WO2023017822A1 - 発泡成形用マスターバッチ及び発泡成形体 - Google Patents
発泡成形用マスターバッチ及び発泡成形体 Download PDFInfo
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- WO2023017822A1 WO2023017822A1 PCT/JP2022/030432 JP2022030432W WO2023017822A1 WO 2023017822 A1 WO2023017822 A1 WO 2023017822A1 JP 2022030432 W JP2022030432 W JP 2022030432W WO 2023017822 A1 WO2023017822 A1 WO 2023017822A1
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- masterbatch
- thermally expandable
- expandable microcapsules
- foam
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- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
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- WDIWAJVQNKHNGJ-UHFFFAOYSA-N trimethyl(propan-2-yl)silane Chemical compound CC(C)[Si](C)(C)C WDIWAJVQNKHNGJ-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
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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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
Definitions
- the present invention relates to a foam molding masterbatch and a foam molding using the foam molding masterbatch.
- Plastic foam can exhibit heat insulation, heat insulation, sound insulation, sound absorption, vibration insulation, weight reduction, etc. depending on the material of the foam and the state of the formed cells, so it can be used in various applications. used.
- a method for producing such a plastic foam there is a method in which a masterbatch containing a chemical foaming agent is heated to foam and then molded.
- Patent Document 1 by using masterbatch pellets of an ethylene- ⁇ -olefin copolymer containing a chemical blowing agent, regardless of the type of resin, high hardness and expansion ratio, uniform cells are formed. It is described that an injection foamed molded article having a Further, Patent Document 2 describes a foamed resin masterbatch that uses a polyolefin resin or a styrene resin as a base resin and uses thermally expandable microcapsules as a foaming agent instead of a chemical foaming agent.
- a masterbatch containing a chemical foaming agent may not foam even when heated, and there is a possibility that the foaming agent may rapidly decompose in an injection foam molding machine, making handling difficult. Moreover, depending on the type of resin, a sufficient expansion ratio cannot be obtained, and it may be difficult to obtain a desired hardness as a molded product.
- the chemical foaming agent when thermally decomposed, it produces a decomposition gas and a foaming residue at the same time, and the residue remaining on the molded product may affect the adhesion performance of the molded product.
- a chemical foaming agent when a chemical foaming agent is used, there is a problem that it is difficult to maintain foaming over time. Furthermore, even when thermally expandable microcapsules are used, the expansion ratio of the obtained foam is low, and it is difficult to obtain a foamed molded article with little overfoaming.
- the present disclosure (1) is a masterbatch for foam molding containing a base resin and thermally expandable microcapsules, and the ratio of voids with a diameter of 0.001 ⁇ m or more to the interfacial area per unit weight (diameter of 0.001 ⁇ m or more).
- the masterbatch for foam molding has a porosity/interface area per unit weight of 0.015%/cm 2 /g or less and a volatile content of 0.7% by weight or less.
- the present disclosure (2) is the masterbatch for foam molding according to the present disclosure (1), which has a particle size distribution (CV value) of 20% or less.
- the present disclosure (3) is the masterbatch for foam molding according to the present disclosure (1) or (2), which has a porosity of 4% or less with a diameter of 0.1 ⁇ m or more.
- (4) of the present disclosure is the masterbatch for foam molding according to any one of (1) to (3) of the present disclosure, which has a porosity of 11% or less with a diameter of 0.001 ⁇ m or more.
- the present disclosure (5) is the foam molding master according to any one of the present disclosure (1) to (4), wherein the base resin is at least one selected from the group consisting of polyethylene resins and acrylic resins. Batch.
- the content of the base resin is 30% by weight or more and 80% by weight or less, and the content of the thermally expandable microcapsules is 20% by weight or more and 70% by weight or less.
- the present disclosure (7) is the foam molding masterbatch according to any one of the present disclosures (1) to (6), which has an interfacial area per unit weight of 500 to 1600 cm 2 /g.
- the present disclosure (8) is a foam molded article using the foam molding masterbatch according to any one of the present disclosure (1) to (7). The present invention will be described in detail below.
- the foam molding masterbatch of the present invention preferably has a porosity of 11% or less with a diameter of 0.001 ⁇ m or more.
- the more preferable upper limit of the porosity with a diameter of 0.001 ⁇ m or more is 10%, the more preferable upper limit is 9.0%, the still more preferable upper limit is 8.5%, and the preferable lower limit is 1%, such as 5% or more, especially 6% or more, especially 7% or more.
- the porosity with a diameter of 0.001 ⁇ m or more means the volume of voids with a pore diameter of 0.001 ⁇ m or more in the volume of the foam molding masterbatch.
- the foam molding masterbatch of the present invention preferably has a porosity of 4% or less with a diameter of 0.1 ⁇ m or more.
- the more preferable upper limit of the porosity with a diameter of 0.1 ⁇ m or more is 3%, the more preferable upper limit is 2%, the even more preferable upper limit is 1.8%, and the preferable lower limit is 0.1%, for example, 0.2% or more. , in particular not less than 0.3%.
- the porosity with a diameter of 0.1 ⁇ m or more means the volume of voids with a pore diameter of 0.1 ⁇ m or more in the volume of the foam molding masterbatch.
- the porosity with a diameter of 0.001 ⁇ m or more and the porosity with a diameter of 0.1 ⁇ m or more can be measured by a mercury intrusion method using, for example, a porosimeter (Thermo Pascal 14B, manufactured by Thermo Fisher Scientific).
- the area of the contact interface between the thermally expandable microcapsules and the base resin (interface area per unit weight) in 1 g of the foam molding masterbatch is 500 cm 2 /g or more and 1600 cm 2 /g.
- the following are preferable.
- the interfacial area per unit weight is within the above range, it is possible to obtain a highly foamable masterbatch.
- a more preferable lower limit of the interface area per unit weight is 650 cm 2 /g, a more preferable lower limit is 670 cm 2 /g, a more preferable upper limit is 1400 cm 2 /g, and a further preferable upper limit is 1200 cm 2 /g.
- the interfacial area per unit weight can be calculated from the volume average particle diameter and true specific gravity of the thermally expandable microcapsules, and the content of the thermally expandable microcapsules in the masterbatch for foam molding. .
- the masterbatch for foam molding of the present invention has a ratio of voids with a diameter of 0.001 ⁇ m or more to an interface area per unit weight (void ratio with a diameter of 0.001 ⁇ m or more/interface area per unit weight) of 0.015%/ cm 2 /g or less.
- a preferable lower limit of the interfacial area per unit weight of void ratio with a diameter of 0.001 ⁇ m or more is 0.005%/cm 2 /g
- a preferable upper limit is 0.013%/cm 2 /g
- a more preferable lower limit is 0. 007%/cm 2 /g
- a more preferred upper limit is 0.012%/cm 2 /g.
- the preferred lower limit of the average pore size is 0.01 ⁇ m, and the preferred upper limit is 0.05 ⁇ m.
- the average pore diameter is within the above range, volatile matter can be further suppressed.
- a more preferable lower limit of the average pore diameter is 0.012 ⁇ m, and a more preferable upper limit thereof is 0.04 ⁇ m.
- the average pore diameter can be measured by a mercury intrusion method in the same manner as the porosity with a diameter of 0.001 ⁇ m or more and the porosity with a diameter of 0.1 ⁇ m or more.
- the foam molding masterbatch of the present invention has a volatile content of 0.7% by weight or less.
- the volatile content is 0.7% by weight or less, uniform foam cells can be formed when mixed with other resins in foam molding.
- the preferred lower limit of the volatile content is 0.2% by weight, the more preferred lower limit is 0.3% by weight, the preferred upper limit is 0.6% by weight, and the more preferred upper limit is 0.5% by weight.
- the volatile content can be measured from weight change after heating in an oven at 70° C. for 60 minutes.
- the foam molding masterbatch of the present invention preferably has an average outer diameter of 1.0 mm or more and 4.0 mm or less. Within the above range, the thermally expandable microcapsules contained in the masterbatch can be uniformly dispersed.
- a more preferable lower limit of the outer diameter is 1.3 mm, a more preferable lower limit is 1.5 mm, a more preferable upper limit is 3.5 mm, and a further preferable upper limit is 3.0 mm.
- the masterbatch for foam molding of the present invention preferably has a particle size distribution (CV value) of 20% or less.
- CV value particle size distribution
- a preferable lower limit of the CV value is 0.5%, and a more preferable upper limit is 5.0%.
- the shape of the foam molding masterbatch of the present invention is not particularly limited, it is preferably columnar.
- the columnar shape is preferably a columnar shape, a prismatic shape, or a similar shape. Examples thereof include a columnar shape, an elliptical columnar shape, and a polygonal columnar shape (triangular columnar shape, square columnar shape, pentagonal columnar shape, hexagonal columnar shape, etc.), and the columnar shape is particularly preferable from the viewpoint of ease of handling. Moreover, it may have minute unevenness.
- the preferred lower limit of the true specific gravity of the foam molding masterbatch of the present invention is 0.80 g/cm 3 . If the true specific gravity is 0.80 g/cm 3 or more, it means that the thermally expandable microcapsules in the masterbatch are swollen. can be done. A more preferable lower limit of the true specific gravity is 0.90 g/cm 3 and a preferable upper limit thereof is 1.0 g/cm 3 .
- the true specific gravity is the specific gravity of the material only, excluding voids, and represents the ratio of the mass of a unit volume of the masterbatch at 20°C to the mass of water of the same volume at 4°C. The true specific gravity can be measured by a method conforming to JIS K 7112 A method (water substitution method).
- the foam molding masterbatch of the present invention contains a base resin.
- the base resin contains at least one selected from acrylic resins and polyethylene resins. This makes it possible to produce a foam molded article with good appearance quality.
- acrylic resin examples include homopolymers of acrylic monomers such as acrylic acid, methacrylic acid, and (meth)acrylic acid esters, and (meth)acrylic copolymers containing these.
- acrylic acid ester examples include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate and the like.
- Examples of the (meth)acrylic acid ester include n-amyl (meth)acrylate, isoamyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, and the like.
