a small particle size and has good storage stability.
• the polyoxyethylene alkyl ether phosphate has an alkyl group having 12 to 13 carbon atoms and a polyoxyethylene group having 4 to 10 carbon atoms.
• the alkyl acetate has an alkyl group having 8 to 22 carbon atoms, and the salts are sodium, potassium, and ammonium.
• the component (B) anionic surfactant which is an emulsifier is 0.1 to 15.0 parts by mass with respect to 100 parts by mass of the organopolysiloxane which is the component (A). It is preferably 0.1 to 10.0 parts by mass, and more preferably 0.1 to 8.0 parts by mass. If it is less than 0.1 parts by mass, the mechanical stability of the mold release agent for plastics of the present invention may decrease. On the other hand, if it is more than 15.0 parts by mass, the releasability may decrease.
• C Polyoxyethylene alkyl ether
• C Polyoxyethylene alkyl ethers represented by the following general formula (2): 1.0 to 30.0 parts by C m H 2m + 1 (OCH 2 CH 2) n OH (2).
• M is an integer of 12 to 20
• n is an integer of 4 to 50. However, when m is 12 to 15, n is 8 to 50, and when m is 16 to 20, n is 4. It is an integer of ⁇ 50.
• the m of the alkyl group of the polyoxyethylene alkyl ether (C) of the above formula (2) is an integer of 12 to 20, preferably an integer of 13 to 18, and more preferably an integer of 13 to 16. If m is smaller than 12, cracks may occur in the plastic coated with the mold release agent for plastics of the present invention. On the other hand, if it is larger than 20, the particle size of the mold release agent for plastics of the present invention is unlikely to become fine, and there is a risk that storage stability, dilution stability, and mechanical stability will deteriorate. Further, the alkyl group can be either branched or linear, and may be selected depending on the ease of emulsification of the organopolysiloxane of the component (A) and the resistance of cracks to occur when the plastic is coated.
• n of the component polyoxyethylene alkyl ether (C) of the above formula (2) is an integer of 4 to 50. It is preferably 4 to 30, and more preferably 4 to 25. If n is less than 4, cracks may occur in the plastic coated with the mold release agent for plastics of the present invention. On the other hand, when n is larger than 50, the polyoxyethylene alkyl ether of the above formula (2) becomes a solid, which makes it difficult to handle. Further, when the alkyl group is short and the polyoxyethylene chain is short, cracks are more likely to occur in the plastic. Therefore, when using polyoxyethylene alkyl ethers with short alkyl groups, those with short polyoxyethylene chains should be avoided. Specifically, when m is 12 to 15, n is preferably an integer of 8 to 50, and when m is 16 to 20, n is preferably an integer of 4 to 50.
• the polyoxyethylene alkyl ether as the component (C) may be used alone or in combination of two or more.
• the HLB of the polyoxyethylene alkyl ether of the component (C) can be 8 to 18, preferably 10 to 17, and more preferably 13 to 16. If storage stability, mechanical stability, and dilution stability cannot be obtained, store by using a combination of a high HLB of 15 to 18 and a low HLB of 8 to 12 so as to have an HLB of 13 to 16. Improves stability, mechanical stability, and dilution stability.
• the mold release agent for plastics of the present invention may cause cracks in the plastic, and therefore (C) having such a structure. ) It is preferable that the amount of the ingredients is small.
• the blending amount of the component polyoxyethylene alkyl ether (C) is 1.0 to 30.0 parts by mass. It is preferably 2.0 to 25.0 parts by mass, and more preferably 3.0 to 21.0 parts by mass. If it is less than 1.0 part by mass, there is a risk that the storage stability, dilution stability, mechanical stability and wettability of the plastic release agent of the present invention may decrease. On the other hand, if it is more than 30.0 parts by mass, cracks may occur when the plastic release agent of the present invention is applied to the plastic.
• polyoxyethylene alkyl ether of the component (C) examples include, but are not limited to, those represented by the following.
• Polyoxyethylene lauryl ether polyoxyethylene oleyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene hexyl decyl ether, polyoxyethylene isostearyl ether, polyoxyethylene octyldodecyl ether.
