WO2023223911A1 - Resin particle - Google Patents

Resin particle 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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WIPO (PCT)
Prior art keywords
resin
examples
resin particles
particles
polyamide
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PCT/JP2023/017569
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French (fr)
Japanese (ja)
Inventor
充輝 六田
芳樹 中家
大輔 藤木
Original Assignee
ポリプラ・エボニック株式会社
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Publication of WO2023223911A1 publication Critical patent/WO2023223911A1/en

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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

The present disclosure provides a resin particle which does not easily absorb moisture and in which the specific gravity of a resin composition for resin particles is low, said resin particle also containing a first resin that easily absorbs moisture and has an amide bond. The present disclosure relates to a resin particle containing: 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 which can react with the first functional group.

Description

樹脂粒子resin particles
　本開示は、樹脂粒子に関する。 The present disclosure relates to resin particles.
　従来、アミド結合を有する樹脂を含む樹脂粒子用樹脂組成物で形成された樹脂粒子は、様々な分野で用いられている。
　例えば、熱硬化性樹脂を含む熱硬化性樹脂組成物が硬化された硬化物の靭性を高めるという観点等から、該熱硬化性樹脂組成物に前記樹脂粒子を含ませている（例えば、特許文献１）。
　また、複数の前記樹脂粒子を圧縮成形することにより、板材や棒材などを作製している（例えば、特許文献２、３）。 Conventionally, resin particles formed from a resin composition for resin particles containing a resin having an amide bond have been used in various fields.
For example, from the viewpoint of increasing the toughness of a cured product obtained by curing a thermosetting resin composition containing a thermosetting resin, the resin particles are included in the thermosetting resin composition (for example, Patent Document 1).
In addition, 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).
国際公開第２０１５／０１９９６５号International Publication No. 2015/019965 日本国特開平３－４１１２５号公報Japanese Patent Application Publication No. 3-41125 日本国特開平４－２８３２４１号公報Japanese Patent Publication No. 4-283241
　また、前記樹脂粒子は、液晶ディスプレイのスペーサー、３Ｄプリンターで構造物を作製する際の材料などとしても用いることができる。 Additionally, the resin particles can be used as spacers for liquid crystal displays, materials for producing structures with 3D printers, and the like.
　ところで、樹脂粒子に含まれるポリアミド樹脂は、比較的水分を吸収しやすい樹脂である。
　ここで、前記熱硬化性樹脂組成物に前記樹脂粒子を含ませる際には、硬化物に含まれるボイドを抑制するためや、樹脂粒子と熱硬化性樹脂とを混合しやすくするために、樹脂粒子に含まれる水分を抑制することが求められ得る。
　また、３Ｄプリンターで樹脂粒子を加熱により溶融させる際には、エネルギー効率を高めるため等に、樹脂粒子に含まれる水分を抑制することが求められ得る。
　すなわち、水分を吸収し難い樹脂粒子が求められ得る。 By the way, the polyamide resin contained in the resin particles is a resin that relatively easily absorbs moisture.
Here, when including 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.
Further, when melting resin particles by heating with a 3D printer, it may be required to suppress moisture contained in the resin particles in order to improve energy efficiency.
That is, resin particles that are difficult to absorb moisture may be required.
　また、硬化物、板材、棒材は、各種の用途の部品として用いられるが、該部品は軽量であることが求められることがあるため、樹脂粒子用樹脂組成物の比重が低いことが求められ得る。 In addition, 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.
　そこで、本開示は、水分を吸収しやすい樹脂である、アミド結合を有する第１の樹脂を含有しつつ水分を吸収し難く、且つ、樹脂粒子用樹脂組成物の比重が低い、樹脂粒子を提供することを課題とする。 Therefore, 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.
　本開示の第一は、アミド結合及び第１の官能基を有する第１の樹脂と、前記第１の官能基と反応可能な第２の官能基を有するポリオレフィン樹脂たる第２の樹脂とを含有する、樹脂粒子に関する。 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.
　本開示によれば、水分を吸収しやすい樹脂である、アミド結合を有する第１の樹脂を含有しつつ水分を吸収し難く、且つ、樹脂粒子用樹脂組成物の比重が低い、樹脂粒子を提供し得る。 According to the present disclosure, there are provided 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.
実施例Ａ－１における樹脂粒子の断面のＳＥＭ写真（断面において樹脂粒子がトルエンでエッチングされており、穴が開いている部分は、ポリオレフィン樹脂があった部分である。）。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).
　以下、添付図面を参照しつつ、本開示の一実施形態について説明する。 Hereinafter, one embodiment of the present disclosure will be described with reference to the accompanying drawings.
　なお、各実施形態における各構成及びそれらの組み合わせ等は、一例であって、本開示の主旨から逸脱しない範囲内で、適宜、構成の付加、省略、置換、及びその他の変更が可能である。本開示は、実施形態によって限定されることはなく、クレームの範囲によってのみ限定される。
　また、本明細書に開示された各々の態様は、本明細書に開示された他のいかなる特徴とも組み合わせることができる。 Note that the configurations and combinations thereof in each embodiment are merely examples, and additions, omissions, substitutions, and other changes to the configurations can be made as appropriate without departing from the gist of the present disclosure. This disclosure is not limited by the embodiments, but only by the scope of the claims.
Additionally, each aspect disclosed herein can be combined with any other feature disclosed herein.
　本実施形態に係る樹脂粒子は、アミド結合及び第１の官能基を有する第１の樹脂と、前記第１の官能基と反応可能な第２の官能基を有するポリオレフィン樹脂たる第２の樹脂とを含有する。
　言い換えれば、本実施形態に係る樹脂粒子は、アミド結合及び第１の官能基を有する第１の樹脂と、前記第１の官能基と反応可能な第２の官能基を有するポリオレフィン樹脂たる第２の樹脂とを含有する樹脂粒子用樹脂組成物で形成されている。 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. Contains.
In other words, 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. It is formed from a resin composition for resin particles containing a resin.
　前記第１の官能基としては、アミノ基、カルボキシ基、酸無水物基、エポキシ基、イソシアネート基、カルボジイミド基等が挙げられる。
　前記アミノ基としては、「－ＮＨ２」、「－ＮＨＲ」が挙げられる。
　Ｒは、アルキル基である。Ｒとしては、例えば、メチル基、エチル基、プロピル基などが挙げられる。
　前記酸無水物基としては、カルボン酸無水物基などが挙げられる。 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.
　前記第１の樹脂は、ポリアミド樹脂及び／又はポリイミド樹脂を含むことが好ましい。 Preferably, the first resin includes a polyamide resin and/or a polyimide resin.
　前記ポリアミド樹脂としては、脂肪族ポリアミド樹脂、脂環式ポリアミド樹脂、芳香族ポリアミド樹脂などが挙げられる。
　前記ポリアミド樹脂は、ホモポリアミド樹脂又はコポリアミド樹脂であってもよい。 Examples of the polyamide resin include aliphatic polyamide resin, alicyclic polyamide resin, and aromatic polyamide resin.
The polyamide resin may be a homopolyamide resin or a copolyamide resin.
　前記脂肪族ポリアミド樹脂としては、脂肪族ジアミン成分と脂肪族ジカルボン酸成分とのポリアミド樹脂、ラクタムのポリアミド樹脂、アミノカルボン酸のポリアミド樹脂、脂肪族ジアミン成分と脂肪族ジカルボン酸成分とラクタム及び／又はアミノカルボン酸とのポリアミド樹脂等が挙げられる。 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.
　前記脂肪族ジアミン成分としては、例えば、Ｃ４－１６アルキレンジアミン（例えば、テトラメチレンジアミン、ヘキサメチレンジアミン、ドデカンジアミン等）等が挙げられる。前記脂肪族ジアミン成分は、好ましくはＣ６－１４アルキレンジアミン、さらに好ましくはＣ６－１２アルキレンジアミンである。 Examples of the aliphatic diamine component 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.
　前記脂肪族ジカルボン酸成分としては、例えば、Ｃ４－２０アルカンジカルボン酸（例えば、アジピン酸、セバシン酸、ドデカン二酸等）等が挙げられる。前記脂肪族ジカルボン酸成分は、好ましくはＣ５－１６アルカンジカルボン酸、さらに好ましくはＣ６－１４アルカンジカルボン酸である。 Examples of the aliphatic dicarboxylic acid component 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.
　前記ラクタムとしては、例えば、炭素数４～２０のラクタム（例えば、ε－カプロラクタム、ω－ラウロラクタム等）等が挙げられる。前記ラクタムは、好ましくは炭素数４～１６のラクタムである。 Examples of the lactam include lactams having 4 to 20 carbon atoms (eg, ε-caprolactam, ω-laurolactam, etc.). The lactam is preferably a lactam having 4 to 16 carbon atoms.
　前記アミノカルボン酸としては、例えば、Ｃ４－２０アミノカルボン酸（例えば、ω－アミノウンデカン酸等）等が挙げられる。前記アミノカルボン酸は、好ましくはＣ４－１６アミノカルボン酸、さらに好ましくはＣ６－１４アミノカルボン酸である。 Examples of the aminocarboxylic acids include C4-20 aminocarboxylic acids (eg, ω-aminoundecanoic acid, etc.). The aminocarboxylic acid is preferably a C4-16 aminocarboxylic acid, more preferably a C6-14 aminocarboxylic acid.
　前記脂肪族ポリアミド樹脂としては、例えば、ポリアミド６、ポリアミド１１、ポリアミド１２、ポリアミド４６、ポリアミド６６、ポリアミド６１０、ポリアミド６１１、ポリアミド６１２、ポリアミド６１３、ポリアミド１０１０、ポリアミド６６／１１、ポリアミド６６／１２、ポリアミド６／１２／６１２などが挙げられる。 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.