- the above (meth)acrylic acid indicates acrylic acid or methacrylic acid.
- (meth)acrylic copolymer other comonomers to be copolymerized together with acrylic monomers include ⁇ -olefin, styrene, ⁇ -methylstyrene, vinyltoluene, acrylonitrile, methacrylonitrile, vinyl acetate, and the like. can be mentioned. Among them, copolymers of acrylic monomers and ⁇ -olefins are preferred, and ethylene-methyl methacrylate copolymers (EMMA) are more preferred. These comonomers can exist in the form of random copolymers, graft copolymers, and block copolymers in the acrylic resin.
- the content of methyl methacrylate (MMA) is preferably 32% by weight or less, more preferably 25% by weight or less, and usually 0% by weight. % or more.
- the acrylic resin has a weight average molecular weight of 10,000 or more. By setting the weight-average molecular weight within the above range, a molded product with excellent appearance can be obtained.
- the weight average molecular weight (Mw) is measured as polystyrene equivalent molecular weight by gel permeation chromatography (GPC).
- the melt index of the acrylic resin has a preferable lower limit of 1 g/10 minutes, a preferable upper limit of 500 g/10 minutes, and a more preferable upper limit of 50 g/10 minutes.
- the melt index means an index indicating the fluidity of the resin. Pressurized with a load (for example, 2.16 kg), the amount of resin extruded per 10 minutes from an opening (nozzle) provided at the bottom of the container is indicated. The unit is g/10 minutes and is measured by the measurement method specified in JIS K7210-1.
- the polyethylene-based resin is not particularly limited, and examples thereof include polyethylene resins such as low-density polyethylene resin, high-density polyethylene resin, linear low-density polyethylene resin, and ultra-high molecular weight polyethylene resin. Also, ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-dimethylaminomethyl methacrylate copolymer, ethylene-vinyl alcohol Examples thereof include copolymers such as copolymers and ethylene-vinyl alcohol copolymers. Among them, the ethylene-based resin is preferably a low-density polyethylene resin.
- the base resin may be a mixed resin of an acrylic resin and a polyethylene resin.
- the mixing ratio of acrylic resin and polyethylene resin is preferably 3:7 to 7:3.
- At least one selected from acrylic resins and polyethylene resins may be 100% by weight of the base resin.
- a mixture is also possible.
- the proportion of the acrylic resin is preferably 80% by weight or more, more preferably 90% by weight or more, and usually less than 100% by weight.
- a rubber component is mentioned as said other resin component.
- the rubber components include natural rubber (NR), butadiene rubber (BR), styrene-butadiene rubber (SBR), isoprene rubber (IR), acrylonitrile-butadiene rubber (NBR), butyl rubber (IIR), chloroprene rubber (CR), Urethane rubber (U), silicone rubber (Si), or the like can be used. Also, one or two or more selected from the above rubber components may be used in combination.
- thermoplastic resin examples include general thermoplastic resins such as polyvinyl chloride, polypropylene, polypropylene oxide, and polystyrene, and engineering plastics such as polybutylene terephthalate, nylon, polycarbonate, and polyethylene terephthalate. Among these, at least one selected from the group consisting of low-density polyethylene, high-density polyethylene, polypropylene and polystyrene is preferable.
- the preferred lower limit of the base resin content in the foam molding masterbatch of the present invention is 30% by weight, and the preferred upper limit is 80% by weight.
- the content of the base resin is 30% by weight or more, foaming can be prevented during preparation of the masterbatch, and when the content of the base resin is 80% by weight or less, a desired expansion ratio can be obtained. can be done.
- a more preferable lower limit to the content of the base resin is 40% by weight, and a more preferable upper limit is 75% by weight.
- the foam molding masterbatch of the present invention preferably contains a component derived from methyl methacrylate in both the thermally expandable microcapsules and the base resin. Further, the content of the component derived from methyl methacrylate in the shell of the thermally expandable microcapsule is 15 to 25% by weight, and the content of the component derived from methyl methacrylate in the base resin is 3 to 25% by weight. %.
- the foam molding masterbatch of the present invention contains thermally expandable microcapsules.
- a preferable lower limit of the content of the thermally expandable microcapsules in the foam molding masterbatch of the present invention is 20% by weight, and a preferable upper limit thereof is 70% by weight.
- a desired expansion ratio can be obtained by setting the content of the thermally expandable microcapsules to 20% by weight or more.
- By setting the content of the thermally expandable microcapsules to 70% by weight or less it is possible to prevent foaming during the preparation of the masterbatch and, as a result, to improve the foaming ratio of the foam-molded product.
- a more preferable lower limit of the content of the thermally expandable microcapsules is 25% by weight, a more preferable upper limit is 60% by weight, and a further preferable upper limit is 55% by weight.
- the shell constituting the thermally expandable microcapsule is made of a polymer obtained by polymerizing a monomer mixture containing a polymerizable monomer (I) consisting of at least one selected from acrylonitrile, methacrylonitrile and vinylidene chloride. is preferred.
- a polymerizable monomer (I) consisting of at least one selected from acrylonitrile, methacrylonitrile and vinylidene chloride. is preferred.
- the shell constituting the thermally expandable microcapsule has 40 to 90% by weight of the polymerizable monomer (I) and a carboxyl group, and has 3 to 8 carbon atoms. is preferably composed of a polymer obtained by polymerizing a monomer mixture containing 5 to 50% by weight of the radically polymerizable unsaturated carboxylic acid monomer (II).
- a preferable lower limit of the content of the polymerizable monomer (I) in the monomer mixture is 40% by weight, and a preferable upper limit thereof is 90% by weight.
- the content of the polymerizable monomer (I) in the monomer mixture is less than 40% by weight, the gas barrier properties of the shell are lowered, which may lower the expansion ratio. If the content of the polymerizable monomer (I) in the monomer mixture exceeds 90% by weight, the heat resistance may not be improved.
- a more preferable lower limit to the content of the polymerizable monomer (I) in the monomer mixture is 50% by weight, and a more preferable upper limit is 80% by weight.
- radical polymerizable unsaturated carboxylic acid monomer (II) having 3 to 8 carbon atoms and having a carboxyl group for example, one having one or more free carboxyl groups per molecule for ionic cross-linking can be used.
- Specific examples include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids and anhydrides thereof, monoesters of unsaturated dicarboxylic acids and derivatives thereof, and the like.
- the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid and cinnamic acid.
- Examples of the unsaturated dicarboxylic acid include maleic acid, itaconic acid, fumaric acid, citraconic acid, and chloromaleic acid.
- Examples of monoesters of unsaturated dicarboxylic acids include monomethyl maleate, monoethyl maleate, monobutyl maleate, monomethyl fumarate, monoethyl fumarate, monomethyl itaconate, monoethyl itaconate, and monobutyl itaconate. These may be used alone or in combination of two or more. Among these, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, and itaconic acid are particularly preferred.
- the preferred lower limit of the content of the segment derived from the radically polymerizable unsaturated carboxylic acid monomer (II) having 3 to 8 carbon atoms and having a carboxyl group is 5% by weight, and the preferred upper limit is 50% by weight. %. If the content of the segment derived from the radically polymerizable unsaturated carboxylic acid monomer (II) is less than 5% by weight, the maximum foaming temperature may be 190° C. or lower, and the radically polymerizable unsaturated carboxylic acid monomer When the content of the segment derived from (II) exceeds 50% by weight, the maximum expansion temperature is improved, but the expansion ratio is lowered. A more preferable lower limit to the content of the segment derived from the radically polymerizable unsaturated carboxylic acid monomer (II) is 10% by weight, and a more preferable upper limit is 40% by weight.
- the content of the polymerizable monomer (I) and the segment derived from the radically polymerizable unsaturated carboxylic acid monomer (II) having 3 to 8 carbon atoms and having the carboxyl group is as described above. Although it is not particularly limited as long as it is within the range, it is preferable to use the following monomer mixtures (1) to (3).
- the monomer mixture (1) contains 40 to 90% by weight of the polymerizable monomer (I) and 5 to 50 radically polymerizable unsaturated carboxylic acid monomers (II) having 3 to 8 carbon atoms and having the carboxyl group. % by weight and does not contain the polymerizable monomer (III) having two or more double bonds in the molecule.
- the monomer mixture (1) does not contain the polymerizable monomer (III) having two or more double bonds in the molecule.
- the polymerizable monomer (III) is generally used as a cross-linking agent.
- a shell having sufficient strength is obtained by using a monomer mixture containing predetermined amounts of the polymerizable monomer (I) and the radically polymerizable unsaturated carboxylic acid monomer (II).
- the thermally expandable microcapsules have excellent shear resistance, heat resistance, and foamability. can do.
- thermally expandable microcapsules having sufficient strength and heat resistance are obtained without using the polymerizable monomer (III) having two or more double bonds in the molecule. making it possible.
- "does not contain a polymerizable monomer (III) having two or more double bonds in the molecule in the monomer mixture” means that the polymerizable monomer (III) is not substantially contained.
- the polymerizable monomer (III) is contained in a very small amount, it is regarded as not containing the polymerizable monomer (III).
- the monomer which has two or more radically polymerizable double bonds is mentioned.
- divinylbenzene ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth) ) acrylates and the like.
- trimethylolpropane tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, triallylformal tri(meth)acrylate and the like are included.
- pentaerythritol tetra(meth)acrylate dipentaerythritol hexa(meth)acrylate, dimethylol-tricyclodecane di(meth)acrylate and the like are included.
- the monomer mixture (2) comprises 40 to 90% by weight of the polymerizable monomer (I) and 5 to 50 radically polymerizable unsaturated carboxylic acid monomers (II) having 3 to 8 carbon atoms and having the carboxyl group. 0.2% by weight or less of the polymerizable monomer (III) and 0.1 to 10% by weight of the metal cation hydroxide (IV).
- the monomer mixture (2) preferably contains a polymerizable monomer (III) having two or more double bonds in the molecule.
- the polymerizable monomer (III) serves as a cross-linking agent.
