JP7025067B1 - Manufacturing method of masterbatch and polyester resin molded products - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a modifier, a polyester resin molded product, and a method for manufacturing a polyester container, which are suitable as a raw material for producing a polyester resin molded product having excellent slipperiness and transparency while suppressing smoke generation during molding. The modifier of the present invention is a complete esterified product of (A) a trihydric polyhydric alcohol and a fatty acid having an alkyl group having 12 to 22 carbon atoms, and (B) 3 to 3. A partial esterified product of a hexahydric polyhydric alcohol and a fatty acid having an alkyl group having 12 to 22 carbon atoms, which contains a partially esterified product having a hydroxy group, and comprises the components (A) and (B). The content ratio is 45 to 85% by mass and 15 to 55% by mass, respectively, when the total of these is 100% by mass. [Selection diagram] None

Description

The present invention relates to a masterbatch and a method for producing a polyester resin molded product, which is suitable as a raw material for producing a polyester resin molded product having excellent transparency and excellent slipperiness.

Conventionally, polyester resin has good water and gas barrier properties, excellent chemical resistance, and has various physical properties such as non-toxicity and light weight. Therefore, by secondary processing of a sheet or film containing a thermoplastic polyester resin, it is used for manufacturing containers in a wide range of fields such as foodstuffs, soft drinks, pharmaceuticals, and cosmetics. Further, since it has excellent transparency, it is widely used as a raw material for manufacturing a non-colored transparent container in which the internal filling can be easily visually recognized.
As a polyester resin, polyethylene terephthalate (PET) has become an indispensable material in daily life. Further, when transparency, strength and the like exceeding those of polyethylene terephthalate are required, glycol-modified polyethylene terephthalate (PETG), which is a copolymerized polyester, may be used.

When, for example, films or sheets, containers (including trays), etc. are stacked as molded products containing polyester resin, these molded products will block each other due to the inherent adhesiveness of polyester resin, and for use. It may be difficult to take them out one by one. Therefore, a method for improving the slipperiness when the molded products overlap each other has been studied.

Patent Document 1 describes particles (silica, talc, etc.) having an average particle size of 1 to 20 μm as secondary particles in a polyester polymer at 10 to 5000 ppm, a polyol having three or more hydroxyl groups, and 12 carbon atoms. A polyester sheet containing 0.01 to 5% by weight of an ester product with one or more aliphatic monocarboxylic acids is disclosed.
Patent Document 2 describes inactive particles (crosslinked particles, silica, etc.) having an average particle size of 10 μm or less in the skin layer, a polyhydric alcohol having 0 to 10000 ppm, and a polyhydric alcohol having 3 or more hydroxyl groups, and the number of carbon atoms. A substantially amorphous heat-molded polyester container obtained by heat-molding a polyester sheet containing 0.01 to 5% by weight of an ester product with 12 or more aliphatic monocarboxylic acids is disclosed.
Further, in Patent Document 3, the number of carbon atoms of the antiblocking agent (inorganic particles such as silica) and the constituent higher alcohol is 16 to 22 in 100 parts by mass of the polyester resin, and the number of carbon atoms of the fatty acid is 16. Disclosed is a polyester resin composition comprising 0.1 to 0.5 parts by mass of each of the higher alcohol fatty acid esters having a total carbon atom number of about 22 and 33 to 40. ..

Japanese Unexamined Patent Publication No. 7-224176 Japanese Unexamined Patent Publication No. 8-156210 Japanese Unexamined Patent Publication No. 2014-65549

In all of the above techniques, a modifier containing an esterified product of a polyhydric alcohol and an aliphatic monocarboxylic acid and inert particles is used in combination with polyethylene terephthalate or the like, and has excellent transparency and slipperiness. While a film, sheet or molded product can be obtained, smoke is emitted during molding, and the film, sheet, or molded product becomes dirty due to contamination of the manufacturing equipment by the smoking substance, which requires regular maintenance of the manufacturing equipment. There was a problem. As a result, sufficient productivity could not be obtained.
An object of the present invention is to provide a masterbatch containing a modifier suitable as a raw material for producing a polyester resin molded product having excellent slipperiness and transparency while suppressing smoke generation during molding. Further, another problem of the present invention is a polyester resin having improved productivity by suppressing thermal decomposition of a modifier and accompanying smoke generation from a molding apparatus when manufacturing a molded product such as a film or a sheet. It is to provide a method of manufacturing a molded product.

