JP4720142B2 - Resin composition and molded article comprising the same - Google Patents

Description

  The present invention comprises a resin composition excellent in moldability, surface appearance, impact resistance and durability, comprising a polyester resin, a natural organic filler, and a polymer containing an epoxy group-containing vinyl-based unit. The present invention relates to a molded product comprising the same.

  As one of the methods for improving the mechanical properties and heat resistance of polyester resins, methods using inorganic fillers such as glass fibers have been studied. However, since it is necessary to add a large amount, the specific gravity of the molded product is low. There has been a problem such as an increase in the amount of residue that becomes garbage during incineration or disposal, and places a burden on the environment.

  Therefore, from the viewpoint of protecting the global environment, many attempts have been made to use naturally-derived organic materials such as wood powder, paper powder, bamboo powder, and kenaf as resin fillers. Also in resin, the proposal which mix | blends paper powder as a natural origin organic filler is made | formed (for example, refer patent document 1). However, since naturally-derived organic materials usually contain a certain amount of moisture, when melted and mixed, the polyester resin undergoes hydrolysis, and the resulting resin composition has impact resistance, durability, etc. There has been a problem that the characteristics are greatly deteriorated.

Furthermore, for the purpose of improving the weld appearance and weld strength, a method of blending a polymer comprising monomers having various functional groups such as thermoplastic resin, wood flour, and epoxy groups has been studied (for example, patents). Literature 2.). However, by simply using a polymer composed of monomers having various functional groups such as epoxy groups, all of the properties such as moldability, surface appearance, impact resistance and durability can be practically satisfied. However, further improvements were needed.
Japanese Patent Laid-Open No. 10-323810 (page 2-4) JP-A-9-40877 (pages 2-6)

  The present invention has been achieved as a result of studying the solution of the problems in the prior art described above as an issue.

  Accordingly, an object of the present invention is to provide a resin composition excellent in moldability, surface appearance, impact resistance and durability, and a molded product comprising the same.

  As a result of intensive studies to solve the above problems, the present inventors have blended a polyester resin, a natural organic filler, and a polymer containing an epoxy group-containing vinyl-based unit having a specific weight average molecular weight. The present inventors have found that the composition exhibits excellent characteristics that meet the above-mentioned purpose, and have reached the present invention.

That is, the present invention
(1) From 100 parts by weight of the polyester resin used as a raw material, 1 to 350 parts by weight of a naturally-derived organic filler and a weight average molecular weight of 1000 to 20000 and a glass transition temperature of 30 to 100 ° C. Epoxy group-containing vinyl units, acrylic vinyl units, carboxylic acid vinyl ester units, aromatic vinyl units, unsaturated dicarboxylic acid anhydride units, unsaturated dicarboxylic acid units, aliphatic vinyl units A resin composition comprising 0.01 to 30 parts by weight of a polymer containing at least one selected from maleimide units,
(2) The resin composition according to (1), wherein the natural organic filler contains at least one selected from paper powder, wood powder, bamboo powder, bamboo fiber, kenaf fiber, hemp fiber, and jute fiber. object,
(3) The resin composition according to (1) or (2), wherein the polyester resin used as the raw material is a polylactic acid resin,
(4) The composition according to any one of (1) to (3), wherein 0.1 to 50 parts by weight of a crystallization accelerator is blended with 100 parts by weight of the polyester resin used as the raw material . Resin composition,
(5) The resin composition according to any one of (1) to (4), wherein an epoxy value of the polymer including the epoxy group-containing vinyl-based unit is in a range of 0.1 to 10 meq / g,
(6) The polymer containing the epoxy group-containing vinyl unit is a polymer containing an epoxy group-containing vinyl unit, at least one selected from an acrylic vinyl unit and an aromatic vinyl unit. The resin composition according to any one of to (5),
(7) The polyester resin used as a raw material in the resin composition and the polyester resin obtained by reaction with the polymer containing the epoxy group-containing vinyl-based unit have a weight average molecular weight of 300,000 to 1,000,000 (1) to The resin composition according to any one of (6),
(8) A molded article comprising the resin composition according to any one of (1) to (7),
(9) Extruded product comprising the resin composition according to any one of (1) to (7),
(10) A foam comprising the resin composition according to any one of (1) to (7).

  The resin composition of the present invention is excellent in moldability, surface appearance, impact resistance and durability. In addition, the molded product made of the resin composition can be used for various applications such as civil engineering materials, building materials, furniture members, materials for gaming machines, electrical / electronic parts, automobile parts, various daily necessities, utilizing the above characteristics. . In addition, the resin composition of the present invention can be preferably used for an extruded product or a foam.

  Hereinafter, the present invention will be described in detail.

  The polyester resin used in the present invention is a polymer having an ester bond in the main chain and capable of being melt-molded, and obtained from a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof as a raw material. And a polymer obtained by using a hydroxycarboxylic acid or an ester-forming derivative thereof as a raw material, and any of aliphatic polyester resins, aromatic polyester resins, aliphatic aromatic polyester resins and the like can be used.

  Examples of the dicarboxylic acid component include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid, 4,4 ′. -Aromatic dicarboxylic acids such as diphenyldicarboxylic acid and 5-sodiumsulfoisophthalic acid, oxalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, malonic acid, glutaric acid, dimer acid and other aliphatic dicarboxylic acids Examples thereof include alicyclic dicarboxylic acids such as acids, 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, and ester-forming derivatives thereof.

The diol component includes aliphatic glycols having 2 to 20 carbon atoms, that is, ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol. , Decamethylene glycol, cyclohexanedimethanol, cyclohexanediol, or the like, or long-chain glycols having a molecular weight of 400 to 6000, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, and the like, and ester-forming derivatives thereof. Etc.
Examples of the hydroxycarboxylic acid or ester-forming derivative thereof include glycolic acid, lactic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid, 5-hydroxyvaleric acid, 6-hydroxycaproic acid, and the like. Examples thereof include ester-forming derivatives.

  Examples of the polyester resin of the present invention include polyethylene terephthalate resin, polypropylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, polybutylene naphthalate resin, polycyclohexylenedimethylene terephthalate resin, polyethylene adipate resin, and polyethylene succinate resin. , Polybutylene adipate resin, polybutylene succinate resin, polyethylene terephthalate / isophthalate resin, polybutylene terephthalate / isophthalate resin, polyethylene succinate / adipate resin, polybutylene succinate / adipate resin, polyethylene succinate / terephthalate resin, poly Butylene succinate / terephthalate resin, polyethylene adipate / tele Talate resin, polybutylene adipate / terephthalate resin, polybutylene decanedicarboxylate / terephthalate resin, polybutylene succinate / naphthalate resin, polybutylene succinate / naphthalate resin, polyethylene terephthalate / 5-sodium sulfoisophthalate resin, polybutylene terephthalate / 5-sodium sulfoisophthalate resin, polyglycolic acid resin, polylactic acid resin, poly-3-hydroxybutyric acid resin, poly-4-hydroxybutyric acid resin, poly-4-hydroxyvaleric acid resin, poly-3-hydroxyhexanoic acid resin, etc. In particular, polylactic acid resin that uses plant resources as a raw material and has biodegradability is preferable.

  These polyester resins can be used alone or in combination of two or more.

  In the present invention, the polylactic acid resin is a polymer containing L-lactic acid and / or D-lactic acid as a main constituent component, but may contain other copolymerization components other than lactic acid. Other monomer units include ethylene glycol, propylene glycol, butanediol, heptanediol, hexanediol, octanediol, nonanediol, decanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, glycerin, pentane. Glycol compounds such as erythritol, bisphenol A, polyethylene glycol, polypropylene glycol and polytetramethylene glycol, oxalic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, malonic acid, glutaric acid, 1,4-cyclohexanedicarboxylic acid Acid, terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4'-diphenyl ether Dicarboxylic acids such as carboxylic acid, 5-sodium sulfoisophthalic acid, 5-tetrabutylphosphonium isophthalic acid, glycolic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, hydroxybenzoic acid and the like, and Examples include lactones such as caprolactone, valerolactone, propiolactone, undecalactone, and 1,5-oxepan-2-one. Such a copolymerization component is preferably contained in an amount of usually 0 to 30 mol%, and preferably 0 to 10 mol%, in all components.

  In the present invention, from the viewpoint of heat resistance, it is preferable to use a polylactic acid resin having a high optical purity of the lactic acid component. That is, among the total lactic acid components of the polylactic acid resin, it is preferable that the L isomer is contained at 80% or more, or the D isomer is contained at 80% or more, the L isomer is contained at 90% or more, or the D isomer is 90% or more It is particularly preferable that the L-form is contained at 95% or more, or the D-form is more preferably contained at 95% or more, the L-form is contained at 98% or more, or the D-form is contained at 98% or more. Further preferred. Moreover, the upper limit of the content of L-form or D-form is usually 100% or less.

  In the present invention, the melting point of the polylactic acid resin is not particularly limited, but is preferably 120 ° C. or higher, more preferably 150 ° C. or higher, and particularly preferably 160 ° C. or higher. The melting point of the polylactic acid resin is usually increased by increasing the optical purity of the lactic acid component, and the polylactic acid resin having a melting point of 120 ° C. or higher contains 90% or more of the L form or 90% or more of the D form. In addition, a polylactic acid resin having a melting point of 150 ° C. or higher can be obtained by containing 95% or more of L-form or 95% or more of D-form. In the present invention, the melting point of the polylactic acid resin is a value measured with a differential scanning calorimeter (DSC) at a heating rate of 20 ° C./min.

  In the present invention, a modified polylactic acid resin may be used. For example, by using a maleic anhydride-modified polylactic acid resin, an epoxy-modified polylactic acid resin, an amine-modified polylactic acid resin, etc. In addition, the mechanical properties tend to be improved, which is preferable.

  In the present invention, as a method for producing a polylactic acid resin, a known polymerization method can be used, and examples thereof include a direct polymerization method from lactic acid and a ring-opening polymerization method via lactide.

  In the present invention, the molecular weight and molecular weight distribution of the polyester resin used as a raw material are not particularly limited, but in terms of molding processability, the weight average molecular weight is preferably 20,000 or more, more preferably 40,000 or more, and 80,000. The above is more preferable. The upper limit is not particularly limited, but is preferably 500,000 or less, more preferably 300,000 or less, and further preferably 250,000 or less in terms of moldability. The weight average molecular weight here refers to the molecular weight in terms of polymethyl methacrylate (PMMA) measured by gel permeation chromatography.

  The naturally-occurring organic filler used in the present invention is derived from a natural product, and preferably contains cellulose, and any can be used.

  Specific examples of organic fillers of natural origin include rice husk, wood chips, okara, waste paper pulverized material, clothing pulverized material chips, cotton fiber, hemp fiber, bamboo fiber, wood fiber, kenaf fiber, hemp Fibers such as fiber, jute fiber, banana fiber, coconut fiber, etc., or pulp and cellulose fibers processed from these plant fibers, and fiber such as animal fibers such as silk, wool, Angola, cashmere, camel, paper powder , Wood powder, bamboo powder, cellulose powder, rice husk powder, fruit husk powder, chitin powder, chitosan powder, protein, starch, etc. From the viewpoint of heat resistance, paper powder, wood powder, bamboo powder , Cellulose powder, rice husk powder, fruit husk powder, chitin powder, chitosan powder, protein powder, starch powder, cotton fiber, hemp fiber, bamboo fiber, wood fiber, kenaf fiber Plant fibers such as hemp fiber, jute fiber, banana fiber, coconut fiber, paper powder, wood powder, bamboo powder, bamboo fiber, kenaf fiber, hemp fiber, jute fiber are more preferable, and paper powder and wood powder are further Preferably, paper dust is particularly preferable. In addition, these naturally-derived organic fillers may be collected directly from natural products, but from the viewpoint of protecting the global environment and conserving resources, waste materials such as waste paper, waste wood and old clothes are recycled. May be used. Waste paper is OA paper such as newspaper, magazine, and copy paper, other recycled pulp, or paperboard such as corrugated cardboard, cardboard, paper tube, etc. Although it may be used, from the viewpoint of heat resistance, crushed products of paperboard such as newspaper and corrugated cardboard, cardboard and paper tube are preferable. Specific examples of the wood include coniferous wood such as pine, cedar, oak, and fir, and broad-leaved wood such as beech, shii, and eucalyptus, and the type is not limited.

