WO2023223911A1 - Particules de résine - Google Patents

Particules de résine Download PDF

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Publication number
WO2023223911A1
WO2023223911A1 PCT/JP2023/017569 JP2023017569W WO2023223911A1 WO 2023223911 A1 WO2023223911 A1 WO 2023223911A1 JP 2023017569 W JP2023017569 W JP 2023017569W WO 2023223911 A1 WO2023223911 A1 WO 2023223911A1
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Prior art keywords
resin
examples
resin particles
particles
polyamide
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PCT/JP2023/017569
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English (en)
Japanese (ja)
Inventor
充輝 六田
芳樹 中家
大輔 藤木
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ポリプラ・エボニック株式会社
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Publication of WO2023223911A1 publication Critical patent/WO2023223911A1/fr

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    • 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
    • C08J3/12—Powdering or granulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the present disclosure relates to resin particles.
  • resin particles formed from a resin composition for resin particles containing a resin having an amide bond have been used in various fields.
  • the resin particles are included in the thermosetting resin composition (for example, Patent Document 1).
  • plate materials, rod materials, and the like are produced by compression molding a plurality of the resin particles (for example, Patent Documents 2 and 3).
  • the resin particles can be used as spacers for liquid crystal displays, materials for producing structures with 3D printers, and the like.
  • the polyamide resin contained in the resin particles is a resin that relatively easily absorbs moisture.
  • the resin particles in the thermosetting resin composition in order to suppress voids contained in the cured product and to facilitate mixing of the resin particles and the thermosetting resin, It may be required to suppress the moisture contained in the particles.
  • cured products, plates, and rods are used as parts for various purposes, and because these parts are sometimes required to be lightweight, the resin composition for resin particles is required to have a low specific gravity. obtain.
  • the present disclosure provides resin particles that contain a first resin having an amide bond, which is a resin that easily absorbs moisture, and that do not easily absorb moisture and have a low specific gravity of a resin composition for the resin particles. The task is to do so.
  • a first aspect of the present disclosure includes a first resin having an amide bond and a first functional group, and a second resin that is a polyolefin resin having a second functional group capable of reacting with the first functional group.
  • This invention relates to resin particles.
  • resin particles that contain a first resin having an amide bond, which is a resin that easily absorbs moisture, but that do not easily absorb moisture and have a low specific gravity of a resin composition for the resin particles. It is possible.
  • Example A-1 SEM photograph of a cross section of a resin particle in Example A-1 (in the cross section, the resin particle has been etched with toluene, and the holed part is the part where the polyolefin resin was).
  • the resin particles according to the present embodiment include a first resin having an amide bond and a first functional group, and a second resin which is a polyolefin resin having a second functional group capable of reacting with the first functional group.
  • a first resin having an amide bond and a first functional group and a second resin which is a polyolefin resin having a second functional group capable of reacting with the first functional group. It is formed from a resin composition for resin particles containing a resin.
  • Examples of the first functional group include an amino group, a carboxy group, an acid anhydride group, an epoxy group, an isocyanate group, and a carbodiimide group.
  • Examples of the amino group include "-NH 2 " and "-NHR".
  • R is an alkyl group. Examples of R include a methyl group, an ethyl group, and a propyl group.
  • Examples of the acid anhydride group include a carboxylic acid anhydride group.
  • the first resin includes a polyamide resin and/or a polyimide resin.
  • polyamide resin examples include aliphatic polyamide resin, alicyclic polyamide resin, and aromatic polyamide resin.
  • the polyamide resin may be a homopolyamide resin or a copolyamide resin.
  • the aliphatic polyamide resin includes a polyamide resin of an aliphatic diamine component and an aliphatic dicarboxylic acid component, a polyamide resin of lactam, a polyamide resin of aminocarboxylic acid, a polyamide resin of an aliphatic diamine component and an aliphatic dicarboxylic acid component, and a lactam and/or Examples include polyamide resins with aminocarboxylic acids.
  • aliphatic diamine component examples include C4-16 alkylene diamine (eg, tetramethylene diamine, hexamethylene diamine, dodecane diamine, etc.).
  • the aliphatic diamine component is preferably a C6-14 alkylene diamine, more preferably a C6-12 alkylene diamine.
  • aliphatic dicarboxylic acid component examples include C4-20 alkanedicarboxylic acids (eg, adipic acid, sebacic acid, dodecanedioic acid, etc.).
  • the aliphatic dicarboxylic acid component is preferably a C5-16 alkanedicarboxylic acid, more preferably a C6-14 alkanedicarboxylic acid.
  • lactams having 4 to 20 carbon atoms examples include lactams having 4 to 20 carbon atoms (eg, ⁇ -caprolactam, ⁇ -laurolactam, etc.).
  • the lactam is preferably a lactam having 4 to 16 carbon atoms.
  • aminocarboxylic acids examples include C4-20 aminocarboxylic acids (eg, ⁇ -aminoundecanoic acid, etc.).
  • the aminocarboxylic acid is preferably a C4-16 aminocarboxylic acid, more preferably a C6-14 aminocarboxylic acid.