- the polymerizable monomer (III) is not particularly limited as long as it has a carboxyl group and is different from the radical polymerizable unsaturated carboxylic acid monomer (II) having 3 to 8 carbon atoms, and is generally A monomer having two or more radically polymerizable double bonds is preferably used for .
- a monomer having two or more radically polymerizable double bonds is preferably used for .
- divinylbenzene ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth) ) acrylate, 1,6-hexanediol di(meth)acrylate and the like.
- 1,9-nonanediol di(meth)acrylate, di(meth)acrylate of polyethylene glycol having a molecular weight of 200 to 600, glycerin di(meth)acrylate, trimethylolpropane di(meth)acrylate and the like are included.
- trimethylolpropane tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate and the like be done.
- a preferable upper limit of the content of the polymerizable monomer (III) in the monomer mixture (2) is 0.2% by weight.
- the polymerizable monomer (III) is added in an amount exceeding 0.2% by weight, the particle shape of the thermally expandable microcapsules becomes distorted, resulting in a decrease in bulk specific gravity. If the bulk specific gravity decreases, the heat-expandable microcapsules are likely to be sheared in the next step, especially when a masterbatch is produced using extrusion molding, and the heat-expandable microcapsules tend to foam. . As a result, the true specific gravity of the masterbatch is lowered, making it impossible to produce a stable masterbatch.
- the decrease in bulk specific gravity can be prevented by setting the content of the polymerizable monomer (III) to 0.2% by weight or less.
- a preferred lower limit to the content of the polymerizable monomer (III) is 0% by weight, and a more preferred upper limit is 0.1% by weight.
- the monomer mixture (2) preferably contains a metal cation hydroxide (IV).
- a metal cation hydroxide (IV) By containing the metal cation hydroxide (IV), an ionic bond occurs between the carboxyl group of the radically polymerizable unsaturated carboxylic acid monomer (II), which increases rigidity and heat resistance. becomes possible.
- thermally expandable microcapsules that do not burst or shrink for a long time in a high temperature range.
- the elastic modulus of the shell does not easily decrease even in a high temperature range, even when performing molding such as kneading molding, calendar molding, extrusion molding, injection molding, etc., where strong shearing force is applied, the thermally expandable micro No capsule rupture or shrinkage.
- the particle shape of the thermally expandable microcapsules is nearly spherical, and distortion is less likely to occur. This is because cross-linking by ionic bonds has a weaker binding force than cross-linking by covalent bonds, so when the monomer during polymerization is converted to a polymer, the volume of the thermally expandable microcapsules shrinks uniformly. This is thought to be the cause.
- the metal cation of the metal cation hydroxide (IV) is not particularly limited as long as it is a metal cation that reacts with the radically polymerizable unsaturated carboxylic acid monomer (II) to form an ionic bond.
- a metal cation that reacts with the radically polymerizable unsaturated carboxylic acid monomer (II) to form an ionic bond Li, Zn, Mg, Ca, Ba, Sr, Mn, Al, Ti, Ru, Fe, Ni, Cu, Cs, Sn, Cr, Pb and the like.
- ions of Ca, Zn and Al which are divalent to trivalent metal cations, are preferred, and ions of Zn are particularly preferred.
- These metal cation hydroxides (IV) may be used alone or in combination of two or more.
- a preferable lower limit of the content of the metal cation hydroxide (IV) in the monomer mixture (2) is 0.1% by weight, and a preferable upper limit thereof is 10% by weight. If the content of the metal cation hydroxide (IV) is less than 0.1% by weight, the effect of heat resistance may not be obtained. %, the expansion ratio may be significantly deteriorated.
- a more preferable lower limit to the content of the metal cation hydroxide (IV) is 0.5% by weight, and a more preferable upper limit is 5% by weight.
- the monomer mixture (3) contains 40 to 90% by weight of the polymerizable monomer (I) and 5 to 50% by weight of a radically polymerizable unsaturated carboxylic acid monomer (II) having a carboxyl group and having 3 to 8 carbon atoms. % and 0.1 to 10% by weight of the metal cation hydroxide (IV), and does not contain the polymerizable monomer (III) having two or more double bonds in the molecule.
- the monomer mixture (3) is characterized in that it does not contain the polymerizable monomer (III) having two or more double bonds in the molecule. Polymerization having two or more double bonds in the molecule in the above-mentioned monomer mixture by cross-linking due to ionic bonding between the radically polymerizable unsaturated carboxylic acid monomer (II) and the metal cation hydroxide (IV). The resulting shell has sufficient strength and heat resistance even if it does not contain the curable monomer (III). When the polymerizable monomer (III) is added, the particle shape of the thermally expandable microcapsules becomes distorted, resulting in a decrease in bulk specific gravity.
- the heat-expandable microcapsules are likely to be sheared in the next step, especially when a masterbatch is produced using extrusion molding, and the heat-expandable microcapsules tend to foam. . As a result, the true specific gravity of the masterbatch is lowered, making it impossible to produce a stable masterbatch.
- the monomer mixture (3) cross-linking by ionic bonds is mainly performed and cross-linking by covalent bonds is reduced, so that sufficient strength is obtained without using the polymerizable monomer (III) having two or more double bonds in the molecule. And it is possible to obtain thermally expandable microcapsules having heat resistance.
- "does not contain a polymerizable monomer (III) having two or more double bonds in the molecule in the monomer mixture” means that the polymerizable monomer (III) is not substantially contained. When the polymerizable monomer (III) is contained in a very small amount, it is regarded as not containing the polymerizable monomer (III).
- the radically polymerizable unsaturated carboxylic acid monomer (II), and the like other monomers may be added to the monomer mixture.
- the other monomers include methyl acrylate, ethyl acrylate, butyl acrylate, acrylic acid esters such as dicyclopentenyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobornyl methacrylate, and the like.
- Vinyl monomers such as methacrylic acid esters, vinyl acetate, and styrene are included.
- methyl methacrylate, ethyl methacrylate, methyl acrylate and the like are preferably used.
- the content of other monomers in the total monomers constituting the shell is preferably less than 10% by weight. If the content of the other monomer is 10% by weight or more, the gas barrier property of the cell wall is lowered and the thermal expansion property tends to be deteriorated, which is not preferable.
- the monomer mixture contains a polymerization initiator for polymerizing the monomers.
- a polymerization initiator for example, dialkyl peroxide, diacyl peroxide, peroxyester, peroxydicarbonate, azo compound and the like are preferably used.
- dialkyl peroxide include methyl ethyl peroxide, di-t-butyl peroxide, isobutyl peroxide and dicumyl peroxide.
- diacyl peroxide include benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide and the like.
- peroxyester examples include t-butyl peroxypivalate, t-hexyl peroxypivalate, t-butyl peroxyneodecanoate, t-hexyl peroxyneodecanoate, 1-cyclohexyl-1-methyl ethyl peroxyneodecanoate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate and the like.
- peroxydicarbonate examples include bis(4-t-butylcyclohexyl)peroxydicarbonate, di-n-propyl-oxydicarbonate, diisopropylperoxydicarbonate, di(2-ethylethylperoxy)dicarbonate, and dimethoxybutyl peroxydicarbonate.
- azo compounds include 2,2′-azobisisobutyronitrile, 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile, 2,2′-azobis(2,4-dimethylvalero nitrile), 1,1′-azobis(1-cyclohexanecarbonitrile), and the like.
- a preferable lower limit of the weight average molecular weight of the polymer constituting the shell is 100,000, and a preferable upper limit thereof is 2,000,000. If the weight-average molecular weight is less than 100,000, the strength of the shell may decrease, and if the weight-average molecular weight exceeds 2,000,000, the strength of the shell may become too high and the foaming ratio may decrease.
- the shell may further contain a stabilizer, an ultraviolet absorber, an antioxidant, an antistatic agent, a flame retardant, a silane coupling agent, a coloring agent, and the like, if necessary.
- the thermally expandable microcapsules contain a volatile expanding agent as a core agent in the shell.
- the volatile expanding agent is a substance that becomes gaseous at a temperature below the softening point of the polymer that constitutes the shell, and is preferably a low boiling point organic solvent.
- the volatile swelling agent include low molecular weight hydrocarbons, chlorofluorocarbons, tetraalkylsilanes, and the like.
- Examples of the low molecular weight hydrocarbons include ethane, ethylene, propane, propene, n-butane, isobutane, butene, isobutene, n-pentane, isopentane, neopentane, n-hexane, heptane, isooctane, and petroleum ether.
- Examples of the chlorofluorocarbon include CCl 3 F, CCl 2 F 2 , CClF 3 , CClF 2 —CClF 2 and the like.
- tetraalkylsilane examples include tetramethylsilane, trimethylethylsilane, trimethylisopropylsilane, and trimethyl-n-propylsilane.
- isobutane, n-butane, n-pentane, isopentane, n-hexane, isooctane, petroleum ether, and mixtures thereof are preferred.
- These volatile swelling agents may be used alone or in combination of two or more.
- a thermally decomposable compound that is thermally decomposed by heating into a gaseous state may be used.
- thermally expandable microcapsules it is preferable to use a low boiling point hydrocarbon having 5 or less carbon atoms among the volatile expanding agents described above. By using such a hydrocarbon, it is possible to obtain thermally expandable microcapsules that have a high foaming ratio and start foaming quickly. Further, as the volatile expansion agent, a thermally decomposable compound that is thermally decomposed by heating into a gaseous state may be used.
- the preferable lower limit of the content of the volatile expanding agent used as the core agent is 10% by weight, and the preferable upper limit thereof is 25% by weight.
- the thickness of the shell varies depending on the content of the core agent. If the content of the core agent is reduced and the shell becomes too thick, the foaming performance will decrease, and if the content of the core agent is increased, the strength of the shell will decrease. do. When the content of the core agent is 10 to 25% by weight, it is possible to achieve both prevention of settling of the thermally expandable microcapsules and improvement of foaming performance.