  Naturally-derived organic fillers that have been surface-treated may be used, such as alkali treatment, heat treatment, acetylation treatment, cyanoethylation treatment, silane coupling treatment, and glyogisal treatment. It is preferable to use this organic filler because it tends to improve not only heat resistance but also mechanical properties.

  When the naturally-derived organic filler is paper powder, the paper powder is not particularly limited as long as it satisfies the requirements specified in the present invention, but it can improve heat resistance. It is preferable that an adhesive is included. The adhesive is not particularly limited as long as it is usually used when processing paper. Emulsion adhesives such as vinyl acetate resin emulsions and acrylic resin emulsions, polyvinyl alcohol adhesives, Examples include cellulose-based adhesives, natural rubber-based adhesives, starch paste, and hot-melt adhesives such as ethylene-vinyl acetate copolymer resin-based adhesives and polyamide-based adhesives. Emulsion-based adhesives, polyvinyl alcohol-based adhesives An adhesive and a hot melt adhesive are preferable, and an emulsion adhesive and a polyvinyl alcohol adhesive are more preferable. These adhesives are also used as binders for paper processing agents. Adhesives include clay, talc, kaolinite, montmorillonite, mica, synthetic mica, zeolite, silica, graphite, carbon black, magnesium oxide, calcium oxide, titanium oxide, calcium sulfide, magnesium carbonate, calcium carbonate, and barium carbonate. Inorganic fillers such as barium sulfate, aluminum oxide and neodymium oxide are preferably contained, and clay, talc, kaolinite, montmorillonite, synthetic mica and silica are more preferable.

  In addition, as the paper powder, it is possible to improve the heat resistance, so that chemicals generally used as a raw material for papermaking, for example, rosin-based, alkylketene dimer-based, alkenyl succinic anhydride-based internal additives, etc. Sizing agent, surface sizing agent such as styrene / acrylic, styrene / maleic acid, olefin, paper strength enhancer such as polyacrylamide and starch, yield improver such as polyethyleneimine, polymer flocculant, drainage Enhancer, deinking agent such as nonionic surfactant, slime control agent such as organic halogen, pitch control agent such as organic or enzyme, cleaning agent such as hydrogen peroxide, antifoaming agent, pigment dispersant And organic substances such as lubricants, aluminum sulfate used as a fixing agent for sizing agents, polyaluminum chloride, and others Sodium hydroxide which is used as a papermaking raw material, magnesium hydroxide, sodium sulfate, sodium silicate, aluminum chloride, preferably includes an inorganic material such as chlorine sodium.

  Further, as the paper powder, the ash content is preferably 5% by weight or more, more preferably 5.5% by weight or more, and 7.5% by weight or more from the viewpoint that heat resistance can be improved. More preferably. The upper limit is not particularly limited, but is preferably 60% by weight or less, and more preferably 30% by weight or less. Here, the ash content is a ratio of the weight of the remaining ash content when the organic filler is baked at a high temperature of 450 ° C. or higher for 8 hours using an electric furnace or the like to the weight of the paper powder before baking.

  The paper powder preferably contains at least one selected from aluminum, silicon, calcium, sulfur, magnesium, and titanium from the viewpoint that heat resistance can be improved. More preferably, aluminum, silicon, calcium, and sulfur are all included, and aluminum, silicon, calcium, sulfur, and magnesium are all included.

  Further, the amount of aluminum is preferably larger than the amount of magnesium, more preferably the amount of each of aluminum and silicon is greater than the amount of magnesium, and the amount of each of aluminum, silicon and calcium is greater than the amount of magnesium. More is more preferable. The abundance ratio of aluminum, silicon, calcium, sulfur, magnesium, and titanium is not particularly limited. For example, when the total number of the elements is 100, aluminum is 1 to 60% and silicon is 20 to 20%. 90%, 1-30% calcium, 1-20% sulfur, 0-20% magnesium, 0-20% titanium, 1-50% aluminum, 20-85% silicon, More preferably, calcium is 1 to 20%, sulfur is 1 to 15%, magnesium is 0 to 10%, titanium is 0 to 10%, aluminum is 3 to 50%, silicon is 25 to 80%, and calcium is More preferably, it is 3 to 20%, sulfur is 2 to 10%, magnesium is 0 to 8%, and titanium is 0 to 3%. About these elemental analysis, although it can measure even if it uses either the simple substance of a natural origin organic filler, or the ash content of a natural origin organic filler, it is preferable to use an ash content. Elemental analysis is measured by using an apparatus combining X-ray fluorescence analysis, atomic absorption spectrometry, scanning electron microscope (SEM) or transmission electron microscope (TEM) and energy dispersive X-ray microanalyzer (XMA). However, in the present invention, it is a value measured using fluorescent X-ray analysis.

  In addition, the paper powder preferably contains cellulose to which fine particles adhere on the surface from the viewpoint that heat resistance can be improved. The fine particles are not particularly limited, and may be either organic or inorganic, and may be fine particles generated when the various chemicals are attached. The shape of the fine particles may be any of a needle shape, a plate shape, and a spherical shape. The size of the fine particles is not particularly limited, but is preferably distributed in the range of 0.1 to 5000 nm, more preferably in the range of 0.3 to 1000 nm. More preferably, it is distributed in the range of ˜500 nm, particularly preferably in the range of 1 to 100 nm, and most preferably in the range of 1 to 80 nm. Here, “distributed” in a specific range means that 80% or more of the total number of fine particles is included in the specific range. The adhesion form of the fine particles may be either in an aggregated state or a dispersed state, but is more preferably adhered in a dispersed state. The size of the fine particles can be observed by a transmission electron microscope at a magnification of 80,000 times with a molded product obtained from a resin composition in which a polylactic acid resin and a natural organic filler are blended.

  Moreover, also in the organic filler derived from other natural products other than paper dust, it is preferable to select and use the above characteristics, that is, the ash content, the composition having the ash content, and the fine particles adhered.

  Moreover, in this invention, as long as the resin composition of this invention is obtained, the organic filler derived from another natural product can be used by 1 type, or 2 or more types, However, The paper powder which has the said preferable characteristic is included. It is preferable.

  In the present invention, the blending amount of the naturally derived organic filler is 1 to 350 parts by weight when the polyester resin is 100 parts by weight, and from the viewpoint of heat resistance, it is more preferably 1 to 300 parts by weight. Preferably, 5 to 200 parts by weight is more preferable, 10 to 150 parts by weight is particularly preferable, and 15 to 120 parts by weight is most preferable. If the blending amount of the naturally-derived organic filler is less than 1 part by weight, the effect of improving the heat resistance of the polylactic acid resin tends to be small. If it exceeds 350 parts by weight, the naturally-derived organic filler is added to the polyester resin. In addition to heat resistance, the strength and appearance of the material tend to decrease.

In the present invention, a polymer containing an epoxy group-containing vinyl-based unit is blended.
In the present invention, specific examples of the raw material monomer for forming the epoxy group-containing vinyl-based unit include glycidyl esters of unsaturated monocarboxylic acids such as glycidyl acrylate, glycidyl methacrylate, and glycidyl p-styrylcarboxylate, maleic acid, itacon Examples thereof include monoglycidyl esters or polyglycidyl esters of unsaturated polycarboxylic acids such as acids, unsaturated glycidyl ethers such as allyl glycidyl ether, 2-methylallyl glycidyl ether, and styrene-4-glycidyl ether. Among these, glycidyl acrylate or glycidyl methacrylate is preferably used from the viewpoint of radical polymerizability. These can be used alone or in combination of two or more.

In the present invention, the polymer containing an epoxy group-containing vinyl units, seen containing a vinyl unit other than the epoxy group-containing vinyl units as a copolymerization component, it is possible to adjust the physical properties of the polymer by its selection.

Examples of vinyl units other than epoxy group-containing vinyl units include acrylic vinyl units, carboxylic acid vinyl ester units, aromatic vinyl units, unsaturated dicarboxylic acid anhydride units, unsaturated dicarboxylic acid units, and aliphatic systems. vinyl units, maleimide-based units.

  Examples of the raw material monomer for forming the acrylic vinyl unit include acrylic acid and its ester, methacrylic acid and its ester, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, α-substituted acrylic acid and its ester.

  Specific examples of the raw material monomer for forming the acrylic vinyl unit include acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, and n-butyl acrylate. , N-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate , Isobornyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, Roxypropyl, hydroxypropyl methacrylate, acrylic acid ester or methacrylate ester of polyethylene glycol or polypropylene glycol, trimethoxysilylpropyl acrylate, trimethoxysilylpropyl methacrylate, methyldimethoxysilylpropyl acrylate, methyldimethoxysilylpropyl methacrylate, Acrylic vinyl units having an amino group such as acrylonitrile, methacrylonitrile, N, N-dialkylacrylamide, N, N-dialkylmethacrylamide, α-hydroxymethyl acrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, etc. The raw material monomer etc. which form are mentioned, Especially, acrylic acid, methacrylic acid, methyl acrylate, methacrylic acid Methyl, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, t-butyl acrylate, t-butyl methacrylate, Preferred are 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, acrylonitrile, methacrylonitrile, and acrylic acid, methacrylic acid, methyl acrylate, methacrylic acid. Methyl, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, acrylo Tolyl, methacrylonitrile is used. These may be used alone or in combination of two or more.

  Specific examples of the raw material monomer that forms the vinyl carboxylate unit include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, Monofunctional aliphatic vinyl carboxylates such as vinyl palmitate, vinyl stearate, isopropenyl acetate, 1-butenyl acetate, vinyl pivalate, vinyl 2-ethylhexanoate and vinyl cyclohexanecarboxylate, vinyl benzoate and vinyl cinnamate, etc. And polyfunctional vinyl carboxylates such as vinyl aromatic carboxylate, vinyl monochloroacetate, divinyl adipate, vinyl methacrylate, vinyl crotonic acid and vinyl sorbate. Among them, vinyl acetate is preferably used. These may be used alone or in combination of two or more.

Specific examples of the raw material monomer for forming the aromatic vinyl unit include styrene, α-methylstyrene, p-methylstyrene, α-methyl-p-methylstyrene, p-methoxystyrene, o-methoxystyrene, 2, 4 -Dimethylstyrene, 1-vinylnaphthalene, chlorostyrene, bromostyrene, divinylbenzene, vinyltoluene and the like can be mentioned, among which styrene and α-methylstyrene are preferably used. These may be used alone or in combination of two or more.
Examples of the raw material monomer that forms the unsaturated dicarboxylic acid anhydride unit include maleic anhydride, itaconic anhydride, glutaconic anhydride, citraconic anhydride, or aconitic anhydride, among which maleic anhydride is preferably used. . These may be used alone or in combination of two or more.

  Examples of the raw material monomer for forming the unsaturated dicarboxylic acid-based unit include maleic acid, maleic acid monoethyl ester, itaconic acid, phthalic acid and the like. Among these, maleic acid and itaconic acid are preferably used. These may be used alone or in combination of two or more.

  Examples of the raw material monomer for forming the aliphatic vinyl unit include ethylene, propylene and butadiene. Examples of the raw material monomer for forming the maleimide unit include maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N- As other raw material monomers for forming vinyl units such as isopropylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N- (p-bromophenyl) maleimide, N- (chlorophenyl) maleimide, N-vinyldiethylamine, N- Acetylvinylamine, allylamine, methallylamine, N-methylallylamine, p-aminostyrene, 2-isopropenyl-oxazoline, 2-vinyl-oxazoline, 2-acryloyl-oxazoline or 2-styryl And oxazoline and the like, which alone to be able to use two or more kinds.