  • Examples of the aliphatic polyamide resin include polyamide 6, polyamide 11, polyamide 12, polyamide 46, polyamide 66, polyamide 610, polyamide 611, polyamide 612, polyamide 613, polyamide 1010, polyamide 66/11, polyamide 66/12, Examples include polyamide 6/12/612.
  • the alicyclic polyamide resin examples include polyamide resins having at least one component selected from an alicyclic diamine component and an alicyclic dicarboxylic acid component.
  • the alicyclic polyamide resin includes, as a diamine component and a dicarboxylic acid component, an aliphatic diamine component and/or an aliphatic dicarboxylic acid component as exemplified above, along with an alicyclic diamine component and/or an alicyclic dicarboxylic acid component.
  • Alicyclic polyamide resins are preferred.
  • Such alicyclic polyamide resin has high transparency and is known as a so-called transparent polyamide resin.
  • Examples of the alicyclic diamine component include diaminocycloalkanes, bis(aminocycloalkyl)alkanes, hydrogenated xylylene diamines, and the like.
  • Examples of the diaminocycloalkane include diaminocyclohexane.
  • the diaminocycloalkane is preferably diamino C5-10 cycloalkane.
  • Examples of the bis(aminocycloalkyl)alkanes include bis(4-aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl)methane, and 2,2-bis(4'-aminocyclohexyl)propane. Can be mentioned.
  • the bis(aminocycloalkyl)alkane is preferably bis(aminoC5-8cycloalkyl)C1-3 alkane.
  • the alicyclic diamine component may have a substituent such as an alkyl group.
  • the alkyl group is preferably a C1-6 alkyl group, more preferably a C1-4 alkyl group, and still more preferably a C1-2 alkyl group (methyl group, ethyl group, etc.).
  • alicyclic dicarboxylic acids examples include cycloalkanedicarboxylic acids (eg, cyclohexane-1,4-dicarboxylic acid, cyclohexane-1,3-dicarboxylic acid, etc.).
  • Typical alicyclic polyamide resins include, for example, an alicyclic diamine component [e.g., bis(aminocyclohexyl)alkane, etc.] and an aliphatic dicarboxylic acid component [e.g., alkanedicarboxylic acid (e.g., C 4-20 alkanedicarboxylic acid)] acid components, etc.)].
  • an alicyclic diamine component e.g., bis(aminocyclohexyl)alkane, etc.
  • an aliphatic dicarboxylic acid component e.g., alkanedicarboxylic acid (e.g., C 4-20 alkanedicarboxylic acid)] acid components, etc.
  • the aromatic polyamide resin is a concept that includes a polyamide resin containing at least one of an aromatic diamine component and an aromatic dicarboxylic acid component as a structural unit.
  • the aromatic polyamide resin include polyamide resins in which both the diamine component of the structural unit and the dicarboxylic acid component of the structural unit are aromatic components (also called “fully aromatic polyamide resin", "aramid”, etc.). It will be done.
  • the aromatic polyamide resin may be a modified polyamide resin. Examples of the modified polyamide resin include polyamide resins having a branched chain structure.
  • Examples of the aromatic diamine component include metaxylylene diamine.
  • the aromatic dicarboxylic acid component include terephthalic acid and isophthalic acid. Further, the aromatic dicarboxylic acid component may be a dimer acid or the like.
  • polyimide resin examples include aliphatic polyimide resins and aromatic polyimide resins.
  • the first resin may be used alone or in combination of two or more.
  • semicrystalline polyamide resins eg, alicyclic polyamide resins, aliphatic polyamide resins, etc.
  • they have a large reinforcing effect.
  • the number average molecular weight of the first resin is, for example, 8,000 to 200,000, preferably 9,000 to 150,000, and more preferably 10,000 to 100,000.
  • the number average molecular weight is measured from the polymethyl methacrylate (PMMA) equivalent molecular weight distribution using gel permeation chromatography (GPC) using hexafluoroisopropanol (HFIP).
  • GPC gel permeation chromatography
  • HFIP hexafluoroisopropanol
  • the melting point of the first resin is, for example, 150°C or higher (eg, 155 to 350°C), preferably 160°C or higher (eg, 165 to 300°C), and more preferably 170°C or higher (eg, 175 to 270°C).
  • the melting point can be measured using, for example, a differential scanning calorimeter (DSC). More specifically, first, about 5 mg of a sample for measuring the melting point is prepared, and two containers made of metal (for example, aluminum) with the same shape and weight are prepared. Next, the sample is placed in one of the two containers, and the other container is left empty. Then, from the DSC curve obtained when the container containing the sample and the empty container as a reference were set in the DSC and the sample was heated at a heating rate of 10°C/min while flowing nitrogen gas. The melting point can be determined. Note that the melting point can be determined by performing differential scanning calorimetry twice on the same sample, and is determined as the peak value of the second DSC curve.
  • DSC differential scanning calorimeter
  • the glass transition temperature (Tg) of the first resin is preferably 30°C to 160°C.
  • the glass transition temperature (Tg) means the midpoint glass transition temperature measured using a differential scanning calorimeter (DSC).