- the maximum foaming temperature (Tmax) of the thermally expandable microcapsules preferably has a lower limit of 180°C and a preferred upper limit of 230°C. If the maximum foaming temperature is less than 180°C, the heat resistance will be low, so that the thermally expandable microcapsules will burst and shrink in a high temperature region or during molding. Moreover, foaming occurs due to shearing during the production of the masterbatch, making it impossible to stably produce an unfoamed masterbatch. A more preferable lower limit of the maximum foaming temperature is 190°C. In this specification, the maximum foaming temperature is the temperature at which the diameter of the thermally expandable microcapsules is maximized (maximum displacement) when the diameter of the thermally expandable microcapsules is measured while being heated from room temperature. means temperature.
- the thermally expandable microcapsules preferably have a maximum displacement (Dmax) of 300 ⁇ m as a lower limit and 1200 ⁇ m as an upper limit as measured by thermomechanical analysis.
- the maximum amount of displacement is the value when the diameter of the entire predetermined amount of thermally expandable microcapsules becomes maximum when the diameter is measured while heating a predetermined amount of thermally expandable microcapsules from room temperature.
- the preferred lower limit of the foaming start temperature (Ts) is 160°C, and the preferred upper limit is 200°C.
- the maximum foaming temperature means the temperature at which the thermally expandable microcapsules become the maximum amount of displacement when the diameter is measured while the thermally expandable microcapsules are heated from room temperature.
- a preferable lower limit of the average particle size of the thermally expandable microcapsules is 15 ⁇ m, and a preferable upper limit thereof is 25 ⁇ m.
- the average particle size is 15 ⁇ m or more, the foaming of the obtained molded article is sufficient, and when the average particle size is 25 ⁇ m or less, the strength of the obtained molded article can be made sufficient.
- a more preferable lower limit of the average particle size is 18 ⁇ m, and a more preferable upper limit thereof is 23 ⁇ m.
- the average particle size of the thermally expandable microcapsules means the volume average particle size measured using a particle size distribution analyzer.
- the thermally expandable microcapsules are cut using a single-edged razor, and the cross-sectional diameter of the thermally expandable microcapsules in the cross section is measured by SEM (scanning type 20 or more are measured using an electron microscope), and the average value of the top 80% cross-sectional diameters is taken as the average particle diameter of the thermally expandable microcapsules.
- a preferable lower limit of the true specific gravity of the thermally expandable microcapsules is 0.95 g/cm 3 .
- the true specific gravity is 0.95 g/cm 3 or more, a highly foamable molded article can be obtained.
- a more preferred lower limit to the true specific gravity is 1.0 g/cm 3 and a preferred upper limit is 1.10 g/cm 3 .
- the true specific gravity is the specific gravity of the material only, excluding the pores, and represents the ratio of the mass of the unit volume of the thermally expandable microcapsules to the mass of water of the same volume at 4°C.
- the true specific gravity can be measured by a method conforming to JIS K 7112 A method (water substitution method).
- thermoly expandable microcapsules for example, a step of preparing an aqueous medium, 40 to 90% by weight of the polymerizable monomer (I), and a radical having a carboxyl group and a carbon number of 3 to 8 A step of dispersing an oil mixture containing 5 to 50% by weight of the polymerizable unsaturated carboxylic acid monomer (II) and a volatile swelling agent in an aqueous medium is carried out. Then, the method of performing the process of polymerizing the said monomer, etc. are mentioned.
- the first step is to prepare an aqueous medium.
- an aqueous dispersion medium containing a dispersion stabilizer is prepared by adding water, a dispersion stabilizer, and optionally a co-stabilizer to a polymerization reactor.
- alkali metal nitrite, stannous chloride, stannic chloride, potassium dichromate, etc. may be added.
- dispersion stabilizer examples include silica, calcium phosphate, magnesium hydroxide, aluminum hydroxide, ferric hydroxide, barium sulfate, calcium sulfate, sodium sulfate, calcium oxalate, calcium carbonate, calcium carbonate, barium carbonate, carbonate Magnesium etc. are mentioned.
- the amount of the dispersion stabilizer to be added is not particularly limited, and is appropriately determined depending on the type of the dispersion stabilizer, the particle size of the thermally expandable microcapsules, etc., but the preferable lower limit is 0.1 weight part with respect to 100 parts by weight of the monomer. parts, and the preferred upper limit is 20 parts by weight.
- co-stabilizer examples include a condensation product of diethanolamine and an aliphatic dicarboxylic acid, a condensation product of urea and formaldehyde, and the like. Also included are polyvinylpyrrolidone, polyethylene oxide, polyethyleneimine, tetramethylammonium hydroxide, gelatin, methylcellulose, polyvinyl alcohol, dioctylsulfosuccinate, sorbitan ester, and various emulsifiers.
- the combination of the dispersion stabilizer and the co-stabilizer is not particularly limited, and examples include a combination of colloidal silica and a condensation product, a combination of colloidal silica and a water-soluble nitrogen-containing compound, and magnesium hydroxide or calcium phosphate. A combination with an emulsifier and the like are included. Among these, a combination of colloidal silica and a condensation product is preferred. Further, the condensation product is preferably a condensation product of diethanolamine and an aliphatic dicarboxylic acid, particularly preferably a condensation product of diethanolamine and adipic acid or a condensation product of diethanolamine and itaconic acid.
- water-soluble nitrogen-containing compounds examples include polyvinylpyrrolidone, polyethyleneimine, polyoxyethylenealkylamine, polydialkylaminoalkyl(meth)acrylate, polydialkylaminoalkyl(meth)acrylamide, polyacrylamide, polycationic acrylamide, and polyamine sulfone. , polyallylamine, and the like.
- polydialkylaminoalkyl (meth)acrylates include polydimethylaminoethyl methacrylate and polydimethylaminoethyl acrylate.
- polydialkylaminoalkyl(meth)acrylamide examples include polydimethylaminopropylacrylamide and polydimethylaminopropylmethacrylamide.
- polyvinylpyrrolidone is preferably used.
- the amount of colloidal silica to be added is appropriately determined according to the particle size of the thermally expandable microcapsules, but the preferred lower limit is 1 part by weight and the preferred upper limit is 20 parts by weight with respect to 100 parts by weight of the vinyl monomer. A more preferable lower limit to the amount of colloidal silica added is 2 parts by weight, and a more preferable upper limit is 10 parts by weight.
- the amount of the condensation product or water-soluble nitrogen-containing compound to be added is also appropriately determined depending on the particle size of the thermally expandable microcapsules.
- the upper limit is 2 parts by weight.
- Inorganic salts such as sodium chloride and sodium sulfate may be added in addition to the dispersion stabilizer and co-stabilizer. By adding an inorganic salt, thermally expandable microcapsules having a more uniform particle shape can be obtained.
- the amount of the inorganic salt added is preferably 0 to 100 parts by weight per 100 parts by weight of the monomer.
- the aqueous dispersion medium containing the dispersion stabilizer is prepared by blending the dispersion stabilizer and co-stabilizer with deionized water, and the pH of the aqueous phase at this time is determined by the type of dispersion stabilizer and co-stabilizer used. can be determined as appropriate.
- the type of dispersion stabilizer and co-stabilizer used can be determined as appropriate.
- silica such as colloidal silica
- polymerization is carried out in an acidic medium. ⁇ 4.
- magnesium hydroxide or calcium phosphate the polymerization is carried out in an alkaline medium.
- the method for producing thermally expandable microcapsules 40 to 90% by weight of the polymerizable monomer (I) and a radically polymerizable unsaturated carboxylic acid monomer (II) having a carboxyl group and having 3 to 8 carbon atoms ) dispersing an oil mixture containing 5 to 50% by weight and a volatile swelling agent in an aqueous medium.
- the monomer and the volatile swelling agent may be separately added to the aqueous dispersion medium to prepare an oily mixed solution in the aqueous dispersion medium. , is added to the aqueous dispersion medium.
- an oily mixed solution and an aqueous dispersion medium are prepared in advance in separate containers, and the oily mixed solution is dispersed in the aqueous dispersion medium by stirring and mixing in another container, and then added to the polymerization reaction vessel. You may add.
- a polymerization initiator is used to polymerize the monomers. The polymerization initiator may be added in advance to the oily mixture, and the aqueous dispersion medium and the oily mixture are placed in a polymerization reaction vessel. may be added after stirring and mixing.
- a method of emulsifying and dispersing the above oily mixture in an aqueous dispersion medium to have a predetermined particle size a method of stirring with a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd., for example) or the like, a line mixer or an element type static disperser. and a method of passing through a static dispersing device such as.
- the static dispersing device may be supplied with the aqueous dispersion medium and the polymerizable mixture separately, or may be supplied with a previously mixed and stirred dispersion.
- the thermally expandable microcapsules can be produced by, for example, performing a step of polymerizing a monomer by heating the dispersion liquid obtained through the above steps.
- the thermally expandable microcapsules produced by such a method have a high maximum foaming temperature, are excellent in heat resistance, and do not burst or shrink even in high-temperature regions or during molding. Moreover, since the bulk specific gravity is high, there is no foaming due to shearing during the production of the masterbatch, and an unfoamed masterbatch can be produced stably.
- the foam molding masterbatch of the present invention may contain a chemical foaming agent.
- a chemical foaming agent such as sodium hydrogen carbonate
- foaming performance can be improved by CO 2 generated during decomposition.
- thermally expandable microcapsules together with the chemical foaming agent it is possible to suppress the formation of open cells that tend to occur when the chemical foaming agent is used alone.
- the chemical foaming agent is not particularly limited as long as it is in the form of a powder at room temperature, and conventionally widely used chemical foaming agents can be used.
- inorganic chemical blowing agents such as sodium hydrogen carbonate
- organic blowing agents such as azodicarbonamide, N,N'-dinitrosopentamethylenetetramine, P,P'-oxybisbenzenesulfonyl hydrazide, paratoluenesulfonyl hydrazide, etc. system chemical blowing agents.
- the foam molding masterbatch of the present invention may contain additives such as lubricants.
- additives such as lubricants.