As a result of diligent research to solve the above problems, the present inventors have made a polyhydric alcohol having a value of 3 to 6 and an alkyl group having 12 to 22 carbon atoms as a modifier to be used in combination with the polyester resin. A complete esterified product with a fatty acid, a partial esterified product of a trihydric polyhydric alcohol and a fatty acid having an alkyl group having 12 to 22 carbon atoms, and a partial esterified product having a hydroxy group is specified. It was found that the modifier contained in the above ratio is suitable.
The present invention is shown below.

The master batch of the present invention is a master batch used for producing a polyester resin molded product in combination with a polyester resin, and contains a polyester resin, a modifier, and an inorganic filler, and the modifier is ( A) A complete esterified product of a 3- to 6-valent polyhydric alcohol and a polyester having an alkyl group having 12 to 22 carbon atoms (hereinafter, also referred to as "component (A)"), and (B) 3 to 6. It is a partial esterified product of a valent polyhydric alcohol and a fatty acid having an alkyl group having 12 to 22 carbon atoms, and contains a partially esterified product having a hydroxy group (hereinafter, also referred to as “component (B)”). , The content ratios of the component (A) and the component (B) are 45 to 85% by mass and 15 to 55% by mass, respectively, when the total of these is 100% by mass, and the component (A) and the component (A) and the component (B) are contained. The ratio of the total amount of (B) is 5 to 30 parts by mass when the content of the polyester resin is 100 parts by mass, and the content ratio of the inorganic filler is 5 to 30 parts when the content of the polyester resin is 100 parts by mass. It is characterized by having 35 parts by mass .

In the masterbatch of the present invention, it is preferable that the polyhydric alcohol used for forming the component (A) and the component (B) both contain pentaerythritol or glycerin.

The method for producing a polyester resin molded product of the present invention is characterized in that a molding material containing the polyester resin and the masterbatch of the present invention is subjected to a molding process .

According to the masterbatch of the present invention, a polyester resin molded product having excellent transparency and excellent slipperiness can be efficiently produced in combination with a polyester resin. Further, when the molded product is manufactured, the smoke generated from the modifier is suppressed and the productivity is improved.
The polyester resin molded product obtained by using the masterbatch of the present invention can be a film, a sheet, a lid, a container, a bag-shaped product for accommodating an article inside, etc., all of which have improved slipperiness and a surface surface. Since the adhesiveness of the molded products is reduced, when the molded products are overlapped with each other, they can be easily taken out one by one or one by one without causing blocking.

The modifier according to the present invention is a component (A) which is a complete esterified product of a 3- to 6-valent polyhydric alcohol and a fatty acid having an alkyl group having 12 to 22 carbon atoms, and a 3- to 6-valent polyhydric alcohol. The component (B), which is a partial esterified product of a polyhydric alcohol and a fatty acid having an alkyl group having 12 to 22 carbon atoms and which is a partial esterified product having a hydroxy group, is contained in a specific ratio.

The polyhydric alcohols used to form the components (A) and (B) are compounds having 3 to 6 hydroxy groups that are the same or different from each other.

Examples of the polyhydric alcohol include trimethylolethane, trimethylolpropane, glycerin, diglycerin, triglycerin, tetraglycerin, trimethylolethane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, hexanetriol, sorbitol, erythritol, and mannitol. Examples thereof include galactitol, iditol, taritol, and alitol. Of these, glycerin and pentaerythritol are preferable, and pentaerythritol is particularly preferable.

The fatty acids used to form the components (A) and (B) are compounds having a carboxy group, which are the same or different from each other and have 12 to 22 carbon atoms of the alkyl group.

Examples of the fatty acid include dodecanoic acid, tetradecanoic acid, hexadecanoic acid, 9-hexadecenoic acid, heptadecanoic acid, octadecanoic acid, cis-9-octadecenoic acid, 11-octadecenoic acid, icosanoic acid, docosanoic acid and the like. Of these, it is preferable that 80% or more of hexadecanoic acid, heptadecanoic acid and octadecanoic acid, which are saturated fatty acids having 16 to 18 carbon atoms in the alkyl group, are contained.