　前記脂環式ポリアミド樹脂としては、少なくとも脂環式ジアミン成分及び脂環式ジカルボン酸成分から選択された少なくとも一種を構成成分とするポリアミド樹脂などが挙げられる。
　前記脂環式ポリアミド樹脂としては、ジアミン成分及びジカルボン酸成分として、脂環式ジアミン成分及び／又は脂環式ジカルボン酸成分と共に、前記例示の脂肪族ジアミン成分及び／又は脂肪族ジカルボン酸成分を含む脂環式ポリアミド樹脂が好ましい。このような脂環式ポリアミド樹脂は、透明性が高く、いわゆる透明ポリアミド樹脂として知られている。 Examples of the alicyclic polyamide resin 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.
　前記脂環式ジアミン成分としては、例えば、ジアミノシクロアルカン、ビス（アミノシクロアルキル）アルカン、水添キシリレンジアミン等が挙げられる。
　前記ジアミノシクロアルカンとしては、例えば、ジアミノシクロヘキサン等が挙げられる。前記ジアミノシクロアルカンは、ジアミノＣ５－１０シクロアルカンが好ましい。
　前記ビス（アミノシクロアルキル）アルカンとしては、例えば、ビス（４－アミノシクロヘキシル）メタン、ビス（４－アミノ－３－メチルシクロヘキシル）メタン、２，２－ビス（４’－アミノシクロヘキシル）プロパン等が挙げられる。前記ビス（アミノシクロアルキル）アルカンは、ビス（アミノＣ５－８シクロアルキル）Ｃ１－３アルカンが好ましい。
　前記脂環式ジアミン成分は、例えば、アルキル基などの置換基を有していてもよい。
　該アルキル基は、好ましくはＣ１－６アルキル基、より好ましくはＣ１－４アルキル基、さらに好ましくはＣ１－２アルキル基（メチル基、エチル基等）である。 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.).
　前記脂環式ジカルボン酸としては、例えば、シクロアルカンジカルボン酸（例えば、シクロヘキサン－１，４－ジカルボン酸、シクロヘキサン－１，３－ジカルボン酸等）等が挙げられる。 Examples of the alicyclic dicarboxylic acids include cycloalkanedicarboxylic acids (eg, cyclohexane-1,4-dicarboxylic acid, cyclohexane-1,3-dicarboxylic acid, etc.).
　代表的な脂環式ポリアミド樹脂としては、例えば、脂環式ジアミン成分［例えば、ビス（アミノシクロヘキシル）アルカンなど］と脂肪族ジカルボン酸成分［例えば、アルカンジカルボン酸（例えば、Ｃ４－２０アルカンジカルボン酸成分など）など］との縮合物などが挙げられる。 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.)].
　前記芳香族ポリアミド樹脂は、構成単位として、芳香族ジアミン成分及び芳香族ジカルボン酸成分の少なくとも何れか一方を含むポリアミド樹脂を含む概念である。
　前記芳香族ポリアミド樹脂としては、構成単位のジアミン成分及び構成単位のジカルボン酸成分の両方が芳香族成分であるポリアミド樹脂（「全芳香族ポリアミド樹脂」や「アラミド」等とも呼ばれる。）等が挙げられる。
　前記芳香族ポリアミド樹脂は、変性ポリアミド樹脂であってもよい。変性ポリアミド樹脂としては、分岐鎖構造を有するポリアミド樹脂等が挙げられる。
　前記芳香族ジアミン成分としては、メタキシリレンジアミン等が挙げられる。
　前記芳香族ジカルボン酸成分としては、テレフタル酸、イソフタル酸等が挙げられる。また、前記芳香族ジカルボン酸成分は、ダイマー酸等であってもよい。 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.
Examples of 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.
Examples of 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.
　前記ポリイミド樹脂としては、例えば、脂肪族ポリイミド樹脂、芳香族ポリイミド樹脂などが挙げられる。 Examples of the polyimide resin include aliphatic polyimide resins and aromatic polyimide resins.
　第１の樹脂は、単独で又は２種以上組み合わせてもよい。
　前記第１の樹脂としては、補強効果が大きい点から、半結晶性ポリアミド樹脂（例えば、脂環式ポリアミド樹脂、脂肪族ポリアミド樹脂等）が好ましい。 The first resin may be used alone or in combination of two or more.
As the first resin, semicrystalline polyamide resins (eg, alicyclic polyamide resins, aliphatic polyamide resins, etc.) are preferable because they have a large reinforcing effect.
　前記第１の樹脂の数平均分子量は、例えば８０００～２０００００、好ましくは９０００～１５００００、さらに好ましくは１００００～１０００００である。
　なお、本実施形態において、数平均分子量は、ヘキサフルオロイソプロパノール（ＨＦＩＰ）を用いたゲルパーミエーションクロマトグラフィー（ＧＰＣ）を用い、ポリメチルメタクリレート（ＰＭＭＡ）換算分子量分布より測定されたものをいう。当該ＧＰＣにおけるカラムとしては、前記分子量を測定するのに適切なカラムを使用すればよい。 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.
In this embodiment, the number average molecular weight is measured from the polymethyl methacrylate (PMMA) equivalent molecular weight distribution using gel permeation chromatography (GPC) using hexafluoroisopropanol (HFIP). As a column in the GPC, a column suitable for measuring the molecular weight may be used.
　前記第１の樹脂の融点は、例えば１５０℃以上（例えば１５５～３５０℃）、好ましくは１６０℃以上（例えば１６５～３００℃）、さらに好ましくは１７０℃以上（例えば１７５～２７０℃）である。 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).
　本実施形態において、融点は、例えば、示差走査熱量計（ＤＳＣ）を用いて測定することができる。
　より具体的には、まず、融点を測定するための試料を約５ｍｇ用意するとともに、同じ形状で同じ重量の金属（例えば、アルミニウム）製の容器を２つ用意する。
　次に、２つの前記容器のうち一方の容器に試料を入れ、他方の容器を空のままとする。
　そして、試料を入れた容器と、リファレンスとしての空の容器とをＤＳＣにセットし、窒素ガスを流しながら１０℃／ｍｉｎの昇温速度で前記試料を昇温させた際に得られるＤＳＣ曲線から融点を求めることができる。
　なお、融点は、同一試料に対して２回の示差走査熱量分析を実施して求めることができ、２回目のＤＳＣ曲線のピーク値として求められる。 In this embodiment, 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.
　前記第１の樹脂のガラス転移温度（Ｔｇ）は、好ましくは３０℃～１６０℃である。 The glass transition temperature (Tg) of the first resin is preferably 30°C to 160°C.
　なお、本実施形態において、ガラス転移温度（Ｔｇ）は、示差走査熱量計（ＤＳＣ）を用いて測定した中間点ガラス転移温度を意味する。
　中間点ガラス転移温度は、ＪＩＳ　Ｋ７１２１－１９８７「プラスチックの転移温度測定方法」に記載されている方法に基づいて求めることができる。
　すなわち、まず、中間点ガラス転移温度を測定するための試料を約５ｍｇ用意するとともに、同じ形状で同じ重量の金属（例えば、アルミニウム）製の容器を２つ用意する。
　次に、２つの前記容器のうち一方の容器に試料を入れ、他方の容器を空のままとする。
　そして、試料を入れた容器と、リファレンスとしての空の容器とをＤＳＣにセットし、窒素ガスを流しながら１０℃／ｍｉｎの昇温速度で前記試料を昇温させた際に得られるＤＳＣ曲線から中間点ガラス転移温度を求めることができる。 In addition, in this embodiment, 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.
　第１の樹脂の結晶化度は、好ましくは８０％以下（例えば１～７５％）、より好ましくは５０％以下（例えば１０～５０％）である。
　本実施形態において、結晶化度は、広角Ｘ線回折（ＷＡＸＤ）に基づいて測定できる。
　例えば、粉末Ｘ線解析ソフトウェア（リガク社製「ＰＤＸＬ　Ｖｅｒ２．３．１．０」）を用いて、広角Ｘ線回折で得られた回折曲線にフィッティング（方法：ＦＰ法、ピーク形状：対数正規分布、バックグラウンド精密化：なし）を行うことにより、結晶回折ピーク、非晶質ハローを分離し、下記式から結晶化度（％）を求めることができる。
　　結晶化度　＝　［結晶回折ピークの積分強度総和（ｃｐｓ・ｄｅｇ）］／［結晶回折ピーク及び非晶質ハローの積分強度総和（ｃｐｓ・ｄｅｇ）］×１００％ The crystallinity of the first resin is preferably 80% or less (eg, 1 to 75%), more preferably 50% or less (eg, 10 to 50%).
In this embodiment, crystallinity can be measured based on wide-angle X-ray diffraction (WAXD).
For example, using powder X-ray analysis software (Rigaku Co., Ltd. "PDXL Ver2.3.1.0"), fitting a diffraction curve obtained by wide-angle X-ray diffraction (method: FP method, peak shape: lognormal distribution). , background refinement: None), the crystal diffraction peak and amorphous halo can be separated, and the degree of crystallinity (%) can be determined from the following formula.
Crystallinity = [sum of integrated intensities of crystal diffraction peaks (cps/deg)]/[sum of integrated intensities of crystal diffraction peaks and amorphous halo (cps/deg)] x 100%
　前記樹脂粒子は、第１の樹脂を、好ましくは５０重量％以上、より好ましくは６０～９９重量％、さらにより好ましくは７０～９５重量％含有する。 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.