  • the midpoint glass transition temperature can be determined based on the method described in JIS K7121-1987 "Method for Measuring Plastic Transition Temperature.” That is, first, about 5 mg of a sample for measuring the midpoint glass transition temperature is prepared, and two containers made of metal (for example, aluminum) of the same shape and weight are prepared. Next, the sample is placed in one of the two containers, and the other container is left empty. Then, from the DSC curve obtained when the container containing the sample and the empty container as a reference were set in the DSC and the sample was heated at a heating rate of 10°C/min while flowing nitrogen gas. The midpoint glass transition temperature can be determined.
  • the crystallinity of the first resin is preferably 80% or less (eg, 1 to 75%), more preferably 50% or less (eg, 10 to 50%).
  • the resin particles preferably contain the first resin in an amount of 50% by weight or more, more preferably 60 to 99% by weight, even more preferably 70 to 95% by weight.
  • the resin particles according to this embodiment include a second resin that is a polyolefin resin having a second functional group that can react with the first functional group. Since polyolefin resin has a low specific gravity and is a resin that does not easily absorb moisture, such resin particles contain a second resin that is a polyolefin resin, so that it is difficult to absorb moisture and is a resin for resin particles. The composition becomes resin particles with a low specific gravity. Moreover, since the second resin has a second functional group that can react with the first functional group of the first resin, the first resin and the second resin are easily mixed, and the second resin The resin particles according to this embodiment are easier to produce than when the resin does not contain the second functional group.
  • the second resin which is the polyolefin resin, is a resin containing an olefin as a constituent unit.
  • the olefin include ⁇ -olefin, ethylene, 2-butene, isoprene, and 2-pentene.
  • ⁇ -olefin examples include ⁇ -olefins having 3 to 20 carbon atoms, and specifically, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-Nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3- Methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4, Examples include 4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene,
  • Examples of the second functional group include a carboxy group, an amino group, a carboxylic acid anhydride group, an epoxy group, an isocyanate group, and a carbodiimide group.
  • the polyolefin resin may have the epoxy group by having a glycidyl group.
  • the melting point of the polyolefin resin is, for example, 30 to 200°C, preferably 35 to 175°C, and more preferably 40 to 160°C.
  • the resin particles preferably contain the first resin and the second resin in a total amount of 80 to 100% by weight, more preferably 90 to 100% by weight, and even more preferably 95 to 100% by weight.
  • the resin particles preferably contain the second resin in an amount of 5 to 40% by weight, more preferably 5 to 30% by weight.
  • the resin particles may further contain an additive.
  • the resin composition for resin particles may further contain an additive.
  • the additives include stabilizers, colorants, dispersants, preservatives, antioxidants, antifoaming agents, and the like.
  • the additives may be used alone or in combination of two or more.
  • the total content of the additives is, for example, 10 parts by weight or less (for example, 0.01 to 10 parts by weight) based on the total of 100 parts by weight of the first resin and the second resin.
  • the median diameter of the resin particles can be selected from a range of, for example, 2 ⁇ m or more (for example, 3 to 40 ⁇ m), preferably 4 ⁇ m or more (for example, 5 to 40 ⁇ m), more preferably 6 ⁇ m or more (for example, 7 to 35 ⁇ m), and even more preferably 8 ⁇ m. or more (for example, 9 to 30 ⁇ m), particularly preferably 10 ⁇ m or more (for example, 11 to 30 ⁇ m).
  • the median diameter of the resin particles means a value measured by dispersing the resin particles in water and using a laser diffraction/scattering particle size distribution analyzer.
  • the median diameter of the resin particles means the volume-based median diameter of the resin particles.
  • the median diameter of the resin particles means the median diameter of the resin particles as primary particles.
  • the resin particles have a matrix-domain structure (also referred to as a "sea-island structure") including a matrix and domains, the matrix contains the first resin, and the domains contain the second resin. It is preferable to contain.
  • a matrix-domain structure also referred to as a "sea-island structure"
  • the matrix contains the first resin
  • the domains contain the second resin. It is preferable to contain.
  • a plurality of the domains are dispersed in the matrix.
  • the matrix contains the first resin means "the first resin is contained in the matrix in a larger amount than in the domain.”
  • the domain contains the second resin means that "the second resin is contained in the domain in a larger amount than in the matrix.”
  • the resin particles have a matrix-domain structure including a matrix and a domain, and the matrix contains the first resin and the domain contains the second resin as follows. You can check it like this. First, a resin particle is cut to obtain a cross section. Next, the cross section is etched with toluene. Then, the etched cross section is observed with a scanning electron microscope (SEM) to confirm the presence or absence of a matrix-domain structure (matrix: the first resin, domain: the second resin). In addition, in the cross section, the part where the resin particle is etched with toluene and has a hole is the part where the polyolefin resin was.
  • SEM scanning electron microscope
  • the average particle size of the domain is preferably 1/3 or less of the average particle size of the resin particles, more preferably 1/4 or less of the average particle size of the resin particles, and is more preferably 1/4 or less of the average particle size of the resin particles. It is even more preferably 1/5 or less, still more preferably 1/8 or less of the average particle size of the resin particles, and particularly preferably 1/10 or less of the average particle size of the resin particles. Further, the average particle diameter of the domain is, for example, 1/2000 of the average particle diameter of the resin particles.
  • the specific gravity of the resin composition for resin particles is preferably 0.80 to 1.25, more preferably 0.85 to 1.20.