• R 2 is an alkyl group having from 12 to 18 carbon atoms, and the sum of a + b + c is 20.
• polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monooleate, and polyoxyethylene sorbitan monostearate having 12, 16 and 18 carbon atoms are recognized as food additives, and therefore, according to the present invention. Suitable for use as a plastic mold release agent for food containers and packaging.
• the blending amount of the polyoxyethylene sorbitan fatty acid ester, which is the component (D), is 0.5 to 15.0 parts by mass. It is preferably 0.5 to 10.0 parts by mass, and more preferably 2.0 to 10.0 parts by mass. If the component (D) is not blended or the amount of the component (D) blended is less than 0.5 parts by mass, the stability of the emulsion obtained by emulsifying the organopolysiloxane as the component (A) may decrease. On the other hand, if it is more than 15.0 parts by mass, cracks may occur when the plastic release agent of the present invention is applied to the plastic.
• the amount of water as the component (E) is 50 to 100,000 parts by mass. It is preferably 500 to 20,000 parts by mass, more preferably 2,000 to 10,000 parts by mass. (E) If the amount of water is less than 50 parts by mass, stickiness, uneven coating, and cracks may occur when the plastic release agent of the present invention is applied to the plastic. On the other hand, if the amount of (E) water is more than 100,000 parts by mass, the mechanical stability is lowered, and oil floating may occur after dilution and stirring.
• the mold release agent for plastics of the present invention further contains (F) a sorbitan fatty acid ester represented by the following general formula (4) in an amount of 5.0 parts by mass or less with respect to 100 parts by mass of the (A) organopolysiloxane. It is preferable to do so.
• R 3 is an alkyl group having 12 to 22 carbon atoms.
• R 3 is an alkyl group having 12 to 22 carbon atoms. From the viewpoint of emulsifying property, it is preferably 12 to 20, and more preferably 12 to 18. When the alkyl group of R 3 has 12 or more carbon atoms, there is no possibility that cracks will occur when the synthetic resin is coated. On the other hand, if the number of carbon atoms in the alkyl group R 3 is a 22 or less, nor whitening synthetic resin was applied.
• Sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monooleate, sorbitan monopalmitate, and sorbitan monostearate are also approved for use as food additives, and are voluntary standards for food containers and packaging of the Sanitary Council for Polyolefins, etc. It is a compound approved on the positive list of, and is most suitable for the use of the present invention.
• the blending amount of the sorbitan fatty acid ester, which is the component (F), can be 0.1 to 5.0 parts by mass. It is preferably 0.1 to 3.0 parts by mass, and more preferably 0.2 to 3.0 parts by mass. When the sorbitan fatty acid ester as the component (F) is 5.0 parts by mass or less, cracks are less likely to occur when the mold release agent for plastics of the present invention is applied.
• a combination of high HLB and low HLB (C) component polyoxyethylene alkyl ether is used. It is effective to use, but on the other hand, a mold release agent for plastics containing a large amount of polyoxyethylene alkyl ether, which is a component (C) of 8 to 12 HLBs, may cause stress cracks in the plastic.
• the HLB of the sorbitan fatty acid ester which is the component (F)
• the HLB of the sorbitan fatty acid ester is generally as low as 3.0 to 10.0, but it is less likely to cause stress cracks on the plastic than the component (C) of the HLB of the same level, and
• the stability of the mold release agent for plastics is further improved. Further, by blending the component (F), the foaming property may be lowered and the handling may be facilitated.
• the total of the components (C), (D), and (F), which are nonionic surfactants, can be 2.5 to 50.0 parts by mass with respect to 100 parts by mass of the component (A). It is preferably 2.5 to 35.0 parts by mass, and more preferably 3.0 to 30.0 parts by mass. When it is 2.5 parts by mass or more, the stability of the mold release agent for plastics of the present invention is not lowered, and shading separation and oil floating are unlikely to occur. In addition, repelling is less likely to occur when the plastic is coated. On the other hand, if it is 50.0 parts by mass or less, stress cracks are unlikely to occur in the plastic when the plastic release agent is applied.
• composition An example of a specific preparation method of the mold release agent for plastics of the present invention is mainly as shown below.