The component (A) is a complete esterified product of the polyhydric alcohol and the fatty acid, and the component (A) contained in the masterbatch of the present invention may be one or more. May be good.
Further, the component (B) is a partially esterified product containing a hydroxy group. The number of hydroxy groups contained in the component (B) is not particularly limited, and is usually (n-1) or less, preferably (n-1) or less, when the number of hydroxy groups in the polyhydric alcohol is n. 3 or less. The component (B) contained in the master batch of the present invention may be only one kind or two or more kinds.

In the modifier according to the present invention , the content ratios of the above components (A) and (B) are such that a polyester resin molded product having excellent transparency and excellent slipperiness is more efficient when the masterbatch is used in combination with the polyester resin. Since it is often produced, when the total of these is 100% by mass, it is 45 to 85% by mass and 15 to 55% by mass, preferably 60 to 80% by mass and 20 to 40% by mass, respectively. be.

The modifier according to the present invention is produced by mixing the component (A), the component (B), and other components used in combination as necessary by using a conventionally known mixing device. be able to. For example, when the modifier is produced in combination with the inorganic filler, the shape and size of the inorganic filler raw material are not particularly limited. When the secondary particles are measured by the laser diffraction / scattering method, the average particle diameter D50 is preferably 2 to 10 μm.

Since the masterbatch of the present invention contains specific components (A) and (B), it is suitable as a raw material for producing a polyester resin molded product which is transparent, has improved slipperiness, and has reduced surface adhesiveness. Not only that, when the resin molded product is manufactured, the smoke generated from the modifier is suppressed, and the productivity can be improved.

The masterbatch of the present invention comprises a composition containing the above-mentioned modifier, polyester resin, inorganic filler, and other components blended as necessary, and is a raw material for producing a polyester resin molded product. be. The polyester resin contained in the masterbatch of the present invention may be only one kind or two or more kinds.

The polyester resin is a thermoplastic resin, and may be either an aromatic polyester resin or an aliphatic polyester resin, or a combination of both. Further, these polyester resins may be either homopolyester or copolyester.

The polyester resin is usually a resin obtained by polycondensation of a dicarboxylic acid component with a dihydroxy component, polycondensation of a dicarboxylic acid component with a dihydroxy component and an oxycarboxylic acid component, ring-opening polymerization of a lactone component, or the like. be.

Examples of the dicarboxylic acid component include terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid (2,6-naphthalenedicarboxylic acid, etc.), diphenyldicarboxylic acid, diphenyletherdicarboxylic acid, diphenylmethanedicarboxylic acid, diphenylethanedicarboxylic acid, and diphenylketonedicarboxylic acid. Aromatic dicarboxylic acid having 8 to 16 carbon atoms such as acid or a derivative thereof, cyclohexanedicarboxylic acid, hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, hymic acid and the like have about 8 to 12 carbon atoms. Adicyclic dicarboxylic acid having 2 to 40 carbon atoms such as adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecandicarboxylic acid, hexadecanedicarboxylic acid, dimeric acid and the like. Or a derivative thereof and the like.

The dihydroxy component may be linear or linear such as ethylene glycol, trimethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, hexanediol, octanediol, and decanediol. Alicyclic alkylene diols such as branched alkylene diols having 2 to 12 carbon atoms, cyclohexane diols, alicyclic diols such as cyclohexanedimethanol and hydride bisphenol A, hydroquinone, resorcin, dihydroxyphenyl, naphthalene diol and dihydroxy. Aromatic diols such as diphenyl ethers, bisphenol A, bisphenol A with alkylene oxides such as ethylene oxide and propylene oxide added (diethoxylated bisphenol A, etc.), diethylene glycol, triethylene glycol, polyoxyethylene glycol, ditetra Examples thereof include polyoxyalkylene glycols such as methylene glycol, polytetramethylene ether glycol, dipropylene glycol, tripropylene glycol, polyoxypropylene glycol and polytetramethylene ether glycol.