  • the specific gravity of the resin composition for resin particles can be determined as follows. First, a dumbbell test piece specified by ISO is produced by injection molding from the resin composition for resin particles. Then, using the dumbbell test piece, the specific gravity of the resin composition for resin particles is measured according to method A (underwater displacement method) of JIS K7112:1999.
  • the sphericity of the resin particles is preferably 95% or more and 100% or less, more preferably 97% or more and 100% or less, and even more preferably 99% or more and 100% or less.
  • the sphericity of particles can be measured by the following method. That is, the particles are observed with a scanning electron microscope (SEM), the major axis and the minor axis of 30 randomly selected particles are measured, and the minor axis/long axis ratio of each particle is determined. Then, the arithmetic mean value of the short axis/long axis ratio is determined, and this arithmetic mean value is taken as the sphericity of the particle. Note that the closer the sphericity of the particles is to 100%, the more true the particles can be determined to be.
  • the resin particles according to this embodiment are configured as described above, and next, a method for manufacturing the resin particles will be described.
  • Examples of the method for producing resin particles include a freeze pulverization method, a chemical pulverization method, a polymerization method, a forced emulsification method, a laser method, and the like.
  • a forced emulsification method is preferred.
  • the first resin, the second resin, and an aqueous medium incompatible with the first resin and the second resin are melt-kneaded by heating.
  • the resin particles are obtained.
  • the resin particles may be obtained by performing a step (D) of drying the melt-kneaded product using a dehumidifying dryer or the like after the step (C), if necessary.
  • the resin particles may be obtained by performing step (E) of classifying the melt-kneaded material.
  • the aqueous medium used in the step (A) is selected depending on the types of the first resin and the second resin.
  • the aqueous medium include heat-melting saccharides, water-soluble polymers, and the like.
  • the heat-melting saccharides include oligosaccharides (eg, sucrose, maltotriose, etc.), sugar alcohols (eg, xylitol, erythritol, sorbitol, mannitol, etc.), and the like.
  • water-soluble polymer examples include water-soluble synthetic polymers (eg, polyethylene glycol, polyvinyl alcohol, sodium polyacrylate, polyacrylamide, etc.), polysaccharides (eg, starch, methylcellulose, etc.), and the like.
  • water-soluble synthetic polymers eg, polyethylene glycol, polyvinyl alcohol, sodium polyacrylate, polyacrylamide, etc.
  • polysaccharides eg, starch, methylcellulose, etc.
  • aqueous medium can be used alone or in combination of two or more.
  • polyethylene glycol is preferable from the viewpoint that the resin particles can be easily adjusted to an appropriate particle size.
  • the aqueous medium is, for example, 10 to 100 parts by weight, preferably 20 to 100 parts by weight, more preferably 100 parts by weight in total of the first resin and the second resin. is 30 to 100 parts by weight.
  • the volume ratio of the aqueous medium is, for example, 50 volume % or more (for example, 50 to 90 volume %) with respect to the total volume of the aqueous medium, the first resin, and the second resin.
  • the temperature during melt-kneading in the step (A) may be a temperature higher than the melting point or softening point of the first resin and a temperature higher than the melting point or softening point of the second resin, for example 190°C. or higher (for example, 190 to 350°C), preferably 200 to 320°C, more preferably 210 to 300°C.
  • the melt-kneaded product may be naturally cooled or the melt-kneaded product may be forcedly cooled, but from the viewpoint of productivity, it is preferable to forcibly cool the melt-kneaded product.
  • the cooling rate of the melt-kneaded material is preferably, for example, 1° C./min or more (eg, 1 to 10° C./min).
  • hydrophilic solvent used in the step (C) examples include alcohol (such as ethanol), water-soluble ketones (such as acetone), and the like.
  • the resin particles according to this embodiment can be used as spacers for liquid crystal displays, materials for producing structures with 3D printers, and the like.
  • the resin particles according to this embodiment can be used to produce a plate material, a bar material, etc. by compression molding a plurality of resin particles.
  • the resin particles according to the present embodiment may be included in the thermosetting resin composition.
  • thermosetting resin composition includes a thermosetting resin and resin particles.
  • thermosetting resin examples include epoxy resin, phenol resin, unsaturated polyester resin, vinyl ester resin, acrylic resin, urea resin, melamine resin, aniline resin, polyimide resin, and bismaleimide resin. These thermosetting resins may be used alone or in combination of two or more.
  • thermosetting resin epoxy resins and phenol resins are preferable, and epoxy resins are particularly preferable. Since epoxy resin and polyamide resin have excellent compatibility, when the thermosetting resin contains epoxy resin, the resin particles containing the polyamide resin are easily dispersed in the epoxy resin, and the toughness due to the resin particles is increased. The effect of improvement will be more easily realized.
  • epoxy resins examples include glycidyl ether type epoxy resins, glycidyl amine type epoxy resins, glycidyl ester type epoxy resins, alkene oxides (such as vinyl cyclohexene dioxide), triglycidyl isocyanurate, and the like.
  • Examples of the glycidyl ether type epoxy resin include bisphenol type epoxy resin, phenol type epoxy resin, dicyclopentadiene type epoxy resin, epoxy resin having an aromatic skeleton (polyglycidyl ether), alkanediol diglycidyl ether, and polyalkanediol.