- the shear applied to the thermally expandable microcapsules during the production of the masterbatch is suppressed, the occurrence of microfoaming etc. becomes difficult, and the dispersibility of the thermally expandable microcapsules can be improved. It becomes easier to manufacture a masterbatch. As a result, a masterbatch having a high concentration of thermally expandable microcapsules can be stably produced with high production efficiency.
- the lubricant is not particularly limited as long as it melts at the temperature during the production of the masterbatch.
- Specific examples include polyethylene waxes having a viscosity average molecular weight of 3,000 or less, glycerin fatty acid esters such as glycerin monostearate and diglycerin stearate, fatty acids such as stearic acid, and composite lubricants.
- the method for producing the foam molding masterbatch of the present invention is not particularly limited. It can be manufactured by performing a cutting step of cutting the strand after the step (cold cut method). Moreover, after performing the said mixing process, you may use the method (hot cut method) which performs a cutting process, without performing a cooling process. Furthermore, a method (sheet cutting method) of extruding into a sheet and performing a cooling step and a cutting step may be used.
- two or more feeders are connected to the feed port of the extruder, and the base resin and the thermally expandable microcapsules are fed into the extruder from separate feeders and mixed by kneading in the extruder. method, and a method of pre-mixing and then feeding into an extruder.
- Extruders used in the mixing step include those having a feed port, a vent, a screw, a temperature control function, and a discharge port (head).
- the extruder there are various extrusion methods such as single screw, twin screw and multi-screw, but the twin screw is preferable.
- the biaxial screw can include a different direction system, a same direction system (conical system, parallel system), etc. In the production method of the present invention, it does not matter whether it is a same direction system (conical system or parallel system). ) is preferably employed.
- the mixing step it is preferable to replace the inside of the extruder with an inert gas such as nitrogen, or to deaerate with a single-stage or multi-stage vent (that is, open the vent). Further, forced degassing may be performed by vacuuming from the vent.
- an inert gas such as nitrogen
- the temperature of the cylinder of the extruder is in the range of 90 to 110°C. It is preferable to set the temperature of the region near the raw material addition portion of the extruder within the above range. Further, the screw rotation speed in the mixing step is preferably in the range of 270 to 330 rpm. (In this case, the discharge amount is about 100 kg/hour)
- an air cooling method and a water cooling method can be mentioned, but it is preferable to use the water cooling method.
- a cooling method by the water cooling system for example, there is a method of conveying the strand in the direction of a cutter (cutter) while contacting the strand with water to cool the strand.
- the submerged distance (water cooling distance) in the cooling method using the water cooling system is preferably 60 to 200 cm when the discharge amount is around 100 kg.
- the strand take-up speed is preferably about 0.2 to 0.6 m/s.
- a strand cutter or the like is used to cut the cooled strands at appropriate intervals and pelletize them.
- the strand cutter is not particularly limited and can be appropriately selected according to the purpose.
- the properties of the masterbatch for foam molding of the present invention can be appropriately controlled by each composition and content ratio of. Further, the properties of the foam molding masterbatch of the present invention can be appropriately controlled by the temperature in the extruder in the mixing process, the opening and closing of the vent, the submersion distance in the cooling process, and the like.
- a resin composition obtained by adding a matrix resin such as a thermoplastic resin to the foam molding masterbatch of the present invention is molded using a molding method such as injection molding, and the thermally expandable microcapsules expand by heating during molding.
- a foam molded article can be produced by allowing the Such a foam molded article is also one aspect of the present invention.
- the foamed molded article of the present invention obtained by such a method has a high expansion ratio and high appearance quality, has uniformly formed closed cells, and is excellent in lightness, heat insulation, impact resistance, rigidity, etc. It can be suitably used for housing building materials, automobile members, shoe soles, and the like.
- the matrix resin such as the thermoplastic resin is not particularly limited as long as it does not interfere with the object of the present invention.
- general thermoplastic resins such as polyvinyl chloride, polystyrene, polypropylene, polypropylene oxide, and polyethylene are used.
- Engineering plastics such as polybutylene terephthalate, nylon, polycarbonate, and polyethylene terephthalate are also included.
- Thermoplastic elastomers such as ethylene, vinyl chloride, olefin, urethane, and ester may also be used, and these resins may be used in combination.
- the matrix resin it is preferable to use the same resin as the base resin.
- the amount of the masterbatch for foam molding of the present invention added to 100 parts by weight of the thermoplastic resin is preferably 0.5 to 20 parts by weight, more preferably 1 to 10 parts by weight.
- the method for molding the foam molded article of the present invention is not particularly limited, and examples thereof include kneading molding, calendar molding, extrusion molding, injection molding and the like.
- the method is not particularly limited, and the short-short method, in which a part of the resin material is put into the mold and foamed, or the core-back method, in which the mold is fully filled with the resin material and then opened to the desired foaming point. etc.
- Examples of uses of the molded product obtained by the molding method of the present invention include automotive interior materials such as door trims and instrument panels, and automotive exterior materials such as bumpers. Other uses include building materials such as wood powder plastics, and uses such as shoe soles and artificial cork.
- the masterbatch for foam molding which can maintain foaming with time and can manufacture a foam molding with little overfoaming can be provided. Also, a foam molded product using the foam molding masterbatch can be provided.
- a polymerization reaction vessel was charged with 300 parts by weight of water, 89 parts by weight of sodium chloride as a modifier, 0.07 parts by weight of sodium nitrite as a water-soluble polymerization inhibitor, and 8 parts by weight of colloidal silica (manufactured by Asahi Denka Co., Ltd.) as a dispersion stabilizer. and 0.3 parts by weight of polyvinylpyrrolidone (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) were added to prepare an aqueous dispersion medium.
- a dispersion was prepared by adding and mixing an oil-based mixture containing the metal salt, monomer, volatile swelling agent, and polymerization initiator in the amounts shown in Table 1 to the aqueous dispersion medium. Total dispersion is 15 kg. The resulting dispersion is stirred and mixed with a homogenizer, charged into a nitrogen-substituted pressurized polymerization vessel (20 L), pressurized (0.2 MPa), and reacted at 60 ° C. for 20 hours to prepare a reaction product. bottom. The resulting reaction product was repeatedly dehydrated and washed with water using a centrifuge, and then dried to obtain thermally expandable microcapsules (Nos. 1 to 4).
- the polymerizable monomer (I) is defined as monomer (I)
- the radically polymerizable unsaturated carboxylic acid monomer (II) is defined as monomer (II)
- the polymerizable monomer (III) is defined as monomer (III).
- Example 1 Preparation of masterbatch pellets
- LDPE low-density polyethylene
- fatty acid ester 4 parts by weight
- 28 parts by weight of the obtained thermally expandable microcapsules were added and mixed. It was supplied to a twin-screw extruder (TEM48SS manufactured by Toshiba Machine Co., Ltd., co-directional system). After that, kneading was carried out with the cylinder temperatures of the areas (C2 part, C3 part) close to the raw material addition part set to 98° C. for the C2 part and 99° C. for the C3 part.
- LDPE low-density polyethylene
- the vent installed in the extruder was open
- Manufacturing foam molded product 3 parts by weight of the obtained masterbatch pellets and 100 parts by weight of an olefin elastomer (TPO, manufactured by Mitsui Chemicals, Milastomer 7030BS) are mixed, and the obtained mixed pellets are supplied to the hopper of an extruder and melt-kneaded. Then, extrusion molding was performed to obtain a plate-like foamed molding.
- the extrusion conditions were a mold temperature of 190°C.
- Examples 2 to 10, Comparative Examples 1 to 5 Preparation of masterbatch pellets
- EMMA in Table 2 represents an ethylene-methyl methacrylate copolymer (Acryft CM5021 manufactured by Sumitomo Chemical Co., Ltd.).
- Aclift CM5021 has an MMA content of 28% by weight and a melt index of 450 g/10 minutes. The melt index is measured by the measuring method specified in JIS K7210-1.
- thermally expandable microcapsules surface area of 1 thermally expandable microcapsules x number per 1 g of thermally expandable microcapsules
- Surface area of 1 thermally expandable microcapsules 4 x ⁇ x (volume average particle diameter/2 ) 2
- interfacial area per unit weight The ratio of the porosity with a diameter of 0.001 ⁇ m or more (porosity with a diameter of 0.001 ⁇ m or more/interfacial area per unit weight) was calculated.
- CV value (standard deviation / average value) ⁇ 100
- the masterbatch for foam molding which can maintain foaming with time and can manufacture a foam molding with little overfoaming can be provided. Also, a foam molded product using the foam molding masterbatch can be provided.
