Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
  • C08L1/02—Cellulose; Modified cellulose
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
  • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
  • B29C70/06—Fibrous reinforcements only
  • B29C70/10—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres
  • B29C70/12—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of short length, e.g. in the form of a mat
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
  • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
  • B29C70/28—Shaping operations therefor
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/07—Aldehydes; Ketones
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/15—Heterocyclic compounds having oxygen in the ring
  • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
  • C08K5/1545—Six-membered rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/10—Homopolymers or copolymers of propene
  • C08L23/12—Polypropene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L93/00—Compositions of natural resins; Compositions of derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L99/00—Compositions of natural macromolecular compounds or of derivatives thereof not provided for in groups C08L89/00 - C08L97/00
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
  • C08K3/08—Metals
  • C08K2003/0812—Aluminium
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
  • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
  • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
  • C08L2205/16—Fibres; Fibrils
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2207/00—Properties characterising the ingredient of the composition
  • C08L2207/06—Properties of polyethylene
  • C08L2207/066—LDPE (radical process)
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2207/00—Properties characterising the ingredient of the composition
  • C08L2207/20—Recycled plastic

Definitions

• the present invention relates to a resin composite material and a resin molded product.
• thermoplastic resin is excellent in moldability, and the molded product using the thermoplastic resin is excellent in mechanical physical characteristics, electrical characteristics, chemical resistance, etc. Therefore, the thermoplastic resin is widely used as a material for the resin molded product. There is.
• thermoplastic resin molded body in addition to being molded using a virgin material, a thermoplastic resin molded body using a recycled resin is known.
• a technique for obtaining a thermoplastic resin composite material using a used material containing polyolefin such as laminated paper and a beverage pack has also been reported.
• the cellulose fibers derived from paper act as reinforcing fibers of the resin in the obtained composite material, and the mechanical properties of the thermoplastic resin molded body obtained by using this composite material are brought to a desired level. It is said that it can be increased.
• Patent Document 1 proposes a resin composite material using coffee residue and a method for producing the same.
• portion-capsule coffee which contains powdered coffee in plastic capsules, has been sold, and it has become popular that you can easily enjoy fresh flavors, and the market is expanding. Since the coffee residue after extraction of such portion capsule type coffee is still trapped in the capsule, it is difficult to recycle the coffee residue. In addition to coffee, potion capsule-type beverages using black tea, matcha, etc. are also sold, and it is similarly difficult to recycle these extraction residues.
• the powder that is the extraction residue of the above coffee, tea, matcha, etc. contains polysaccharides in its components, so it is mixed with a thermoplastic resin to form a resin composite.
• a thermoplastic resin to form a resin composite.
• the fiber strengthening effect of the resin by the polysaccharide is expected.
• the present inventors examined a resin composite material using a powder containing a polysaccharide as described above the inclusion of these powders may adversely affect the moldability and impact resistance of the resin composite material. , It has become clear that improvement is needed.
• the present invention provides a resin composite material which is excellent in moldability and mechanical properties such as impact resistance while containing a powder containing a polysaccharide in a thermoplastic resin, and a resin molded product using the same. Make it an issue.
• thermoplastic resin The powder containing polysaccharides dispersed in the thermoplastic resin, A resin composite material containing monosaccharides.
• the polyolefin resin contains an acid-modified polyolefin resin [6].
• the resin composite material contains resin particles containing a resin different from the polyolefin resin, the melting point of the resin different from the polyolefin resin is 10 ° C. or higher higher than the melting point of the polyolefin resin, and the maximum diameter of the resin particles is 10 ⁇ m or more.
• the resin composite material of the present invention is excellent in moldability and mechanical properties such as impact resistance while containing a powder containing a polysaccharide in the thermoplastic resin. Further, the molded product of the present invention is excellent in moldability in its production while containing a powder containing a polysaccharide in the thermoplastic resin, and is also excellent in mechanical properties such as impact resistance.
• the resin composite material of the present invention contains a thermoplastic resin, a powder containing polysaccharides dispersed in the thermoplastic resin, and monosaccharides. do. That is, a powder containing a polysaccharide is dispersed in a thermoplastic resin, and a monosaccharide is further contained.
• the resin composite material means a material in which each component constituting the composite material is mixed and integrated substantially uniformly.
• a part of the components constituting the resin composite material may form an agglomerate. These agglomerates are in a state of being almost uniformly dispersed in the matrix resin when viewed as a whole composite material.
• the powder containing a polysaccharide can be used without limitation as long as it contains a polysaccharide as its component.
• powders of coffee beans, tea leaves, beans, grains (including rice, wheat, corn, buckwheat, etc.), organic residues after extracting beverages, etc. from these (coffee residues, tea leaves, etc.) Can be given.
• the term "vegetable powder” is used in the sense that it includes both the above powder and the organic residue. That is, unless otherwise specified, the "vegetable powder” is the powder before extraction (before use) and / or the organic residue after extraction (after use).
• the term "vegetable” means that it contains a plant-derived component (preferably, the main component is a plant-derived component, more preferably 50% by mass or more of the plant-derived component, and more preferably 80 plant-derived components. (Including mass% or more).
• organic means that it contains an organic substance (preferably, the main component is an organic substance, more preferably 50% by mass or more of the organic substance is contained, and more preferably 80% by mass or more of the organic substance is contained).
• Examples of the form of the powder include powder, fibrous, plate and the like.
• the polysaccharide include arabinogalactan, galactomannan, cellulose and the like.
• the powder may contain at least one polysaccharide. These polysaccharides are contained as components of the coffee beans and the like.
• the powder containing the polysaccharide is preferably the organic residue, more preferably a coffee residue and / or a coffee powder.
• a case where coffee residue and / or coffee powder is used as the powder containing a polysaccharide will be described as an example.
• the description described below (maximum diameter of coffee residue and / or coffee powder, content in composite material, monosaccharides to be used in combination, thermoplastic resin to be used in combination, cellulose fibers and / or resin particles to be used in combination may be further used in combination.
• the method for producing a composite material, the production conditions, etc. also applies when a powder and / or an organic residue other than "coffee powder and coffee residue" is used.
• the residue after coffee is extracted from the coffee powder can be used without particular limitation, and unused (unextracted) coffee powder waste or the like can be used or included.
• the coffee powder include crushed coffee beans, and specific examples thereof include crushed roasted coffee beans. From the viewpoint of effective use of resources, it is preferable that the powder containing a polysaccharide contains a coffee residue, and further, the powder containing a polysaccharide is preferably a coffee residue.
• Coffee beans contain polysaccharides such as arabinogalactan, galactomannan, and cellulose.
• the maximum diameter of the coffee residue and / or coffee powder to be used is not particularly limited, and examples thereof include those having a diameter of 0.1 ⁇ m to 1 mm.
• the size of the coffee residue and / or the coffee powder is within the above range, a composite material having excellent moldability and appearance quality can be obtained, which is preferable.
• the lower limit of the maximum diameter of the coffee residue and / or coffee powder is preferably 1 ⁇ m or more, more preferably 5 ⁇ m or more.
• the upper limit of the maximum diameter of the coffee residue and / or the coffee powder is preferably 900 ⁇ m or less. More preferably, it is 800 ⁇ m or less.
• the maximum diameter of the coffee residue and / or coffee powder is obtained by observing the cross section of the composite material under a microscope and averaging the maximum diameters of the observed coffee powder. More specifically, the maximum diameter can be obtained in the same manner as the maximum diameter of the resin fine particles, which will be described later.
• the content of the coffee residue and / or coffee powder in the composite material is not particularly limited, but is preferably 1 to 80% by mass, more preferably 5 to 70% by mass in the composite material.
• the "content of coffee residue and / or coffee powder” means the total content of coffee residue and coffee powder when the composite material contains coffee residue and / or coffee powder. When either the residue or the coffee powder is contained, it means the content of either of them.) If the content of the coffee residue and / or the coffee powder in the composite material is within the above range, coffee It is possible to obtain a composite material having better moldability, mechanical properties, appearance quality, etc., while suppressing the cost for compounding the residue and / or coffee powder with the resin.