  • Examples include diglycidyl ether, epoxy resin having an aliphatic skeleton (polyglycidyl ether), and the like.
  • Examples of the bisphenol type epoxy resin include a reaction product of bisphenols and epichlorohydrin, a reaction product of an alkylene oxide adduct of bisphenols and epichlorohydrin, and the like.
  • Examples of the bisphenols include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, and brominated bisphenol epoxy resin.
  • the number of moles of alkylene oxide added per mole of hydroxyl group of the bisphenol is, for example, 1 mole or more (for example, 1 to 20 moles), preferably 1 to 15 moles, more preferably 1 mole. ⁇ 10 moles.
  • phenolic epoxy resin examples include phenol novolak epoxy resin, cresol novolac epoxy resin, naphthol novolac epoxy resin, bisphenol A novolac epoxy resin, bisphenol F novolac epoxy resin, biphenyl skeleton-containing phenol novolak resin, and xylylene.
  • phenol novolak epoxy resin cresol novolac epoxy resin, naphthol novolac epoxy resin, bisphenol A novolac epoxy resin, bisphenol F novolac epoxy resin, biphenyl skeleton-containing phenol novolak resin, and xylylene.
  • cresol novolac epoxy resin cresol novolac epoxy resin
  • naphthol novolac epoxy resin bisphenol A novolac epoxy resin
  • bisphenol F novolac epoxy resin bisphenol F novolac epoxy resin
  • biphenyl skeleton-containing phenol novolak resin examples include skeleton-containing phenol novolac resins.
  • Examples of the epoxy resin (polyglycidyl ether) having an aromatic skeleton include glycidyl ether having a naphthalene skeleton.
  • Examples of the glycidyl ether having a naphthalene skeleton include di(glycidyloxy)naphthalene, bis[2,7-di(glycidyloxy)naphthyl]methane, and the like.
  • Examples of the di(glycidyloxy)naphthalene include 1,5-di(glycidyloxy)naphthalene.
  • alkanediol diglycidyl ether examples include C 2-10 alkanediol diglycidyl ether.
  • Examples of the C 2-10 alkanediol diglycidyl ether include butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and the like.
  • Examples of the polyalkanediol diglycidyl ether include polyC 2-4 alkanediol diglycidyl ether.
  • Examples of the polyC 2-4 alkanediol diglycidyl ether include polypropylene glycol diglycidyl ether.
  • Examples of the epoxy resin (polyglycidyl ether) having an aliphatic skeleton include glycidyl polyether of polyol.
  • Examples of the polyols include alkanetriols, alkanetetraols, alkane pentaols, alkane hexaols, and the like.
  • Examples of the alkane triol include C 3-10 alkane triol.
  • Examples of the alkanetetraol include C 3-10 alkanetetraol.
  • Examples of the glycidyl polyether include diglycidyl ether, triglycidyl ether, tetraglycidyl ether, pentaglycidyl ether, hexaglycidyl ether, and the like.
  • Examples of the glycidyl polyether of the polyol include trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin diglycidyl ether, and glycerin triglycidyl ether.
  • Examples of the glycidylamine type epoxy resin include tetraglycidyldiaminodiphenylmethane, triglycidyl-p-aminophenol, triglycidyl aminocresol, diglycidylaniline, N,N-diglycidyl-4-glycidyloxyaniline, and the like.
  • Examples of the glycidyl ester type epoxy resin include diglycidyl ester of dicarboxylic acid.
  • Examples of the dicarboxylic acid include aromatic dicarboxylic acids, hydrogenated aromatic dicarboxylic acids, and the like.
  • Examples of the aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, tetrahydrophthalic acid, and hexahydrophthalic acid.
  • epoxy resins may be used alone or in combination of two or more.
  • epoxy resins having an aromatic skeleton are preferred, and bisphenol type epoxy resins are particularly preferred.
  • phenolic resin examples include resins having one or more, preferably two or more, phenolic hydroxyl groups in one molecule.
  • examples of the phenol resin include novolac type phenol resin, resol type phenol resin, and polyoxystyrene resin.
  • the novolac type phenol resin is a condensate of phenols and aldehydes.
  • the novolac type phenolic resin is obtained, for example, by condensation polymerization of phenols and aldehydes in the presence of an acidic catalyst.
  • the resol type phenolic resin is a condensate of phenols and aldehydes.
  • the resol type phenolic resin is obtained, for example, by condensation polymerization of phenols and aldehydes in the presence of an alkaline catalyst.
  • phenols examples include phenol, cresol, trimethylphenol, xylenol, resorcinol, catechol, butylphenol, octylphenol, nonylphenol, phenylphenol, dihydroxybenzene, bisphenol A, and naphthol.
  • cresol examples include o-cresol, m-cresol, and p-cresol.
  • trimethylphenol examples include 2,3,5-trimethylphenol.
  • xylenol examples include 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol, and 3,5-xylenol.
  • aldehydes examples include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, glyoxal, glutaraldehyde, terephthalaldehyde, isophthalaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, 3-methylbutyraldehyde, and p-tolylaldehyde. , phenylacetaldehyde, and the like.
  • hydroxybenzaldehyde examples include o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, and p-hydroxybenzaldehyde.