　本実施形態に係る樹脂粒子は、前記第１の官能基と反応可能な第２の官能基を有するポリオレフィン樹脂たる第２の樹脂を有する。
　ポリオレフィン樹脂は、比重が低く、且つ、水分を吸収し難い樹脂であることから、斯かる樹脂粒子は、ポリオレフィン樹脂たる第２の樹脂を含有することにより、水分を吸収し難く、樹脂粒子用樹脂組成物の比重が低い樹脂粒子となる。
　また、第２の樹脂は、第１の樹脂の前記第１の官能基と反応可能な第２の官能基を有することから、第１の樹脂と第２の樹脂とが混ざりやすくなり、第２の樹脂が前記第２の官能基を含まない場合に比べて、本実施形態に係る樹脂粒子は作製しやすいものとなる。 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.
　前記ポリオレフィン樹脂たる第２の樹脂は、オレフィンを構成単位として含む樹脂である。
　前記オレフィンとしては、α－オレフィン、エチレン、２－ブテン、イソプレン、２－ペンテンなどが挙げられる。
　前記α－オレフィンとしては、炭素原子数が３～２０であるα－オレフィンが挙げられ、具体的には、プロピレン、１－ブテン、１－ペンテン、１－ヘキセン、１－ヘプテン、１－オクテン、１－ノネン、１－デセン、１－ウンデセン、１－ドデセン、１－トリデセン、１－テトラデセン、１－ペンタデセン、１－ヘキサデセン、１－ヘプタデセン、１－オクタデセン、１－ノナデセン、１－エイコセン、３－メチル－１－ブテン、３－メチル－１－ペンテン、３－エチル－１－ペンテン、４－メチル－１－ペンテン、４－メチル－１－ヘキセン、４，４－ジメチル－１－ヘキセン、４，４－ジメチル－１－ペンテン、４－エチル－１－ヘキセン、３－エチル－１－ヘキセン、９－メチル－１－デセン、１１－メチル－１－ドデセン、１２－エチル－１－テトラデセン等が挙げられる。
　前記ポリオレフィン樹脂は、単独重合体であってもよく、また、共重合体であってもよい。 The second resin, which is the polyolefin resin, is a resin containing an olefin as a constituent unit.
Examples of the olefin include α-olefin, ethylene, 2-butene, isoprene, and 2-pentene.
Examples of the α-olefin include α-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, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene, etc. It will be done.
The polyolefin resin may be a homopolymer or a copolymer.
　前記第２の官能基としては、カルボキシ基、アミノ基、カルボン酸無水物基、エポキシ基、イソシアネート基、カルボジイミド基などが挙げられる。
　前記ポリオレフィン樹脂は、グリシジル基を有することにより前記エポキシ基を有してもよい。 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.
　前記ポリオレフィン樹脂の融点は、例えば３０～２００℃、好ましくは３５～１７５℃、さらに好ましくは４０～１６０℃である。 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.
　前記樹脂粒子は、前記第１の樹脂及び前記第２の樹脂を合計で、好ましくは８０～１００重量％、より好ましくは９０～１００重量％、更に好ましくは９５～１００重量％含有する。 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.
　前記樹脂粒子は、前記第２の樹脂を、好ましくは５～４０重量％、より好ましくは５～３０重量％含有する。 The resin particles preferably contain the second resin in an amount of 5 to 40% by weight, more preferably 5 to 30% by weight.
　また、前記樹脂粒子は、添加剤を更に含んでもよい。言い換えれば、前記樹脂粒子用樹脂組成物は、添加剤を更に含んでもよい。
　前記添加剤としては、例えば、安定剤、着色剤、分散剤、防腐剤、抗酸化剤、消泡剤などが挙げられる。
　前記添加剤は、単独で又は２種以上組み合わせてもよい。
　前記添加剤の含有割合の合計は、前記第１の樹脂と前記第２の樹脂との合計１００重量部に対して、例えば１０重量部以下（例えば０．０１～１０重量部）である。 Moreover, the resin particles may further contain an additive. In other words, the resin composition for resin particles may further contain an additive.
Examples of 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.
　前記樹脂粒子のメジアン径は、例えば２μｍ以上（例えば３～４０μｍ）の範囲から選択でき、好ましくは４μｍ以上（例えば５～４０μｍ）、より好ましくは６μｍ以上（例えば７～３５μｍ）、さらに好ましくは８μｍ以上（例えば９～３０μｍ）、特に好ましくは１０μｍ以上（例えば１１～３０μｍ）である。
　前記樹脂粒子のメジアン径は、樹脂粒子を水に分散させて、レーザー回折／散乱式粒度分布測定装置によって測定した値を意味する。また、前記樹脂粒子のメジアン径は、樹脂粒子の体積基準のメジアン径を意味する。
　さらに、前記樹脂粒子のメジアン径は、１次粒子の樹脂粒子のメジアン径を意味する。 The median diameter of the resin particles can be selected from a range of, for example, 2 μm or more (for example, 3 to 40 μm), preferably 4 μm or more (for example, 5 to 40 μm), more preferably 6 μm or more (for example, 7 to 35 μm), and even more preferably 8 μm. or more (for example, 9 to 30 μm), particularly preferably 10 μm or more (for example, 11 to 30 μm).
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. Moreover, the median diameter of the resin particles means the volume-based median diameter of the resin particles.
Furthermore, the median diameter of the resin particles means the median diameter of the resin particles as primary particles.
　前記樹脂粒子は、マトリックス及びドメインを含むマトリックス－ドメイン構造（「海島構造」とも呼ばれる。）を有し、前記マトリックスは、前記第１の樹脂を含有し、前記ドメインは、前記第２の樹脂を含有することが好ましい。
　前記マトリックス－ドメイン構造を有する樹脂粒子では、複数個の前記ドメインが前記マトリックスに分散している。
　前記樹脂粒子において前記マトリックスが前記第１の樹脂を含有することにより、第１の樹脂を含む樹脂粒子による硬化物の靭性の向上効果を十分に発揮しやすくなる。
　また、第２の樹脂を含むドメインが前記マトリックスに分散していることにより、第２の樹脂を樹脂粒子に多く含ませやすくなる。
　「前記マトリックスは、前記第１の樹脂を含有する」とは、「前記第１の樹脂が前記ドメインよりも前記マトリックスに多く含まれる」ことを意味する。また、「前記ドメインは、前記第２の樹脂を含有する」とは、「前記第２の樹脂が前記マトリックスよりも前記ドメインに多く含まれる」ことを意味する。 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.
In the resin particles having the matrix-domain structure, a plurality of the domains are dispersed in the matrix.
When the matrix of the resin particles contains the first resin, it becomes easy to sufficiently exhibit the effect of improving the toughness of the cured product by the resin particles containing the first resin.
Further, since domains containing the second resin are dispersed in the matrix, it becomes easier to include a large amount of the second resin in the resin particles.
"The matrix contains the first resin" means "the first resin is contained in the matrix in a larger amount than in the domain." Furthermore, "the domain contains the second resin" means that "the second resin is contained in the domain in a larger amount than in the matrix."
　なお、前記樹脂粒子は、マトリックス及びドメインを含むマトリックス－ドメイン構造を有し、前記マトリックスは、前記第１の樹脂を含有し、前記ドメインは、前記第２の樹脂を含有することは、以下のようにして確認することができる。
　まず、樹脂粒子を切断して断面を得る。
　次に、該断面をトルエンでエッチングする。
　そして、エッチングした断面を走査電子顕微鏡（ＳＥＭ）で観察し、マトリックス－ドメイン構造（マトリックス：前記第１の樹脂、ドメイン：前記第２の樹脂）の有無を確認する。
　なお、断面において樹脂粒子がトルエンでエッチングされて穴が開いている部分は、ポリオレフィン樹脂があった部分である。 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.
　前記ドメインの平均粒子径は、前記樹脂粒子の平均粒子径の１／３以下であることが好ましく、前記樹脂粒子の平均粒子径の１／４以下がより好ましく、前記樹脂粒子の平均粒子径の１／５以下がより一層好ましく、前記樹脂粒子の平均粒子径の１／８以下が更に好ましく、前記樹脂粒子の平均粒子径の１／１０以下が特に好ましい。また、前記ドメインの平均粒子径は、例えば、前記樹脂粒子の平均粒子径の１／２０００である。 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.
　前記樹脂粒子用樹脂組成物の比重は、好ましくは０．８０～１．２５、より好ましくは０．８５～１．２０である。
　前記樹脂粒子用樹脂組成物の比重は、以下のようにして求めることができる。
　まず、前記樹脂粒子用樹脂組成物から射出成形によりＩＳＯに規定されているダンベル試験片を作製する。
　そして、該ダンベル試験片を用いて、ＪＩＳ　Ｋ７１１２：１９９９のＡ法（水中置換法）に準拠して、前記樹脂粒子用樹脂組成物の比重を測定する。 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.
　前記樹脂粒子の真球度は、好ましくは９５％以上１００％以下、より好ましくは９７％以上１００％以下、さらに好ましくは９９％以上１００％以下である。
　なお、本実施形態において、粒子の真球度は、次の方法により測定できる。すなわち、走査型電子顕微鏡（ＳＥＭ）で粒子を観察し、無作為に選択した３０個の粒子の長径と短径を測定し、各粒子の短径／長径比を求める。そして、短径／長径比の算術平均値を求め、この算術平均値を粒子の真球度とする。なお、粒子の真球度が１００％に近いほど、粒子が真球であると判断できる。 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.