Examples of the oxycarboxylic acid component include lactic acid, glycolic acid, 2-hydroxy-n-butyric acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid, 2-hydroxycaproic acid, and 2-hydroxyisocaproic acid. Examples include oxycarboxylic acids such as 6-hydroxycaproic acid, 2-hydroxy-3,3-dimethylbutyric acid, 2-hydroxy-3-methylbutyric acid, oxybenzoic acid, oxynaphthoic acid, diphenyleneoxycarboxylic acid and derivatives thereof. Be done.

Examples of the lactone component include ε-propiolactone, δ-butyrolactone, β-butyrolactone, γ-butyrolactone, pivalolactone, δ-valerolactone, and ε-caprolactone.

When the polyester resin is an aromatic homopolyester, it is preferably a polycondensate of a dicarboxylic acid component and a dihydroxy component.
The dicarboxylic acid component is preferably terephthalic acid, naphthalenedicarboxylic acid or the like, and the dihydroxy component is preferably ethylene glycol, diethylene glycol, butanediol, cyclohexanedimethanol or the like. Typical homopolyesters are polyalkylene terephthalates such as polyethylene terephthalate (PET), polypropylene terephthalate (PPT), polybutylene terephthalate (PBT), polyhexamethylene terephthalate, polycyclohexane-1,4-dimethylterephthalate, and polyneopentyl terephthalate. , Polyalkylene naphthalate such as polyethylene isophthalate, polyethylene naphthalate, polybutylene naphthalate, polyhexamethylene naphthalate and the like. Of these, PET is particularly preferable.

When the polyester resin is an aromatic copolyester, it is preferably a polycondensate of a dicarboxylic acid component, a dihydroxy component, and an oxycarboxylic acid component.
The dicarboxylic acid component is preferably one or more selected from isophthalic acid, phthalic acid, terephthalic acid, naphthalenedicarboxylic acid, adipic acid, sebacic acid and the like, and the dihydroxy component is preferably ethylene glycol. One or more of diethylene glycol, propylene glycol, butanediol, 4-cyclohexanedimethanol, neopentyl glycol and the like, and the oxycarboxylic acid is, for example, p-oxybenzoic acid and the like. Typical copolyester resins are condensates of terephthalic acid, ethylene glycol and 4-cyclohexanedimethanol (sometimes referred to as "PETG resin"), polyethylene terephthalate / isophthalate resins and the like.

When the above polyester resin is an aliphatic polyester resin, a ring-opening polymerization reaction of a cyclic lactone, a polycondensation reaction of an aliphatic hydroxycarboxylic acid (oxycarboxylic acid), an aliphatic dibasic acid (succinic acid, adipic acid, azelaic acid, etc.) Sevacinic acid, α, ω-dodecandicarboxylic acid, dodecenylsuccinic acid, octadecenyldicarboxylic acid, cyclohexanedicarboxylic acid, etc.) and / or ester-forming compounds thereof (dimethyl succinate, dimethyl adipate, dimethyl azelaite, dimethyl sebacate) Aliphatic compounds having two or more ester bond-forming functional groups in the molecule, such as, and aliphatic diols (ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butane). A resin obtained by a polycondensation reaction with a diol (diol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanediol, cyclohexanedimethanol, etc.) is preferable.

Examples of the aliphatic polyester resin obtained by the ring-opening polymerization reaction of the cyclic lactone include poly (ε-propiolactone) resin, poly (δ-butyrolactone) resin, poly (β-butyrolactone) resin, and poly (γ-butyrolactone). Examples thereof include a resin, a poly (pivalolactone) resin, a poly (δ-valerolactone) resin, and a poly (ε-caprolactone) resin.

Examples of the aliphatic polyester resin obtained by the polycondensation reaction of the aliphatic hydroxycarboxylic acid (oxycarboxylic acid) include polylactic acid resin, polyglycolic acid resin, poly (3-hydroxybutyric acid) resin, and poly (4-hydroxybutyric acid). Examples thereof include resins and poly (4-hydroxyvaleric acid) resins.

The polyester resin preferably contains an aromatic polyester resin.

As described above, the masterbatch of the present invention comprises a composition containing a polyester resin, at least the components (A) and (B) derived from the modifier of the present invention, and an inorganic filler . The ratio of the total content of the components (A) and (B) is transparent, the slipperiness is improved, and the adhesiveness of the surface is reduced. Therefore, the polyester resin molded product is efficiently produced. When the resin is 100 parts by mass, it is 5 to 30 parts by mass.