  • novolak-type phenolic resin examples include novolak resin (a condensate of phenol and formaldehyde), cresol novolak resin (a condensate of cresol and formaldehyde), and the like.
  • the phenolic resins may be used alone or in combination of two or more.
  • the hydroxyl equivalent of the phenol resin is preferably 50 to 500 g/eq. More preferably 100 to 350 g/eq. It is.
  • thermosetting resin composition preferably contains a thermosetting resin in an amount of 40 to 99% by weight, more preferably 80 to 97% by weight.
  • thermosetting resin composition preferably contains the thermosetting resin and the resin particles in a total amount of 50 to 99% by weight, more preferably 80 to 97% by weight.
  • the resin particles are preferably 1 to 30 parts by weight, more preferably 3 to 25 parts by weight, and more preferably 5 to 20 parts by weight, based on 100 parts by weight of the thermosetting resin. Department.
  • the thermosetting resin composition may include reinforcing fibers. That is, the cured product obtained by thermosetting the thermosetting resin composition may be fiber reinforced plastic (FRP).
  • the reinforcing fibers include carbon fibers, glass fibers, aramid fibers, boron fibers, polyparaphenylene benzobis oxazole (PBO) fibers, polyethylene fibers, alumina fibers, and silicon carbide fibers.
  • the reinforcing fibers are preferably carbon fibers. That is, the cured product is preferably carbon fiber reinforced plastic (CFRP).
  • the reinforcing fibers may be monofilaments or multifilaments.
  • the fineness of the single fibers of the reinforcing fibers is preferably 0.2 to 2.0 dtex, more preferably 0.4 to 1.8 dtex.
  • the number of filaments in the fiber is preferably 2,500 to 50,000.
  • the reinforcing fibers may be continuous fibers or may be discontinuous. When higher mechanical properties are required for the cured product, continuous fibers are preferred as the reinforcing fibers.
  • the continuous fibers may be included in the thermosetting resin composition according to the present embodiment in the form of, for example, a unidirectional base material, knitted fabric, woven fabric, tow, or roving.
  • the reinforcing fibers in a discontinuous form may be included in the thermosetting resin composition according to the present embodiment, for example, in the form of a nonwoven fabric or chopped yarn.
  • thermosetting resin composition preferably contains the reinforcing fibers in an amount of 1 to 50 parts by weight, more preferably 5 to 30 parts by weight, based on 100 parts by weight of the thermosetting resin.
  • the thermosetting resin composition may include a monofunctional epoxy compound.
  • the monofunctional epoxy compound include monoglycidyl ether, alkene oxide (eg, octylene oxide, styrene oxide, etc.).
  • the monoglycidyl ethers include alkyl glycidyl ethers (e.g., 2-ethylhexyl glycidyl ether, etc.), alkenyl glycidyl ethers (e.g., allyl glycidyl ether, etc.), aryl glycidyl ethers (e.g., phenyl glycidyl ether, etc.), and the like.
  • the ratio of the weight of the epoxy resin to the weight of the monofunctional epoxy compound is, for example, 99/1 to 50/50, preferably 97/3 to 60/40, more preferably It is from 95/5 to 70/30.
  • the thermosetting resin composition may include a curing agent.
  • the curing agent can be appropriately selected depending on the type of the thermosetting resin.
  • examples of the curing agent include amine curing agents, phenolic resin curing agents, acid anhydride curing agents, polymercaptan curing agents, and latent curing agents. .
  • amine curing agent examples include aromatic amine curing agents, aliphatic amine curing agents, imidazoles, salts of imidazoles, and alicyclic amine curing agents.
  • aromatic amine curing agent examples include polyaminoarenes, polyamino-alkylarenes, poly(aminoalkyl)arenes, poly(aminoaryl)alkanes, poly(amino-alkylaryl)alkanes, and bis(aminoarylalkyl)arenes. , di(aminoaryl)ethers (e.g., diaminodiphenyl ether, etc.), di(aminoaryloxy)arenes (e.g., 1,3-bis(3-aminophenoxy)benzene, etc.), di(aminoaryl)sulfones (e.g., diamino diphenyl sulfone, etc.).
  • di(aminoaryl)ethers e.g., diaminodiphenyl ether, etc.
  • di(aminoaryloxy)arenes e.g., 1,3-bis(3-aminophenoxy)benzene,
  • polyaminoarene examples include diaminoarene (eg, paraphenylenediamine, metaphenylenediamine, etc.).
  • polyamino-alkylarene examples include diamino-alkylarene (eg, diethyltoluenediamine, etc.).
  • poly(aminoalkyl)arenes examples include di(aminoalkyl)arenes (eg, xylylene diamine, etc.).
  • poly(aminoaryl)alkanes examples include di(aminoaryl)alkanes (eg, diaminodiphenylmethane, etc.).
  • poly(amino-alkylaryl)alkanes examples include di(amino-alkylaryl)alkanes (eg, 4,4'-methylenebis(2-ethyl-6-methylaniline), etc.).
  • bis(aminoarylalkyl)arene examples include 1,3-bis[2-(4-aminophenyl)-2-propyl)]benzene, 1,4-bis[2-(4-aminophenyl)- 2-propyl)]benzene and the like.