In addition, in this embodiment, 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.
　本実施形態に係る樹脂粒子は、上記の如く構成されているが、次に、樹脂粒子の製造方法について説明する。 The resin particles according to this embodiment are configured as described above, and next, a method for manufacturing the resin particles will be described.
　樹脂粒子の製造方法としては、冷凍粉砕法、化学粉砕法、重合法、強制乳化法、レーザー法等が挙げられる。
　樹脂粒子の製造方法としては、強制乳化法が好ましい。 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.
As a method for producing resin particles, a forced emulsification method is preferred.
　前記強制乳化法では、前記第１の樹脂と、前記第２の樹脂と、前記第１の樹脂及び前記第２の樹脂に非相溶な水性媒体とを加熱により溶融混練することにより、溶融混練物を得る工程（Ａ）と、該溶融混練物を冷却する工程（Ｂ）と、冷却された該溶融混練物から親水性溶媒又は水で前記水性媒体を除去する工程（Ｃ）とを実施することにより、前記樹脂粒子を得る。
　前記強制乳化法では、必要に応じて、前記工程（Ｃ）後に、前記溶融混練物を除湿乾燥機等で乾燥させる工程（Ｄ）を実施することにより、前記樹脂粒子を得てもよい。
　また、所望の粒径の樹脂粒子を得るために、前記強制乳化法では、前記工程（Ｃ）後に（前記工程（Ｄ）を実施する場合には、前記工程（Ｄ）後又は前記工程（Ｄ）前に）、前記溶融混練物を分級する工程（Ｅ）を実施することにより、前記樹脂粒子を得てもよい。 In the forced emulsification method, the first resin, the second resin, and an aqueous medium incompatible with the first resin and the second resin are melt-kneaded by heating. A step (A) of obtaining a product, a step (B) of cooling the melt-kneaded product, and a step (C) of removing the aqueous medium from the cooled melt-kneaded product using a hydrophilic solvent or water. By doing so, the resin particles are obtained.
In the forced emulsification method, 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.
In order to obtain resin particles having a desired particle size, in the forced emulsification method, after the step (C) (if the step (D) is carried out, after the step (D) or after the step (D) ), the resin particles may be obtained by performing step (E) of classifying the melt-kneaded material.
　前記工程（Ａ）で用いる前記水性媒体は、前記第１の樹脂及び前記第２の樹脂の種類に応じて選択する。
　前記水性媒体としては、例えば、熱溶融性の糖類、水溶性高分子などが挙げられる。
　前記熱溶融性の糖類としては、例えば、オリゴ糖（例えば、スクロース、マルトトリオースなど）、糖アルコール（例えば、キシリトール、エリスリトール、ソルビトール、マンニトールなど）などが挙げられる。
　前記水溶性高分子としては、例えば、水溶性合成高分子（例えば、ポリエチレングリコール、ポリビニルアルコール、ポリアクリル酸ナトリウム、ポリアクリルアミドなど）、多糖類（例えば、デンプン、メチルセルロースなど）などが挙げられる。
　これらの水性媒体は、単独で又は二種以上組み合わせて使用できる。
　前記水性媒体としては、樹脂粒子を適度な粒径に調整し易いという観点から、ポリエチレングリコールが好ましい。 The aqueous medium used in the step (A) is selected depending on the types of the first resin and the second resin.
Examples of the aqueous medium include heat-melting saccharides, water-soluble polymers, and the like.
Examples of the heat-melting saccharides include oligosaccharides (eg, sucrose, maltotriose, etc.), sugar alcohols (eg, xylitol, erythritol, sorbitol, mannitol, etc.), and the like.
Examples of the water-soluble polymer include water-soluble synthetic polymers (eg, polyethylene glycol, polyvinyl alcohol, sodium polyacrylate, polyacrylamide, etc.), polysaccharides (eg, starch, methylcellulose, etc.), and the like.
These aqueous media can be used alone or in combination of two or more.
As the aqueous medium, polyethylene glycol is preferable from the viewpoint that the resin particles can be easily adjusted to an appropriate particle size.
　水性媒体の重量割合については、前記第１の樹脂と前記第２の樹脂との合計１００重量部に対して、水性媒体が、例えば１０～１００重量部、好ましくは２０～１００重量部、さらに好ましくは３０～１００重量部である。
　水性媒体の体積割合は、水性媒体、前記第１の樹脂、及び、前記第２の樹脂の総体積に対して、例えば５０体積％以上（例えば５０～９０体積％）である。 Regarding the weight ratio of the aqueous medium, 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.
　前記工程（Ａ）で溶融混練する際の温度は、第１の樹脂の融点又は軟化点以上の温度で、且つ、第２の樹脂の融点又は軟化点以上の温度であればよく、例えば１９０℃以上（例えば１９０～３５０℃）、好ましくは２００～３２０℃、さらに好ましくは２１０～３００℃である。 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.
　前記工程（Ｂ）では、溶融混練物を自然冷却してもよく、溶融混練物を強制冷却してもよいが、生産性の観点から、溶融混練物を強制冷却することが好ましい。
　溶融混練物の冷却速度は、例えば、１℃／分以上（例えば１～１０℃／分）が好ましい。 In the step (B), 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).
　前記工程（Ｃ）で用いる親水性溶媒としては、例えば、アルコール（エタノールなど）、水溶性ケトン（アセトンなど）などが挙げられる。 Examples of the hydrophilic solvent used in the step (C) include alcohol (such as ethanol), water-soluble ketones (such as acetone), and the like.
　本実施形態に係る樹脂粒子は、液晶ディスプレイのスペーサー、３Ｄプリンターで構造物を作製する際の材料などとして用いることができる。 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.
　また、複数の樹脂粒子を圧縮成形するなどして、板材や棒材などを作製するのに、本実施形態に係る樹脂粒子を用いることができる。 Furthermore, 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.
　さらに、熱硬化性樹脂を含む熱硬化性樹脂組成物が硬化された硬化物の靭性を高めるという観点等から、該熱硬化性樹脂組成物に本実施形態に係る樹脂粒子を含ませてもよい。 Furthermore, from the viewpoint of increasing the toughness of a cured product obtained by curing a thermosetting resin composition containing a thermosetting resin, the resin particles according to the present embodiment may be included in the thermosetting resin composition. .
　該熱硬化性樹脂組成物は、熱硬化性樹脂、及び、樹脂粒子を含む。 The thermosetting resin composition includes a thermosetting resin and resin particles.
　前記熱硬化性樹脂としては、例えば、エポキシ樹脂、フェノール樹脂、不飽和ポリエステル樹脂、ビニルエステル樹脂、アクリル樹脂、尿素樹脂、メラミン樹脂、アニリン樹脂、ポリイミド樹脂、ビスマレイミド樹脂などが挙げられる。これらの熱硬化性樹脂は、単独で又は２種以上組み合わせてもよい。 Examples of the thermosetting resin 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.
　前記熱硬化性樹脂としては、エポキシ樹脂、フェノール樹脂が好ましく、エポキシ樹脂が特に好ましい。
　エポキシ樹脂とポリアミド樹脂とは相溶性に優れることから、前記熱硬化性樹脂がエポキシ樹脂を含むことにより、前記ポリアミド樹脂を含む樹脂粒子が前記エポキシ樹脂中に分散されやすくなり、前記樹脂粒子による靭性の向上の効果が発揮されやすくなる。 As the 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.
　エポキシ樹脂としては、例えば、グリシジルエーテル型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、グリシジルエステル型エポキシ樹脂、アルケンオキシド類（例えば、ビニルシクロヘキセンジオキシドなど）、トリグリシジルイソシアヌレートなどが挙げられる。 Examples of epoxy resins 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.
　前記グリシジルエーテル型エポキシ樹脂としては、例えば、ビスフェノール型エポキシ樹脂、フェノール型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、芳香族骨格を有するエポキシ樹脂（ポリグリシジルエーテル）、アルカンジオールジグリシジルエーテル、ポリアルカンジオールジグリシジルエーテル、脂肪族骨格を有するエポキシ樹脂（ポリグリシジルエーテル）等が挙げられる。 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.
　前記ビスフェノール型エポキシ樹脂としては、例えば、ビスフェノール類とエピクロロヒドリンとの反応物、ビスフェノール類のアルキレンオキシド付加体とエピクロロヒドリンとの反応物等が挙げられる。
　前記ビスフェノール類としては、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、臭素化ビスフェノール型エポキシ樹脂などが挙げられる。
　前記ビスフェノール類のアルキレンオキシド付加体においては、ビスフェノール類のヒドロキシル基１モルに対するアルキレンオキシドの付加モル数は、例えば１モル以上（例えば１～２０モル）、好ましくは１～１５モル、さらに好ましくは１～１０モルである。 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.
In the alkylene oxide adduct of bisphenols, 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.
　前記フェノール型エポキシ樹脂としては、例えば、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ナフトールノボラック型エポキシ樹脂、ビスフェノールＡノボラック型エポキシ樹脂、ビスフェノールＦノボラック型エポキシ樹脂、ビフェニル骨格含有フェノールノボラック樹脂、キシリレン骨格含有フェノールノボラック樹脂などが挙げられる。 Examples of the phenolic epoxy resin 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. Examples include skeleton-containing phenol novolac resins.
　前記芳香族骨格を有するエポキシ樹脂（ポリグリシジルエーテル）としては、例えば、ナフタレン骨格を有するグリシジルエーテル等が挙げられる。
　前記ナフタレン骨格を有するグリシジルエーテルとしては、例えば、ジ（グリシジルオキシ）ナフタレン、ビス［２，７－ジ（グリシジルオキシ）ナフチル］メタン等が挙げられる。
　前記ジ（グリシジルオキシ）ナフタレンとしては、例えば、１，５－ジ（グリシジルオキシ）ナフタレンなどが挙げられる。 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.