The constituent materials of the inorganic filler according to the present invention are not particularly limited, but silica, diatomaceous earth, titanium oxide, alumina, zirconia, zinc oxide, calcium carbonate, strontium carbonate, iron oxide, ferrite, zeolite, pyrophyllite, talc, etc. Examples thereof include smectite, vermiculite, wollastonite, mica, clay, barium sulfate and the like. Of these, silica, zeolite and talc are preferred. The inorganic filler has a modified portion formed of paraffin, fatty acid, polyhydric alcohol, silane coupling agent, silicone oil, citric acid, etc. formed on at least a part of the surface of the particle portion made of these materials. May be.
As described above, the masterbatch of the present invention may contain other components as needed, as long as the transparency of the resin molded product can be obtained, for example, a plasticizer, an antioxidant, and ultraviolet absorption. It can contain an agent, a weather resistant agent, a heat stabilizer, an antistatic agent, a lubricant, a flame retardant, a crystal nucleating agent and the like.

The content ratio of the inorganic filler in the master batch of the present invention is 5 to 35 parts by mass when the polyester resin is 100 parts by mass.

The masterbatch of the present invention may have, for example, a columnar shape, a prismatic shape, a spherical shape, an elliptical spherical shape, or the like.

The masterbatch of the present invention is produced by heating a mixture containing the above-mentioned modifier, polyester resin, and inorganic filler to form a melt-kneaded product, and then subjecting the mixture to a conventionally known extrusion method. can do. The specific manufacturing method is shown below.
(1) The above-mentioned modifier, polyester resin, and inorganic filler are put into a mixer such as a tumbler blender, a henschel mixer, or a super mixer and mixed, and then a single-screw extruder, a multi-screw extruder, or the like is used. Method of obtaining a masterbatch by granulating while melt-kneading with an extruder (2) The above-mentioned modifier and inorganic filling are made in a molten state by an extruder such as a single-screw extruder or a multi-screw extruder. A method of mixing agents, additives, etc. by side feed or liquid injection and granulating while melt-kneading to obtain a masterbatch.

A polyester resin molded product can be produced by subjecting a composition obtained by combining the masterbatch of the present invention with another component (which may be a masterbatch or the like) to a conventionally known molding method. Therefore, the masterbatch of the present invention is suitable as a raw material for producing a resin molded product having excellent transparency, improved slipperiness, and reduced surface adhesiveness. It is particularly preferable to contain a polyester resin as a component of.

The polyester resin molded product obtained from the method for producing a polyester resin molded product of the present invention is an article comprising a composition containing the above-mentioned modifier and the polyester resin. That is, the polyester resin molded product contains at least the polyester resin and the above components (A) and (B), has transparency, has improved slipperiness, and has reduced surface adhesiveness. Is. The polyester resin contained in the molded product of the present invention may be only one kind or two or more kinds.

As the polyester resin, the resin that can be contained in the masterbatch of the present invention can be applied as it is.

As described above , the polyester resin molded product comprises a composition containing the polyester resin and the masterbatch of the present invention, and the polyester resin and the components (A) and (B) derived from the above modifier. ) And an inorganic filler. The ratio of the total content of the components (A) and (B) is such that the polyester resin molded product is transparent, the slipperiness is improved, and the adhesiveness of the surface is reduced. In the case of parts, it is preferably 0.004 to 0.600 parts by mass.

The polyester resin molded product contains an inorganic filler, and the content ratio thereof is preferably 0.008 to 0.350 parts by mass when the polyester resin is 100 parts by mass.

The shape of the polyester resin molded product is not particularly limited, and may be either a fixed shape or an amorphous product. A film, a sheet, a lid, a container, a bag-shaped object for accommodating an article inside, and the like are preferable, and a sheet and a container are particularly preferable. In the case of a sheet and a container, the thickness is not particularly limited, but is preferably 100 to 800 μm, and more preferably 200 to 500 μm. Further, when the polyester resin molded product is a sheet, it may be either a single-layer type or a multi-layer type, and in the latter case, it is a laminated sheet in which the film which is the polyester resin molded product is arranged on at least one side. There may be.