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Abstract
Description
また、特許文献2には、ポリオレフィン樹脂又はスチレン樹脂をベースレジンとし、発泡剤として、化学発泡剤に代えて熱膨張性マイクロカプセルを用いた発泡樹脂マスターバッチが記載されている。
また、化学発泡剤は、加熱分解すると分解ガスと同時に発泡残さを生じ、成形体に残った残さが成形体の接着性能に影響を与えることがある。また、化学発泡剤を使用すると、経時的に発泡を維持することが難しいといった問題点がある。
更に、熱膨張性マイクロカプセルを用いた場合でも、得られる発泡体の発泡倍率は低く、過発泡が少ない発泡成形体を得ることが困難である。
本開示(2)は、粒度分布(CV値)が20%以下である、本開示(1)に記載の発泡成形用マスターバッチである。
本開示(3)は、直径0.1μm以上の空隙率が4%以下である、本開示(1)又は(2)に記載の発泡成形用マスターバッチである。
本開示(4)は、直径0.001μm以上の空隙率が11%以下である、本開示(1)~(3)のいずれかに記載の発泡成形用マスターバッチである。
本開示(5)は、ベースレジンが、ポリエチレン系樹脂及びアクリル系樹脂からなる群より選択される少なくとも1種である、本開示(1)~(4)のいずれかに記載の発泡成形用マスターバッチである。
本開示(6)は、ベースレジンの含有量が30重量%以上80重量%以下であり、熱膨張性マイクロカプセルの含有量が20重量%以上70重量%以下である、本開示(1)~(5)のいずれかに記載の発泡成形用マスターバッチである。
本開示(7)は、単位重量当たりの界面面積が500~1600cm2/gである、本開示(1)~(6)のいずれかに記載の発泡成形用マスターバッチである。
本開示(8)は、本開示(1)~(7)のいずれかに記載の発泡成形用マスターバッチを用いてなる発泡成形体である。
以下に本発明を詳述する。
なお、本明細書において上記直径0.001μm以上の空隙率とは、発泡成形用マスターバッチの体積に占める細孔直径0.001μm以上の空隙の容積を意味する。
なお、本明細書において上記直径0.1μm以上の空隙率とは、発泡成形用マスターバッチの体積に占める細孔直径0.1μm以上の空隙の容積を意味する。
上記直径0.001μm以上の空隙率、直径0.1μm以上の空隙率は、例えば、ポロシメーター(Thermo Pascal 14B、Thermo Fisher Scientific社製)を用い、水銀圧入法で測定することができる。
なお、本明細書において上記単位重量当たりの界面面積は、熱膨張性マイクロカプセルの体積平均粒子径、真比重、発泡成形用マスターバッチ中における熱膨張性マイクロカプセルの含有量から算出することができる。
なお、本明細書において上記平均細孔径は、上記直径0.001μm以上の空隙率、直径0.1μm以上の空隙率の場合と同様に水銀圧入法で測定することができる。
なお、本明細書において上記揮発分は、オーブンで70℃で60分間加熱した後の重量変化から測定することができる。
なお、上記平均外径、CV値は、ノギスによる実寸測定のn増し評価(例えばn=10)によって測定することができる。
上記真比重のより好ましい下限は0.90g/cm3、好ましい上限は1.0g/cm3である。
上記真比重とは、空孔を除いた素材のみの比重をいい、20℃におけるマスターバッチの単位体積の質量と、それと等体積の4℃における水の質量との比を表す。上記真比重は、JIS K 7112 A法(水中置換法)に準拠した方法により測定することができる。
本発明では、上記ベースレジンとして、アクリル系樹脂及びポリエチレン系樹脂から選択される少なくとも1種を含有する。これにより、外観品質が良好な発泡成形体を製造することができる。
上記(メタ)アクリル酸エステルとしては、例えば、メチル(メタ)アクリレート、エチル(メタ)アクリレート、イソプロピル(メタ)アクリレート、n-ブチル(メタ)アクリレート、イソブチル(メタ)アクリレート等が挙げられる。また、上記(メタ)アクリル酸エステルとしては、n-アミル(メタ)アクリレート、イソアミル(メタ)アクリレート、n-ヘキシル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、n-オクチル(メタ)アクリレート等がある。ただし上記の(メタ)アクリル酸とはアクリル酸もしくはメタクリル酸を示す。
なかでも、アクリル系モノマーとα-オレフィンとの共重合体が好ましく、エチレン-メチルメタクリレート共重合体(EMMA)がより好ましい。
これらの共単量体は、アクリル系樹脂中に、ランダム共重合体、グラフト共重合体、ブロック共重合体の形で存在することができる。
上記MMA含有量が上記範囲内である(メタ)アクリル共重合体を使用することで、成形性や熱膨張性マイクロカプセルの分散性を向上させることができる。
上記重量平均分子量を上記範囲内とすることで、外観の優れた成形品を得ることができる。
上記重量平均分子量(Mw)は、ゲルパミエーションクロマトグラフィ(GPC)法によりポリスチレン換算分子量として測定される。
上記メルトインデックスを1g/10分以上とすることで、マスターバッチの変形を防止することができ、500g/10分以下とすることで、得られる成形体の外観を良好なものとすることができる。
なお、メルトインデックスとは、樹脂の流動性を示す指数を意味し、ヒーターで加熱された円筒容器内で一定量の合成樹脂を、定められた温度(例えば、190℃)で加熱、定められた荷重(例えば2.16kg)で加圧し、容器底部に設けられた開口部(ノズル)から10分間あたりに押出された樹脂量で示す。単位はg/10分が使用され、JIS K7210-1で規定されている測定方法で測定する。
なお、上記他の樹脂成分を使用する場合、上記アクリル系樹脂の比率は、80重量%以上であることが好ましく、90重量%以上であることがより好ましく、通常100重量%未満である。
上記熱可塑性樹脂としては、例えば、ポリ塩化ビニル、ポリプロピレン、ポリプロピレンオキシド、ポリスチレン等の一般的な熱可塑性樹脂、ポリブチレンテレフタレート、ナイロン、ポリカーボネート、ポリエチレンテレフタレート等のエンジニアリングプラスチックが挙げられる。なお、これらのなかでは、低密度ポリエチレン、高密度ポリエチレン、ポリプロピレン及びポリスチレンからなる群より選択される少なくとも1種が好ましい。
また、熱膨張性マイクロカプセルのシェルに占めるメチルメタクリレートに由来する成分の含有量が15~25重量%であり、かつ、上記ベースレジンに占めるメチルメタクリレートに由来する成分の含有量が3~25重量%であることが好ましい。
本発明の発泡成形用マスターバッチにおける上記熱膨張性マイクロカプセルの含有量の好ましい下限は20重量%、好ましい上限は70重量%である。上記熱膨張性マイクロカプセルの含有量を20重量%以上とすることで、所望の発泡倍率を得ることができる。上記熱膨張性マイクロカプセルの含有量を70重量%以下とすることで、マスターバッチ作製時の発泡を防止して、結果として発泡成形品の発泡倍率を向上させることができる。上記熱膨張性マイクロカプセルの含有量のより好ましい下限は25重量%、より好ましい上限は60重量%、更に好ましい上限は55重量%である。
上記重合性モノマー(I)を添加することで、シェルのガスバリア性を向上させることができる。
上記不飽和モノカルボン酸としては、アクリル酸、メタクリル酸、エタクリル酸、クロトン酸、ケイ皮酸等が挙げられる。上記不飽和ジカルボン酸としては、マレイン酸、イタコン酸、フマル酸、シトラコン酸、クロロマレイン酸等が挙げられる。上記不飽和ジカルボン酸のモノエステルとしては、マレイン酸モノメチル、マレイン酸モノエチル、マレイン酸モノブチル、フマル酸モノメチル、フマル酸モノエチル、イタコン酸モノメチル、イタコン酸モノエチル、イタコン酸モノブチル等が挙げられる。これらは単独で用いてもよく、2種以上を併用してもよい。これらのなかでは、特にアクリル酸、メタクリル酸、マレイン酸、無水マレイン酸、イタコン酸が好ましい。
上記モノマー混合物(1)では、上記重合性モノマー(I)とラジカル重合性不飽和カルボン酸モノマー(II)とを所定量含有するモノマー混合物を用いることで、充分な強度を有するシェルが得られる。これにより、上記モノマー混合物中に分子内に二重結合を2つ以上有する重合性モノマー(III)を含有しない場合でも、優れた耐剪断性、耐熱性、発泡性を有する熱膨張性マイクロカプセルとすることができる。上述のように充分な強度を有する理由は明確でないが、カルボキシル基同士の脱水縮合反応による架橋が関係していると考えられる。
また、上記重合性モノマー(III)を添加した場合、熱膨張性マイクロカプセルの粒子形状が歪なものとなり、結果として嵩比重が低下してしまう。嵩比重が低下してしまうと、次工程において、特に押出成形を用いてマスターバッチを製造する場合に、熱膨張性マイクロカプセルに剪断がかかりやすくなるため、熱膨張性マイクロカプセルが発泡気味となる。その結果、マスターバッチの真比重が低下する等によって、安定したマスターバッチが作れず、その後に射出成形等を用いて発泡成形を行う場合に、発泡倍率にバラツキが生じやすくなる。
更に、トリメチロールプロパントリ(メタ)アクリレート、エチレンオキサイド変性トリメチロールプロパントリ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、トリアリルホルマールトリ(メタ)アクリレート等が挙げられる。
加えて、ペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、ジメチロール-トリシクロデカンジ(メタ)アクリレート等が挙げられる。
上記重合性モノマー(III)を含有することにより、シェルの強度を強化することができ、熱膨張時にセル壁が破泡し難くなる。
また、1,9-ノナンジオールジ(メタ)アクリレート、分子量が200~600のポリエチレングリコールのジ(メタ)アクリレート、グリセリンジ(メタ)アクリレート、トリメチロールプロパンジ(メタ)アクリレート等が挙げられる。
更に、トリメチロールプロパントリ(メタ)アクリレート、エチレンオキサイド変性トリメチロールプロパントリ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート等が挙げられる。
上記金属カチオン水酸化物(IV)を含有することで、上記ラジカル重合性不飽和カルボン酸モノマー(II)のカルボキシル基との間でイオン結合が起こることから、剛性が上がり、耐熱性を高くすることが可能となる。その結果、高温領域において長時間破裂、収縮の起こらない熱膨張性マイクロカプセルとすることが可能となる。また、高温領域においてもシェルの弾性率が低下しにくいことから、強い剪断力が加えられる混練成形、カレンダー成形、押出成形、射出成形等の成形加工を行う場合であっても、熱膨張性マイクロカプセルの破裂、収縮が起こることがない。