  In the present invention, the polymer containing an epoxy group-containing vinyl-based unit has a weight average molecular weight in the range of 1000 to 20000. Furthermore, it is preferably 3000 to 15000, more preferably 5000 to 12000 in that a bleed-out phenomenon can be suppressed and a resin composition having excellent impact resistance can be obtained. If it is less than 1000, the bleed-out phenomenon tends to increase, and if it exceeds 20000, the impact resistance improving effect tends to be insufficient. Here, the weight average molecular weight is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) using chloroform as a solvent.

  In the present invention, the polymer containing an epoxy group-containing vinyl-based unit may have an epoxy value in the range of 0.1 to 10 meq / g in that a resin composition having excellent impact resistance can be obtained. Preferably, it is in the range of 0.5-7 meq / g, more preferably in the range of 1-5 meq / g, particularly preferably in the range of 1.5-4 meq / g, Most preferably, it is in the range of 3 meq / g. If the epoxy value is less than 0.1 meq / g, the effect of improving the melt viscosity property is insufficient, and if the epoxy value is more than 10 meq / g, the moldability tends to be greatly reduced due to gelation or the like, which is not preferable. . Here, the epoxy value is a value measured by a hydrochloric acid-dioxane method. The epoxy value of the polymer containing the epoxy group-containing vinyl unit can be adjusted by adjusting the content of the epoxy group-containing vinyl unit.

In the present invention, the glass transition temperature of the polymer containing an epoxy group-containing vinyl units, from the viewpoint of Ha Ndoringu resistance, Ri range der of 30 to 100 ° C., more preferably in the range of 40 to 70 ° C., Most preferably, it is in the range of 50-65 ° C. The method for measuring the glass transition temperature is not particularly limited, and any of a method of measuring with a differential scanning calorimeter (DSC) and a method of measuring with a dynamic viscoelasticity test can be used. Used the method of measuring by DSC. In addition, the glass transition temperature of the polymer containing an epoxy group-containing vinyl-based unit can be adjusted by adjusting the composition of the copolymerization component. The glass transition temperature can usually be increased by copolymerizing aromatic vinyl units such as styrene, and can be decreased by copolymerizing acrylic ester units such as butyl acrylate .
In the present invention, the polymer containing an epoxy group-containing vinyl-based unit usually contains a volatile component because unreacted raw material monomers and solvents remain. The amount of the non-volatile component that is the balance is not particularly limited, but it is preferable that the non-volatile component amount is large from the viewpoint of suppressing the generation of gas. Specifically, it is preferably 95% by weight or more, more preferably 97% by weight or more, further preferably 98% by weight or more, and most preferably 98.5% by weight or more. preferable. In addition, the non-volatile component here represents the remaining amount ratio when the sample 10g is heated at 110 degreeC for 1 hour in nitrogen atmosphere.

  In the present invention, a polymer containing an epoxy group-containing vinyl-based unit may use a sulfur compound as a chain transfer agent (molecular weight modifier) in order to obtain a low molecular weight product. Contains sulfur. Here, although sulfur content is not specifically limited, From the viewpoint of suppressing an unpleasant odor, it is preferable that the sulfur content is small. Specifically, the sulfur atom is preferably 1000 ppm or less, more preferably 100 ppm or less, further preferably 10 ppm or less, and most preferably 1 ppm or less.

  In the present invention, the method for producing a polymer containing an epoxy group-containing vinyl-based unit is not particularly limited as long as the conditions specified in the present invention are satisfied. Bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc. The known polymerization method can be used. When these methods are used, a polymerization initiator, a chain transfer agent, a solvent, and the like may be used, but these remain as impurities in the finally obtained polymer containing an epoxy group-containing vinyl-based unit. There are things to do. The amount of these impurities is not particularly limited, but it is preferable that the amount of impurities is small from the viewpoint of suppressing a decrease in heat resistance and weather resistance. Specifically, the amount of impurities is preferably 10% by weight or less, more preferably 5% by weight or less, further preferably 3% by weight or less, particularly 1% by weight or less, with respect to the finally obtained polymer. Most preferred.

  As a method for producing a polymer containing an epoxy group-containing vinyl-based unit that satisfies the molecular weight, glass transition temperature, nonvolatile component amount, sulfur content, impurity amount, and the like, a high temperature of 150 ° C. or higher is applied. A method of continuous bulk polymerization under a pressure condition (preferably 1 MPa or more) in a short time (preferably 5 to 30 minutes) is a high polymerization rate, a polymerization initiator or a chain transfer agent that causes impurities and sulfur content And from the point of not using a solvent.

  In the present invention, the amount of the polymer containing an epoxy group-containing vinyl-based unit is 0.01 to 30 parts by weight, based on 100 parts by weight of the polyester resin. 20 parts by weight is preferable, 0.1 to 15 parts by weight is more preferable, 1 to 10 parts by weight is further preferable, and 2 to 8 parts by weight is most preferable. If the amount of the polymer containing an epoxy group-containing vinyl-based unit is less than 0.01 parts by weight, the effect of improving the melt viscosity characteristics of the resin composition tends to be insufficient, and if it exceeds 30 parts by weight, the gel There is a risk that moldability may be reduced due to the increase in the size.

  In the present invention, at least selected from a crystallization accelerator, a thermoplastic resin other than a polyester resin, a filler other than a naturally-derived organic filler, and a carboxyl group-reactive compound other than a polymer containing an epoxy group-containing vinyl-based unit. It is preferable to mix 1 type. By blending these with polyester resins, naturally-occurring organic fillers, and polymers containing epoxy group-containing vinyl units, it has excellent moldability, mechanical properties, heat resistance, and surface appearance or durability. A resin composition and a molded product comprising the same can be obtained.

  In the present invention, it is preferable to blend a crystallization accelerator. By blending a polyester resin, an organic filler derived from nature, a polymer containing an epoxy group-containing vinyl-based unit and a crystallization accelerator, a resin composition and a molded article excellent in moldability and heat resistance can be obtained. Even if it is a polyester resin that is difficult to crystallize, such as polylactic acid, the polyester resin is sufficiently crystallized in normal injection molding, and a molded product having excellent heat resistance can be obtained. The crystallization accelerator used in the present invention can be selected from a wide variety of compounds, but the crystal nucleating agent that promotes the formation of crystal nuclei of the polymer, or the softening of the polymer to facilitate movement and promote crystal growth. A plasticizer can be preferably used.

  The blending amount of the crystallization accelerator used in the present invention is preferably in the range of 0.01 to 50 parts by weight, more preferably in the range of 0.05 to 30 parts by weight with respect to 100 parts by weight of the polyester resin. The range of 0.1-30 parts by weight is more preferred, the range of 0.5-15 parts by weight is more preferred, and the range of 1-10 parts by weight is most preferred.

  As the crystal nucleating agent used as a crystallization accelerator in the present invention, those generally used as a polymer crystal nucleating agent can be used without any particular limitation, and both inorganic crystal nucleating agents and organic crystal nucleating agents can be used. Can be used. Specific examples of inorganic crystal nucleating agents include talc, kaolin, montmorillonite, synthetic mica, clay, zeolite, silica, graphite, carbon black, zinc oxide, magnesium oxide, titanium oxide, calcium sulfide, boron nitride, calcium carbonate, sulfuric acid Examples thereof include metal salts of barium, aluminum oxide, neodymium oxide and phenylphosphonate. These inorganic crystal nucleating agents are preferably modified with an organic substance in order to enhance dispersibility in the composition.

  Specific examples of organic crystal nucleating agents include sodium benzoate, potassium benzoate, lithium benzoate, calcium benzoate, magnesium benzoate, barium benzoate, lithium terephthalate, sodium terephthalate, potassium terephthalate, Calcium oxide, sodium laurate, potassium laurate, sodium myristate, potassium myristate, calcium myristate, sodium octacosanoate, calcium octacosanoate, sodium stearate, potassium stearate, lithium stearate, calcium stearate, magnesium stearate, Barium stearate, sodium montanate, calcium montanate, sodium toluate, sodium salicylate, potassium salicylate, salicylic acid , Metal salts of organic carboxylic acids such as aluminum dibenzoate, potassium dibenzoate, lithium dibenzoate, sodium β-naphthalate, sodium cyclohexanecarboxylate, organic sulfonates such as sodium p-toluenesulfonate, sodium sulfoisophthalate, stearic acid Amido, ethylene bislauric acid amide, palmitic acid amide, hydroxy stearic acid amide, erucic acid amide, organic carboxylic acid amides such as trimesic acid tris (t-butylamide), low density polyethylene, high density polyethylene, polypropylene, polyisopropylene, Polymers such as polybutene, poly-4-methylpentene, poly-3-methylbutene-1, polyvinylcycloalkane, polyvinyltrialkylsilane, and high melting point polylactic acid -Sodium salt of a polymer having a carboxyl group such as sodium salt of ethylene-acrylic acid or methacrylic acid copolymer, sodium salt of styrene-maleic anhydride copolymer (so-called ionomer), benzylidene sorbitol and its derivatives, sodium- Examples include phosphorus compound metal salts such as 2,2′-methylenebis (4,6-di-t-butylphenyl) phosphate, and 2,2-methylbis (4,6-di-t-butylphenyl) sodium. Can do.

  As the crystal nucleating agent used in the present invention, among those exemplified above, at least one selected from talc and organic carboxylic acid metal salts is particularly preferable from the viewpoint of crystallization characteristics. The crystallization accelerator used in the present invention may be only one kind, or two or more kinds may be used in combination.

  The compounding amount of the crystal nucleating agent is preferably in the range of 0.01 to 50 parts by weight, more preferably in the range of 0.05 to 30 parts by weight, with respect to 100 parts by weight of the polyester resin. A range of parts is more preferred. When the compounding amount of the crystal nucleating agent is less than 0.01 parts by weight or more than 50 parts by weight, the heat resistance improvement effect of the polyester resin tends to be small.

  As the plasticizer that also functions as a crystallization accelerator in the present invention, generally known plasticizers can be used. For example, polyester plasticizers, glycerin plasticizers, polyvalent carboxylic acid ester plasticizers, Examples thereof include phosphate ester plasticizers, polyalkylene glycol plasticizers, and epoxy plasticizers.

  Specific examples of the polyester plasticizer include dicarboxylic acid components such as adipic acid, sebacic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, propylene glycol, 1,3-butanediol, 1,4- Examples thereof include polyesters composed of diol components such as butanediol, 1,6-hexanediol, ethylene glycol and diethylene glycol, and polyesters composed of hydroxycarboxylic acids such as polycaprolactone. These polyesters may be end-capped with a monofunctional carboxylic acid or monofunctional alcohol, or may be end-capped with an epoxy compound or the like.

  Specific examples of the glycerin plasticizer include glycerin monoacetomonolaurate, glycerin diacetomonolaurate, glycerin monoacetomonostearate, glycerin diacetomonooleate, and glycerin monoacetomonomontanate.