• the content of coffee residue and / or coffee powder in the composite material is, for example, a cellulose fiber that is not derived from coffee residue and is not derived from coffee powder (also referred to as coffee residue and cellulose fiber not derived from coffee powder). In the non-form form, it can be grasped by measuring the cellulose fiber described later.
• the lower limit of the content of coffee residue and / or coffee powder in the composite material is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 25% by mass or more.
• the upper limit of the content of coffee residue and / or coffee powder in the composite material is preferably 70% by mass or less, more preferably 65% by mass or less, still more preferably 55% by mass or less.
• the composite material of the present invention contains monosaccharides.
• containing monosaccharides means that a monosaccharide is detected by the [determination of monosaccharide] method described in Examples described later.
• monosaccharides include mannose, glucose, galactose and the like. Further, the monosaccharide may be generated by positively decomposing the components of the coffee residue, or may be added separately.
• the kneading is carried out in the presence of water to promote the hydrolysis of the polysaccharide component contained in the coffee residue and / or the coffee powder.
• the content of the monosaccharide is not particularly limited, but is preferably 0.001 to 5% by mass, more preferably 0.002 to 4% by mass, and 0.003 to 3% by mass in the composite material. Is more preferable.
• the moldability can be further improved while maintaining the mechanical properties of the composite material.
• the content of monosaccharides in the composite material can be grasped by, for example, extracting the crushed composite material with water and measuring the components in the water using high performance liquid chromatography (HPLC) / differential refractometer detector or the like. ..
• the thermoplastic resin is a resin that serves as a matrix of the composite material.
• the thermoplastic resin preferably contains a polyolefin resin.
• the proportion of the polyolefin resin in the thermoplastic resin is preferably 50% by mass or more, preferably 70% by mass or more, preferably 80% by mass or more, and 90% by mass. It is also preferable to make the above. It is also preferable that the thermoplastic resin is made of a polyolefin resin.
• thermoplastic resin instead of the polyolefin resin, or in addition to the polyolefin resin, a polyvinyl chloride resin, an acrylonitrile-butadiene-styrene copolymer resin (ABS resin), an acrylonitrile-styrene copolymer resin (AS resin), Polypolymer resin (nylon), polyethylene terephthalate resin, polybutylene terephthalate resin, thermoplastic resin such as polystyrene resin, 3-hydroxybutyrate-co-3-hydroxyhexanoate polymer resin (PHBH), polybutylene succinate resin, It is also preferable to use a thermoplastic biodegradable resin such as a polylactic acid resin.
• thermoplastic resin constituting the composite material of the present invention one or more of these resins can be used. Of these, it is preferable to contain a polyolefin resin.
• a polyolefin resin used as the matrix resin will be mainly described. Unless otherwise specified, the description regarding the polyolefin resin described below also applies to the case where a thermoplastic resin other than the "polyolefin resin" is used.
• polyethylene resin or a polypropylene resin is preferable, or a mixture (blended resin) of a polyethylene resin and a polypropylene resin is also preferable.
• An ethylene-based copolymer (copolymer containing ethylene as a constituent) such as an ethylene-propylene copolymer and a resin such as polybutene are also preferable as the polyolefin resin used for the composite material.
• the polyolefin resin constituting the composite material is preferably a polyethylene resin and / or a polypropylene resin, and more preferably a polypropylene resin.
• the polyethylene include low density polyethylene (LDPE) and high density polyethylene (HDPE).
• LDPE low density polyethylene
• HDPE high density polyethylene
• the low density polyethylene has a density means the polyethylene of less than 880 kg / m 3 or more 940 kg / m 3.
• the high-density polyethylene means polyethylene having a density higher than that of the low-density polyethylene.
• the low-density polyethylene may be a so-called “low-density polyethylene” or “ultra-low-density polyethylene” having a long-chain branch, and is a linear low-density polyethylene obtained by copolymerizing ethylene with a small amount of ⁇ -olefin monomer.
• LLDPE low-density polyethylene
• the polyolefin resin may be acid-modified with an unsaturated carboxylic acid or a derivative thereof, which is usually used.
• a polyolefin resin that has not been acid-modified and an acid-modified polyolefin resin may be used in combination. It may contain a silane-modified polyolefin resin.
• polypropylene it is preferable to use it in combination with an acid-modified polypropylene resin.
• acid-modified polypropylene resin maleic acid-modified polypropylene resin is particularly preferable.
• the polyolefin resin constituting the composite material of the present invention may contain a trace amount of carbonyl group.
• carbonyl groups appears to enhance the adhesiveness of the composite.
• the presence of such a carbonyl group can be derived from, for example, oxidation of the polyolefin resin itself or a raw material, and the carbonyl group is contained in the polyolefin resin component of the polyethylene laminated paper having the polyolefin thin film layer and the aluminum thin film layer. There may be.
• the polyolefin resin has a low melt softening temperature, if the polyolefin resin is used, the coffee residue and / or coffee powder contained in the composite material can be melt-kneaded without being exposed to a high temperature, and can be molded. Therefore, it is possible to prevent or reduce deterioration, significant decomposition, and carbonization of coffee residue and / or coffee powder due to high temperature.
• the above-mentioned polyolefin resin has a low melt softening temperature
• the polyolefin resin when used, when the composite material contains cellulose fibers as described later, the contained cellulose fibers can be melt-kneaded without being exposed to a high temperature. It becomes possible to mold. Therefore, it is possible to prevent or reduce the deterioration of the cellulose fiber due to high temperature.
• the composite material contains resin particles as described later, if a polyolefin resin is used, exposure of the resin particles to a high temperature can be avoided, and the original mechanical properties of the resin particles can be sufficiently expressed. Become.
• the resin particles are polyester-based resins such as polyethylene terephthalate and polybutylene terephthalate
• these resins when these resins are exposed to a high temperature such as softening and melting, if the prior drying is insufficient, these resins may be used. Deterioration due to hydrolysis may be accelerated.
• the composite material can be kneaded and molded without being exposed to high temperatures, the above deterioration can be suppressed. As a result, the burden of moisture management on the material before melt-kneading is reduced.
• the content of the polyolefin resin in the composite material is not particularly limited as long as the content is such that the composite is integrated.
• 10 to 80% by mass of the composite material is preferably a polyolefin resin, and more preferably 15 to 70% by mass is a polyolefin resin. More preferably, it is 20 to 60% by mass.
• the polyolefin resin contains a polypropylene resin (preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, still more preferably 80% by mass or more of the polyolefin resin. Is a polypropylene resin).
• the polyolefin resin contains low density polyethylene (preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, still more preferably 80% by mass or more of the polyolefin resin. It is preferable that the mass% or more is low density polyethylene).
• Another form of the composite material of the present invention is a form in which the polyolefin resin contains a low-density polyethylene resin in an amount of preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less of the polyolefin resin. ..
• Yet another form of the composite material of the present invention is a form in which the polyolefin resin contains a modified polyethylene resin in an amount of preferably 30% by mass or less, more preferably 20% by mass or less of the polyolefin resin.
• the polyolefin resin contains low-density polyethylene and contains resin particles described later, and the resin particles contain polyethylene terephthalate (preferably 50% by mass or more of the resin particles, more preferably 60% by mass or more, still more preferably. 70% by mass or more, more preferably 80% by mass or more is polyethylene terephthalate), which is also preferable as the form of the composite material of the present invention.
• polyethylene terephthalate preferably 50% by mass or more of the resin particles, more preferably 60% by mass or more, still more preferably. 70% by mass or more, more preferably 80% by mass or more is polyethylene terephthalate
• the content in the composite material can be determined based on the thermoxylene-dissolved mass ratio of the composite material.