• A organopolysiloxane
• B anionic surfactant
• C polyoxyethylene alkyl ether
• D polyoxyethylene sorbitan fatty acid ester
• F sorbitan fatty acid ester
• E water
• emulsification of the component (A) is unlikely to occur, a part of each of the components (A) to (D), a part of the component (F) and a part of the component (E) are added and stirred, and then the remaining (A) Emulsification can be easily carried out by adding the components (D) and (F) and further stirring.
• the viscosity of the component (A) is less than 1,000 mm 2 / s, emulsification of the component (A) may be difficult to occur.
• the components (A) to (D) and the component (F) can be easily emulsified by adding them in a divided manner as described above.
• An example of the details of the emulsification formula is as follows.
• Combimix (Primix) with (A) organopolysiloxane, (B) anionic surfactant, (C) polyoxyethylene alkyl ether, (D) polyoxyethylene sorbitan fatty acid ester and, if necessary, (F) sorbitan fatty acid
• the ester and a part of (E) water are mixed and emulsified at a homomixer (stirring by rotating the rotor in the stator) 2,000 rpm or a disper (stirring by rotating the tooth profile blade) 2,000 rpm and an anchor 20 rpm. ..
• the mixture is stirred with a disper 2,000 rpm and an anchor 30 rpm for 15 to 180 minutes until the predetermined particle size is reached, and then the remaining water (E) is added and diluted with a homomixer 2,000 to 3,000 rpm. , Prepare the mold release agent for plastics of the present invention.
• the temperature at the time of emulsification is preferably 0 to 80 ° C, more preferably 10 to 60 ° C. At a temperature of 10 ° C to 80 ° C, it is easy to emulsify, and the produced emulsion tends to be more stable.
• the pressure may be reduced or pressurized as well as normal pressure. When emulsified under reduced pressure or pressure, bubbles are less likely to be mixed and emulsification may be effective.
• the pressure at the time of reducing the pressure is preferably higher than the vapor pressure of the raw material so that the raw material does not volatilize.
• the emulsification time is not particularly specified and may be the time when the target particle size is reached, but it is generally preferably 30 to 360 minutes.
• the emulsifying machine for emulsification is not particularly limited as long as it can stir the raw materials and the emulsified composition.
• Colloidal mill IKA, PUC, Nissei Tokyo, Iwaki
• high-share mixer siverson, Primix
• homodisper Primix
• azihomo mixer Principal Mix
• Combimix (Primix), which is a 3-axis dispersion kneader that combines a homomixer, homodisper, and anchor mixer
• HAAKE Mini LabII (Thermo scientific), which is a 2-axis mixer with a same-direction screw or a different-direction screw. )
• MC15, MC5 (Leo Lab), etc. can be used.
• the plastic release agent of the present invention includes polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose, hydroxymethyl cellulose, polyvinylpyrrolidone, alginate, as protective colloidal agents or thickeners in addition to surfactants, depending on the object of the present invention.
• a water-soluble polymer such as xanthane gum or an acrylic acid polymer may be blended.
• antibacterial agents or preservatives such as oxazoline compounds and aromatic carboxylates, fragrances, antioxidants, rust preventives, dyes, fillers, curing catalysts, organic powders, inorganic powders and the like may be blended. ..
• the average particle size of the mold release agent for plastics of the present invention is 200 nm or less. It is preferably 150 nm or less, more preferably 100 nm or less. If the average particle size is larger than 200 nm, the dilution stability and the mechanical stability are lowered, and there is a possibility that oil floating or the like may occur during dilution or stirring. In addition, when stored for a long period of time, there is a risk of shade separation.
• the lower limit of the average particle size is not particularly limited, but may be, for example, 10 nm. It can be measured by LA920 or LA960 manufactured by HORIBA, Ltd. or N4 PLUS manufactured by Beckman Coulter, but in this specification, the average particle size measured by LA960 is shown.
• the pH of the mold release agent for plastics of the present invention is preferably 4.0 to 10.0 at 25 ° C. It is preferably 4.5 to 9.0, more preferably 4.5 to 8.0.