  Specific examples of polycarboxylic acid ester plasticizers include phthalates such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, diheptyl phthalate, dibenzyl phthalate, and butyl benzyl phthalate. Trimellitic acid esters such as tributyl acid, trioctyl trimellitic acid, trihexyl trimellitic acid, adipic acid esters such as diisodecyl adipate, n-octyl-n-decyl adipate, triethyl acetylcitrate, tributyl acetylcitrate Citrate esters such as azelaic acid esters such as di-2-ethylhexyl azelate, dibutyl sebacate, and sebacic acid esters such as di-2-ethylhexyl sebacate, and bis (methyl Glycol) succinate, bis (butyl diglycol) succinate methyl diglycol butyl diglycol succinate, ethyl diglycol butyl diglycol succinate, propyl diglycol butyl diglycol succinate, benzyl methyl diglycol succinate, methoxycarbonylmethyl methyl Diglycol succinate, ethoxycarbonylmethyl methyl diglycol succinate, benzyl butyl diglycol succinate, bis (methyl diglycol) adipate, bis (butyl diglycol) adipate, methyl diglycol butyl diglycol adipate, ethyl diglycol butyl di Glycol adipate, propyl diglycol butyl diglycol adipate, benzyl methyl diglycol adipate , Benzyl butyl diglycol adipate, methoxycarbonylmethyl methyl diglycol adipate, methoxycarbonylmethyl butyl diglycol adipate, ethoxycarbonylmethyl methyl diglycol adipate, ethoxycarbonylmethyl butyl diglycol adipate, dimethyl diglycol monobutyl diglycol adipate, benzyl Dimethyl diglycol citrate, methoxycarbonyl methyl dimethyl citrate, methoxy carbonyl methyl diethyl citrate, methoxy carbonyl methyl dibutyl citrate, ethoxy carbonyl methyl dimethyl citrate, ethoxy carbonyl methyl dibutyl citrate, ethoxy carbonyl methyl dioctyl citrate, butoxy carbonyl Methyldimethylsa Itolate, butoxycarbonylmethyl diethyl citrate, butoxycarbonylmethyl dibutyl citrate, dimethoxycarbonylmethyl monomethyl citrate, dimethoxycarbonylmethyl monoethyl citrate, dimethoxycarbonylmethyl monobutyl citrate, diethoxycarbonylmethyl monomethyl citrate, diethoxycarbonyl Methyl monobutyl citrate, diethoxycarbonylmethyl monooctyl citrate, dibutoxycarbonylmethyl monomethyl citrate, dibutoxycarbonylmethyl monoethyl citrate, dibutoxycarbonylmethyl monobutyl citrate, ethoxycarbonylmethyldimethyldiglycol citrate, Ethoxycarbonylmethyl dibutyl diglycol cytole And diethoxycarbonylmethyl monomethyl diglycol citrate, diethoxycarbonylmethyl monobutyl diglycol citrate, and the like. Among them, methyl diglycol butyl diglycol succinate, benzyl methyl diglycol succinate, benzyl butyl diglycol succinate Nate, methyl diglycol butyl diglycol adipate, benzyl methyl diglycol adipate, benzyl butyl diglycol adipate, methoxycarbonylmethyl dibutyl citrate, ethoxycarbonylmethyl dibutyl citrate, butoxycarbonylmethyl dibutyl citrate, dimethoxycarbonylmethyl monobutyl citrate , Diethoxycarbonylmethyl monobutyl citrate, dibutoxycarbonyl Mention may be made of mono-butyl citrate. Among these, methyl diglycol butyl diglycol adipate, benzyl methyl diglycol adipate, benzyl butyl diglycol adipate, and ethoxycarbonylmethyl dibutyl citrate are most preferable.

  Specific examples of the phosphate ester plasticizer include tributyl phosphate, tri-2-ethylhexyl phosphate, trioctyl phosphate, triphenyl phosphate, diphenyl-2-ethylhexyl phosphate and tricresyl phosphate. .

  Specific examples of the polyalkylene glycol plasticizer include polyethylene glycol, polypropylene glycol, poly (ethylene oxide / propylene oxide) block and / or random copolymer, polytetramethylene glycol, ethylene oxide addition polymer of bisphenols, bisphenols Polyalkylene glycols such as propylene oxide addition polymers, tetrahydrofuran addition polymers of bisphenols, or terminal-capped compounds such as terminal epoxy-modified compounds, terminal ester-modified compounds, and terminal ether-modified compounds.

  The epoxy plasticizer generally refers to an epoxy triglyceride composed of an alkyl epoxy stearate and soybean oil. In addition, an epoxy resin mainly using bisphenol A and epichlorohydrin is also used. be able to.

  Specific examples of other plasticizers include benzoic acid esters of aliphatic polyols such as neopentyl glycol dibenzoate, diethylene glycol dibenzoate, triethylene glycol di-2-ethylbutyrate, fatty acid amides such as stearamide, oleic acid Examples thereof include aliphatic carboxylic acid esters such as butyl, oxyacid esters such as methyl acetylricinoleate and butyl acetylricinoleate, pentaerythritol, various sorbitols, polyacrylic acid esters, silicone oils, and paraffins.

  The plasticizer used in the present invention may be used alone or in combination of two or more.

  Moreover, the compounding quantity of a plasticizer has the preferable range of 0.01-50 weight part with respect to 100 weight part of polyester, The range of 0.1-30 weight part is more preferable, 0.5-15 weight part The range is more preferable, and the range of 1 to 10 parts by weight is most preferable. When the blending amount of the plasticizer is less than 0.1 parts by weight or more than 50 parts by weight, the effect of improving the heat resistance of the polylactic acid resin tends to be small.

  In the present invention, the crystal nucleating agent and the plasticizer may be used singly, but using both in combination is preferable because the effect of improving crystallization characteristics is remarkably increased.

  In this invention, it is possible to mix | blend thermoplastic resins other than a polyester resin. By blending a polyester resin, a naturally-derived organic filler, a polymer containing an epoxy group-containing vinyl unit as defined in the present invention and a thermoplastic resin other than the polyester resin, surface appearance, moldability, mechanical properties, heat resistance A resin composition excellent in properties and toughness, and a molded product comprising the same can be obtained.

  The thermoplastic resin is not particularly limited. Polyolefin resins such as polyacetal resin, polyamide resin, polyethylene resin and polypropylene resin, polystyrene resin, acrylic resin, polyurethane resin, chlorinated polyethylene resin, chlorinated polypropylene resin , Aromatic and aliphatic polyketone resins, fluororesins, polyphenylene sulfide resins, polyether ether ketone resins, polyimide resins, thermoplastic starch resins, AS resins, ABS resins, AES resins, ACS resins, polyvinyl chloride resins, polychlorinated resins Vinylidene resin, vinyl ester resin, polyurethane resin, MS resin, polycarbonate resin, polyarylate resin, polysulfone resin, polyethersulfone resin, phenoxy resin, polyphenylene oxide Examples include thermoplastic resins such as resin, poly-4-methylpentene-1, polyetherimide resin, cellulose acetate resin, and polyvinyl alcohol resin. Among them, at least one selected from polyacetal resin and polyamide resin is blended. Is preferred. By blending these resins, a molded product having excellent characteristics can be obtained.

  In the present invention, fillers other than naturally derived organic fillers may be blended. As fillers other than naturally-derived organic fillers, inorganic fillers are preferably blended. As the inorganic filler used in the present invention, fibers, plates, granules, and powders that are usually used for reinforcing thermoplastic resins can be used. Specifically, glass fiber, carbon fiber, graphite fiber, metal fiber, potassium titanate whisker, aluminum borate whisker, magnesium-based whisker, silicon-based whisker, wollastonite, sepiolite, asbestos fiber, slag fiber, zonolite, elastadite, Fibrous inorganic fillers such as gypsum fiber, silica fiber, silica / alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber and boron fiber, glass flake, non-swellable mica, swellable mica, graphite, metal foil, ceramic Beads, talc, clay, mica, sericite, zeolite, bentonite, organically modified bentonite, organically modified montmorillonite, dolomite, kaolin, finely divided silicic acid, feldspar powder, potassium titanate, shirasu balloon, calcium carbonate, magnesium carbonate mug Siumu, barium sulfate, calcium oxide, aluminum oxide, titanium oxide, aluminum silicate, silicon oxide, gypsum, novaculite, include plate-like or granular inorganic fillers such as dawsonite and white clay. Among these inorganic fillers, glass fiber, wollastonite, mica and kaolin are particularly preferable. The aspect ratio of the fibrous filler is preferably 5 or more, more preferably 10 or more, and further preferably 20 or more.

  The inorganic filler may be coated or focused with a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin, or a coupling agent such as aminosilane or epoxysilane. May be processed.

  Moreover, 1-100 weight part is preferable with respect to 100 weight part of polyester resins, and, as for the compounding quantity of an inorganic filler, 5-50 weight part is more preferable.

  In this invention, you may mix | blend carboxyl group reactive compounds other than the polymer containing an epoxy-group-containing vinyl-type unit. As the carboxyl group-reactive compound other than the polymer containing an epoxy group-containing vinyl-based unit used in the present invention, any compound that can react with the carboxyl group of the polymer can be used without particular limitation. In the present invention, such a carboxyl group-reactive compound not only reacts with a carboxyl group of a polyester resin, but also a carboxyl group of an acidic low-molecular compound generated by thermal decomposition or hydrolysis of a polyester resin or a naturally-occurring organic filler. Can also react. Further, the carboxyl group-reactive compound is more preferably a compound that can also react with a hydroxyl group that an acidic low-molecular compound is generated by thermal decomposition.

  It is preferable to use at least one compound selected from an epoxy compound, an oxazoline compound, an oxazine compound, and a carbodiimide compound as a carboxyl group-reactive compound other than a polymer containing such an epoxy group-containing vinyl-based unit. However, epoxy compounds and / or carbodiimide compounds are preferred.

  The amount of the carboxyl group-reactive compound other than the polymer containing an epoxy group-containing vinyl-based unit is preferably 0.01 to 20 parts by weight and more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the polyester resin. 1 to 8 parts by weight is most preferable.

  The addition time of the carboxyl group-reactive compound other than the polymer containing the epoxy group-containing vinyl-based unit is not particularly limited, but it is a polyester resin in that not only the heat resistance is improved but also the mechanical properties and durability can be improved. It is preferable to knead with a natural organic filler after melt-kneading in advance.

  In the present invention, it is preferable to use a foaming agent. By using a foaming agent, a foam can be obtained.

  Any foaming agent may be used as long as it can be used to obtain a foam. Chemical foaming agents, physical foaming agents, and the like can be used, and the foam of the present invention can be suitably obtained. A chemical foaming agent is preferred in terms of easy control of magnification and bubbles.

  Chemical foaming agents include azo compounds such as azodicarbonamide, azobisisobutyronitrile, barium azodicarboxylate, hydrazide compounds such as 4,4′-oxybisbenzenesulfonyl hydrazide and p-toluenesulfonyl hydrazide, dinitrosopenta Nitroso compounds such as methylenetetramine, hydrazo compounds such as hydrazodicarbonamide, 5-phenyltetrazole, 5-aminotetrazole, azobistetrazole, bistetrazole and other tetrazole compounds, hydrazodicarboxylic acid esters, azodicarboxylic acid esters, Examples thereof include ester compounds such as citric acid esters, isocyanate compounds, sodium bicarbonate, sodium carbonate, and the like, and azodicarbonamide and azobis Preferred are azo compounds such as butyronitrile and barium azodicarboxylate, tetrazole compounds such as 5-phenyltetrazole, 5-aminotetrazole, azobistetrazole, and bistetrazole, and isocyanate compounds, and azodicarbonamide and azobisisobutyridine. Azo compounds such as nitrile and barium azodicarboxylate are more preferred, and azodicarbonamide is more preferred.

  Physical foaming agents include ethane, butane, pentane, hexane, heptane, ethylene, propylene, petroleum ether, methyl chloride, monochlorotrifluoromethane, dichlorodifluoromethane, dichlorotetrafluoroethane, water, air, carbon dioxide, nitrogen gas Butane, pentane, hexane, water, air, carbon dioxide gas, nitrogen gas are preferred, water, air, carbon dioxide gas, nitrogen gas are more preferred, water, air, Carbon dioxide gas is more preferable. In addition, it is preferable to use a substance that can be used as a supercritical fluid such as carbon dioxide gas or nitrogen gas as a foaming agent in a supercritical fluid state because a foam that does not decrease in strength can be obtained.

  The addition amount of the foaming agent may be an effective amount for obtaining a desired expansion ratio, and varies slightly depending on the type, but is preferably 0.01 to 18 parts by weight with respect to 100 parts by weight of the polyester resin. 0.1 to 15 parts by weight is more preferable, and 0.5 to 10 parts by weight is even more preferable. If the amount is too small, the effect of the foaming agent is not sufficient, and if the amount is too large, the surface appearance tends to be impaired.