　前記アルカンジオールジグリシジルエーテルとしては、例えば、Ｃ２－１０アルカンジオールジグリシジルエーテル等が挙げられる。
　前記Ｃ２－１０アルカンジオールジグリシジルエーテルとしては、例えば、ブタンジオールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、１，６－ヘキサンジオールジグリシジルエーテル等が挙げられる。 Examples of the alkanediol diglycidyl ether 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.
　前記ポリアルカンジオールジグリシジルエーテルとしては、例えば、ポリＣ２－４アルカンジオールジグリシジルエーテル等が挙げられる。
　前記ポリＣ２－４アルカンジオールジグリシジルエーテルとしては、例えば、ポリプロピレングリコールジグリシジルエーテル等が挙げられる。 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.
　前記脂肪族骨格を有するエポキシ樹脂（ポリグリシジルエーテル）としては、ポリオールのグリシジルポリエーテル等が挙げられる。
　前記ポリオールとしては、例えば、アルカントリオール、アルカンテトラオール、アルカンペンタオール、アルカンヘキサオール等が挙げられる。前記アルカントリオールとしては、Ｃ３－１０アルカントリオール等が挙げられる。前記アルカンテトラオールとしては、Ｃ３－１０アルカンテトラオール等が挙げられる。
　前記グリシジルポリエーテルとしては、ジグリシジルエーテル、トリグリシジルエーテル、テトラグリシジルエーテル、ペンタグリシジルエーテル、ヘキサグリシジルエーテル等が挙げられる。
　前記ポリオールのグリシジルポリエーテルとしては、例えば、トリメチロールプロパンジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、グリセリンジグリシジルエーテル、グリセリントリグリシジルエーテル等が挙げられる。 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.
　前記グリシジルアミン型エポキシ樹脂としては、例えば、テトラグリシジルジアミノジフェニルメタン、トリグリシジル－ｐ－アミノフェノール、トリグリシジルアミノクレゾール、ジグリシジルアニリン、Ｎ，Ｎ－ジグリシジル－４－グリシジルオキシアニリン等が挙げられる。 Examples of the glycidylamine type epoxy resin include tetraglycidyldiaminodiphenylmethane, triglycidyl-p-aminophenol, triglycidyl aminocresol, diglycidylaniline, N,N-diglycidyl-4-glycidyloxyaniline, and the like.
　前記グリシジルエステル型エポキシ樹脂としては、例えば、ジカルボン酸のジグリシジルエステル等が挙げられる。
　前記ジカルボン酸としては、例えば、芳香族ジカルボン酸、芳香族ジカルボン酸の水添物等が挙げられる。
　前記芳香族ジカルボン酸としては、例えば、テレフタル酸、イソフタル酸、フタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸等が挙げられる。 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.
　これらのエポキシ樹脂は、単独で又は２種以上組み合わせてもよい。
　これらのエポキシ樹脂のうち、強度などの点で、芳香族骨格を有するエポキシ樹脂が好ましく、ビスフェノール型エポキシ樹脂が特に好ましい。 These epoxy resins may be used alone or in combination of two or more.
Among these epoxy resins, in terms of strength and the like, epoxy resins having an aromatic skeleton are preferred, and bisphenol type epoxy resins are particularly preferred.
　前記フェノール樹脂としては、例えば、１分子中にフェノール性水酸基を、１個以上、好ましくは２個以上有する樹脂が挙げられる。
　前記フェノール樹脂としては、例えば、ノボラック型フェノール樹脂、レゾール型フェノール樹脂、ポリオキシスチレン樹脂などが挙げられる。 Examples of the phenolic resin 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.
　前記ノボラック型フェノール樹脂は、フェノール類とアルデヒド類と縮合物である。前記ノボラック型フェノール樹脂は、例えば、フェノール類とアルデヒド類とを酸性触媒の存在下で縮合重合させることで得られる。
　前記レゾール型フェノール樹脂は、フェノール類とアルデヒド類と縮合物である。前記レゾール型フェノール樹脂は、例えば、フェノール類とアルデヒド類とをアルカリ性触媒の存在下で縮合重合させることで得られる。 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.
　前記フェノール類としては、例えば、フェノール、クレゾール、トリメチルフェノール、キシレノール、レゾルシノール、カテコール、ブチルフェノール、オクチルフェノール、ノニルフェノール、フェニルフェノール、ジヒドロキシベンゼン、ビスフェノールＡ、ナフトール等が挙げられる。
　前記クレゾールとしては、ｏ－クレゾール、ｍ－クレゾール、ｐ－クレゾールが挙げられる。
　前記トリメチルフェノールとしては、２，３，５－トリメチルフェノール等が挙げられる。
　前記キシレノールとしては、２，３－キシレノール、２，４－キシレノール、２，５－キシレノール、３，４－キシレノール、３，５－キシレノール等が挙げられる。 Examples of the phenols include phenol, cresol, trimethylphenol, xylenol, resorcinol, catechol, butylphenol, octylphenol, nonylphenol, phenylphenol, dihydroxybenzene, bisphenol A, and naphthol.
Examples of the cresol include o-cresol, m-cresol, and p-cresol.
Examples of the trimethylphenol include 2,3,5-trimethylphenol.
Examples of the xylenol include 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol, and 3,5-xylenol.
　前記アルデヒド類としては、例えば、ホルムアルデヒド、パラホルムアルデヒド、アセトアルデヒド、ベンズアルデヒド、ヒドロキシベンズアルデヒド、グリオキサール、グルタルアルデヒド、テレフタルアルデヒド、イソフタルアルデヒド、プロピオンアルデヒド、ブチルアルデヒド、イソブチルアルデヒド、３－メチルブチルアルデヒド、ｐ－トリルアルデヒド、フェニルアセトアルデヒド等が挙げられる。
　前記ヒドロキシベンズアルデヒドとしては、ｏ－ヒドロキシベンズアルデヒド、ｍ－ヒドロキシベンズアルデヒド、ｐ－ヒドロキシベンズアルデヒドが挙げられる。 Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, glyoxal, glutaraldehyde, terephthalaldehyde, isophthalaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, 3-methylbutyraldehyde, and p-tolylaldehyde. , phenylacetaldehyde, and the like.
Examples of the hydroxybenzaldehyde include o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, and p-hydroxybenzaldehyde.
　前記ノボラック型フェノール樹脂としては、例えば、ノボラック樹脂（フェノールとホルムアルデヒドとの縮合物）、クレゾールノボラック樹脂（クレゾールとホルムアルデヒドとの縮合物）等が挙げられる。 Examples of the novolak-type phenolic resin include novolak resin (a condensate of phenol and formaldehyde), cresol novolak resin (a condensate of cresol and formaldehyde), and the like.
　前記フェノール樹脂は、１種単独で、又は２種以上を組み合わせて使用してもよい。 The phenolic resins may be used alone or in combination of two or more.
　前記フェノール樹脂の水酸基当量は、好ましくは５０～５００ｇ／ｅｑ．より好ましくは１００～３５０ｇ／ｅｑ．である。 The hydroxyl equivalent of the phenol resin is preferably 50 to 500 g/eq. More preferably 100 to 350 g/eq. It is.
　前記熱硬化性樹脂組成物は、熱硬化性樹脂を、好ましくは４０～９９重量％、より好ましくは８０～９７重量％有する。 The thermosetting resin composition preferably contains a thermosetting resin in an amount of 40 to 99% by weight, more preferably 80 to 97% by weight.
　前記熱硬化性樹脂組成物は、前記熱硬化性樹脂及び前記樹脂粒子を合計で、好ましくは５０～９９重量％、より好ましくは８０～９７重量％有する。 The 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.
　前記熱硬化性樹脂組成物は、前記熱硬化性樹脂１００重量部に対して、前記樹脂粒子を、好ましくは１～３０重量部、より好ましくは３～２５重量部、より好ましくは５～２０重量部である。 In the thermosetting resin composition, 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.
　前記熱硬化性樹脂組成物は、強化繊維を含んでもよい。すなわち、前記熱硬化性樹脂組成物が熱硬化された硬化物は、繊維強化プラスチック（ＦＲＰ）であってもよい。
　前記強化繊維としては、例えば、炭素繊維、ガラス繊維、アラミド繊維、ボロン繊維、ポリパラフェニレン・ベンゾビス・オキサゾール（ＰＢＯ）繊維、ポリエチレン繊維、アルミナ繊維、炭化ケイ素繊維などが挙げられる。
　前記強化繊維としては、炭素繊維が好ましい。すなわち、前記硬化物は、炭素繊維強化プラスチック（ＣＦＲＰ）であることが好ましい。 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).
Examples of 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).
　前記強化繊維は、モノフィラメントであってもよく、マルチフィラメントであってもよい。
　前記強化繊維の単繊維の繊度は、好ましくは０．２～２．０ｄｔｅｘ、より好ましくは０．４～１．８ｄｔｅｘである。 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.
　前記強化繊維がマルチフィラメントである場合、前記繊維におけるフィラメント数は、２５００～５００００本であることが好ましい。 When the reinforcing fiber is a multifilament, the number of filaments in the fiber is preferably 2,500 to 50,000.