• the mass ratio of hot xylene dissolved- is determined as follows. In accordance with the cross-linking degree measurement of the automobile electric wire standard JASOD618, 0.1 to 1 g of a composite molded sheet is cut out as a sample, and this sample is wrapped in 400 mesh stainless mesh and immersed in 100 ml of xylene at a predetermined temperature for 24 hours. do. The sample is then pulled up and then dried in vacuum at 80 ° C. for 24 hours.
• the thermal xylene dissolved mass ratio G (%) is calculated from the following formula.
• G ⁇ (W0-W) / W0 ⁇ x 100
• W0 Mass of composite material before immersion in hot xylene
• W Mass of composite material after immersion in hot xylene and dry removal of xylene
• Ga Mass of composite material before immersion in hot xylene
• Gb Mass of composite material after immersion in hot xylene and dry removal of xylene
• Ga mass ratio of the composite material dissolved in hot xylene at 138 ° C
• Gb The mass ratio dissolved in hot xylene at 105 ° C.
• Ga is the mass ratio of polyolefin (%)
• Ga-Gb is the mass ratio of polypropylene (%)
• Gb is polyethylene. Corresponds to the mass ratio (%).
• Ga ⁇ (W0-Wa) / W0 ⁇ x 100
• Gb ⁇ (W0-Wb) / W0 ⁇ ⁇ 100 W0: Mass of composite material before immersion in hot xylene
• Wa Mass of composite material after immersion in hot xylene at 138 ° C and drying and removal of xylene
• Wb Mass of composite material after immersion in hot xylene at 105 ° C, then dry xylene The mass of the composite after removal.
• Gc the thermal xylene insoluble mass ratio at 138 ° C.
• Gc is the total amount of the composite material excluding the polyolefin resin.
• the amount of resin particles can be calculated from the difference between this amount Gc and the amount of cellulose fibers.
• Gc ⁇ Wa / W0 ⁇ x 100
• the matrix resin may contain, for example, a resin compatible with the polyolefin resin as long as the effects of the present invention are not impaired.
• a resin a resin having a melting point and a softening temperature close to those of a polyolefin resin is preferable.
• polystyrene resin or polystyrene-based copolymer copolymer containing a styrene component
• the composite material of the present invention is excellent in moldability while containing coffee residue and / or coffee powder, and is also excellent in mechanical properties such as impact resistance. The reason is not clear, but it is considered that monosaccharides act as a lubricating component during processing, while acting as a binding component of coffee residue and / or coffee powder in a cooled composite material.
• One form of the resin composite material of the present invention may be a form in which resin particles are further dispersed in addition to coffee residue and / or coffee powder in a polyolefin resin.
• These "resin particles” are a type of resin different from the resin (matrix resin) (for example, polyolefin resin) that constitutes the matrix.
• the resin has a melting point higher than the melting point of the polyolefin resin by 10 ° C. or more (a resin of a type different from the polyolefin resin).
• the maximum diameter of the resin particles is preferably 10 ⁇ m or more.
• one form of the resin composite material of the present invention is a resin composite material in which coffee residue and / or coffee powder and the above resin particles are dispersed in a polyolefin resin, and further contains monosaccharides. good.
• the resin particles can be granular lumps of various shapes.
• the fact that the matrix resin and the resin particles are composed of "different types of resins" can be known by visually recognizing the contours of the resin particles by observing with an optical microscope or the like, as will be described later.
• the maximum diameter of the resin particles is 10 ⁇ m or more.
• the melting point of the resin particles is preferably 15 ° C. or higher, more preferably 20 ° C. or higher, higher than the melting point of the matrix resin.
• the "melting point of the matrix resin” is the melting point of the resin having the lowest melting point when the matrix resin is a blend of two or more kinds of resins.
• the composite material of the present invention preferably has a form in which the above resin particles are dispersed. As described above, by forming the composite material into a form containing the resin particles, the moldability of the composite material can be further enhanced, and the desired mechanical physical properties can also be further enhanced.
• the resin particles can be, for example, in the form of scales, small sheets, or granules and dispersed in the composite material, and when the resin particles are in the form of scales or small sheets, they can be folded. They may be dispersed in a bent, curved, or winding state (collectively referred to as a "bent structure").
• the resin constituting the resin particles is preferably a resin that is incompatible with the matrix resin (for example, polyolefin resin).
• “Incompatible” means that different types of resins (polymers) are not uniformly mixed at the molecular level by simple melt-kneading or the like. In general, in a composition or a molded product containing a plurality of resins that are incompatible with each other, phase separation is observed and a sea-island structure may be formed.
• the resin particles contained in the composite material of the present invention preferably have a maximum diameter of 10 ⁇ m or more.
• the maximum diameter is 10 ⁇ m or more, the mechanical characteristics, particularly the impact resistance characteristics can be further improved.
• the maximum diameter of the resin particles is preferably 20 ⁇ m or more, more preferably 50 ⁇ m or more, more preferably 100 ⁇ m or more, still more preferably 200 ⁇ m or more. .. Further, the maximum diameter is preferably 400 ⁇ m or more, and preferably 600 ⁇ m or more.
• the maximum diameter of the resin particles is preferably less than 4 mm from the viewpoint of moldability.
• the resin particles preferably have an aspect ratio (value of the ratio of the maximum diameter to the minimum diameter [maximum diameter / minimum diameter]) of 5 or more, more preferably 10 or more, and 20 or more. More preferably, it is more preferably 30 or more.
• the resin particles contained in the composite material of the present invention preferably have a bent structure (usually an irregular bent structure) from the viewpoint of further enhancing mechanical properties. Mechanical properties can be further enhanced by the anisotropy due to the bent structure and the anchor effect.
• the maximum diameter of the resin particles being X ⁇ m or more means the following. That is, the cross section of the composite material or its press sheet is observed with an optical microscope or the like as an observation surface, and the resin particles are observed in order of increasing area on the observation surface (that is, in a plan view from the observation surface). 10 are selected, and the maximum diameters of the 10 individual resin particles are measured to obtain the average value of the maximum diameters of the 10 resin particles. The observation surface is changed, and the average value of the maximum diameters of the 10 resin particles is obtained in the same manner on the observation surface. This is repeated to obtain the average value of the maximum diameters of the 10 resin particles for each of the three different observation surfaces.
• the average value of the obtained three average values is X ⁇ m or more
• it is determined that the maximum diameter of the resin particles is X ⁇ m or more. If the number of resin particles does not satisfy 10 on one observation surface, the observation surface is increased by 1 until the number of resin particles satisfies 10.
• the plurality of observed observation surfaces are collectively positioned as one observation surface for obtaining the average value of the maximum diameters of the above 10 resin particles.
• the aspect ratio of the resin particles being Y or more means the following. That is, the cross section of the composite material or its press sheet is observed with an optical microscope or the like as an observation surface, and 10 resin particles are selected in the order in which the area is recognized by visual observation on the observation surface, and 10 individual particles are selected.
• the aspect ratio of the resin particles (maximum diameter / minimum diameter of each resin particle) is measured to obtain the average value of the aspect ratios of the 10 resin particles.
• the observation surface is changed, and the average value of the aspect ratios of the 10 resin particles is obtained in the same manner on the observation surface. Similarly, for each of the three different observation surfaces, the average value of the aspect ratios of the 10 resin particles is obtained. When the average value of the obtained three average values is Y or more, it is determined that the aspect ratio of the resin particles is Y or more. If the number of resin particles does not satisfy 10 on one observation surface, the observation surface is increased by 1 until the number of resin particles satisfies 10.
• the plurality of observed observation surfaces are collectively positioned as one observation surface for obtaining the average value of the aspect ratios of the above 10 resin particles.