  In the present invention, in order to stabilize the foaming behavior and obtain a foam having good foaming ratio, foam density and cell size, as a foaming aid, metal oxides such as zinc oxide, calcium oxide and aluminum oxide, stearin Can contain aliphatic salts such as zinc acid, calcium stearate, magnesium stearate, aluminum stearate calcium montanate, magnesium montanate, aluminum montanate, paraffin, alumina, talc, calcium carbonate, mica, silica, kaolin, etc. preferable.

The addition amount of the foaming aid is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, and 0.1 to 1 part by weight with respect to 100 parts by weight of the polyester resin. More preferably, it is a part. If the amount is less than 0.01 parts by weight, the effect of adding the foaming aid is not sufficient, and if the amount exceeds 10 parts by weight, the surface appearance tends to be impaired. Brominated flame retardants, phosphorus flame retardants, silicone flame retardants, nitrogen compound flame retardants, antimony compounds, other inorganic flame retardants, etc.), slidability improvers (graphite, fluororesins, etc.), antibacterial agents, stabilizers One or more other components that are usually added to the resin composition, such as a colorant including a release agent, a pigment and a dye, a lubricant, an antistatic agent, and a weathering agent, can be added.

  In the present invention, when the polyester resin is a polylactic acid resin, the temperature-falling crystallization temperature (Tc) derived from the polylactic acid resin in the resin composition is preferably 80 ° C. or more, more preferably 85. ° C or higher, more preferably 100 ° C or higher, particularly preferably 110 ° C or higher. The upper limit of Tc is not particularly limited, and the higher the value, the better the crystallization characteristics. Therefore, the upper limit of Tc may be less than the melting point of the polylactic acid resin. Here, Tc is a crystallization temperature at the time of temperature decrease derived from the polylactic acid resin in the resin composition measured by DSC at a temperature decrease rate of 20 ° C./min, and the melting point is Tm described later. Such a resin composition having Tc can be obtained by using a polylactic acid resin having a preferred embodiment or a natural organic filler, or by using a polyvalent carboxylic acid ester plasticizer. Preferably, it can be obtained by using a polylactic acid resin having a preferred embodiment and a naturally occurring organic filler.

  In the present invention, when the polyester resin is a polylactic acid resin, the temperature rising crystallization temperature (Tcc) derived from the polylactic acid resin in the resin composition is not particularly limited, but is preferably 120 ° C. or less, more preferably Is 100 ° C. or lower, more preferably 80 ° C. or lower. Here, Tcc is the crystallization temperature at the time of temperature increase derived from the polylactic acid resin in the resin composition measured by DSC at a temperature increase rate of 20 ° C./min. In the present invention, after complete melting, The value obtained using a sample rapidly cooled with dry ice. Such a resin composition having Tcc can be obtained by using a polylactic acid resin having a preferred embodiment or a natural organic filler, or by using a polyvalent carboxylic acid ester plasticizer. Preferably, it can be obtained by using a polylactic acid resin and a polyvalent carboxylic acid ester plasticizer having preferred embodiments.

  In the present invention, when the polyester resin is a polylactic acid resin, the relationship between Tc and Tcc preferably satisfies Tc−Tcc ≧ 20 ° C., and more preferably Tc−Tcc ≧ 25 ° C. Preferably, Tc−Tcc ≧ 30 ° C. is more preferable, and Tc−Tcc ≧ 40 ° C. is most preferable. The resin composition having such characteristics can be obtained by using a polylactic acid resin having a preferred embodiment or a naturally-derived organic filler, or by using a polyvalent carboxylic acid ester plasticizer.

  In the present invention, when the polyester resin is a polylactic acid resin, the relationship between the melting point (Tm) derived from the polylactic acid resin in the resin composition and Tc is Tm-Tc in the range of 30 to 65 ° C. It is preferable that it is in the range of 35-60 ° C, more preferably in the range of 40-55 ° C. Here, Tm is a melting point derived from the polylactic acid resin in the resin composition measured by DSC at a temperature rising rate of 20 ° C./min. A resin composition having such characteristics can be obtained by using a polylactic acid resin having a preferred embodiment or a naturally-derived organic filler.

  In the present invention, when the polyester resin is a polylactic acid resin, the relationship between Tm and Tcc is preferably Tm-Tcc in the range of 75 to 105 ° C, and in the range of 80 to 100 ° C. Is more preferable and it is still more preferable that it exists in the range of 85-95 degreeC. The resin composition having such characteristics can be obtained by using a polylactic acid resin having a preferred embodiment, or by using a polyvalent carboxylic acid ester plasticizer.

In the present invention, the weight average molecular weight of the polyester resin obtained by the reaction with the polyester resin used as a raw material in the resin composition and the polymer containing the epoxy group-containing vinyl-based unit is not particularly limited, but is 20,000 or more. It is preferably 100,000 or more, more preferably 300,000 or more, and most preferably 400,000 or more. The upper limit is not particularly limited, but may be 1 million or less in terms of moldability. Further, the weight average molecular weight of the polyester resin in the resin composition is compared with the weight average molecular weight of the polyester resin used as a raw material by reacting when the polymer having an epoxy group-containing vinyl-based unit of the present invention is used. Increase. The weight average molecular weight of the polyester resin in the resin composition is preferably 1.1 times or more, more preferably 1.5 times or more, and more preferably 2 times the weight average molecular weight of the raw material polyester resin. More preferably, it is more preferably 2.5 times or more. The upper limit is not particularly limited, but may be 6 times or less in terms of moldability. The weight average molecular weight of the polyester resin in the resin composition can be determined by directly measuring the resin composition as a reaction of the polyester resin and a polymer having an epoxy group-containing vinyl unit. Depending on their composition, isolation operation such as extraction is performed as a pretreatment, and what is confirmed to be a polyester resin by infrared spectroscopy (IR) or nuclear magnetic resonance spectroscopy (NMR) is measured. Is preferred.

  The method for producing the resin composition of the present invention is not particularly limited as long as the requirements specified in the present invention are satisfied. For example, a polyester resin, a natural organic filler, and a heavy resin containing an epoxy group-containing vinyl-based unit are used. Preferred is a method of blending and blending other additives as necessary, and then uniformly melting and kneading with a single screw or twin screw extruder above the melting point, or a method of removing the solvent after mixing in a solution. Used.

  When the resin composition of the present invention is produced, the melt kneading temperature is preferably 170 to 300 ° C, more preferably 175 to 250 ° C, further preferably 180 to 240 ° C, and most preferably 185 to 220 ° C.

  The resin composition of the present invention is a composition having unique characteristics, and can be processed and used for various molded products by a method such as injection molding or extrusion molding. The mold temperature for injection molding is preferably 30 ° C. or higher, more preferably 60 ° C. or higher, further preferably 70 ° C. or higher, from the viewpoint of crystallization, and preferably 140 ° C. or lower from the viewpoint of deformation of the test piece. 120 ° C. or lower is more preferable, and 110 ° C. or lower is further preferable.

  The resin composition of the present invention is a composition having unique characteristics, and can be formed into a molded product by various molding methods. As the molding method, for example, extrusion molding, injection molding, press molding, blow molding and the like are preferable, among which injection molding and extrusion molding are more preferable, and extrusion molding is more preferable. It can be used particularly effectively by processing into an extruded product by extrusion molding.

  In addition, examples of the molded product made of the resin composition of the present invention include injection molded products, extrusion molded products, and blow molded products, and can also be used as sheets, films, fibers, and the like.

  In addition, these molded products can be used for various applications such as electric / electronic parts (various housings, gears, gears, etc.), building members, civil engineering members, agricultural materials, automobile parts (interior / exterior parts, etc.) and daily necessities. it can.

Specifically, notebook personal computer housings and internal parts, CRT display housings and internal parts, printer housings and internal parts, mobile terminal housings and internal parts such as mobile phones, mobile personal computers and handheld mobiles, recording media (CD, DVD, PD, FDD, etc.) Drive housing and internal parts, copier housing and internal parts, facsimile housing and internal parts, parabolic antennas, and other electric / electronic parts. Furthermore, audio equipment parts such as VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, video cameras, audio / laser disks (registered trademark) / compact disks, lighting parts, refrigerator parts, Examples include home and office electrical product parts such as air conditioner parts, typewriter parts, and word processor parts. Also, housings and internal parts of electronic musical instruments, home game machines, portable game machines, various gears, various cases, sensors, LEP lamps, connectors, sockets, resistors, relay cases, motor cases, switches, capacitors, variable capacitor cases , Optical pickups, oscillators, various terminal boards, transformers, plugs, printed wiring boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brushes Electric and electronic parts such as holders, transformer members, coil bobbins, sash doors, blind curtain parts, piping joints, curtain liners, blind parts, gas meter parts, water meter parts, water heater parts, roof panels Thermal insulation walls, adjusters, plastic bundles, ceiling fishing gear, stairs, doors, floors and other building components, fishing lines, fishing nets, seaweed aquaculture nets, fishing bait bags and other marine products, vegetation nets, vegetation mats, weed bags Grass net, curing sheet, slope protection sheet, fly ash holding sheet, drain sheet, water retention sheet, sludge / sludge dewatering bag, concrete formwork and other civil engineering components, air flow meter, air pump, thermostat housing, engine mount, ignition hobbin , Ignition case, clutch bobbin, sensor housing, idle speed control valve, vacuum switching valve, ECU housing, vacuum pump case, inhibitor switch, rotation sensor, acceleration sensor, distributor cap, coil base, A S actuator case, radiator tank top and bottom, cooling fan, fan shroud, engine cover, cylinder head cover, oil cap, oil pan, oil filter, fuel cap, fuel strainer, distributor cap, vapor canister housing, air cleaner housing , Timing belt covers, brake booster parts, various cases, various tubes, various tanks, various hoses, various clips, various valves, various pipes, automotive underhood parts, torque control levers, safety belt parts, register blades, washer levers , Window regulator handle, window regulator handle knob, passing light lever, sun Automotive interior parts such as visor brackets, various motor housings, spare tire covers, door trims, roof rails, fenders, garnishes, bumpers, door mirror stays, spoilers, hood louvers, wheel covers, wheel caps, grill apron cover frames, lamp reflectors, lamps Automotive exterior parts such as bezels and door handles, wire harness connectors, SMJ connectors, PCB connectors, door grommet connectors and other automotive connectors, gears, screws, springs, bearings, levers, key stems, cams, ratchets, rollers, water supply parts , Toy parts, Fans, Tegs, Pipes, Cleaning jigs, Motor parts, Microscopes, Binoculars, Cameras, Watches and other mechanical parts, Multi films, Tunnel films, Bird sheet, vegetation protection nonwoven fabric, seedling pot, vegetation pile, seed string tape, germination sheet, house lining sheet, agricultural PVC film stopper, slow-release fertilizer, root control sheet, garden net, insect net, Infant tree nets, printed laminates, fertilizer bags, sample bags, sandbags, beast damage nets, incentive straps, windproof nets and other agricultural components, disposable diapers, sanitary wrapping materials, cotton swabs, towels, toilet seat wipes and other hygiene products, medical care Non-woven fabric (stitching reinforcement, adhesion prevention film, prosthetic repair material), wound dressing, wound tape bandage, sticker base fabric, surgical suture, fracture reinforcement, medical film and other medical supplies, calendar, Stationery, clothing, food packaging film, tray, blister, knife, fork, spoon, tube, plastic can, pouch, container, tank, basket, etc. Tofill containers, microwave cooking containers, cosmetic containers, wraps, foam buffers, paper lami, shampoo bottles, beverage bottles, cups, candy packaging, shrink labels, lid materials, envelopes with windows, fruit baskets, hand-cut tape , Easy peel packaging, egg packs, HDD packaging, compost bags, recording media packaging, shopping bags, containers and packaging for wrapping films for electrical and electronic parts, natural fiber composites, polo shirts, T-shirts, inners, uniforms, sweaters , Various clothing such as socks and ties, curtains, chairs, carpets, tablecloths, futon mats, wallpaper, furoshiki and other interior goods, carrier tape, print laminate, thermal stencil printing film, release film, porous film , Container bag, credit card, cash Card, ID card, IC card, hot melt binder such as paper, leather, nonwoven fabric, magnetic material, zinc sulfide, electrode material powder binder, optical element, conductive embossed tape, IC tray, golf tee, garbage bag, Plastic bags, various nets, toothbrushes, stationery, draining nets, body towels, hand towels, tea packs, drainage filters, clear files, coating agents, adhesives, bags, chairs, tables, cooler boxes, kumade, hose reels, planters It is useful as a hose nozzle, dining table, desk surface, furniture panel, kitchen cabinet, pen cap, gas lighter, etc. The extruded product of the present invention is obtained by using a general thermoplastic resin extrusion method. Can do. For example, the above resin composition is melt-kneaded with an extruder, extruded using molding dies for forming various shapes such as plates, rods, and pipes, and cooled and solidified by water cooling or air cooling. Thus, an extrusion-molded product having a desired shape can be obtained.