また、共有結合でなくイオン結合であるから、熱膨張性マイクロカプセルの粒子形状が真球に近くなり、歪みが生じにくくなる。これは、イオン結合による架橋が、共有結合による架橋に比べて結合力が弱いため、重合中のモノマーからポリマーへ転化時において、熱膨張性マイクロカプセルの体積が収縮する際に均一に収縮が生じることが原因と考えられる。
ラジカル重合性不飽和カルボン酸モノマー(II)と金属カチオン水酸化物(IV)との間でイオン結合による架橋が起こることで、上記モノマー混合物中に分子内に二重結合を2つ以上有する重合性モノマー(III)を含有しない場合でも、得られるシェルは充分な強度及び耐熱性を有する。なお、上記重合性モノマー(III)を添加した場合、熱膨張性マイクロカプセルの粒子形状が歪なものとなり、結果として嵩比重が低下してしまう。嵩比重が低下してしまうと、次工程において、特に押出成形を用いてマスターバッチを製造する場合に、熱膨張性マイクロカプセルに剪断がかかりやすくなるため、熱膨張性マイクロカプセルが発泡気味となる。その結果、マスターバッチの真比重が低下する等によって、安定したマスターバッチが作れず、その後に射出成形等を用いて発泡成形を行う場合に、発泡倍率にバラツキが生じやすくなる。
上記重合開始剤としては、例えば、過酸化ジアルキル、過酸化ジアシル、パーオキシエステル、パーオキシジカーボネート、アゾ化合物等が好適に用いられる。
上記過酸化ジアルキルとしては、メチルエチルパーオキサイド、ジ-t-ブチルパーオキサイド、イソブチルパーオキサイド、ジクミルパーオキサイド等が挙げられる。
上記過酸化ジアシルとしては、ベンゾイルパーオキサイド、2,4-ジクロロベンゾイルパーオキサイド、3,5,5-トリメチルヘキサノイルパーオキサイド等が挙げられる。
上記パーオキシエステルとしては、t-ブチルパーオキシピバレート、t-ヘキシルパーオキシピバレート、t-ブチルパーオキシネオデカノエート、t-ヘキシルパーオキシネオデカノエート、1-シクロヘキシル-1-メチルエチルパーオキシネオデカノエート、1,1,3,3-テトラメチルブチルパーオキシネオデカノエート等が挙げられる。
上記パーオキシジカーボネートとしては、ビス(4-t-ブチルシクロヘキシル)パーオキシジカーボネート、ジ-n-プロピル-オキシジカーボネート、ジイソプロピルパーオキシジカーボネート、ジ(2-エチルエチルパーオキシ)ジカーボネート、ジメトキシブチルパーオキシジカーボネート等が挙げられる。
上記アゾ化合物としては、2,2’-アゾビスイソブチロニトリル、2,2’-アゾビス(4-メトキシ-2,4-ジメチルバレロニトリル、2,2’-アゾビス(2,4-ジメチルバレロニトリル)、1,1’-アゾビス(1-シクロヘキサンカルボニトリル)等が挙げられる。
上記揮発性膨張剤は、シェルを構成するポリマーの軟化点以下の温度でガス状になる物質であり、低沸点有機溶剤が好適である。
上記揮発性膨張剤としては、例えば、低分子量炭化水素、クロロフルオロカーボン、テトラアルキルシラン等が挙げられる。
上記低分子量炭化水素としては、エタン、エチレン、プロパン、プロペン、n-ブタン、イソブタン、ブテン、イソブテン、n-ペンタン、イソペンタン、ネオペンタン、n-へキサン、ヘプタン、イソオクタン、石油エーテル等が挙げられる。
上記クロロフルオロカーボンとしては、CCl3F、CCl2F2、CClF3、CClF2-CClF2等が挙げられる。
上記テトラアルキルシランとしては、テトラメチルシラン、トリメチルエチルシラン、トリメチルイソプロピルシラン、トリメチル-n-プロピルシラン等が挙げられる。
なかでも、イソブタン、n-ブタン、n-ペンタン、イソペンタン、n-へキサン、イソオクタン、石油エーテル、及び、これらの混合物が好ましい。これらの揮発性膨張剤は単独で用いてもよく、2種以上を併用してもよい。
また、揮発性膨張剤として、加熱により熱分解してガス状となる熱分解型化合物を用いてもよい。
また、揮発性膨張剤として、加熱により熱分解してガス状になる熱分解型化合物を用いることとしてもよい。
上記シェルの厚みはコア剤の含有量によって変化するが、コア剤の含有量を減らして、シェルが厚くなり過ぎると発泡性能が低下し、コア剤の含有量を多くすると、シェルの強度が低下する。上記コア剤の含有量を10~25重量%とした場合、熱膨張性マイクロカプセルのへたり防止と発泡性能向上とを両立させることが可能となる。
なお、本明細書において、最大発泡温度は、熱膨張性マイクロカプセルを常温から加熱しながらその径を測定したときに、熱膨張性マイクロカプセルの径が最大となったとき(最大変位量)における温度を意味する。
なお、上記最大変位量は、所定量の熱膨張性マイクロカプセルを常温から加熱しながらその径を測定したときに、所定量全体の熱膨張性マイクロカプセルの径が最大となるときの値をいう。
また、発泡開始温度(Ts)の好ましい下限は160℃、好ましい上限は200℃である。
なお、本明細書において、最大発泡温度は、熱膨張性マイクロカプセルを常温から加熱しながらその径を測定したときに、熱膨張性マイクロカプセルが最大変位量となったときにおける温度を意味する。
なお、上記熱膨張性マイクロカプセルの平均粒子径は、粒度分布径測定器を用いて測定した体積平均粒子径を意味する。
ただし、マスターバッチ中の存在する熱膨張性マイクロカプセルの平均粒子径を求める場合、熱膨張性マイクロカプセルを片刃剃刀を用いて切断し、断面における熱膨張性マイクロカプセルの断面径をSEM(走査型電子顕微鏡)を用いて20個以上測り、上位80%の断面径の平均値を、熱膨張性マイクロカプセルの平均粒子径とする。
上記真比重のより好ましい下限は1.0g/cm3、好ましい上限は1.10g/cm3である。
上記真比重とは、空孔を除いた素材のみの比重をいい、上記熱膨張性マイクロカプセルの単位体積の質量と、それと等体積の4℃における水の質量との比を表す。上記真比重は、JIS K 7112 A法(水中置換法)に準拠した方法により測定することができる。
更に、上記縮合生成物としては、ジエタノールアミンと脂肪族ジカルボン酸との縮合生成物が好ましく、特にジエタノールアミンとアジピン酸との縮合物やジエタノールアミンとイタコン酸との縮合生成物が好ましい。
上記ポリジアルキルアミノアルキル(メタ)アクリレートとしては、ポリジメチルアミノエチルメタクリレート、ポリジメチルアミノエチルアクリレート等が挙げられる。
上記ポリジアルキルアミノアルキル(メタ)アクリルアミドとしては、ポリジメチルアミノプロピルアクリルアミドやポリジメチルアミノプロピルメタクリルアミド等が挙げられる。これらのなかでは、ポリビニルピロリドンが好適に用いられる。
なお、上記モノマーを重合するために、重合開始剤が使用されるが、上記重合開始剤は、予め上記油性混合液に添加してもよく、水性分散媒体と油性混合液とを重合反応容器内で攪拌混合した後に添加してもよい。
なお、上記静止型分散装置には水系分散媒体と重合性混合物を別々に供給してもよいし、予め混合、攪拌した分散液を供給してもよい。
また、上記混合工程を行った後、冷却工程を行わずに切断工程を行う方法(ホットカット法)を用いてもよい。更に、シート状に押し出して冷却工程、切断工程を行う方法(シートカット法)を用いてもよい。
上記混合工程において用いられる押出機としては、フィード口、ベント、スクリュー、温調機能、排出口(ヘッド)を有するものが挙げられる。
また、上記押出機としては、単軸、二軸、多軸等の種々の押出方式があるが、二軸スクリューであるものが好ましい。更に、二軸スクリューは、異方向方式、同方向方式(コニカル方式、パラレル方式)などを挙げることができるが、本発明の製造方法においては同方向方式(コニカル方式、パラレル方式はどちらでも構わない)を採用することが好ましい。
また、上記混合工程におけるスクリュー回転数は、270~330rpmの範囲で行うことが好ましい。(この場合、吐出量は約100kg/時間)
また、上記水冷方式を採用する場合、ストランドに付着した水を除くため、ストランドをカットするペレタイザーの前に水切り器や乾燥器を導入することが望ましい。
上記水冷方式による冷却方法としては、例えば、ストランドを水に接触させて冷却させながら、ストランドを切断器(カッター)の方向に搬送する方法が挙げられる。
上記水冷方式による冷却方法における水没距離(水冷距離)としては、吐出量100kg前後の場合は60~200cmが好ましい。更に、ストランド引き取り速度は、0.2~0.6m/s程度が好ましい。
また、本発明の発泡成形用マスターバッチの特性は、上記混合工程における押出機内の温度、ベントの開閉、上記冷却工程における水没距離等によっても、適宜制御することができる。
このような方法で得られる本発明の発泡成形体は、高発泡倍率かつ高外観品質が得られ、独立気泡が均一に形成されており、軽量性、断熱性、耐衝撃性、剛性等に優れるものとなり、住宅用建材、自動車用部材、靴底等の用途に好適に用いることができる。
重合反応容器に、水300重量部と、調整剤として塩化ナトリウム89重量部、水溶性重合禁止剤として亜硝酸ナトリウム0.07重量部、分散安定剤としてコロイダルシリカ(旭電化社製)8重量部及びポリビニルピロリドン(第一工業製薬社製)0.3重量部を投入し、水性分散媒体を調製した。次いで、表1に示した配合量の金属塩、モノマー、揮発性膨張剤、重合開始剤からなる油性混合液を水性分散媒体に添加、混合することにより、分散液を調製した。全分散液は15kgである。得られた分散液をホモジナイザーで攪拌混合し、窒素置換した加圧重合器(20L)内へ仕込み、加圧(0.2MPa)し、60℃で20時間反応させることにより、反応生成物を調製した。得られた反応生成物について、遠心分離機にて脱水と水洗を繰り返した後、乾燥して熱膨張性マイクロカプセル(No.1~4)を得た。
なお、表1では、重合性モノマー(I)をモノマー(I)、ラジカル重合性不飽和カルボン酸モノマー(II)をモノマー(II)、重合性モノマー(III)をモノマー(III)とした。
(マスターバッチペレットの作製)
ベースレジンとして低密度ポリエチレン(LDPE、東ソー社製、ペトロセン248)68重量部と、滑剤として脂肪酸エステル4重量部と、得られた熱膨張性マイクロカプセル28重量部とを添加し、混合したものを二軸押出機(東芝機械社製、TEM48SS、同方向方式)に供給した。その後、原料添加部分に近い領域(C2部分、C3部分)のシリンダ温度を、C2部分98℃、C3部分99℃として混練を行った。なお、押出機に設置されたベントは開放して押出を行った。次いで、押し出されたストランドを水に接触させて冷却させながら(水没距離:80cm)、ストランドを切断器(カッター)の方向に搬送した。その後、ストランドカッターを用いてカッティングすることでペレット化し、マスターバッチペレットを得た。