The polyester resin molded product described above is transparent. For example, when the film is subjected to HAZE measurement by a method according to JIS K 7136, the HAZE is preferably 10% or less, more preferably 5% or less. Therefore, the visibility of the article on the opposite side through the molded article is excellent.

Further, when the film, which is one of the above polyester resin molded products, is subjected to the static friction coefficient measurement by the method according to JIS K 7125, the static friction coefficient is preferably 0.60 or less, more preferably 0.40 or less. be. Since the above -mentioned polyester resin molded product has the above-mentioned properties, the adhesiveness of the surface is reduced, and when the molded products are overlapped with each other, it is easy to make one by one or one by one without causing blocking. Can be taken out.

The above -mentioned polyester resin molded product is a molding material containing the polyester resin and the above-mentioned master batch of the present invention, which is used for injection molding, calendar molding, T-die molding, inflation molding, blow molding, sheet extrusion molding, and deformed extrusion molding. It can be manufactured by subjecting it to conventionally known molding means such as hollow molding, compression molding, vacuum molding, pressure molding, foam molding, injection compression molding, gas assist molding, and water assist molding.

When the polyester resin molded product is a film or a sheet, it can be manufactured by calendar molding, T-die molding, inflation molding, blow molding or the like as described above, and if necessary, stretching processing is performed. be able to. When the above polyester resin molded product is a container, depending on its shape, the obtained sheet is manufactured by subjecting it to secondary processing such as vacuum forming, pneumatic forming, punching, and assembling. be able to.

The polyester resin molded product described above may be a molded product having a single composition or a composite molded product having a different composition. In the latter case, for example, at least a part of the surface may contain the polyester resin, the components (A) and (B) derived from the modifier, and the inorganic filler. As a specific example, in a laminated sheet having a layered structure, the skin layers on the one-side side and the other-side are both a polyester resin, components (A) and (B) derived from the above-mentioned modifier, and inorganic. A three-layer laminated sheet containing the filler in the above resin composition and having a core layer having another resin composition can be obtained. In the skin layer containing the polyester resin, the components (A) and (B) derived from the modifier, and the inorganic filler, the surface has reduced adhesiveness. The skin layer on the one side and the skin layer on the other side may be the same or different from each other in terms of resin composition and thickness. The thickness of the skin layer on the one side, the core layer, and the skin layer on the other side is preferably 15 to 100 μm, 20 to 450 μm, and 15 to 100 μm, respectively. In the laminated sheet of such an embodiment, when the HAZE is preferably 10% or less, more preferably 5% or less, the legibility of the article on the opposite side is excellent through the sheet. The same applies when the composite molded product has other shapes.

The three-layer laminated sheet can be manufactured by a coextrusion method, a laminating method, or the like. Of these, in the case of the coextrusion method, the polyester resin forming the skin layer on the one side and the skin layer on the other side, the components (A) and (B) derived from the modifier, and the inorganic. It is possible to use a method in which a molding material containing a filler (thermoplastic resin composition) and a molding material (thermoplastic resin composition) for forming a core layer are subjected to inflation molding or T-die molding. It can be stretched if necessary. Moreover, as a laminating method, a dry laminating method, a sand laminating method, an extrusion laminating method and the like can be mentioned. When manufactured by these laminating methods, a polyester resin for forming a skin layer on one side and a skin layer on the other side, and components (A) and (B) derived from the above-mentioned modifier are used. ) And the polyester resin film containing the inorganic filler, and the resin film for forming the core layer can be laminated with an adhesive interposed therebetween.
When manufacturing a container having a laminated structure, a method of subjecting a three-layer laminated sheet to secondary processing such as vacuum forming, compressed air forming, punching, and assembling can be applied.

Hereinafter, embodiments of the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples. Here, parts and% are based on mass unless otherwise specified.

1. 1. Test category 1 (raw material for modifier)
Tables 1 and 2 show the complete esterified product and the partially esterified product used in the production of the modifier. These compounds were obtained by esterification reaction using the following raw materials.