  As the extruder, any of a single-screw extruder, a twin-screw extruder, a multi-screw extruder, or a combined extruder such as a combined twin-screw / single-screw extruder can be used. From the viewpoint that operability during operation is easy, a single screw extruder and a twin screw extruder are preferable.

  In the present invention, the ratio (L / D) of the length (L) of the screw of the extruder to the diameter (D) of the screw is not particularly limited, but is 20 to 20 from the viewpoint of the dispersibility of the naturally derived organic filler. 80 is preferable, 22 to 70 is preferable, and 25 to 60 is more preferable.

  In the present invention, the screw rotation speed of the extruder is not particularly limited, but is preferably 10 to 500 rpm, more preferably 20 to 350 rpm, and more preferably 30 to 250 rpm from the viewpoint of suppressing an increase in the resin temperature due to shearing heat generation. Is more preferable, and 40 to 200 rpm is particularly preferable.

  In the present invention, the extrusion molding temperature is preferably 120 to 300 ° C, more preferably 140 to 280 ° C, further preferably 150 to 250 ° C, and most preferably 160 to 220 ° C. Here, the extrusion molding temperature refers to the cylinder set temperature of the extruder, and the resin temperature in the vicinity of the inner wall of the cylinder is 150 to 280 ° C., preferably 160 to 250 ° C., more preferably 170 to 210 ° C. Is set to When the extrusion molding temperature is less than 120 ° C, the resin does not melt completely, so it tends to be difficult to obtain a molded product. When the temperature exceeds 300 ° C, the molded product is severely burned and the polyester resin is thermally decomposed. In addition, it tends to be difficult to obtain a desired molded product.

  In the present invention, it is preferable to introduce an inert gas such as nitrogen and melt knead from the viewpoint that an extruded product having a stable and good color tone can be obtained.

  In the present invention, as a method of supplying raw materials to the extruder, a method of directly supplying each raw material individually, a method of supplying all raw materials in a lump after mixing in advance, a high speed mixer such as a Henschel mixer is used. Any method can be used, such as a method of supplying the raw material after making it into an agglomerate of beans size, a method of supplying after pelletizing with an extruder or the like, from the viewpoint of operability and dispersibility of the natural organic filler. A method of directly supplying each raw material individually and a method of supplying all the raw materials in a lump after premixing them are preferable. Moreover, it is preferable to supply a raw material using a weight feeder from the point of extrusion stability.

  In the present invention, when using a method in which all raw materials are mixed in advance and fed in a lump, the extruder can be operated stably and the dispersibility of the naturally derived organic filler can be improved. From the viewpoint that it can be performed, it is preferable to perform blending using a blender such as a V blender, a ribbon blender, a tumbler blender, a screw blender, or a Henschel mixer as premixing. When this method is used, the raw material may be either granular or powdery, but is preferably powdery from the viewpoint of mixing properties.

  The extruded product of the present invention is useful in various shapes such as a board shape, a sheet shape, a film shape, a plate shape, a rod shape, a column shape, a box shape, a block shape, a tube shape, a fiber shape, and a complex shape. .

  When the extruded product of the present invention is a board or plate, the thickness is preferably 1 to 200 mm, more preferably 2 to 50 mm, and even more preferably 5 to 30 mm. If it is less than 1 mm, it tends to break easily, and if it exceeds 200 mm, the cooling time becomes longer and the productivity tends to decrease.

  When the extruded product of the present invention is rod-shaped, the maximum cross-sectional length is preferably 1 to 200 mm, more preferably 2 to 100 mm, further preferably 3 to 50 mm, and particularly preferably 5 to 30 mm. If it is less than 1 mm, it tends to break because it is brittle, and if it exceeds 200 mm, the cooling time becomes longer and the productivity tends to decrease.

  Examples of the extruded product of the present invention include, for example, concrete molds, scaffolding boards, sheet piles, piles, and other civil engineering materials, pillars, foundations, beams, baseboards, flooring materials, ceiling materials, shojis, fences, window frames, doors, Building materials such as deck materials, furniture materials such as chests, desks, chairs and various shelves, transport and packing materials such as pallets, containers, wooden boxes and barrels, pachinko machine parts such as pachinko machine gauge panels and frame materials, mahjong table , Materials for gaming machines such as billiard tables, door trims, trunk covers, spare tire covers, ceiling materials, floor materials, inner plates, seat materials, door panels, door boards, various panels, etc. and roof rails, fenders, bumpers, spoilers, Automotive parts such as door panels, exterior parts such as center pillars, electrical and electronic parts such as various housings, sports materials, flooring materials, outer panels, interior materials such as ships and vehicles , Agricultural materials, sleepers, musical instruments, tableware, can be suitably used, for example in the coffin. Among these, from the viewpoint of protecting the natural environment, it is more preferable to use it for civil engineering materials, building materials, fittings, furniture, transportation / packaging materials, materials for game machines, automobile parts, electrical / electronic parts, concrete formwork, deck materials. It is further preferable to use it for pachinko machine parts such as window frames, pallets, pachinko machine gauge panels and frame materials, door trims, trunk covers, spare tire covers, musical instruments and the like.

  As a method for producing the foam of the present invention, any of a melt foaming method, a solid phase foaming method and a cast foaming method may be used, but the melt foaming method is preferred because it can be easily carried out. Specifically, a polyester resin, a naturally derived organic filler, a polymer containing an epoxy group-containing vinyl-based unit, and a foaming agent are melt-kneaded to obtain a foam.

  The melt kneading may be performed under normal pressure or under pressure, but is preferably melt-kneaded under pressure and then extruded under atmospheric pressure or injected into a mold to form a foam.

  In the present invention, the method of melt-kneading is not particularly limited. For example, a polyester resin, a naturally-occurring organic filler, a polymer containing an epoxy group-containing vinyl-based unit, a foaming agent, and other additives as necessary are previously added. After blending, above the melting point of the polyester resin, single-screw extruder, twin-screw extruder, single-screw / double-screw composite extruder, multi-screw extruder, tandem type with two single-screw and / or twin-screws connected Foam extrusion molding method that is uniformly melt-kneaded using an extruder such as an extruder to make an extruded foam, foam injection molding method that is directly melt-kneaded with an injection molding machine to make a foam, and uniformly using an extruder After melt-kneading polylactic acid resin, natural organic filler, ester plasticizer to obtain a resin composition, blend with foaming agent to make foam using press or injection molding machine. Preferably it can be used. In addition, when using fine powder as a raw material, the method of adding after compressing a fine powder, the method of supplying to a hopper independently from another additive, etc. are preferable. Moreover, a foaming agent may be mix | blended independently and may be mix | blended after preparing the masterbatch of a foaming agent previously.

  In the present invention, the set temperature of the extruder or injection molding machine is preferably 100 to 300 ° C, more preferably 120 to 280 ° C, further preferably 140 to 250 ° C, and most preferably 160 to 220 ° C. The set temperature refers to the cylinder set temperature. The set temperature is set so that the resin temperature, preferably the resin temperature near the inner wall of the cylinder is 160 to 280 ° C., preferably 170 to 250 ° C., more preferably 175 to 210 ° C.

  In the present invention, the screw rotation speed of the extruder or the injection molding machine is not particularly limited, but is preferably 10 to 500 rpm, more preferably 30 to 350 rpm from the viewpoint of suppressing an increase in the resin temperature due to shearing heat generation. 50 to 250 rpm is more preferable, and 70 to 200 rpm is particularly preferable.

  In the present invention, the ratio (L / D) of the length (L) of the screw of the extruder to the diameter (D) of the screw is not particularly limited, but is 20 to 20 from the viewpoint of the dispersibility of the naturally derived organic filler. 80 is preferable, 25 to 70 is preferable, 30 to 60 is more preferable, and 35 to 50 is particularly preferable.

  In the present invention, the mold temperature in the case of foam injection molding is preferably 30 ° C or higher, more preferably 60 ° C or higher, further preferably 70 ° C or higher, from the viewpoint of crystallization, from the viewpoint of deformation of the test piece, 140 degrees C or less is preferable, 120 degrees C or less is more preferable, and 110 degrees C or less is more preferable.

  In the present invention, it is preferable to introduce an inert gas such as nitrogen because a foam having a stable and good color tone can be obtained.

  In the present invention, as a method of supplying raw materials to an extruder or an injection molding machine, a method of directly supplying each raw material individually, a method of supplying all raw materials in a lump after premixing, a Henschel mixer, etc. Either a method of supplying the raw material after making it agglomerated with a high speed mixer or a method of supplying it after pelletizing with an extruder or the like can be used, but operability and dispersion of organic fillers derived from nature From the viewpoint of properties, a method of directly supplying each raw material individually and a method of supplying all raw materials in a lump after premixing them are preferable. Moreover, it is preferable to supply a raw material using a weight feeder from the point of extrusion stability.

  In the present invention, when using a method in which all raw materials are mixed in advance and then fed together, the extruder or injection molding machine can be operated stably, and the dispersibility of the natural organic filler can be increased. It is preferable to blend using a blender such as a V blender, a ribbon blender, a tumbler blender, a screw blender, and a Henschel mixer as premixing because it can be improved. When this method is used, the raw material may be either granular or powdery, but is preferably powdery from the viewpoint of mixing properties.

  The foam of the present invention preferably has an expansion ratio of 1.02 to 15 times from the viewpoint of lightness. Here, the expansion ratio can be determined from the raw material resin composition density / foam density. The expansion ratio is preferably 1.1 to 12 times, more preferably 1.2 to 10 times, further preferably 1.3 to 8 times, and most preferably 1.4 to 5 times from the viewpoint of heat resistance. . If the expansion ratio is less than 1.02, the lightness is not sufficient, and if it exceeds 15 times, not only the heat resistance is lowered, but also it becomes difficult to obtain a stable product, which is not preferable. The foam having the expansion ratio can be obtained by using a preferable foaming agent in a preferable addition amount and utilizing a preferable manufacturing method. The expansion ratio mainly depends on the amount of the foaming agent. When the amount of the foaming agent used is increased, the expansion ratio tends to increase. On the other hand, the amount of the filler such as a naturally-derived organic filler or inorganic filler is reduced. If it is increased, the expansion ratio tends to decrease. Here, the density of the raw material resin composition means the density of the raw material resin composition in an unfoamed state. If the used raw material is known, it is calculated according to the composition ratio of the used raw material. Can do. Further, even when the raw material used is not known, it can be obtained from a product obtained by solidifying the foamed raw material resin composition as an unfoamed material after the foam is removed.