　前記強化繊維は、連続繊維となっていてもよく、また、不連続の形態となっていてもよい。
　より高い力学特性が硬化物に求められる場合には、前記強化繊維としては、連続繊維が好ましい。
　連続繊維は、例えば、一方向基材、編み物、織物、トウ、又は、ロービング等となって、本実施形態に係る熱硬化性樹脂組成物に含まれていてもよい。
　不連続の形態の強化繊維は、例えば、不織布、又は、チョップド糸等となって、本実施形態に係る熱硬化性樹脂組成物に含まれていてもよい。 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.
　前記熱硬化性樹脂組成物は、前記熱硬化性樹脂１００重量部に対して、前記強化繊維を、好ましくは１～５０重量部、より好ましくは５～３０重量部含む。 The 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.
　前記熱硬化性樹脂がエポキシ樹脂を含む場合には、前記熱硬化性樹脂組成物は、単官能性のエポキシ化合物を含んでもよい。
　前記単官能性のエポキシ化合物としては、モノグリシジルエーテル、アルケンオキシド（例えば、オクチレンオキシド、スチレンオキシドなど）等が挙げられる。
　前記モノグリシジルエーテルとしては、例えば、アルキルグリシジルエーテル（例えば、２－エチルへキシルグリシジルエーテルなど）、アルケニルグリシジルエーテル（例えば、アリルグリシジルエーテルなど）、アリールグリシジルエーテル（例えば、フェニルグリシジルエーテルなど）等が挙げられる。
　前記熱硬化性樹脂組成物において、前記単官能性のエポキシ化合物の重量に対する前記エポキシ樹脂の重量の比は、例えば９９／１～５０／５０、好ましくは９７／３～６０／４０、さらに好ましくは９５／５～７０／３０である。 When the thermosetting resin includes an epoxy resin, the thermosetting resin composition may include a monofunctional epoxy compound.
Examples of the monofunctional epoxy compound include monoglycidyl ether, alkene oxide (eg, octylene oxide, styrene oxide, etc.).
Examples of 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. Can be mentioned.
In the thermosetting resin composition, 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.
　前記熱硬化性樹脂組成物は、硬化剤を含んでもよい。
　前記硬化剤としては、前記熱硬化性樹脂の種類に応じて適宜選択できる。
　熱硬化性樹脂がエポキシ樹脂である場合の硬化剤としては、例えば、アミン系硬化剤、フェノール樹脂系硬化剤、酸無水物系硬化剤、ポリメルカプタン系硬化剤、潜在性硬化剤などが挙げられる。 The thermosetting resin composition may include a curing agent.
The curing agent can be appropriately selected depending on the type of the thermosetting resin.
When the thermosetting resin is an epoxy 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. .
　前記アミン系硬化剤としては、例えば、芳香族アミン系硬化剤、脂肪族アミン系硬化剤、イミダゾール類、イミダゾール類の塩、脂環式アミン系硬化剤などが挙げられる。 Examples of the amine curing agent include aromatic amine curing agents, aliphatic amine curing agents, imidazoles, salts of imidazoles, and alicyclic amine curing agents.
　前記芳香族アミン系硬化剤としては、例えば、ポリアミノアレーン、ポリアミノ－アルキルアレーン、ポリ（アミノアルキル）アレーン、ポリ（アミノアリール）アルカン、ポリ（アミノ－アルキルアリール）アルカン、ビス（アミノアリールアルキル）アレーン、ジ（アミノアリール）エーテル（例えば、ジアミノジフェニルエーテルなど）、ジ（アミノアリールオキシ）アレーン（例えば、１，３－ビス（３－アミノフェノキシ）ベンゼンなど）、ジ（アミノアリール）スルホン（例えば、ジアミノジフェニルスルホンなど）等が挙げられる。
　前記ポリアミノアレーンとしては、例えば、ジアミノアレーン（例えば、パラフェニレンジアミン、メタフェニレンジアミン等）等が挙げられる。
　前記ポリアミノ－アルキルアレーンとしては、例えば、ジアミノ－アルキルアレーン（例えば、ジエチルトルエンジアミン等）等が挙げられる。
　前記ポリ（アミノアルキル）アレーンとしては、例えば、ジ（アミノアルキル）アレーン（例えば、キシリレンジアミン等）等が挙げられる。
　前記ポリ（アミノアリール）アルカンとしては、例えば、ジ（アミノアリール）アルカン（例えば、ジアミノジフェニルメタン等）等が挙げられる。
　前記ポリ（アミノ－アルキルアリール）アルカンとしては、例えば、ジ（アミノ－アルキルアリール）アルカン（例えば、４，４’－メチレンビス（２－エチル－６－メチルアニリン）等）等が挙げられる。
　前記ビス（アミノアリールアルキル）アレーンとしては、例えば、１，３－ビス［２－（４－アミノフェニル）－２－プロピル）］ベンゼン、１，４－ビス［２－（４－アミノフェニル）－２－プロピル）］ベンゼン等が挙げられる。 Examples of the aromatic amine curing agent 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.).
Examples of the polyaminoarene include diaminoarene (eg, paraphenylenediamine, metaphenylenediamine, etc.).
Examples of the polyamino-alkylarene include diamino-alkylarene (eg, diethyltoluenediamine, etc.).
Examples of the poly(aminoalkyl)arenes include di(aminoalkyl)arenes (eg, xylylene diamine, etc.).
Examples of the poly(aminoaryl)alkanes include di(aminoaryl)alkanes (eg, diaminodiphenylmethane, etc.).
Examples of the poly(amino-alkylaryl)alkanes include di(amino-alkylaryl)alkanes (eg, 4,4'-methylenebis(2-ethyl-6-methylaniline), etc.).
Examples of the bis(aminoarylalkyl)arene include 1,3-bis[2-(4-aminophenyl)-2-propyl)]benzene, 1,4-bis[2-(4-aminophenyl)- 2-propyl)]benzene and the like.
　前記脂肪族アミン系硬化剤としては、例えば、エチレンジアミン、ヘキサメチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ジエチルアミノプロピルアミン等が挙げられる。 Examples of the aliphatic amine curing agent include ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, and the like.
　前記脂環式アミン系硬化剤としては、例えば、メンセンジアミン、イソホロンジアミン、ビス（４－アミノ－３－メチルシクロヘキシル）メタン、３，９－ビス（３－アミノプロピル）－２，４，８，１０－テトラオキサスピロ［５．５］ウンデカン、ノルボルナンジアミン等が挙げられる。 Examples of the alicyclic amine curing agent 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.
　前記イミダゾール類としては、例えば、アルキルイミダゾール、アリールイミダゾール等が挙げられる。
　前記アルキルイミダゾールとしては、例えば、２－メチルイミダゾール、２－フェニルイミダゾール、２－へプタデシルイミダゾール、２－エチル－４－メチルイミダゾール等が挙げられる。
　前記アリールイミダゾールとしては、例えば、２－フェニルイミダゾール、２－フェニル－４－メチルイミダゾール、２－フェニル－４－メチル－５－ヒドロキシメチルイミダゾール、１－ベンジル－２－フェニルイミダゾール等が挙げられる。 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.
　前記イミダゾール類の塩としては、例えば、イミダゾール類とギ酸との塩、イミダゾール類とフェノールとの塩、イミダゾール類とフェノールノボラックとの塩、イミダゾール類と炭酸との塩などが挙げられる。 Examples of the 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.
　前記フェノール樹脂系硬化剤としては、例えば、ノボラック樹脂、クレゾールノボラック樹脂等が挙げられる。 Examples of the phenolic resin curing agent include novolac resin, cresol novolac resin, and the like.
　前記酸無水物系硬化剤としては、例えば、脂肪族ジカルボン酸無水物、脂環式ジカルボン酸無水物、芳香族ジカルボン酸無水物などが挙げられる。
　前記脂肪族ジカルボン酸無水物としては、例えば、ドデセニル無水コハク酸などが挙げられる。
　前記脂環式ジカルボン酸無水物としては、例えば、テトラヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸などが挙げられる。
　前記芳香族ジカルボン酸無水物としては、例えば、無水フタル酸、無水トリメリット酸、無水ピロメリット酸、ベンゾフェノンテトラカルボン酸無水物などが挙げられる。 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.
　前記潜在性硬化剤としては、例えば、三フッ化ホウ素－アミン錯体、ジシアンジアミド、カルボン酸ヒドラジド等が挙げられる。 Examples of the latent curing agent include boron trifluoride-amine complex, dicyandiamide, and carboxylic acid hydrazide.
　硬化剤は、単独で又は２種以上組み合わせてもよい。なお、硬化剤は、硬化促進剤として作用する場合もある。
　前記硬化剤としては、アミン系硬化剤（例えば、芳香族アミン系硬化剤）が好ましい。 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.
　前記硬化剤の含有割合は、熱硬化性樹脂の種類（エポキシ当量など）や硬化剤の種類などに応じて適宜選択できるが、例えば、熱硬化性樹脂１００重量部に対して０．１～３００重量部、好ましくは１～２５０重量部、さらに好ましくは３～２００重量部（例えば、４～１５０重量部）、特に好ましくは５～１００重量部である。 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.
　前記熱硬化性樹脂組成物は、硬化促進剤を含んでもよい。
　前記硬化促進剤としては、前記熱硬化性樹脂の種類に応じて適宜選択できる。
　熱硬化性樹脂がエポキシ樹脂である場合の硬化促進剤としては、例えば、ホスフィン類、アミン類、アミン類の塩などが挙げられる。
　前記ホスフィン類としては、例えば、エチルホスフィン、プロピルホスフィン、トリアルキルホスフィン、フェニルホスフィン、トリフェニルホスフィンなどが挙げられる。
　前記アミン類としては、例えば、第２～３級アミン類等が挙げられる。
　第２～３級アミン類としては、例えば、トリエチルアミン、ピペリジン、ベンジルジメチルアミン、トリエタノールアミン、ジメチルアミノエタノール、トリエチレンジアミン、トリス（ジメチルアミノメチル）フェノール、Ｎ，Ｎ－ジメチルピペラジン等が挙げられる。
　硬化促進剤は、単独で又は２種以上組み合わせてもよい。 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.