• the pH is in the range of 4.0 to 10.0, the structure of the component (A) changes when stored at a high temperature, and the effect on the releasability of the plastic is small.
• the emulsion obtained as described above is extremely useful as a mold release agent used for plastic sheets and the like for food packaging.
• the mold release agent for plastics of the present invention having the content of the component (A) of 0.1 to 2.0% by weight can be applied by rotor dampening, gravure method or spray method.
• the coating amount is generally 0.01 to 1.0 g / m 2 on a drying basis, and particularly preferably 0.02 to 0.2 g / m 2 . When it is 0.01 g / m 2 or more, sufficient releasability can be obtained, and when it is 1.0 g / m 2 or less, it is preferable from the viewpoint of transparency and stickiness.
• Plastics for food containers and packaging include polyethylene, polypropylene, polymethylpentene, polybutene, ethylenetetracyclododecene, ethylene2-norbornene, polystyrene, AS resin, ABS resin, polyphenylene ether, polyacrylonitrile, polymethacrylic styrene, and methacrylic resin.
• Examples thereof include nylon, polyethylene terephthalate, polycarbonate, polyvinyl alcohol, polyacetal, polybutylene terephthalate, polycyclohexylene methylene terephthalate, polyethylene naphthalate, vinyl chloride and the like.
• polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester and, if necessary, sorbitan fatty acid ester are blended in a specific ratio, and the organopolysiloxane is emulsified to have excellent releasability. It is possible to provide a mold release agent for plastics which has good dilution stability and mechanical stability and is less likely to cause stress cracks.
• the viscosity is a value at 25 ° C. measured by a BM type or BH type rotational viscometer or an Ostwald viscometer.
• Component (A) represented by the above formula [1] Organopolysiloxane (1a) (L1 is about 550, viscosity 10,000 mm 2 / s) 30 parts by mass (90 g), component (B) [1] Emar 270J (Kao) , Polyoxyethylene alkyl ether sodium sulfate 70% aqueous solution) 0.2 parts by mass (0.6 g), component (C) [1] Leocol TDN90-80 (2a) (made by Lion, polyoxyethylene alkyl ether 80% aqueous solution) ) 6.0 parts by mass (18 g), component (D) [1] Nonion LT-221 (manufactured by Nichiyu, polyoxyethylene sorbitan monolaurate) 1.6 parts by mass (4.8 g), component (F) Nonion LP -20R (manufactured by Nichiyu, sorbitan monolaurate) 0.4 parts by mass (1.2 g) and (E) Organopoly
• Example 2 (A) Component [1] Organopolysiloxane (1a) (L1 is about 550, viscosity 10,000 mm 2 / s) 30 parts by mass (90 g), (B) Component [1] Emar 270J (manufactured by Kao, polyoxyethylene) (70% aqueous solution of alkyl ether sodium sulfate) 1.3 parts by mass (3.9 g), component (C) [1] Leocol TDN90-80 (2a) (manufactured by Lion, 80% aqueous solution of polyoxyethylene alkyl ether) 6.0% by mass Part (18 g), (D) component [1] Nonion LT-221 (manufactured by Nichiyu, polyoxyethylene sorbitan monolaurate) 1.6 parts by mass (4.8 g), (F) component Nonion LP-20R (Nichiyu) (Sorbitan monolaurate) 0.4 parts by mass (1.2 g) and (E) Component
• the mixture is stirred at 1,500 rpm for 20 minutes, and then 59.55 parts by mass (178.65 g) of water, which is the component (E) -2, is added to homomixer MARKII 2.5 type (manufactured by Primex) 1, After stirring and diluting at 500 rpm for 3 minutes, 0.1 part by mass (0.3 g) of sodium benzoate and 0.05 part by mass (0.15 g) of citric acid are added, and Homomixer MARKII 2.5 type (manufactured by Primex) 1 , 500 rpm for 1 minute to prepare an emulsified composition 2.
• Mold manufactured by Primix
• Mix stir at 1,500 rpm for 3 minutes to dilute, then add 0.1 part by mass (0.3 g) of sodium benzoate and 0.05 part by mass (0.15 g) of citrate, and further add homomixer MARKII 2.