(1) Polyhydric alcohol e-1: pentaerythritol e-2: glycerin e-3: sorbitan e-4: dipentaerythritol e-5: propylene glycol (2) fatty acid f-1: palmitic acid / palmitic acid / stearic acid Acid (45/1/54) mixture f-2: Palmitic acid / stearic acid (60/40) mixture f-3: Myristic acid / palmitic acid / stearic acid (20/32/48) mixture f-4 : Mix of palmitic acid / stearic acid / arachidic acid (48/32/20) f-5: Mix of lauric acid / palmitic acid / margaric acid / stearic acid / behenic acid (4/40/1/50/5) f -6: Mix of arachidic acid / behenic acid (60/40) f-7: Mix of lauric acid / myristic acid (40/60) f-8: Mix of myristic acid / palmitic acid / stearic acid (20/40/40) F-9: palmitic acid / stearic acid / arachidic acid (40/40/20) mixture f-10: capric acid f-11: lignoseric acid

The fully esterified products A-1 to A-10 and a-1 to a-3 are shown in Table 1.

The partially esterified products B-1 to B-20 and b-1 to b-5 are shown in Table 2.

2. 2. Test category 2 (manufacturing of modifier)
A modifier was produced using the raw materials shown in Tables 1 and 2 (see Table 3).

Preparation Examples 1-1 to 1-10
The complete esterified products (A-1) to (A-10) in Table 1 and the partially esterified products (B-1) to (B-20) in Table 2 are tumbler-mixed in the amounts shown in Table 3. Modifiers (D-1) to (D-10) were obtained (see Table 3).

Comparative Preparation Examples 1-1 to 1-5
The complete esterified products (a-1) to (a-3), (A-4) or (A-5) in Table 1 and the partial esterified products (b-1) to (b-5) or (b-5) in Table 2 B-6), (B-7) and (B-10) were tumbler-mixed in the amounts shown in Table 3 to obtain modifiers (d-1) to (d-5) (Table 3). reference).

3. 3. Test Category 3 (Manufacturing of Thermoplastic Polyester Resin Masterbatch)
A polyester resin masterbatch was produced using PET or PETG as a thermoplastic polyester resin, the modifier shown in Table 3, and the inorganic filler shown in Table 4 below as other raw materials (see Table 5). The average particle size shown in Table 4 is a measured value of secondary particles measured by a laser diffraction / scattering method.

Example 2-1 (Manufacturing of Polyester Resin Masterbatch M-1)
100 parts of PET resin "BG-80" (trade name) manufactured by Sinopec Yizheng Chemical Fiber Co., Ltd., 16 parts of modifier (D-1), and 19 parts of inorganic filler (C-1) are manufactured by AS ONE. It was charged in "Pot Mixer PM-01" (trade name), stirred for 10 minutes, and then transferred to the raw material hopper of a coaxial twin-screw kneading extruder. Then, the mixture was supplied to the coaxial twin-screw kneading extruder, melt-kneaded at 250 to 270 ° C., extruded from a strand die, and rapidly cooled with water to obtain strands. The strands were cut with a pelletizer to produce a polyester resin masterbatch (M-1) in which a modifier (D-1) and an inorganic filler (C-1) were dispersed in a PET resin (see Table 5). ..

Examples 2-2 to 2-7 and 2-9 to 2-16 (Production of polyester resin masterbatch M-2 to M-7 and M-9 to M- 16 )
Using the raw materials shown in Table 5, polyester resin masterbatches M-2 to M-7 and M-9 to M- 16 were obtained in the same manner as in Example 2-1 (see Table 5).

Example 2-8 (Production of Copolymerized Polyester Resin Masterbatch M-8)
Implemented except that 100 parts of Eastman Chemical Japan's PETG resin "EASER GN001" (trade name), 10 parts of modifier (D-1), and 10 parts of inorganic filler (C-1) were used. A copolymerized polyester masterbatch (M-8) in which a modifier (D-1) and an inorganic filler (C-1) were dispersed in a PETG resin was produced in the same manner as in Example 2-1 (see Table 5). ).

Comparative Examples 2-1 to 2-6 (Manufacturing of polyester resin masterbatch m-1 to m-6 )
Using the raw materials shown in Table 5, polyester resin masterbatches m-1 to m- 6 were obtained in the same manner as in Example 2-1 (see Table 5).

4. Test Category 4 (Manufacturing of thermoplastic polyester resin sheets and containers)
Using the PET resin "BG-80" or PETG resin "EASER GN001" and the masterbatch shown in Table 5, single-layer and three-layer laminated resin sheets are produced, and then these resin sheets are vacuum-formed. A resin container was manufactured by subjecting to.