In the present invention, the lightness can be determined from the foam density. Foam density is not particularly limited but is preferably 0.05~1.25g / cm ^3, more preferably 0.05~1.00g / cm ^3, and most preferably 0.05~0.80g / cm ³ . When foam density is less than 0.05 g / cm ^3, the appearance lead to failure or strength decrease, exceeds 1.25 g / cm ^3, unfavorably effect of weight reduction is small. The foam having the above foam density can be obtained by using a preferable foaming agent in a preferable addition amount and utilizing a preferable manufacturing method. The foam density can be obtained from the weight of the foam (g) / the volume of the foam (cm ³ ) using the weight of the foam and the volume determined by the submerging method.

  The foam of the present invention has various shapes such as a board shape, a sheet shape, a film shape, a plate shape, a rod shape, a column shape, a box shape, a lump shape, a tube shape, a fiber shape, a net shape, a particle shape, and a complex shape. Useful as.

  When the foam of the present invention has a board shape, the thickness is preferably 1 to 30 mm, more preferably 2 to 25 mm, and even more preferably 5 to 20 mm. If the thickness is less than 1 mm, the number of bubbles is reduced and the lightness is not sufficient. If the thickness exceeds 30 mm, it is difficult to control the expansion ratio and the bubble size, and it is difficult to obtain a good product having a uniform thickness. Therefore, it is not preferable.

  The foam of the present invention includes automobile parts (interior / exterior parts, etc.), electric / electronic parts (various housings, gears, gears, etc.), building materials, civil engineering materials, furniture members, agricultural materials, game machine materials, tableware, sports It can be used for various purposes such as materials, musical instruments and daily necessities.

  Specifically, automotive parts include air flow meters, air pumps, thermostat housings, engine mounts, ignition hobbins, ignition cases, clutch bobbins, sensor housings, idle speed control valves, vacuum switching valves, ECU housings, vacuum pump cases, inhibitors Switch, rotation sensor, acceleration sensor, distributor cap, coil base, ABS actuator case, radiator tank top and bottom, cooling fan, fan shroud, engine cover, cylinder head cover, oil cap, oil pan, oil filter, fuel cap , Fuel strainer, distributor cap, vapor Nister housing, air cleaner housing, timing belt cover, brake booster parts, various cases, various tubes, various tanks, various hoses, various clips, various valves, various pipes such as automotive underhood parts, torque control lever, safety belt Parts, register blade, washer lever, window regulator handle, knob of window regulator handle, passing light lever, sun visor bracket, door trim, door pocket, column cover, cowl side, footrest deck trim, front pillar, center pillar, front scuff, Rear scuff, door cuff, front outside, rear outside, seat side, roof side, striker, air Automotive interior parts such as concases, cassette deck cases, various motor housings, roof rails, fenders, garnishes, bumpers, door mirror stays, spoilers, hood louvers, wheel covers, wheel caps, grill apron cover frames, lamp reflectors, lamp bezels, Various automotive connectors such as exterior parts for automobiles such as door handles, wire harness connectors, SMJ connectors, PCB connectors, and door grommet connectors. Electrical and electronic components include notebook PC housings and internal parts, CRT display housings and internal parts, printer housings and internal parts, mobile terminal housings and internal parts such as mobile phones, mobile PCs, handheld mobiles, recording media (CD, (DVD, PD, FDD, etc.) Drive housing and internal parts, copier housing and internal parts, facsimile housing and internal parts, parabolic antennas, and other electric / electronic parts. Furthermore, audio equipment parts such as VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, video cameras, audio / laser disks (registered trademark) / compact disks, lighting parts, refrigerator parts, Household and office electrical product parts represented by air conditioner parts, typewriter parts, word processor parts, etc., housings and internal parts of electronic musical instruments, home game machines, portable game machines, various gears, various cases, sensors, connectors , Sockets, resistors, relay cases, motor cases, switches, capacitors, variable capacitor cases, oscillators, various terminal boards, transformers, plugs, printed wiring boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, Power module, Conductor, liquid crystal, FDD carriage, FDD chassis, motor brush holders, transformer members and coil bobbins and the like. Building materials include sash doors, blind curtain parts, piping joints, curtain liners, blind parts, gas meter parts, water meter parts, water heater parts, roof panels, heat insulation walls, adjusters, plastic bundles, ceiling hanger, stairs, doors, floors Materials, ceiling materials, pillars, foundations, beams, baseboards, window frames, doors, deck materials, etc. Civil engineering materials include vegetation nets, vegetation mats, grass protection bags, grass protection nets, curing sheets, slope protection sheets, fly ash holding sheets, drain sheets, water retention sheets, sludge / sludge dewatering bags, concrete formwork, scaffolding boards , Sheet piles, and piles. Examples of furniture members include a chest, a desk, a chair, and various shelves. Examples of the material for the gaming machine include pachinko parts such as a pachinko machine gauge board and a frame material, and parts such as a mahjong table and a billiard table. Others include fishing lines, fishing nets, seaweed aquaculture nets, fishing bait bags, simulated baits, sea bream-related fishery materials, gears, screws, springs, bearings, levers, key stems, cams, ratchets, rollers, water supply parts, toy parts, Fans, pipes, cleaning jigs, motor parts, microscopes, binoculars, cameras, watches and other mechanical parts, multi-films, tunnel films, bird protection sheets, vegetation protection nonwoven fabrics, seedling pots, vegetation piles, seed string tape , Germination sheet, house lining sheet, agricultural PVC film stopper, slow-release fertilizer, root-proof sheet, garden net, insect net, young tree net, print laminate, fertilizer bag, sample bag, sandbag, animal damage Agricultural materials such as prevention nets, incentive straps, windproof nets, sanitary products such as disposable diapers, sanitary wrapping materials, cotton swabs, towels, and toilet seat wipes, non-woven fabrics for medical use (stitching reinforcement, adhesion prevention) , Prosthetic repair material), wound dressing material, wound tape bandage, sticking material base fabric, surgical suture, fracture reinforcement, medical film and other medical supplies, tray, knife, fork, spoon, tube, plastic can, Blisters, pouches, pallets, containers, tanks, baskets, beverage bottles, cups, containers such as fruit baskets, hot fill containers, microwave cooking containers cosmetic containers, food packaging films, wraps, Paper laminates, shampoo bottles, candy packaging, shrink labels, lid materials, envelopes with windows, hand cut tape, easy peel packaging, egg packs, HDD packaging, compost bags, recording media packaging, shopping bags, electrical / electronic parts, etc. Packaging materials such as wrapping film, buffer, curtains, chairs, carpets, tablecloths Interior items such as sportswear, futon mats, wallpaper, various sports materials, musical instruments, clothing, credit cards, cash cards, ID cards, IC cards, carrier tapes, printed tapes, thermal stencil printing films, release films, porosity Useful as film, conductive embossed tape, IC tray, tea pack, drainage filter, bag, golf tee, toothbrush, stationery, clear file, cooler box, kumade, hose reel, planter, hose nozzle, pen cap, gas lighter, etc. It is.

  The foam of the present invention can be recycled after use to be used for various purposes. For example, the foam after use can be reused as a foam by pulverizing the foam and adding a foaming agent to the molded product. Can do.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, these do not limit this invention. Moreover, the raw material used and the code | symbol in a table | surface are shown below.

(A) Polyester resin (A-1) Poly L lactic acid resin (D body 1.2%, Mw (PMMA) 210,000)
(A-2) Poly L lactic acid resin (D body 1.2%, Mw (PMMA) 160,000)
(A-3) Polybutylene succinate resin (Showa Polymer "Bionore"# 1001, Mw (PMMA) 130,000)
(A-4) Polybutylene adipate / terephthalate resin ("Ecoflex" manufactured by BASF, Mw (PMMA) 70,000)
(A-5) Polybutylene terephthalate (Mw (PMMA) 40,000).

(B) Naturally derived organic filler (B-1) Wood flour (Lettnomeier Lignocell C-300G)
(B-2) Waste paperboard paper powder obtained by pulverizing 1.5 mm thick paperboard (B-3) OA wastepaper paper powder having a fiber length distribution range of 0.05 to 3 mm (B-4) Fiber length 1 to 10 mm (B-5) Bamboo fiber having a fiber length distribution range of 0.05 to 10 mm (B-6) A hemp pellet having a length of 50 mm or less and a diameter of 5 mm.

(C) Polymer containing an epoxy group-containing vinyl-based unit (C-1) Polymer obtained by Production Example 1 (C-2) Polymer obtained by Production Example 2 (C-3) By Production Example 3 The obtained polymer.

(D) Carboxyl group-reactive compound (D-1) Terephthalic acid diglycidyl ester (EX-711 manufactured by Nagase Chemical Industries)
(D-2) Pentaerythritol polyglycidyl ether (EX-411 manufactured by Nagase Chemical Industries)
(D-3) Polycarbodiimide (“Carbodilite” HMV-8CA manufactured by Nisshinbo).

(E) Crystallization accelerator (E-1) Polyethylene glycol (PEG 4000 manufactured by Sanyo Chemical Industries)
(E-2) Aliphatic ester plasticizer ("Daifatty" -101 manufactured by Daihachi Chemical Industry).

(E-3) Talc (Fuji Talc Kogyo LMS300)
(F) Foaming agent (F-1) Azodicarbonamide-based foaming agent (“VINYHALL” AC # 3 manufactured by Eiwa Chemical Industries)
(F-2) Sodium hydrogen carbonate-based foaming agent (“Selbone” SC-K manufactured by Eiwa Chemical Industries).

  Moreover, the measuring method used by this invention is shown below.

(1) Molecular weight measurement of a polymer containing an epoxy group-containing vinyl-based unit It is a value of weight average molecular weight (Mw (PS)) in terms of standard polystyrene (PS) measured by gel permeation chromatography (GPC). Chloroform was used as a solvent, and measurement was performed at a sample concentration of 1 mg / mL.

(2) Molecular weight measurement of polyester resin in raw material and resin composition It is a value of weight average molecular weight (Mw (PMMA)) in terms of standard polymethyl methacrylate (PMMA) measured by gel permeation chromatography (GPC). Hexafluoroisopropanol was used as the solvent, and the measurement was performed at a sample concentration of 1 mg / mL.
(3) Glass transition temperature (Tg) of a polymer containing an epoxy group-containing vinyl-based unit
About each raw material before a mixing | blending, it measured with the differential scanning calorimeter (Seiko Electronics RDC220). The measurement conditions are a sample 10 mg, a nitrogen atmosphere, and a temperature increase rate of 20 ° C./min.
(4) Temperature-falling crystallization temperature (Tc) of the polyester resin in the resin composition
It measured with the differential scanning calorimeter (DSC7 by Perkin-Elmer). The measurement conditions are 0 mg of data, a temperature drop rate of 20 ° C./min in a nitrogen atmosphere.

[Production Example 1]
As a monomer, a mixture of 40 parts by weight of styrene, 15 parts by weight of butyl acrylate, 25 parts by weight of methyl methacrylate and 20 parts by weight of glycidyl methacrylate and a mixture of di-t-butyl peroxide as a polymerization initiator from the raw material storage tank is 220. It supplied to the pressurization type stirring tank type | mold reaction container hold | maintained at (degreeC). While continuously supplying the raw materials, the polymer was continuously taken out from the reaction vessel outlet so that the residence time was 15 minutes under the conditions of 240 ° C. and 2.5 MPa. After continuously removing the polymer from the reaction vessel, the volatile component is continuously removed under high temperature and reduced pressure of 260 ° C. and 10 kPa to obtain a polymer (C-1) containing an epoxy group-containing vinyl unit. It was. With respect to the obtained C-1, the epoxy value measured by the hydrochloric acid-dioxane method was 1.4 meq / g. Moreover, Tg measured with the differential scanning calorimeter (Seiko Electronics RDC220) was 59 degreeC. The Mw (PS) measured by GPC was 10100.

[Production Example 2]
A polymer containing an epoxy group-containing vinyl-based unit in the same manner as in Production Example 1 except that a mixed monomer of 65 parts by weight of styrene, 5 parts by weight of methyl methacrylate and 30 parts by weight of glycidyl methacrylate is used as the monomer (C -2) was obtained. With respect to the obtained C-1, the epoxy value measured by the hydrochloric acid-dioxane method was 2.2 meq / g. Moreover, Tg measured by the differential scanning calorimeter (Seiko Electronics RDC220) was 58 degreeC. The Mw (PS) measured by GPC was 7900.