• the maximum diameter of the resin particles being less than Z ⁇ m means the following. That is, the cross section of the composite material or its press sheet is observed with an optical microscope or the like as an observation surface, and 10 resin particles are selected in the order in which the area is recognized by visual observation on the observation surface, and 10 individual resin particles are selected. The maximum diameter of the resin particles is measured to obtain the average value of the maximum diameters of the 10 resin particles. The observation surface is changed, and the average value of the maximum diameters of the 10 resin particles is obtained in the same manner on the observation surface.
• the average value of the maximum diameters of the 10 resin particles is obtained.
• the average value of the obtained three average values is less than Z ⁇ m, it is determined that the maximum diameter of the resin particles is less than Z ⁇ m. If the number of resin particles does not satisfy 10 on one observation surface, the observation surface is increased by 1 until the number of resin particles satisfies 10. In this case, the plurality of observed observation surfaces are collectively positioned as one observation surface for obtaining the average value of the maximum diameters of the above 10 resin particles.
• the “maximum diameter” of the individual resin particles means the diameter of the smallest circle inscribed with the resin particles in a plan view from the observation surface. That is, it means the diameter of the circle having the smallest diameter inscribed in the circle while containing the resin particles inside.
• the "smallest circle inscribed with the resin particles” is a circle that passes through at least two points on the outer circumference (contour) of the resin particles when the resin particles are viewed in a plan view from the observation surface. It means the smallest circle among the circles that enclose the outer circumference of the resin particles.
• the "minimum diameter" of each resin particle is the thickness of the thinnest portion of the resin particle.
• the thickness of the resin particles depends on the thickness of the sheet-shaped resin raw material.
• the minimum diameter of the resin particles is the thickness of the resin particles.
• the resin particles derived from the sheet-shaped resin raw material are bent to form an overlapping portion (for example, a laminated structure), one layer constituting the overlapping portion (for example, one layer constituting the laminated structure) is formed. ) Is the minimum diameter of the resin particles.
• the sheet-shaped resin raw material is a laminated sheet and the resin particles are formed in a state where the layers constituting the laminated sheet are in close contact with each other, the thickness of the entire laminated structure is the minimum diameter of the resin particles.
• the press pressure at the time of preparing the press sheet can be, for example, about 4.2 MPa.
• the resin of the resin particles may contain a crystalline resin, an amorphous resin, or both of them.
• the crystalline resin As the crystalline resin, a resin having a melting point higher than the melting point of the matrix resin (for example, polyolefin resin) by 10 ° C. or more is preferable. At the time of kneading, the target resin particles can be dispersed in the matrix resin, and the mechanical properties of the composite material can be effectively enhanced. From this point of view, the crystalline resin is preferably a resin having a melting point higher than the melting point of the matrix resin by 20 ° C. or more, more preferably a resin having a melting point higher than the melting point of the matrix resin by 30 ° C. or more, and further preferably a matrix resin. It is a resin having a melting point higher than the melting point of 50 ° C. or more.
• the crystalline resin is preferably a resin having a melting point of 170 ° C. or higher and / or a resin showing an endothermic peak at 170 ° C. or higher and 350 ° C. or lower by differential scanning calorimetry (DSC). Showing an endothermic peak at 170 ° C. or higher and 350 ° C. or lower means that when a plurality of endothermic peaks are detected, at least one endothermic peak is 170 ° C. or higher and 350 ° C. or lower.
• the polymer constituting such a crystalline resin include polyethylene terephthalate, polybutylene terephthalate, polyamide, ethylene-vinyl alcohol copolymer and the like.
• the resin particles include at least one of polyethylene terephthalate, polybutylene terephthalate, and polyamide (preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, still more preferable of the resin particles. 80% by mass or more is at least one of the above). Further, it contains polyethylene terephthalate and / or polyamide (preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, still more preferably 80% by mass or more of the resin particles. Alternatively, it is more preferably polyamide, in other words, the resin particles contain a total of the above mass% or more of a polymer selected from polyethylene terephthalate and polyamide).
• polyethylene terephthalate (preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, still more preferably 80% by mass or more of the resin particles being polyethylene terephthalate).
• the polymer constituting the resin particles is preferably at least one of polyethylene terephthalate, polybutylene terephthalate and polyamide, preferably polyethylene terephthalate and / or polyamide, and particularly preferably polyethylene terephthalate.
• Polyethylene terephthalate has a melting point in the vicinity of 250 to 260 ° C., and has an endothermic peak due to melting in the vicinity of 250 to 260 ° C. by differential scanning calorimetry (DSC).
• the resin particles when the resin particles are polyethylene terephthalate, the resin particles have a melting point in the vicinity of 250 to 260 ° C., and have an endothermic peak due to melting in the vicinity of 250 to 260 ° C. in differential scanning calorimetry (DSC).
• DSC differential scanning calorimetry
• a resin having a glass transition temperature of 70 ° C. or higher is preferable.
• the polymer constituting such a resin include polycarbonate and polyvinyl chloride.
• the resin particles contain polycarbonate and / or polyvinyl chloride (preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, still more preferably 80% by mass or more of the resin particles. / Or it is polyvinyl chloride, in other words, the resin particles contain a total of a polymer selected from polycarbonate and polyvinyl chloride in an amount of the above mass% or more). Further, the polymer constituting the resin particles is preferably at least one of polycarbonate and polyvinyl chloride.
• the resin particles may be in the form in which the above-mentioned plurality of resins are laminated. Further, the resin particles may have a thin film layer of alnium. That is, the aluminum in close contact with the resin of the resin particles constitutes the resin particles in the present invention, and is not regarded as the aluminum dispersoid described later.
• the content of the resin particles is preferably 0.1% by mass or more and 60% by mass or less in the composite material.
• the mechanical properties can be further enhanced.
• the content of the resin particles in the composite material is more preferably 0.3% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, still more preferably. 2% by mass or more.
• the moldability can be further improved.
• the content of the resin particles in the composite material is more preferably 50% by mass or less, further preferably 40% by mass or less, still more preferably 30% by mass or less, still more preferably 20% by mass or less, still more preferable. Is 12% by mass or less, and preferably 10% by mass or less.
• the amount of cellulose fibers obtained by thermal analysis is further subtracted from the amount of insoluble matter obtained by immersing the composite material in thermal xylene at a predetermined temperature and dissolving the polyolefin resin. It can be decided by. If the temperature of the hot xylene is, for example, 138 ° C., polyethylene terephthalate, polyamide resin and the like are not dissolved, and only the polyolefin resin is dissolved.
• the resin composite material of the present invention contains cellulose fibers derived from coffee residue and / or coffee powder (in other words, cellulose fibers derived from vegetable powder), and separately blended cellulose fibers not derived from coffee residue and coffee powder. Even if it contains fibers (in other words, cellulose fibers not derived from vegetable powder.
• cellulose fiber means cellulose fibers not derived from vegetable powder unless otherwise specified). good.
• Mechanical properties can be further enhanced by forming the composite material in a form in which coffee residue and / or coffee powder and cellulose fibers are dispersed and monosaccharides are contained. For example, the impact resistance, flexural modulus, and moldability can be improved to a desired high level in a well-balanced manner.
• the above-mentioned "cellulose fiber not derived from coffee residue and coffee powder” (in other words, cellulose fiber not derived from vegetable powder) is distinguished from the above-mentioned “powder containing polysaccharide”. That is, "cellulose fibers not derived from coffee residue and / or coffee powder” (in other words, cellulose fibers not derived from vegetable powder) are not included in "powder containing polysaccharides”.
• the content of cellulose fibers in the composite material of the present invention is preferably 0.1% by mass or more and 60% by mass or less. By setting the content of the cellulose fiber to 0.1% by mass or more, the mechanical properties can be further enhanced.
• the content of the cellulose fiber in the composite material is more preferably 1% by mass or more, further preferably 5% by mass or more, still more preferably 8% by mass or more, still more preferably 10% by mass or more, and 15% by mass. It is also preferable to set it to% or more. Further, by setting the content of the cellulose fiber to 60% by mass or less, the moldability can be further improved. Further, by setting the content of the cellulose fibers to 60% by mass or less, a composite material in which the cellulose fibers are uniformly dispersed can be stably obtained by melt-kneading, and the water absorption of the obtained composite material can be suppressed.