Examples of the amines include secondary to tertiary amines.
Examples of secondary to tertiary amines 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.
　前記硬化促進剤の含有割合は、例えば、熱硬化性樹脂１００重量部に対して０．０１～１００重量部、好ましくは０．０５～５０重量部、さらに好ましくは１～３０重量部である。 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.
　前記熱硬化性樹脂組成物は、必要に応じて、他の成分として、熱可塑性樹脂及び添加剤の少なくとも何れか一をさらに含んでいてもよい。 The thermosetting resin composition may further contain at least one of a thermoplastic resin and an additive as another component, if necessary.
　前記熱可塑性樹脂としては、例えば、アクリル樹脂、ポリオレフィン樹脂（例えば、ポリプロピレンなど）、ポリアミド樹脂、ポリエステル樹脂、ポリカーボネート樹脂、ポリフェニレンエーテル樹脂、ポリフェニレンスルフィド樹脂、ポリスルホン樹脂、ポリエーテルケトン樹脂、ポリエーテルエーテルケトン樹脂、ポリイミド樹脂、ポリエーテルイミド樹脂などが挙げられる。
　前記ポリエステル樹脂としては、例えば、芳香族ポリエステル樹脂（例えば、ポリエチレンテレフタレートなど）などが挙げられる。 Examples of the thermoplastic resin 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.
Examples of the polyester resin include aromatic polyester resins (eg, polyethylene terephthalate, etc.).
　前記添加剤としては、例えば、非繊維状充填剤、安定剤、着色剤、分散剤、防腐剤、抗酸化剤、消泡剤などが挙げられる。 Examples of the additives include non-fibrous fillers, stabilizers, colorants, dispersants, preservatives, antioxidants, antifoaming agents, and the like.
　他の成分の含有割合は、熱硬化性樹脂１００重量部に対して、例えば１０重量部以下（例えば０．０１～１０重量部）である。 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.
　前記熱硬化性樹脂組成物が熱硬化された硬化物の形状は、一次元的形状（棒状など）、二次元的形状（シート状など）、又は、三次元的形状であってもよい。 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.
〔開示項目〕
　以下の項目のそれぞれは、好ましい実施形態の開示である。 [Disclosure items]
Each of the following items is a disclosure of a preferred embodiment.
〔項目１〕
　アミド結合及び第１の官能基を有する第１の樹脂と、前記第１の官能基と反応可能な第２の官能基を有するポリオレフィン樹脂たる第２の樹脂とを含有する、樹脂粒子。 [Item 1]
A resin particle containing 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.
〔項目２〕
　マトリックス及びドメインを含むマトリックス－ドメイン構造を有し、
前記マトリックスは、前記第１の樹脂を含有し、
前記ドメインは、前記第２の樹脂を含有する、項目１に記載の樹脂粒子。 [Item 2]
has a matrix-domain structure including a matrix and a domain;
The matrix contains the first resin,
The resin particle according to item 1, wherein the domain contains the second resin.
〔項目３〕
　真球度が９５％以上である、項目１又は２に記載の樹脂粒子。 [Item 3]
The resin particles according to item 1 or 2, having a sphericity of 95% or more.
〔項目４〕
　前記第１の樹脂と、前記第２の樹脂とを含有する樹脂組成物で形成され、
前記樹脂組成物の比重が０．８０～１．２５である、項目１～３の何れか１項に記載の樹脂粒子。 [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.
〔項目５〕
　前記第１の樹脂を５０重量％以上含有し、
前記第２の樹脂を５～４０重量％含有する、項目１～４の何れか１項に記載の樹脂粒子。 [Item 5]
Containing 50% by weight or more of the first resin,
The resin particles according to any one of items 1 to 4, containing 5 to 40% by weight of the second resin.
〔項目６〕
　前記第１の樹脂は、ポリアミド樹脂及び／又はポリイミド樹脂を含む、項目１～５の何れか１項に記載の樹脂粒子。 [Item 6]
The resin particles according to any one of items 1 to 5, wherein the first resin includes a polyamide resin and/or a polyimide resin.
〔項目７〕
　前記第２の官能基は、カルボキシ基、アミノ基、カルボン酸無水物基、エポキシ基、イソシアネート基、及び、カルボジイミド基から選ばれる少なくとも１種の官能基を有する、項目１～６の何れか１項に記載の樹脂粒子。 [Item 7]
Any one of items 1 to 6, wherein the second functional group has at least one functional group selected from a carboxy group, an amino group, a carboxylic acid anhydride group, an epoxy group, an isocyanate group, and a carbodiimide group. Resin particles described in Section.
　次に、実施例および比較例を挙げて本開示についてさらに具体的に説明する。なお、本開示はこれらの実施例に何ら限定されるものではない。 Next, the present disclosure will be described in more detail with reference to Examples and Comparative Examples. Note that the present disclosure is not limited to these examples in any way.
　下記材料を用意した。 The following materials were prepared.
（第１の樹脂）
　　ポリアミド１２（ＰＡ１２）：ダイセル・エボニック社製の「Ｌ１９０１」
　　ポリアミド１０１０（ＰＡ１０１０）：ダイセル・エボニック社製の「ＤＳ２２」
　　脂環式ポリアミド（脂環式ＰＡ）：ダイセル・エボニック社製の「トロガミド（登録商標）ＣＸ７３２３」
　　脂環式ポリアミド（脂環式ＰＡ）：ダイセル・エボニック社製の「トロガミド（登録商標）ＣＸ９７０４」
　　ポリアミド６１０（ＰＡ６１０） (First resin)
Polyamide 12 (PA12): “L1901” manufactured by Daicel-Evonik
Polyamide 1010 (PA1010): "DS22" manufactured by Daicel-Evonik
Alicyclic polyamide (alicyclic PA): "Trogamide (registered trademark) CX7323" manufactured by Daicel-Evonik
Alicyclic polyamide (alicyclic PA): “Trogamide (registered trademark) CX9704” manufactured by Daicel-Evonik
Polyamide 610 (PA610)
（第２の樹脂）
　　エチレンと１－ブテンとの共重合体を無水マレイン酸で変性したポリオレフィン樹脂：三井化学社製の「タフマー（登録商標）ＭＨ５０１０」
　　エチレンと１－ブテンとの共重合体を無水マレイン酸で変性したポリオレフィン樹脂：三井化学社製の「タフマー（登録商標）ＭＨ５０４０」
　　ポリプロピレンを無水マレイン酸で変性したポリオレフィン樹脂：三井化学社製の「アドマー（登録商標）ＧＦ５００」 (Second resin)
Polyolefin resin made by modifying a copolymer of ethylene and 1-butene with maleic anhydride: "Tafmer (registered trademark) MH5010" manufactured by Mitsui Chemicals
Polyolefin resin made by modifying a copolymer of ethylene and 1-butene with maleic anhydride: "Tafmer (registered trademark) MH5040" manufactured by Mitsui Chemicals
Polyolefin resin made by modifying polypropylene with maleic anhydride: "Admer (registered trademark) GF500" manufactured by Mitsui Chemicals
（第２の官能基を含まないポリオレフィン樹脂）
　　旭化成社製の「サンテック（登録商標）－ＬＤＭ２２０」 (Polyolefin resin not containing a second functional group)
"Suntech (registered trademark) - LDM220" manufactured by Asahi Kasei Corporation
（シリカフィラー）
　　ヘキサメチルジシラザンで表面処理されたフュームドシリカ（疎水性フュームドシリカ）：アエロジル社製の「ＲＸ５０」 (silica filler)
Fumed silica surface-treated with hexamethyldisilazane (hydrophobic fumed silica): “RX50” manufactured by Aerosil
（実施例Ａ－１）
　７５重量部のポリアミド１２と、２５重量部のポリオレフィン樹脂（ＭＨ５０１０）と、水性溶媒たるポリエチレングリコールとを押出機で加熱により溶融混練し、押出機のダイから押し出し、溶融混練物を得た。
　次に、スポットクーラーを用いて前記溶融混練物を強制的に冷却した。
　そして、アスピレーターとグラスフィルターとを用いて、前記溶融混練物を濾過しつつ、グラスフィルターに留まった前駆体粒子を水で洗浄した。
　次に、除湿乾燥機を用いて前駆体粒子を９０℃で２４時間乾燥させ、樹脂粒子を得た。 (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.
Next, the melt-kneaded material was forcibly cooled using a spot cooler.
Then, while filtering the melt-kneaded material using an aspirator and a glass filter, the precursor particles remaining on the glass filter were washed with water.
Next, the precursor particles were dried at 90° C. for 24 hours using a dehumidifying dryer to obtain resin particles.
（実施例Ａ－１以外の実施例、及び、比較例Ａ－１、Ａ－３）
　樹脂粒子の配合割合を下記表１のようにしたこと以外は、実施例Ａ－１と同様にして樹脂粒子を得た。 (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.