• the emulsified composition 3 was prepared by stirring at 1,500 rpm of type 5 (manufactured by Primex) for 1 minute.
• Emulsified composition 4 was prepared.
• Example 5 (A) Component [1] Organopolysiloxane (1a) (L1 is about 550, viscosity 10,000 mm 2 / s) 30 parts by mass (90 g), (B) Component [1] Emar 270J (manufactured by Kao, polyoxyethylene) Alkyl ether sodium sulfate 70% aqueous solution) 1.3 parts by mass (3.9 g), component (C) [1] Leocol TDN90-80 (2a) (made by Lion, polyoxyethylene alkyl ether 80% aqueous solution) 6.0 mass Part (18 g), component (D) [2] Leodor TW-O120V (manufactured by Kao, polyoxyethylene sorbitan monooleate) 2.0 parts by mass (6.0 g), and (E) -1 component water 1 .0 parts by mass (3.0 g) is stirred at 500 rpm of Homo Disper 2.5 type (manufactured by Primex), and when the whole
• Example 6 (A) Component [1] Organopolysiloxane (1a) (L1 is about 550, viscosity 10,000 mm 2 / s) 30 parts by mass (90 g), (B) Component [1] Emar 270J (manufactured by Kao, polyoxyethylene) (70% aqueous solution of sodium alkyl ether sulfate) 1.3 parts by mass (3.9 g), component (C) [1] Leocol TDN90-80 (2a) (manufactured by Lion, 80% aqueous solution of polyoxyethylene alkyl ether) 6.0% by mass Part (18 g), (D) component [2] Leodor TW-O120V (manufactured by Kao, polyoxyethylene sorbitan monooleate) 1.6 parts by mass (4.8 g), (F) component Nonion LP-20R (Nichiyu) (Sorbitan monolaurate) 0.4 parts by mass (1.2 g) and (E)
• Homomixer MARKII 2.5 type (manufactured by Primix) was stirred at 1,500 rpm for 3 minutes to dilute, and then 0.1 part by mass (0.3 g) of sodium benzoate and 0.05 part by mass (0.15 g) of citric acid. was further added, and the mixture was further stirred at 1,500 rpm of Homomixer MARKII type 2.5 (manufactured by Primix) for 1 minute to prepare an emulsified composition 10.
• the same amount of isopropyl alcohol was added to 100 parts by mass of this emulsion to extract dimethylpolysiloxane, and the extracted oil was washed with water and dried at 105 ° C., and the viscosity of dimethylpolysiloxane obtained was about 25 ° C. It was 10,000 mm 2 / s. Further, the emulsion contained 1.9% of octamethylcyclotetrasiloxane, 0.8% of decamethylcyclopentasiloxane, and 0.15% of dodecamethylcyclohexasiloxane.
• Leocol TDN90-80 (2a) (manufactured by Lion, 80% aqueous solution of polyoxyethylene alkyl ether) 8.5 parts by mass with respect to 91.35 parts by mass (274.05 g) of this emulsion polymerized emulsion. (25.5 g), 0.1 part by mass (0.3 g) of sodium benzoate, and 0.05 part by mass (0.15 g) of citric acid are added and mixed with a Ikari-shaped stirring rod at 100 rpm for 30 minutes to form an emulsion composition.
• Object 12 was prepared.
• the same amount of isopropyl alcohol was added to 100 parts by mass of this emulsion to extract dimethylpolysiloxane, and the extracted oil was washed with water and dried at 105 ° C., and the viscosity of dimethylpolysiloxane obtained was about 25 ° C. It was 10,000 mm 2 / s. Further, the emulsion contained 1.9% of octamethylcyclotetrasiloxane, 0.8% of decamethylcyclopentasiloxane, and 0.15% of dodecamethylcyclohexasiloxane.
• Average particle size It is a value measured by HORIBA LA960 after diluting the emulsified compositions 1 to 15 with water about 10 times.
• pH It is a value measured by the emulsified compositions 1 to 15 at 25 ° C. with a pH meter (LAQUA manufactured by HORIBA).