• the content of the cellulose fiber in the composite material is more preferably 50% by mass or less, further preferably 40% by mass or less, still more preferably 30% by mass or less.
• the cellulose fibers dispersed in the composite material preferably contain cellulose fibers having a fiber length of 0.3 mm or more.
• cellulose fibers having a fiber length of 0.3 mm or more By containing cellulose fibers having a fiber length of 0.3 mm or more, mechanical properties such as impact resistance and tensile strength can be further improved. From this point of view, it is preferable to contain cellulose fibers having a fiber length of 0.5 mm or more, more preferably a fiber length of 0.8 mm or more, and further preferably a fiber length of 1 mm or more.
• the cellulose fibers dispersed in the composite material preferably have a length-weighted average fiber length of 0.3 mm or more.
• the mechanical properties of the composite material or its molded product can be further improved.
• the length-weighted average fiber length of the cellulose fibers is more preferably 0.6 mm or more.
• the length-weighted average fiber length of the cellulose fibers in the composite material is usually 1.3 mm or less.
• the length-weighted average fiber length is the pulp defined in ISO 16065 2001 (JIS P8226 2006) with respect to the dissolution residue (insoluble matter) of the composite material when the composite material is immersed in a soluble solvent of the resin component. It is determined by the fiber length measurement method by the optical automatic analysis method.
• the length-weighted average fiber length can be determined by the same measurement method for the dissolution residue (insoluble matter) in hot xylene (130 to 150 ° C.).
• the length-weighted average fiber length is the sum of the squares of the fiber lengths of each fiber used for measurement divided by the total of the measured fiber lengths.
• this length-weighted average fiber length are the influence of the fiber length of the fiber having a longer fiber length than the number average fiber length, which is a simple average of the fiber length, and the probability density of the fiber longer than the number average fiber length. The impact will be greater.
• the total content of the cellulose fibers, coffee residue and / or coffee powder in the composite material is preferably 2 to 90% by mass.
• the mechanical properties can be further enhanced.
• the total content of the cellulose fibers, the coffee residue and / or the coffee powder in the composite material is more preferably 5% by mass or more, further preferably 10% by mass or more, and particularly preferably 15% by mass or more.
• the moldability can be further improved.
• the total content of the cellulose fibers and the coffee residue and / or coffee powder in the composite material is more preferably 80% by mass or less, further preferably 75% by mass or less, still more preferably 65% by mass or less, and particularly preferably 50. It is less than mass%.
• the composite material of the present invention contains cellulose fibers, resin particles, coffee residue and / or coffee powder
• the total content of the cellulose fibers, resin particles, coffee residue and / or coffee powder in the composite material is 2. It is preferably about 80% by mass.
• the mechanical properties can be further enhanced by setting the total content of the cellulose fibers, the resin particles, the coffee residue and / or the coffee powder in the composite material to 2% by mass or more.
• the total content of the cellulose fibers, the resin particles, the coffee residue and / or the coffee powder in the composite material is more preferably 5% by mass or more, further preferably 10% by mass or more, and particularly preferably 15% by mass or more. ..
• the moldability can be further improved.
• the total content of the cellulose fibers, the resin particles, the coffee residue and / or the coffee powder in the composite material is more preferably 60% by mass or less, still more preferably 50% by mass or less, still more preferably 40% by mass or less. , Particularly preferably 35% by mass or less.
• the total content (% by mass) of the cellulose fibers derived from coffee residue and / or coffee powder and the cellulose fibers not derived from coffee residue and coffee powder contained in the composite material of the present invention is 100% by mass of the composite material. It is preferably 10 to 50% by mass, and preferably 20 to 40% by mass.
• the total content (% by mass) of the cellulose fibers derived from the coffee residue and / or the coffee powder and the cellulose fibers not derived from the coffee residue and the coffee powder contained in the composite material of the present invention is calculated as follows. It can be determined by adopting the value obtained by weight analysis. ⁇ Method of determining the total content of cellulose fibers (effective mass ratio of cellulose)> A composite sample (10 mg) previously dried at 80 ° C. for 1 hour in an air atmosphere is subjected to thermal weight analysis (TGA) from 23 ° C. to 400 ° C. at a heating rate of + 10 ° C./min in a nitrogen atmosphere.
• TGA thermal weight analysis
• the content of cellulose fibers (also referred to as mass% or effective mass ratio of cellulose) is calculated by the following [Formula I].
• the mass% calculated by the above [Formula I] is regarded as the content of the cellulose fibers contained in the composite material.
• the mass% calculated by [Formula I] is used as the "cellulose fiber amount" for grasping the content of the cellulose fiber, but the amount of the cellulose fiber and the composite material thus obtained are used.
• the relationship between mechanical properties is highly relevant.
• thermogravimetric analysis of the cellulose fibers about 50 to 55% by mass, typically 53% by mass, of the coffee residue disappears at 200 ° C to 380 ° C where the cellulose fibers disappear. That is, when the composite material does not contain cellulose fibers and contains coffee residue, 100/53 times the amount of disappearance (200 to 380 ° C. reduced mass%) by the thermogravimetric analysis is converted into the content of coffee residue. ..
• the coffee powder also shows the same tendency of thermogravimetric analysis as the coffee residue, and is converted in the same manner.
• the form of the composite material of the present invention may be one in which coffee residue and / or coffee powder and resin particles are dispersed, and a cellulose fiber having a fiber length of 0.3 mm or more and a monosaccharide may be contained. It is possible to achieve a high degree of compatibility between the moldability of the composite material and the mechanical properties.
• the composite material of the present invention is formed by dispersing aluminum in a polyolefin resin.
• the content of aluminum (hereinafter, also referred to as aluminum dispersoid) in the composite material is preferably 0.1% by mass or more and 40% by mass or less.
• aluminum dispersoid the thermal conductivity, visual recognition, and light shielding property of the composite material are improved.
• the composite material of the present invention containing resin particles by setting the aluminum content within this range, the workability of the composite material can be further improved, and lumps of aluminum are less likely to occur during processing of the composite material. Become.
• This aluminum can be derived from the aluminum thin film layer of the polyethylene-laminated paper as a raw material.
• the aluminum thin film layer of the polyethylene-laminated paper does not melt during melt-kneading, but is gradually sheared and made finer by the shearing force during kneading.
• the composite material of the present invention preferably has an aluminum content of 0.5% by mass or more and 30% by mass or less, and further. It is preferably 1% by mass or more and 20% by mass or less.
• the composite material of the present invention preferably contains an aluminum dispersoid having a maximum XY length of 0.005 mm or more. It is preferable that the ratio of the number of aluminum dispersoids having a maximum XY length of 3 mm or more to the number of aluminum dispersoids having a maximum XY length of 0.005 mm or more is less than 10%. By setting this ratio to less than 10%, the workability of the composite material can be further improved, and lumps of aluminum are less likely to occur during the processing of the composite material.
• the maximum XY length is determined by observing the surface of the composite material.
• a straight line is randomly drawn with respect to the aluminum dispersoid in a specific direction (X-axis direction), and the distance connecting the two intersections where the straight line and the outer periphery of the aluminum dispersoid intersect is maximized.
• the distance (maximum length on the X-axis) is measured, and a straight line is drawn in the direction perpendicular to the specific direction (Y-axis direction), and the distance connecting the two intersections where this straight line and the outer circumference of the aluminum dispersoid intersect.
• the distance (maximum length on the Y-axis) at which is maximum is measured, and the longer of the maximum length on the X-axis and the maximum length on the Y-axis is defined as the maximum length of XY.
• the maximum XY length can be determined by using image analysis software as described in Examples described later.