（比較例Ａ－２）
　樹脂粒子の配合割合を下記表１のようにしたこと以外は、実施例Ａ－１と同様にして樹脂粒子を得ようと試みたところ、押出機のダイから押し出した溶融混練物が、ポリアミド１２と、ポリオレフィン樹脂とに分離してしまい、樹脂粒子が作製できなかった。 (Comparative example A-2)
When an attempt was made to obtain resin particles 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 melt-kneaded product extruded from the die of the extruder was found to be polyamide 12. and polyolefin resin, and resin particles could not be produced.
（樹脂粒子を構成する樹脂粒子用樹脂組成物の飽和水分量）
　前記樹脂粒子を構成する樹脂粒子用樹脂組成物の飽和水分量は、以下の方法で測定した。
　まず、前記樹脂粒子を構成する樹脂粒子用樹脂組成物から射出成形により正方形状試験片（１００ｍｍ×１００ｍｍ×２ｍｍ）を用意した。
　そして、ＪＩＳ　Ｋ７２０９：２０００（ＩＳＯ６２：１９９９）「プラスチック－吸水率の求め方」のＡ法（２３℃の水に浸漬）で正方形状試験片に水分を吸収させ、飽和水分量を測定した。
　下記表１に樹脂粒子用樹脂組成物の飽和水分量を示す。 (Saturated water content of resin composition for resin particles constituting resin particles)
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.
（飽和水分量の低下率）
　各実施例で用いた第１の樹脂のみからなる対比用の樹脂組成物を用意した。
　なお、実施例Ａ－１に対する対比用の樹脂組成物は、比較例Ａ－１の樹脂粒子用樹脂組成物である。
　次に、対比用の樹脂組成物の飽和水分量を測定した。
　そして、下記式により、飽和水分量の低下率を求めた。
　　飽和水分量の低下率（％）　＝　〔（対比用の樹脂組成物の飽和水分量－実施例の樹脂粒子用樹脂組成物の飽和水分量）／実施例の樹脂粒子用樹脂組成物の飽和水分量〕×１００（％）
　下記表１に飽和水分量の低下率を示す。 (Decrease rate of saturated water content)
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.
Next, the saturated water content of the resin composition for comparison was measured.
Then, 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.
（樹脂粒子の真球度）
　樹脂粒子の真球度は、上述した方法で測定した。
　樹脂粒子の真球度を下記表１に示す。 (Sphericity of resin particles)
The sphericity of the resin particles was measured by the method described above.
The sphericity of the resin particles is shown in Table 1 below.
（比重）
　樹脂粒子を構成する樹脂粒子用樹脂組成物の比重は、上述した方法で測定した。
　樹脂粒子用樹脂組成物の比重を下記表１に示す。 (specific gravity)
The specific gravity of the resin composition for resin particles constituting the resin particles was measured by the method described above.
The specific gravity of the resin composition for resin particles is shown in Table 1 below.
（マトリックス－ドメイン構造（マトリックス：前記第１の樹脂、ドメイン：前記第２の樹脂）の有無）
　まず、樹脂粒子を切断して断面を得た。
　次に、樹脂粒子の断面をトルエンでエッチングした。
　そして、エッチングした断面を走査電子顕微鏡（ＳＥＭ）で観察し、マトリックス－ドメイン構造（マトリックス：前記第１の樹脂、ドメイン：前記第２の樹脂）の有無を確認した。
　なお、断面において樹脂粒子がトルエンでエッチングされて穴が開いている部分は、ポリオレフィン樹脂があった部分である。
　図１には、実施例Ａ－１における樹脂粒子の断面のＳＥＭ写真を示す。 (Presence or absence of matrix-domain structure (matrix: said first resin, domain: said second resin))
First, the resin particles were cut to obtain a cross section.
Next, the cross section of the resin particle was etched with toluene.
Then, the etched cross section was 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.
FIG. 1 shows a SEM photograph of a cross section of resin particles in Example A-1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１に示すように、本開示の範囲内である各実施例において飽和水分量の低下率が正の数となった。
　また、表１に示すように、本開示の範囲内である実施例Ａ－１、Ａ－２では、シリカを含有する比較例Ａ－３に比べて、樹脂粒子用樹脂組成物の比重が低かった。
　従って、本開示によれば、水分を吸収しやすい樹脂である、アミド結合を有する第１の樹脂を含有しつつ水分を吸収し難く、且つ、樹脂粒子用樹脂組成物の比重が低い、樹脂粒子を提供し得ることがわかる。 As shown in Table 1, in each Example within the scope of the present disclosure, the rate of decrease in saturated water content was a positive number.
Furthermore, as shown in Table 1, in Examples A-1 and A-2, which are within the scope of the present disclosure, 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.

Claims (7)

  1. 　アミド結合及び第１の官能基を有する第１の樹脂と、前記第１の官能基と反応可能な第２の官能基を有するポリオレフィン樹脂たる第２の樹脂とを含有する、樹脂粒子。 Resin particles containing 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.
  2. 　マトリックス及びドメインを含むマトリックス－ドメイン構造を有し、
    前記マトリックスは、前記第１の樹脂を含有し、
    前記ドメインは、前記第２の樹脂を含有する、請求項１に記載の樹脂粒子。     has a matrix-domain structure including a matrix and a domain;
    The matrix contains the first resin,
    The resin particle according to claim 1, wherein the domain contains the second resin.
  3. 　真球度が９５％以上である、請求項１又は２に記載の樹脂粒子。 The resin particles according to claim 1 or 2, having a sphericity of 95% or more.
  4. 　前記第１の樹脂と、前記第２の樹脂とを含有する樹脂組成物で形成され、
    前記樹脂組成物の比重が０．８０～１．２５である、請求項１又は２に記載の樹脂粒子。     formed of a resin composition containing the first resin and the second resin,
    The resin particles according to claim 1 or 2, wherein the resin composition has a specific gravity of 0.80 to 1.25.
  5. 　前記第１の樹脂を５０重量％以上含有し、
    前記第２の樹脂を５～４０重量％含有する、請求項１又は２に記載の樹脂粒子。     Containing 50% by weight or more of the first resin,
    The resin particles according to claim 1 or 2, containing 5 to 40% by weight of the second resin.
  6. 　前記第１の樹脂は、ポリアミド樹脂及び／又はポリイミド樹脂を含む、請求項１又は２に記載の樹脂粒子。 The resin particles according to claim 1 or 2, wherein the first resin includes a polyamide resin and/or a polyimide resin.
  7. 　前記第２の官能基は、カルボキシ基、アミノ基、カルボン酸無水物基、エポキシ基、イソシアネート基、及び、カルボジイミド基から選ばれる少なくとも１種の官能基を有する、請求項１又は２に記載の樹脂粒子。 3. The second functional group according to claim 1 or 2, wherein the second functional group has at least one functional group selected from a carboxy group, an amino group, a carboxylic acid anhydride group, an epoxy group, an isocyanate group, and a carbodiimide group. resin particles.
PCT/JP2023/017569 2022-05-17 2023-05-10 Resin particle WO2023223911A1 (en)

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JPH06287401A (en) * 1993-04-06 1994-10-11 Mitsubishi Kasei Corp Production of resin composition
JPH07258541A (en) * 1994-03-23 1995-10-09 Toyobo Co Ltd Polyamide resin composition and its molded article
JPH08319419A (en) * 1995-05-26 1996-12-03 Satoshi Sanzen Pattern colorant for synthetic resin, its production and synthetic resin molding having colored pattern
JPH0931325A (en) * 1995-07-18 1997-02-04 Mitsubishi Eng Plast Kk Polyamide resin composition
JPH11140237A (en) * 1997-11-10 1999-05-25 Mitsui Chem Inc Thermoplastic resin composition and molded product comprising the same composition
JP2002020619A (en) * 2000-07-11 2002-01-23 Mitsui Chemicals Inc Polyamide resin pellet
JP2005060547A (en) * 2003-08-13 2005-03-10 Daicel Chem Ind Ltd Resin structure of long fiber-reinforced polymer alloy and molded article
JP2007254567A (en) * 2006-03-23 2007-10-04 Toray Ind Inc Thermoplastic resin composition and method for producing the same
CN102250465A (en) * 2011-07-13 2011-11-23 江门市奇德工程塑料科技有限公司 Toughened nylon compound and preparation method thereof
WO2013122008A1 (en) * 2012-02-15 2013-08-22 東レ株式会社 Composite polyamide particles and method for producing same

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06287401A (en) * 1993-04-06 1994-10-11 Mitsubishi Kasei Corp Production of resin composition
JPH07258541A (en) * 1994-03-23 1995-10-09 Toyobo Co Ltd Polyamide resin composition and its molded article
JPH08319419A (en) * 1995-05-26 1996-12-03 Satoshi Sanzen Pattern colorant for synthetic resin, its production and synthetic resin molding having colored pattern
JPH0931325A (en) * 1995-07-18 1997-02-04 Mitsubishi Eng Plast Kk Polyamide resin composition
JPH11140237A (en) * 1997-11-10 1999-05-25 Mitsui Chem Inc Thermoplastic resin composition and molded product comprising the same composition
JP2002020619A (en) * 2000-07-11 2002-01-23 Mitsui Chemicals Inc Polyamide resin pellet
JP2005060547A (en) * 2003-08-13 2005-03-10 Daicel Chem Ind Ltd Resin structure of long fiber-reinforced polymer alloy and molded article
JP2007254567A (en) * 2006-03-23 2007-10-04 Toray Ind Inc Thermoplastic resin composition and method for producing the same
CN102250465A (en) * 2011-07-13 2011-11-23 江门市奇德工程塑料科技有限公司 Toughened nylon compound and preparation method thereof
WO2013122008A1 (en) * 2012-02-15 2013-08-22 東レ株式会社 Composite polyamide particles and method for producing same

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