[Production Example 3]
Epoxy group-containing vinyl by emulsion polymerization at 85 ° C. for 6 hours using a mixed monomer of 69 parts by weight of styrene, 21 parts by weight of acrylonitrile and 10 parts by weight of glycidyl methacrylate as a monomer and potassium persulfate as a polymerization initiator. A polymer (C-3) containing a system unit was obtained. With respect to the obtained C-3, the epoxy value measured by the hydrochloric acid-dioxane method was 0.1 meq / g. Moreover, Tg measured by the differential scanning calorimeter (Seiko Electronics RDC220) was 101 degreeC. Mw (PS) measured by GPC was 110,000.

[Examples 1-12, Comparative Examples 1-7]
As shown in Table 1, a polyester resin, a naturally-derived organic filler, a polymer containing an epoxy group-containing vinyl unit, and a carboxyl group-reactive compound are mixed and rotated at a cylinder temperature of 190 ° C. with a 30 mm diameter twin screw extruder. Melt kneading was performed under conditions of several hundred rpm to obtain a resin composition.

  The obtained resin composition was melt-kneaded and extruded using a 30 mm diameter single screw extruder (L / D = 30) under the conditions of a cylinder temperature of 190 ° C., a rotation speed of 40 rpm, and a molding die temperature of 200 ° C., and a width of 300 mm. A plate-like extruded product having a thickness of 5 mm was obtained.

  The moldability was judged by whether a good shape was obtained.

  Regarding surface appearance, surface smoothness and glossiness were determined by touch and visual observation.

  The weight average molecular weight of the polyester resin in the obtained molded product was measured.

  The obtained extrusion-molded product was cut out to a size of 100 mm square, a drop test was performed with a DuPont impact tester using a weight with a load of 1 kgf, and impact resistance was determined. That is, it can be said that the higher the drop position, the better the impact resistance.

  In addition, for heat resistance, a test piece cut out to a size of 100 mm square is held in a hot air dryer at four points 25 mm inside from the corner at a height of 10 mm from the table, and heat treated at 80 ° C. for 1 hour. It was determined from the amount of deflection at the center. That is, it can be said that the smaller the amount of deflection, the better the heat resistance.

  Moreover, about durability (moisture-heat resistance), the test piece cut out to the magnitude | size of a 100 mm square is hold | maintained at the height of 10 mm from a stand at four points inside 25 mm from a corner, and 60 degreeC. Then, wet heat treatment was performed for 100 hours at a relative humidity of 80%, and the weight average molecular weight retention before and after the treatment ((Mw after treatment (PMMA) / Mw before treatment (PMMA)) × 100) (%) was determined and determined. That is, it can be said that the higher the weight average molecular weight retention, the better the durability.

  These results are shown in Table 1.

  Further, the used paperboard paper powder (B-2) and OA wastepaper paper powder (B-6) used in the examples were treated in an electric furnace at 450 ° C. for 12 hours to determine the ash content. Furthermore, the obtained ash was analyzed using a fluorescent X-ray apparatus. The analysis results are shown in Table 2.

  From the results of Table 1, it can be seen that the resin composition and molded product of the present invention are excellent in moldability, surface appearance, impact resistance, and durability. Also, from the results of Table 1 and Table 2, use paperboard waste paper powder containing aluminum, silicon, calcium, sulfur, magnesium and titanium as the naturally-occurring organic filler, and the amount of aluminum being greater than magnesium. Thus, it can be seen that a resin composition and a molded product having excellent heat resistance can be obtained.

[Examples 13 to 14, Comparative Examples 8 to 10]
As shown in Table 3, a polyester resin, a naturally-occurring organic filler, a polymer containing an epoxy group-containing vinyl unit, and a carboxyl group-reactive compound are mixed, and a cylinder temperature is 240 ° C. in a 30 mm diameter twin screw extruder. Melt kneading was performed at a rotation speed of 100 rpm to obtain a resin composition.

  The obtained resin composition was melt-kneaded and extruded using a 30 mm diameter single screw extruder (L / D = 30) under the conditions of a cylinder temperature of 240 ° C., a rotation speed of 40 rpm, and a molding die temperature of 240 ° C., and a width of 300 mm. A plate-like extruded product having a thickness of 5 mm was obtained.

    Various evaluations were performed in the same manner as in Example 1.

  These results are shown in Table 3.

  From the results in Table 3, it can be seen that the resin composition and molded product of the present invention are excellent in moldability, surface appearance, impact resistance, heat resistance, and durability.

[Examples 15 to 24, Comparative Examples 11 to 18]
As shown in Table 4, a polyester resin, a naturally-derived organic filler, a polymer containing an epoxy group-containing vinyl unit and other additives as necessary are mixed, and a 44 mm diameter twin screw extruder (L / D = 35), melt kneading was performed under the conditions of a cylinder temperature of 190 ° C. and a rotation speed of 100 rpm to obtain a resin composition.

  Tc and weight average molecular weight of the polyester resin in the obtained resin composition were measured.

  The obtained resin composition was injection-molded at a cylinder temperature of 190 ° C. and a mold temperature of 80 ° C. to obtain an ASTM test piece having a thickness of 3 mm. The molding cycle time was 60 seconds, and when taking out from the mold, the deformation of the tensile test piece was visually observed to determine the moldability.

  Regarding surface appearance, surface smoothness and glossiness were determined by touch and visual observation.

  About impact resistance, the notched Izod impact test was done according to ASTM method D256 using the test piece obtained above.

  About heat resistance, the deflection temperature under load (0.45 MPa) was measured according to ASTM method D648 using the test piece obtained above.

  For durability (moisture and heat resistance), the tensile specimen was wet-heat treated at 60 ° C. and 95% relative humidity for 100 hours in a thermo-hygrostat, and the tensile strength retention before and after treatment ((tensile strength after treatment / treatment) It was determined by the previous tensile strength) × 100). That is, it can be said that the higher the tensile strength retention rate, the better the durability.

  Furthermore, about the bleed-out property at the time of wet heat, it determined by observing the test surface after the said wet heat processing visually.

  These results are shown in Table 4.

  From the results of Table 4, the resin composition of the present invention is excellent in crystallization characteristics, the weight average molecular weight of the polyester resin in the resin composition is greatly improved, and the molded product obtained from the resin composition has moldability. It can be seen that the surface appearance, impact resistance and durability are excellent. Moreover, it turns out that it is excellent also in heat resistance and bleed-out resistance by using a preferable crystallization promoter.

[Examples 25 to 27, Comparative Examples 19 to 23]
Various raw materials such as polyester resin shown in Table 5 were mixed in the ratio shown in Table 5, and a 50 mm diameter twin screw extruder (L / D = 35) was used. The cylinder temperature was 190 ° C., the screw rotation speed was 100 rpm, Melt kneading extrusion was performed under the conditions of a molding die temperature of 180 ° C. to obtain a foam having a width of 300 mm and a thickness of 10 mm.

  The moldability was judged by whether a good shape was obtained.

  Regarding surface appearance, surface smoothness and glossiness were determined by touch and visual observation.

  Tc of the polyester resin in the obtained foam was measured.

  The obtained foam is cut into a size of 100 mm × 100 mm × 3 mm, the weight and the volume by submersion method are obtained up to three significant figures, the density (foam density) is calculated, and the lightness is calculated from the value. Judged.

  Further, the expansion ratio was determined from the raw material resin composition density / foam density.

  The obtained foam was cut out to a size of 100 mm square, a drop test was performed with a DuPont impact tester using a weight with a load of 1 kgf, and impact resistance was determined. That is, it can be said that the higher the drop position, the better the impact resistance.

    Moreover, about the heat resistance, about the foam cut out to the said size, after processing for 100 hours and 100 degreeC using a hot air dryer, deformation | transformation (dry heat deformation), such as a warp and shrinkage | contraction, was observed visually and determined.

    For durability, the foam cut out to the above size was treated for 50 hours at a temperature of 60 ° C. and a relative humidity of 95% using a constant temperature and humidity chamber, and then the weight average molecular weight retention before and after the treatment ((treatment It was determined by the following Mw (PMMA) / Mw (PMMA) before treatment) × 100) (%). That is, it can be said that the higher the weight average molecular weight retention rate, the better the durability.

  These results are also shown in Table 5.

  From the results of Table 5, it can be seen that the foam of the present invention is excellent in crystallization characteristics, moldability, surface appearance, light weight, impact resistance and durability. Moreover, it turns out that the foam of this invention is excellent also in heat resistance by using a preferable crystallization promoter.

[Examples 28-30, Comparative Examples 24-26]
Various raw materials such as polyester resin were mixed in the ratio shown in Table 6, and melt kneading was performed at a cylinder temperature of 190 ° C. using a 50 mm diameter twin screw extruder (L / D = 42) to obtain a resin composition. Obtained.

  The weight average molecular weight of the polyester resin in the obtained resin composition was measured.

  A foaming agent was blended with the obtained resin composition, and injection molding was performed under conditions of a cylinder temperature of 210 ° C. and a mold temperature of 85 ° C. to obtain a foam having a thickness of 20 mm, a length of 150 mm, and a width of 150 mm.

  The moldability was judged by whether a good shape was obtained.

About surface appearance, about surface smoothness and glossiness, it judged by touch and visual observation Tc of the polyester resin in the obtained foam was measured.

  The obtained foam was cut into a size of 100 mm × 100 mm, and the lightness, foaming magnification, impact resistance, heat resistance, and durability were evaluated according to the same criteria as in Example 25.

  These results are shown in Table 6.

  From the results of Table 6, the resin composition of the present invention has a greatly improved weight average molecular weight of the polyester resin in the resin composition, and the foam of the present invention has crystallization characteristics, moldability, surface appearance, light weight. It can be seen that it has excellent resistance, impact resistance and durability. Moreover, it turns out that the foam of this invention is excellent also in heat resistance by using a preferable crystallization promoter.

Claims (10)

1 to 350 parts by weight of a naturally-derived organic filler and a weight average molecular weight of 1000 to 20000 and a glass transition temperature of 30 to 100 ° C. with respect to 100 parts by weight of a polyester resin used as a raw material . , Epoxy group-containing vinyl units, acrylic vinyl units, carboxylic acid vinyl ester units, aromatic vinyl units, unsaturated dicarboxylic anhydride units, unsaturated dicarboxylic acid units, aliphatic vinyl units, maleimides The resin composition formed by mix | blending 0.01-30 weight part of polymer containing at least 1 sort (s) selected from a unit. The resin composition according to claim 1, wherein the natural organic filler contains at least one selected from paper powder, wood powder, bamboo powder, bamboo fiber, kenaf fiber, hemp fiber, and jute fiber. The resin composition according to claim 1 or 2, wherein the polyester resin used as the raw material is a polylactic acid resin. The resin composition according to any one of claims 1 to 3, wherein 0.1 to 50 parts by weight of a crystallization accelerator is blended with 100 parts by weight of the polyester resin used as the raw material . The resin composition according to any one of claims 1 to 4, wherein an epoxy value of the polymer including the epoxy group-containing vinyl-based unit is in a range of 0.1 to 10 meq / g. The polymer containing the epoxy group-containing vinyl unit is a polymer containing an epoxy group-containing vinyl unit, at least one selected from an acrylic vinyl unit and an aromatic vinyl unit. The resin composition according to any one of the above. The weight average molecular weight of the polyester resin obtained by reaction with the polyester resin used as a raw material in the resin composition and the polymer containing the epoxy group-containing vinyl-based unit is from 300,000 to 1,000,000. 2. The resin composition according to item 1. A molded article comprising the resin composition according to any one of claims 1 to 7. An extrusion molded article comprising the resin composition according to any one of claims 1 to 7. The foam which consists of a resin composition in any one of Claims 1-7.