得られたマスターバッチペレット3重量部と、オレフィン系エラストマー(TPO、三井化学社製、ミラストマー7030BS)100重量部とを混合し、得られた混合ペレットを押出成形機のホッパーに供給して溶融混練し、押出成形を行い、板状の発泡成形体を得た。なお、押出条件は、金型温度:190℃とした。
(マスターバッチペレットの作製)
表2に示す種別・添加量の熱膨張性マイクロカプセル、ベースレジン、滑剤を用い、表2に示すように、押出機温度、ベント開閉、水没距離を調整した以外は実施例1と同様にして、マスターバッチペレット、発泡成形体を作製した。なお、表2中のEMMAはエチレン-メチルメタクリレート共重合体(住友化学社製、アクリフトCM5021)を表す。なお、アクリフトCM5021のMMA含有量は28重量%、メルトインデックスは450g/10分である。なお、上記メルトインデックスは、JIS K7210-1で規定されている測定方法で測定したものである。
熱膨張性マイクロカプセル(No.1~4)、及び、実施例1~10及び比較例1~5で得られた成形体について、下記性能を評価した。結果を表1及び表2に示した。
(1-1)体積平均粒子径
粒度分布径測定器(LA-910、HORIBA社製)を用い、体積平均粒子径を測定した。
熱機械分析装置(TMA)(TMAQ400、TA instruments社製)を用い、発泡開始温度(Ts)、最大変位量(Dmax)及び最大発泡温度(Tmax)を測定した。具体的には、試料25μgを直径7mm、深さ1mmのアルミ製容器に入れ、上から0.1Nの力を加えた状態で、5℃/minの昇温速度で80℃から250℃まで加熱し、測定端子の垂直方向における変位を測定し、変位が上がり始める温度を発泡開始温度、その変位の最大値を最大変位量とし、最大変位量における温度を最大発泡温度とした。
得られた熱膨張性マイクロカプセル2.7~2.8gを乾式自動密度計(株式会社島津製作所製、AccuPycII 1340)に投入し真比重を測定した。(ガスは空気で0.15~0.18MPaまで加圧)
(2-1)空隙率、平均細孔径
得られたマスターバッチペレットについて、ポロシメーター(Thermo Pascal 14B)を用い、水銀圧入法にて空隙率、平均細孔径を測定した。なお、空隙率については、細孔直径0.1μm以上の空隙の容積比(直径0.1μm以上の空隙率)、細孔直径0.001μm以上の空隙の容積比(直径0.001μm以上の空隙率)を測定した。
熱膨張性マイクロカプセルの体積平均粒子径、真比重、マスターバッチ中の熱膨張性マイクロカプセル含有量を用い、計算にて単位重量当たりの界面面積を算出した。具体的には、以下の式を用いた。
単位重量当たりの界面面積(cm2/g)=熱膨張性マイクロカプセル1g当たりの表面積×マスターバッチ中の熱膨張性マイクロカプセル含有量
また、上記熱膨張性マイクロカプセル1g当たりの表面積は以下の式を用いた。
熱膨張性マイクロカプセル1g当たりの表面積=熱膨張性マイクロカプセル1個の表面積×熱膨張性マイクロカプセル1g当たりの個数
熱膨張性マイクロカプセル1個の表面積=4×π×(体積平均粒子径/2)2
熱膨張性マイクロカプセル1g当たりの個数=1/1個の体積/真比重=1/(4/3×π×(体積平均粒子径/2)3)/真比重
また、単位重量当たりの界面面積に対する直径0.001μm以上の空隙率の比率(直径0.001μm以上の空隙率/単位重量当たりの界面面積)を算出した。
マスターバッチ約10gをアルミカップに計量し、70℃で60分間加熱した後、デシケーター中で40℃以下まで放冷し、その重量を量る。次の式により揮発分を算出した。
V=[(B-C)/(B-A)]×100
V:揮発分(%)
A:アルミカップの重量(g)
B:試料の入ったアルミカップの質量(g)
C:試料の入ったアルミカップの加熱放冷後の重量(g)
得られたマスターバッチペレットを無作為に10個取り、おのおのの外径についてノギスを用いて測定し、平均外径を算出した。
上記(2-4)で得られた10個の平均値と標準偏差から以下の式によりCV値を求めた。
CV値=(標準偏差/平均値)×100
6分加熱後と8分加熱後の発泡変位を測定した後、これらの発泡変位から、発泡性維持率を算出した。以下に、発泡変位、発泡性維持率の算出方法を示す。
[発泡変位]
得られたマスターバッチペレットを秤量(0.25±0.01g)して試験管(φ=約14mm、Fisherbrand Cat.No.141-961-29同等品)に投入する。その試験管を200℃に設定したオーブンにて6分間加熱した後の発泡高さを測定し、次式にてマスターバッチペレット1g当たりの6分加熱後の発泡変位を算出した。また、同様の方法で8分加熱後の発泡変位も算出した。
発泡変位(mm/g)=発泡高さ(mm)/投入したペレット重量(g)
[発泡性維持率]
得られた6分加熱後及び8分加熱後の発泡変位から、次式にて発泡性維持率を算出した。
発泡性維持率(%)=(8分加熱後の発泡変位/6分加熱後の発泡変位)×100
(3-1)断面状態
成形体の断面をカッターで切断し、走査型電子顕微鏡(日本電子社製、JEOL JSM-6510A)で断面状態を観察して、単位面積(1cm2)当たりの破胞(破れた発泡セル)の個数を計数した。
3D形状測定機(キーエンス社製)により、成形体表面の表面粗さ(Rz)を計測した。
Claims (8)
- ベースレジン、熱膨張性マイクロカプセルを含有する発泡成形用マスターバッチであり、単位重量当たりの界面面積に対する直径0.001μm以上の空隙率の比率(直径0.001μm以上の空隙率/単位重量当たりの界面面積)が0.015%/cm2/g以下であり、揮発分が0.7重量%以下である、発泡成形用マスターバッチ。
- 粒度分布(CV値)が20%以下である、請求項1に記載の発泡成形用マスターバッチ。
- 直径0.1μm以上の空隙率が4%以下である、請求項1又は2に記載の発泡成形用マスターバッチ。
- 直径0.001μm以上の空隙率が11%以下である、請求項1~3のいずれかに記載の発泡成形用マスターバッチ。
- ベースレジンが、ポリエチレン系樹脂及びアクリル系樹脂からなる群より選択される少なくとも1種である、請求項1~4のいずれかに記載の発泡成形用マスターバッチ。
- ベースレジンの含有量が30重量%以上80重量%以下であり、熱膨張性マイクロカプセルの含有量が20重量%以上70重量%以下である、請求項1~5のいずれかに記載の発泡成形用マスターバッチ。
- 単位重量当たりの界面面積が500~1600cm2/gである、請求項1~6のいずれかに記載の発泡成形用マスターバッチ。
- 請求項1~7のいずれかに記載の発泡成形用マスターバッチを用いてなる発泡成形体。
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11343362A (ja) | 1998-06-02 | 1999-12-14 | Asahi Chem Ind Co Ltd | 熱可塑性エラストマー発泡体 |
JP2000178372A (ja) | 1998-12-18 | 2000-06-27 | Kyowa Leather Cloth Co Ltd | 発泡性ペレット、射出発泡成形体、および射出発泡成形体の製造方法 |
WO2015119048A1 (ja) * | 2014-02-04 | 2015-08-13 | 松本油脂製薬株式会社 | マスターバッチおよびその用途 |
JP2020045485A (ja) * | 2018-09-18 | 2020-03-26 | 積水化学工業株式会社 | 発泡成形用マスターバッチ及び発泡成形体 |
JP2020045484A (ja) * | 2018-09-18 | 2020-03-26 | 積水化学工業株式会社 | 発泡成形用マスターバッチ及び発泡成形体 |
JP7128371B1 (ja) * | 2021-08-06 | 2022-08-30 | 積水化学工業株式会社 | 熱膨張性マイクロカプセル、発泡性マスターバッチ及び発泡成形体 |
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JPH08323743A (ja) * | 1995-05-31 | 1996-12-10 | Sekisui Plastics Co Ltd | ペレット用熱可塑性樹脂の押出用金型 |
US9126178B2 (en) * | 2009-06-09 | 2015-09-08 | Matsumoto Yushi-Seiyaku Co., Ltd. | Heat-expandable microspheres and a method of making heat-expandable microspheres and application thereof |
WO2019073825A1 (ja) * | 2017-10-13 | 2019-04-18 | 積水化学工業株式会社 | 発泡成形用マスターバッチ及び発泡成形体 |
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Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11343362A (ja) | 1998-06-02 | 1999-12-14 | Asahi Chem Ind Co Ltd | 熱可塑性エラストマー発泡体 |
JP2000178372A (ja) | 1998-12-18 | 2000-06-27 | Kyowa Leather Cloth Co Ltd | 発泡性ペレット、射出発泡成形体、および射出発泡成形体の製造方法 |
WO2015119048A1 (ja) * | 2014-02-04 | 2015-08-13 | 松本油脂製薬株式会社 | マスターバッチおよびその用途 |
JP2020045485A (ja) * | 2018-09-18 | 2020-03-26 | 積水化学工業株式会社 | 発泡成形用マスターバッチ及び発泡成形体 |
JP2020045484A (ja) * | 2018-09-18 | 2020-03-26 | 積水化学工業株式会社 | 発泡成形用マスターバッチ及び発泡成形体 |
JP7128371B1 (ja) * | 2021-08-06 | 2022-08-30 | 積水化学工業株式会社 | 熱膨張性マイクロカプセル、発泡性マスターバッチ及び発泡成形体 |
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