• the average of the maximum XY lengths of the individual aluminum dispersoids is preferably 0.02 to 2 mm, preferably 0.04 to 1 mm. More preferred.
• the average of the maximum XY lengths is the average of the maximum XY lengths measured by using image analysis software, as will be described later.
• At least a part of the above-mentioned coffee residue and / or coffee powder, monosaccharide, matrix resin, resin particles, cellulose fiber and the like that can constitute the composite material of the present invention can be derived from a recycled material. .. Further, at least a part of aluminum that can be contained in the composite material of the present invention can be derived from a recycled material. By using the recycled material, the manufacturing cost of the composite material can be suppressed.
• the recycled material examples include coffee residue and / or coffee powder itself, and portion capsules containing coffee residue and / or coffee powder.
• Potion capsules may also contain monosaccharides in addition to coffee residues and / or coffee powder.
• the container constituting the portion capsule generally includes a lid, a container body, a structure (for example, a partition plate, a filter, etc.) arranged in the container body, and a resin such as a polyolefin resin as a material constituting these. Contains components and / or aluminum and the like.
• Potion capsules may contain water.
• Beverage packs and / or food packs comprising.
• the term "thin film” means a film (sheet) having a thickness of preferably 2 mm or less, more preferably 1 mm or less in a dry state.
• the "thin film” may have a thickness of 500 ⁇ m or less, 200 ⁇ m or less, or 100 ⁇ m or less in a dry state.
• cellulose fibers used paper, recycled resin, or the like can be used as a source of cellulose fibers.
• the above-mentioned beverage packs and food packs may be unused, used recovered products, or waste paper such as polyolefin laminated paper discharged in the manufacturing process of beverage packs and food packs. However, these may be used in combination.
• a polyolefin thin film piece to which cellulose fibers are attached obtained by treating the above-mentioned laminated paper and / or beverage / food pack with a pulper and peeling off the paper portion to remove the paper portion.
• the thin film pieces obtained by treating polyethylene laminated paper having an aluminum thin film layer with a pulper are also referred to as "cellulose fiber aluminum-attached polyolefin thin film pieces"). It can also be used as a recycled material. Further, a laminate having a resin sheet different from the polyolefin resin (resin sheet corresponding to the resin particles) and a polyolefin resin sheet and a resin sheet different from the polyolefin resin (resin sheet corresponding to the resin particles) is recycled. It can be used as a material. Further, a laminate having a structure in which an aluminum thin film sheet is laminated on this laminate can also be used as a recycled material.
• crushed products and the like can also be used.
• a packaging material such as a food pack having a laminated structure having a polyolefin resin sheet and a resin sheet different from the polyolefin resin (resin sheet corresponding to resin particles) can also be used as a recycled material.
• the ratio of the recycled material-derived component to the composite material of the present invention is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, still more preferably 40% by mass or more, based on the dry mass. Is.
• the composite material of the present invention having the desired physical properties can be obtained by melt-kneading described later.
• the composite material of the present invention may contain an inorganic material other than the above-mentioned aluminum dispersoid. Bending elasticity, impact resistance, and flame retardancy can be improved by containing an inorganic material.
• the inorganic material include calcium carbonate, talc, clay, magnesium oxide, aluminum hydroxide, magnesium hydroxide, titanium oxide and the like.
• a preferred embodiment of the present invention contains 5 to 70% by mass of coffee residue and / or coffee powder, 0.001 to 5% by mass of monosaccharides, and 10 to 80% by mass of polyolefin resin in 100% by mass of the composite material.
• Another preferred embodiment of the present invention is not derived from coffee residue and / or coffee powder 5 to 70% by weight, monosaccharide 0.001 to 5% by weight, and coffee residue and coffee powder in 100% by weight of the composite material. Contains 0.1-40% by mass of cellulose fibers and 10-80% by mass of polyolefin resin.
• Yet another preferred embodiment of the present invention is not derived from coffee residue and / or coffee powder 5 to 70% by weight, monosaccharide 0.001 to 5% by weight, coffee residue and coffee powder in 100% by weight of the composite material. It contains 0.1 to 40% by mass of cellulose fibers, 0.1 to 10% by mass of resin particles, and 10 to 80% by mass of polyolefin resin.
• Another preferred embodiment of the present invention is not derived from coffee residue and / or coffee powder 5 to 70% by mass, monosaccharide 0.001 to 5% by mass, coffee residue and coffee powder in 100% by mass of the composite material. It contains 0.1 to 40% by mass of cellulose fibers, 0.1 to 10% by mass of resin particles, 0.1 to 3% by mass of aluminum, and 10 to 80% by mass of polyolefin resin.
• the composite material of the present invention may contain a flame retardant, an antioxidant, a stabilizer, a weather resistant agent, a compatibilizer, an impact improver, a modifier, etc., depending on the purpose.
• a flame retardant an antioxidant, a stabilizer, a weather resistant agent, a compatibilizer, an impact improver, a modifier, etc.
• an oil component and various additives can be included. Examples thereof include paraffin, modified polyethylene wax, stearate, hydroxystearate, vinylidene fluoride-based copolymer such as vinylidene fluoride-hexafluoropropylene copolymer, and organically modified siloxane.
• the composite material of the present invention can contain carbon black, various pigments, and dyes.
• the composite material of the present invention may also contain a metallic luster-based coloring material.
• a conductive component such as conductive carbon black can be contained.
• the composite material of the present invention can contain a heat conductive imparting component.
• the composite material of the present invention may be crosslinked.
• the cross-linking agent include organic peroxides, and specific examples thereof include dicumyl peroxide.
• the composite material of the present invention may be in the form of being crosslinked by a silane crosslinking method.
• the composite material of the present invention preferably has a melt flow rate (MFR) of 0.1 to 100 g / 10 min at a temperature of 230 ° C. and a load of 5 kgf.
• MFR melt flow rate
• the shape of the composite material of the present invention is not particularly limited.
• the composite material of the present invention may be pelletized, or the composite material of the present invention may be molded into a desired shape.
• the pellets are suitable as a material for forming a molded product (resin product).
• the composite material of the present invention is a modified masterbatch containing a polyolefin resin such as high-density polyethylene or polypropylene, containing coffee residue and / or coffee powder, and monosaccharides, and further containing resin particles and cellulose fibers. It can also be used.
• the composite material of the present invention preferably has a water content of less than 1% by mass.
• the composite material of the present invention is not limited to that obtained by the following method.
• the method for producing a composite material of the present invention at least the polyolefin resin, the coffee residue and / or the coffee powder, and the monosaccharide are melted by the polyolefin resin (that is, equal to or higher than the melting point of the polyolefin resin), and the coffee residue and / or Alternatively, it comprises a step of melt-kneading the coffee powder and the monosaccharide at a temperature at which carbonization does not proceed to obtain a resin composite material in which the coffee residue and / or the coffee powder is dispersed in the polyolefin resin and contains the monosaccharide.
• melt-kneading under the above temperature conditions deterioration of coffee residue and / or coffee powder and monosaccharides can be prevented.
• At least a polyolefin resin and coffee residue and / or coffee powder are melt-kneaded in the presence of water, and the polysaccharide component in the coffee residue and / or coffee powder is kneaded.
• the amount of water present at the time of kneading is 100 mass by mass of the coffee residue and / or the coffee powder (dry matter equivalent). 25 parts by mass or more is preferable, 50 parts by mass or more is more preferable, and 150 parts by mass or more is more preferable. From the viewpoint of manufacturability, the amount of water present at the time of kneading is preferably 1000 parts by mass or less with respect to 100 parts by mass of the coffee residue and / or coffee powder in terms of dry matter. 500 parts by mass or less is more preferable, and 300 parts by mass or less is further preferable.
• the source of water present at the time of kneading is not particularly limited.
• the water present at the time of kneading may be contained in the raw material or may be blended separately.