• Water dilution stability 2 g of each emulsified composition 1 to 15 and 98 g of water were mixed to prepare a mold release agent 1 for plastics. The whole amount was placed in a 200 mL beaker and allowed to stand for one day, and the surface of the plastic release agent 1 was observed.
• ⁇ The mold release agent for plastics is dispersed without separating the shades. There is no oil spot or interference film on the surface, or about 10 to 30% of the interference film is formed on the surface.
• ⁇ The mold release agent for plastics is dispersed without separating the shades. There are no oil spots or interference films on the surface, or about 30 to 60% of the interference films are formed on the surface.
• X The mold release agent for plastic is unevenly dispersed. Alternatively, 60% or more of the interference film or oil spot is formed on the surface. ⁇ and ⁇ are accepted.
• the plastic release agent 1 is applied to the OPS sheet with gauze. Wrap the OPS sheet around a cylinder with a diameter of 37 mm and visually check for cracks. ⁇ : No crack occurs within 75 seconds after winding around the cylinder ⁇ : Crack occurs within 75 seconds after winding around the cylinder ⁇ is accepted.
• Component (A) and comparative organopolysiloxane Ingredients (A) [1]: Organopolysiloxane (1a) (L1 is about 550, viscosity 10,000 mm 2 / s) Ingredients (A) [2]: Organopolysiloxane (1b) (L2 is about 200, viscosity 1,000 mm 2 / s)
• the contents of each of the above components (A) [1] and [2], such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane, are less than 0.1%.
• Organopolysiloxane (1c) (L1 is about 550, the content of each of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane is 3.3%, and the viscosity is 7,000 mm 2 / s).
• Organopolysiloxane (1c) is a mixture of component (A) organopolysiloxane (1a) with octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane at 3.3% each. ..
• Organopolysiloxane (1d) (L1 is about 550) Organopolysiloxane (1d) was prepared by emulsion polymerization, and in 100 parts by mass of organopolysiloxane (1d), octamethylcyclotetrasiloxane 6.3%, decamethylcyclopentasiloxane 2.7%, dodecamethylcyclohexane. Contains 0.5% sasiloxane.
• Component (B) Ingredients (B) [1]: Emar 270J (made by Kao) Polyoxyethylene (2) Alkylation ether Sodium sulfate 70% aqueous solution Component (B) [2]: Neucol 291M (manufactured by Nippon Emulsion) Dioctyl sulfosuccinate sodium 70% aqueous solution component (B) [3]: Emar 2FG (manufactured by Kao) Lauryl sulfate
• Component (C) and comparative surfactant Ingredients (C) [1]: Leocol TDN90-80 (made by Lion, 80% aqueous solution of polyoxyethylene alkyl ether) (2a) (C m H 2m + 1 ( OCH 2 CH 2) 80% aqueous solution of n OH, m is 13, n is 9)
• Component (D) Ingredient (D) [1]: Nonion LT-221 (manufactured by NOF) Polyoxyethylene sorbitan monolaurate component (D) [2]: Leodor TW-O120V (manufactured by Kao) Polyoxyethylene sorbitan monooleate
• Component (F) Ingredient (F): Nonion LP-20R (manufactured by NOF) Sorbitan monolaurate
• the mold release agent for plastics of the present invention is an emulsion of an organopolysiloxane that has excellent dilution stability, mechanical stability, good wettability, and is less likely to crack the plastic. It can be seen that it is.
• Comparative Examples 1 and 6 containing neither the component (D) nor (F) in the present invention the mechanical stability and the crack property were inferior. Further, in Comparative Examples 2, 6 and 7, the average particle size of the release agent was larger than 200 nm, which is considered to have lowered the mechanical stability.
• Comparative Example 7 which did not contain the components (C), (D), and (F) in the present invention, the nonionic surfactant was not used, cissing occurred, and the wettability was inferior.
• Comparative Example 8 in which the component (C) was contained in excess of the upper limit of the blending amount range with respect to the component (A) in the present invention, cracks were likely to occur.
• the present invention is not limited to the above embodiment.
• the above-described embodiment is an example, and any object having substantially the same configuration as the technical idea described in the claims of the present invention and exhibiting the same effect and effect is the present invention. Is included in the technical scope of.

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