  • aliphatic amine curing agent examples include ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, and the like.
  • alicyclic amine curing agent examples include menzendiamine, isophoronediamine, bis(4-amino-3-methylcyclohexyl)methane, 3,9-bis(3-aminopropyl)-2,4,8 , 10-tetraoxaspiro[5.5]undecane, norbornanediamine, and the like.
  • Examples of the imidazoles include alkylimidazole and arylimidazole.
  • Examples of the alkylimidazole include 2-methylimidazole, 2-phenylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, and the like.
  • Examples of the arylimidazole include 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and 1-benzyl-2-phenylimidazole.
  • salts of imidazoles include salts of imidazoles and formic acid, salts of imidazoles and phenol, salts of imidazoles and phenol novolak, salts of imidazoles and carbonic acid, and the like.
  • phenolic resin curing agent examples include novolac resin, cresol novolac resin, and the like.
  • Examples of the acid anhydride curing agent include aliphatic dicarboxylic anhydrides, alicyclic dicarboxylic anhydrides, aromatic dicarboxylic anhydrides, and the like.
  • Examples of the aliphatic dicarboxylic anhydride include dodecenyl succinic anhydride.
  • Examples of the alicyclic dicarboxylic anhydride include tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, and the like.
  • Examples of the aromatic dicarboxylic anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, and the like.
  • latent curing agent examples include boron trifluoride-amine complex, dicyandiamide, and carboxylic acid hydrazide.
  • the curing agents may be used alone or in combination of two or more. Note that the curing agent may also act as a curing accelerator. As the curing agent, an amine curing agent (for example, an aromatic amine curing agent) is preferable.
  • an amine curing agent for example, an aromatic amine curing agent
  • the content ratio of the curing agent can be appropriately selected depending on the type of thermosetting resin (epoxy equivalent, etc.) and the type of curing agent, but for example, it is 0.1 to 300 parts by weight per 100 parts by weight of the thermosetting resin. Parts by weight, preferably 1 to 250 parts by weight, more preferably 3 to 200 parts by weight (for example, 4 to 150 parts by weight), particularly preferably 5 to 100 parts by weight.
  • the thermosetting resin composition may include a curing accelerator.
  • the curing accelerator can be appropriately selected depending on the type of the thermosetting resin.
  • Examples of the curing accelerator when the thermosetting resin is an epoxy resin include phosphines, amines, and salts of amines.
  • Examples of the phosphines include ethylphosphine, propylphosphine, trialkylphosphine, phenylphosphine, and triphenylphosphine.
  • the amines include secondary to tertiary amines.
  • secondary to tertiary amines examples include triethylamine, piperidine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, triethylenediamine, tris(dimethylaminomethyl)phenol, and N,N-dimethylpiperazine.
  • the curing accelerators may be used alone or in combination of two or more.
  • the content ratio of the curing accelerator is, for example, 0.01 to 100 parts by weight, preferably 0.05 to 50 parts by weight, and more preferably 1 to 30 parts by weight, based on 100 parts by weight of the thermosetting resin.
  • thermosetting resin composition may further contain at least one of a thermoplastic resin and an additive as another component, if necessary.
  • thermoplastic resin examples include acrylic resin, polyolefin resin (such as polypropylene), polyamide resin, polyester resin, polycarbonate resin, polyphenylene ether resin, polyphenylene sulfide resin, polysulfone resin, polyether ketone resin, and polyether ether ketone.
  • examples include resin, polyimide resin, polyetherimide resin, and the like.
  • polyester resin include aromatic polyester resins (eg, polyethylene terephthalate, etc.).
  • additives examples include non-fibrous fillers, stabilizers, colorants, dispersants, preservatives, antioxidants, antifoaming agents, and the like.
  • the content ratio of other components is, for example, 10 parts by weight or less (for example, 0.01 to 10 parts by weight) based on 100 parts by weight of the thermosetting resin.
  • the shape of the cured product obtained by thermosetting the thermosetting resin composition may be a one-dimensional shape (such as a rod shape), a two-dimensional shape (such as a sheet shape), or a three-dimensional shape.
  • [Item 2] has a matrix-domain structure including a matrix and a domain;
  • the matrix contains the first resin,
  • [Item 4] formed of a resin composition containing the first resin and the second resin, The resin particles according to any one of items 1 to 3, wherein the resin composition has a specific gravity of 0.80 to 1.25.
  • Example A-1 75 parts by weight of polyamide 12, 25 parts by weight of polyolefin resin (MH5010), and polyethylene glycol as an aqueous solvent were melt-kneaded by heating in an extruder and extruded through a die of the extruder to obtain a melt-kneaded product.
  • the melt-kneaded material was forcibly cooled using a spot cooler.
  • the precursor particles remaining on the glass filter were washed with water.
  • the precursor particles were dried at 90° C. for 24 hours using a dehumidifying dryer to obtain resin particles.
  • Examples other than Example A-1 and Comparative Examples A-1 and A-3) Resin particles were obtained in the same manner as in Example A-1, except that the blending ratio of the resin particles was as shown in Table 1 below.