• the water content in the raw material may be any water content such that the total water content in the total of the raw materials is the water content with respect to the coffee residue and / or the coffee powder. It cannot be uniquely determined because it varies depending on the type, blending amount, etc. of the matrix resin, coffee residue and / or coffee powder used, but from the viewpoint of promoting hydrolysis, the temperature at the time of melt kneading is 175. It is preferably set to ° C. or higher, and more preferably set to 175 to 185 ° C.
• the melt-kneading time in the presence of water is preferably set to at least 30 seconds or more, preferably 1 minute or more. Further, although it depends on the kneading method, it is preferable that the time is such that the water sufficiently evaporates.
• a polyolefin resin, coffee residue and / or coffee powder, cellulose fibers, and a resin sheet for guiding the resin particles in the present invention, when simply referred to as "resin sheet", a matrix A sheet containing a resin different from the resin, preferably a sheet made of a resin different from the matrix resin) and a monosaccharide are melted by the polyolefin resin (that is, above the melting point of the polyolefin resin), and the coffee residue and /
• the coffee powder, the monosaccharides, and the cellulose fibers are melt-kneaded at a temperature at which the carbonization does not proceed at a temperature at which the resin sheet does not melt (that is, below the melting point of the resin of the resin sheet), and the coffee residue and / or the resin sheet is contained in the polyolefin resin.
• a resin composite material containing monosaccharides by dispersing coffee powder, cellulose fibers, and resin particles.
• the monosaccharide may be produced by promoting the hydrolysis of the polysaccharide component by performing melt-kneading in the presence of water.
• the resin constituting the resin sheet is the resin of the resin particles, and the preferred form thereof is as described above.
• the resin sheet becomes resin particles in the obtained composite material.
• the resin sheet may be used as it is and may be fragmented by melt-kneading into resin particles. Further, the resin sheet may be prepared as a cut product or a crushed product of a resin sheet having a certain size in advance, and then subjected to melt-kneading. In the method for producing a composite material of the present invention, it is preferable that the resin sheet is not positively melted when kneading under the above temperature conditions.
• a laminate having the polyolefin resin sheet and the resin sheet can be used as a common source of the polyolefin resin and the resin sheet.
• a polyolefin resin, the resin sheet, or the like that is not derived from the laminate may be blended.
• a polyolefin resin comprises at least a polyolefin resin, coffee residue and / or coffee powder, monosaccharides, and the resin particles whose size has been adjusted in advance. Melting and kneading at a melting temperature (that is, above the melting point of the polyolefin resin) and at a temperature at which carbonization of the coffee residue and / or coffee powder does not proceed and the resin particles do not melt (that is, below the melting point of the resin of the resin particles). Includes obtaining a resin composite material containing monosaccharides by dispersing coffee residue and / or coffee powder and resin particles in a polyolefin resin.
• the monosaccharide may be produced by promoting the hydrolysis of the polysaccharide component by performing melt-kneading in the presence of water.
• a material mainly composed of cellulose can be used as a raw material. Specifically, pulp, paper, used paper, paper dust, recycled pulp, paper sludge, laminated paper, waste paper of laminated paper, and a resin thin film to which cellulose fibers are attached, which is the residue after removing some paper from the laminated paper.
• other plant-derived cellulose fibers and the like can be mentioned.
• the above-mentioned paper and used paper may contain fillers (for example, kaolin, talc), sizing agents, etc., which are generally contained to enhance the whiteness of the paper.
• the sizing agent is added for the purpose of suppressing the permeability of a liquid such as ink to paper, preventing set-off and bleeding, and imparting a certain degree of water resistance.
• the main ones include rosin soap, alkyl ketene dimer, alkenyl succinic anhydride, polyvinyl alcohol and the like.
• the surface sizing agent include oxidized starch, a styrene / acrylic copolymer, and a styrene / methacrylic copolymer.
• various additives, ink components, lignin and the like may be contained in paper, used paper and the like.
• the laminated paper may contain a polyolefin resin, a cellulose fiber, a filler generally contained for enhancing the whiteness of the paper (for example, kaolin, talc), a sizing agent, and the like.
• the pulp includes mechanical pulp and chemical pulp, and the mechanical pulp contains lignin and impurities.
• chemical pulp contains almost no lignin, but may contain impurities other than lignin.
• polyolefin resin laminated paper and / or cellulose fiber-attached polyolefin thin film pieces can also be used.
• polyolefin resins, cellulose fibers, etc. that are not derived from these may be blended.
• an alnium thin film sheet can be mixed in the above melt kneading.
• the coffee residue and / or the coffee powder, the resin particles, and the aluminum are dispersed in the polyolefin resin, and a resin composite material containing a monosaccharide can be obtained.
• a laminate having the polyolefin resin sheet, the resin sheet, and the aluminum thin film sheet can be used as a supply source of the polyolefin resin, the resin sheet, and the aluminum thin film sheet.
• a polyolefin resin, the resin sheet, the aluminum thin film sheet, etc., which are not derived from the laminate may be blended.
• a polyolefin resin laminated paper having an aluminum thin film layer and / or a cellulose fiber aluminum-attached polyolefin thin film piece can also be used as a common source of the polyolefin resin and the aluminum thin film sheet.
• a polyolefin resin laminated paper having an aluminum thin film layer and / or a cellulose fiber aluminum-attached polyolefin thin film piece can also be used as a common source of the polyolefin resin and the aluminum thin film sheet.
• polyolefin resin laminated paper having an aluminum thin film layer and / or a cellulose fiber aluminum-attached polyolefin thin film piece can also be used as a common source of the polyolefin resin and the aluminum thin film sheet.
• polyolefin resin laminated paper having an aluminum thin film layer and / or a cellulose fiber aluminum-attached polyolefin thin film piece can also be used as a common source of the polyolefin resin and the aluminum thin film sheet.
• the above-mentioned recycled material can be used as a common source of polyolefin resin, coffee residue and / or coffee powder, cellulose fiber, resin sheet for guiding resin particles, monosaccharide, aluminum thin film sheet and the like.
• melt kneading can also be carried out by blending water.
• the formulation of water promotes the production of monosaccharides by hydrolysis, while suppressing the carbonization (dehydration reaction) of sugars. Further, the blending of water affects the properties and physical properties of the composite material, and contributes to the production of the target composite material in which resin particles having a desired shape are uniformly dispersed, for example.
• the resin of the resin sheet is melt-kneaded at a temperature at which the resin of the resin sheet does not melt even when water is mixed, the effect on the physical properties of the resin itself constituting the resin sheet or the resin particles is small.
• the blending of water in the melt-kneading may be performed from the beginning of the melt-kneading or may be performed from the middle of the melt-kneading. It is preferable to mix water from the beginning of melt-kneading.
• melt-kneading is performed by blending water in the presence of water, the blending amount of water is "when the monosaccharides contained in the composite material are generated by decomposing the coffee residue and / or the components of the coffee powder. It is the same as the abundance of water explained.
• the blending amount of each raw material can be appropriately set so as to satisfy the content in the above-mentioned composite material.
• the molded product of the present invention is a molded product formed into a desired shape using the composite material of the present invention.
• the molded product of the present invention include a sheet-shaped, plate-shaped, tube (ring) -shaped, and various-structured molded product.
• the tubular molded body include a straight tube having a substantially circular cross section and a quadrangular cross section, a curved tube, and a corrugated tube having a wavy shape.
• a multi-divided body obtained by dividing a tubular molded body such as a straight pipe having a substantially circular cross section or a quadrangular cross section, a curved pipe, and a corrugated pipe having a wavy shape by half-splitting or the like can be mentioned.
• the molded body of the present invention can be used as a member for civil engineering, building materials, automobiles, or electric wire protection.
• the molded product of the present invention can be obtained by subjecting the composite material of the present invention to ordinary molding means such as injection molding, extrusion molding, press molding, and blow molding.
• the molded product of the present invention has excellent mechanical properties and can be used for multiple purposes.
• the molded body of the present invention can be a cup, a tray, a plate, various containers, tableware, a shelf board, a storage case, a chest of drawers, or the like.
• the composite material was press-processed (press pressure 4.2 MPa) to obtain a molded product having a thickness of 6 mm.
• the average maximum diameter of 10 resin particles was 400 ⁇ m or more and less than 4 mm ( ⁇ )
• 10 resin particles were measured using the vertical cross section (6 mm thickness direction cross section) of the molded product as an observation surface.
• the case where the average of the maximum diameters was 10 ⁇ m or more and less than 400 ⁇ m or 4 mm or more was defined as ( ⁇ )
• the case where the average of the maximum diameters of 10 resin particles was less than 10 ⁇ m was defined as (x).
• the composite material was press-processed (press pressure 4.2 MPa) to obtain a molded product having a thickness of 6 mm.
• the case where the average aspect ratio of the 10 resin particles is 30 or more ( ⁇ ) measured by the method described above using the vertical cross section of the molded body as the observation surface is the case where the average aspect ratio of the 10 resin particles is 5 or more and less than 30.
• the case of ( ⁇ ) was defined as ( ⁇ ), and the case where the average aspect ratio of 10 resin particles was less than 5 was defined as (x).
• Tensile strength was evaluated as an index of mechanical properties.
• a test piece was prepared by injection molding, and the tensile strength of the No. 2 test piece was measured in accordance with JIS K 7113. The unit is "MPa”.
• the tensile strength of 20 MPa or more was defined as ( ⁇ )
• the tensile strength of 10 MPa or more and less than 20 MPa was defined as ( ⁇ )
• the tensile strength of less than 10 MPa was defined as (x).
• the flexural modulus and bending strength were evaluated as one index of mechanical properties. Using a composite material, the flexural modulus was measured at a sample thickness of 4 mm and a bending speed of 2 mm / min in accordance with JIS K 7171 2016. Specifically, a test piece (thickness 4 mm, width 10 mm, length 80 mm) is prepared by injection molding, and a load is applied at a distance between fulcrums of 64 mm, a radius of curvature of the fulcrum and the point of action of 5 mm, and a test speed of 2 mm / min.
• the amount of deflection S for obtaining the bending stress at this time is It can be calculated by the following formula.
• Bending elastic modulus is 2500 MPa or more ( ⁇ ), 2000 MPa or more and less than 2500 MPa ( ⁇ ), 1400 MPa or more and less than 2000 MPa ( ⁇ ), less than 1400 Ma ( ⁇ ).
• the bending strength was 40 MPa or more ( ⁇ ), 20 MPa or more and less than 40 MPa was ( ⁇ ), 10 MPa or more and less than 20 MPa was ( ⁇ ), and less than 10 MPa was (x).
• Impact resistance was evaluated as an index of mechanical properties.
• a test piece (thickness 4 mm, width 10 mm, length 80 mm) was prepared by injection molding, and the Izod impact strength was measured using the test piece with a notch according to JIS K 7110.
• the unit of impact resistance is "kJ / m 2 ".
• the Izod impact value of 2.0 kJ / m 2 or more was defined as ( ⁇ )
• 1.0 kJ / m 2 or more and less than 2.0 kJ / m 2 was defined as ( ⁇ )
• 1.0 kJ / m 2 or less was defined as (x).
• a used coffee capsule 1 was prepared.
• the used coffee capsule 1 contains coffee residue in a plastic container mainly made of polypropylene resin (PP).
• the plastic container has a partition aluminum foil.
• the main body of the plastic container is PP, and the lid of the container is made of a laminated film of polyethylene terephthalate (PET) / PP. Since the coffee capsule 1 is used, it contains water, and the water content (moisture content) in the entire used coffee capsule 1 is 60% by mass. When the used coffee capsule 1 is dried, it contains 70% by mass of coffee residue, 29% by mass of PP, and 1% by mass of aluminum (Al) and PET in total.
• PP polypropylene resin
• PET polyethylene terephthalate
• the amount of the used coffee capsule 1 and the modified PP resin 1 (polypropylene resin modified with maleic anhydride, acid value 41 mgKOH / g) are converted into a dry state for the used coffee capsule 1 and shown in Table 1. Then, it was put into a kneader, which is a batch type kneader, and in the presence of water (meaning the presence of water contained in the used coffee capsule 1), the maximum temperature reached during kneading was 180 ° C. for 10 minutes. It was kneaded to obtain a composite material.
• Example 2 A composite material was obtained in the same manner as in Example 1 except that the modified PP resin 1 was not blended.
• Table 1 shows the empty capsule 1 (the used coffee capsule 1 is made by cutting the container and removing the coffee residue inside to make only the capsule (plastic container body)), the used coffee capsule 1 and the modified PP resin 1.
• a composite material was obtained in the same manner as in Example 1 except that the compounding amount was as shown.
• Table 1 shows waste paper 1 (polyethylene laminated paper waste paper crushed using a rotary blade type crusher (manufactured by Horai)), used coffee capsules 1, and modified PP resin 1.
• a composite material was obtained in the same manner as in Example 1 except that the compounding amount was shown in 1.
• the polyethylene-laminated paper has a paper, a polyethylene thin film layer and an aluminum thin film layer, and the composition ratio is 75% by mass of paper, 18% by mass of low-density polyethylene (LDPE), and 7% by mass of aluminum foil.
• LDPE low-density polyethylene
• Example 6 A composite material was obtained in the same manner as in Example 1 except that the waste paper 1, the empty capsule 1, the used coffee capsule 1, and the modified PP resin 1 were blended in the blending amounts shown in Table 1.
• ⁇ Comparative example 1> The used coffee capsule 1 was dried to a moisture content of 0.2% by mass, and then put into a kneader, which is a batch kneader, and kneaded for 10 minutes at a maximum temperature reached at 180 ° C. during kneading. In this case, it was not possible to obtain a composite material in which each component was integrated.
• ⁇ Comparative example 3> The used coffee capsule 1 (moisture content: 60% by mass) was put into a kneader, which is a batch type kneader, and kneaded for 5 minutes at a maximum temperature of 170 ° C. to obtain a composite material.
• the upper part of Table 1 below (“used coffee capsule 1” to “waste paper 1”) shows the blending amount of each raw material when the total amount of the raw material is 100% by mass.
• the middle stage (“coffee residue” to “Al”), the content (% by mass) of coffee residue, PP, LDPE, modified PP resin, cellulose fiber, PET, and aluminum in the composite material, and the presence or absence of monosaccharides are present. Is shown together with the cellulose fiber length, the cellulose fiber content, the maximum diameter of the resin particles, and the aspect ratio.
• the lower row shows the evaluation results of each composite material.
• Example 2 when the particle size of the coffee residue was observed by observing the cross section of the composite material of Example 1 and Example 2 with an optical microscope, the maximum diameter was 14.3 ⁇ m in Example 1 and 18.5 ⁇ m in Example 2. Met. From the table, it can be seen that the composite materials of the examples containing monosaccharides are all excellent in moldability despite containing coffee residue. Further, when comparing Example 2 and Comparative Example 1, it can be seen that the composite material of Example 2 has a high MFR and is excellent in mechanical properties, although the composition is the same except for the presence or absence of monosaccharides. ..
• Example 5 As compared with Example 5 and Comparative Example 2, they have the same composition except for the presence or absence of monosaccharides, and all contain paper-derived cellulous fibers, which have relatively high strength and low MFR. It is a thing. However, Example 5 has a higher MFR, higher mechanical characteristics, and better moldability than Comparative Example 2. The composite material of Comparative Example 2 has poor moldability that causes breakage on the spool, whereas the composite material of Example 5 has good moldability without breakage on the spool. However, it is considered that this is because the composite material of Example 5 has a better balance between MFR and mechanical properties.

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• 2021
  • 2021-02-16 JP JP2021549292A patent/JPWO2021166914A1/ja active Pending
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