  • the saturated water content of the resin composition for resin particles constituting the resin particles was measured by the following method. First, a square test piece (100 mm x 100 mm x 2 mm) was prepared by injection molding from the resin composition for resin particles constituting the resin particles. Then, the square test piece was allowed to absorb water using method A (immersion in 23°C water) of JIS K7209:2000 (ISO62:1999) "Plastics - How to determine water absorption rate", and the saturated water content was measured. Table 1 below shows the saturated water content of the resin composition for resin particles.
  • a comparative resin composition consisting only of the first resin used in each Example was prepared.
  • the comparative resin composition for Example A-1 is the resin composition for resin particles of Comparative Example A-1.
  • the saturated water content of the resin composition for comparison was measured.
  • the rate of decrease in saturated water content was determined using the following formula.
  • Reduction rate of saturated water content (%) [(Saturated water content of comparative resin composition - Saturated water content of resin composition for resin particles of Example) / Saturated water content of resin composition for resin particles of Example Amount ⁇ 100(%)
  • Table 1 below shows the rate of decrease in saturated water content.
  • FIG. 1 shows a SEM photograph of a cross section of resin particles in Example A-1.
  • the rate of decrease in saturated water content was a positive number.
  • the specific gravity of the resin composition for resin particles was lower than that in Comparative Example A-3 containing silica. Ta. Therefore, according to the present disclosure, the resin particles contain the first resin having an amide bond, which is a resin that easily absorbs moisture, but do not easily absorb moisture, and the specific gravity of the resin composition for resin particles is low. It can be seen that it can be provided.

Abstract

La présente invention concerne des particules de résine qui qui n'absorbent pas facilement l'humidité et dans lesquelles la densité d'une composition de résines pour des particules de résine est faible, lesdites particules de résine contenant également une première résine qui absorbe facilement l'humidité et a une liaison amide. La présente invention se rapporte à des particules de résine contenant : une première résine ayant une liaison amide et un premier groupe fonctionnel ; et une seconde résine qui est une résine de polyoléfine ayant un second groupe fonctionnel qui peut réagir avec le premier groupe fonctionnel.
PCT/JP2023/017569 2022-05-17 2023-05-10 Particules de résine WO2023223911A1 (fr)

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Publication number Priority date Publication date Assignee Title
JPH06287401A (ja) * 1993-04-06 1994-10-11 Mitsubishi Kasei Corp 樹脂組成物の製造法
JPH07258541A (ja) * 1994-03-23 1995-10-09 Toyobo Co Ltd ポリアミド樹脂組成物およびその成形物
JPH08319419A (ja) * 1995-05-26 1996-12-03 Satoshi Sanzen 合成樹脂用模様着色材料及びその製造方法並びに着色模様を有する合成樹脂成形体
JPH0931325A (ja) * 1995-07-18 1997-02-04 Mitsubishi Eng Plast Kk ポリアミド系樹脂組成物
JPH11140237A (ja) * 1997-11-10 1999-05-25 Mitsui Chem Inc 熱可塑性樹脂組成物およびそれからなる成形品
JP2002020619A (ja) * 2000-07-11 2002-01-23 Mitsui Chemicals Inc ポリアミド樹脂ペレット
JP2005060547A (ja) * 2003-08-13 2005-03-10 Daicel Chem Ind Ltd 長繊維強化ポリマーアロイ樹脂構造体及び成形品
JP2007254567A (ja) * 2006-03-23 2007-10-04 Toray Ind Inc 熱可塑性樹脂組成物およびその製造方法
CN102250465A (zh) * 2011-07-13 2011-11-23 江门市奇德工程塑料科技有限公司 一种增韧尼龙复合物及其制备方法
WO2013122008A1 (fr) * 2012-02-15 2013-08-22 東レ株式会社 Particules composites de polyamide et procédé de production de celles-ci

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06287401A (ja) * 1993-04-06 1994-10-11 Mitsubishi Kasei Corp 樹脂組成物の製造法
JPH07258541A (ja) * 1994-03-23 1995-10-09 Toyobo Co Ltd ポリアミド樹脂組成物およびその成形物
JPH08319419A (ja) * 1995-05-26 1996-12-03 Satoshi Sanzen 合成樹脂用模様着色材料及びその製造方法並びに着色模様を有する合成樹脂成形体
JPH0931325A (ja) * 1995-07-18 1997-02-04 Mitsubishi Eng Plast Kk ポリアミド系樹脂組成物
JPH11140237A (ja) * 1997-11-10 1999-05-25 Mitsui Chem Inc 熱可塑性樹脂組成物およびそれからなる成形品
JP2002020619A (ja) * 2000-07-11 2002-01-23 Mitsui Chemicals Inc ポリアミド樹脂ペレット
JP2005060547A (ja) * 2003-08-13 2005-03-10 Daicel Chem Ind Ltd 長繊維強化ポリマーアロイ樹脂構造体及び成形品
JP2007254567A (ja) * 2006-03-23 2007-10-04 Toray Ind Inc 熱可塑性樹脂組成物およびその製造方法
CN102250465A (zh) * 2011-07-13 2011-11-23 江门市奇德工程塑料科技有限公司 一种增韧尼龙复合物及其制备方法
WO2013122008A1 (fr) * 2012-02-15 2013-08-22 東レ株式会社 Particules composites de polyamide et procédé de production de celles-ci

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