Example 3-1
100 parts of the PET resin "BG-80" and 1.0 part of the polyester masterbatch (M-1) are charged in the "pot mixer PM-01", stirred for 10 minutes, and placed in a coaxial twin-screw kneading extruder. It was transferred to the provided raw material hopper. After that, the resin raw material stored in the raw material hopper is supplied to the coaxial twin-screw kneading extruder, melt-kneaded at 260 to 280 ° C., and then the supply amount of the molten resin and the screw rotation speed are adjusted from the multi-manifold T-die. While doing so, it was wound onto a cooling roll whose temperature was adjusted to 30 ° C. to obtain a single-layer sheet (S1) having a thickness of 200 μm (see Table 6).

The obtained single-layer sheet (S1) was evaluated for slipperiness, transparency and smoke resistance by the following methods, and the results are also shown in Table 6.

(1) The slippery single-layer sheet (S1) was subjected to 20 ° C. and 65% R. H. After adjusting the humidity for 24 hours, the static friction coefficient was measured in the same atmosphere using a friction measuring machine "TR-2" (model name) manufactured by Toyo Seiki Co., Ltd. in accordance with JIS K7125. The measurement was performed on an arbitrary surface of three single-layer sheets, and the average value of a total of three points was adopted to evaluate the slipperiness according to the following criteria.
⊚: 0.40 or less 〇: Over 0.40 to 0.60 or less ×: Over 0.60

(2) Transparency The HAZE of the single-layer sheet (S1) was measured using a haze meter "NDH5000" (model name) manufactured by Nippon Denshoku Kogyo Co., Ltd. in accordance with JIS K7136. The measurement was performed on an arbitrary position of five single-layer sheets, and the average value of a total of five points was adopted to evaluate the transparency according to the following criteria.
◎: 5% or less 〇: Over 5% to 10% or less ×: Over 10%

(3) Smoke resistance A predetermined amount of the resin raw material of the raw material hopper is supplied to the coaxial twin-screw kneading extruder, and in the process of melt-kneading at 290 ° C., the manufacturing equipment is not contaminated due to the smoke-generating component. The time during continuous operation was measured, and the smoke resistance was evaluated according to the following criteria.
◎: Over 20 hours 〇: Over 4 hours to under 20 hours ×: Over 4 hours

Next, this single-layer sheet (S1) was put into a vacuum forming machine equipped with a mold having an opening of 110 mm × 110 mm, a bottom of 95 mm × 95 mm and a depth of 20 mm, and the heater temperature was 400 ° C. and the mold temperature was 55 ° C. Under the above conditions, vacuum forming was performed with the single layer temperature in the preheating step set to 110 ° C. to obtain a container-shaped molded product. When the obtained molded product was visually observed, the transparency was good, and no defects in appearance such as breakage, cracks, and bubbles were observed.

Example 3-2
The single-layer sheet (S2) is the same as in Example 3-1 except that the polyester masterbatch (M-2) is used instead of the polyester masterbatch (M-1) charged in the above "pot mixer PM-01". ) Was manufactured and various evaluations were performed (see Table 6). After that, a container was manufactured by vacuum forming, and it was confirmed that both transparency and appearance were good.

Example 3-3
Same as Example 3-1 except that 0.9 part of polyester masterbatch (M-3) was used instead of 1 part of polyester masterbatch (M-1) charged in the above "pot mixer PM-01". A single-layer sheet (S3) was manufactured and various evaluations were performed (see Table 6). After that, a container was manufactured by vacuum forming, and it was confirmed that both transparency and appearance were good.

Example 3-4
The same as in Example 3-1 except that 3.2 parts of the polyester masterbatch (M-4) were used instead of 1 part of the polyester masterbatch (M-1) charged in the above "pot mixer PM-01". A single-layer sheet (S4) was manufactured and various evaluations were performed (see Table 6). After that, a container was manufactured by vacuum forming, and it was confirmed that both transparency and appearance were good.

Example 3-5
The same as in Example 3-1 except that 1.2 parts of the polyester masterbatch (M-5) was used instead of 1 part of the polyester masterbatch (M-1) charged in the above "pot mixer PM-01". A single-layer sheet (S5) was manufactured and various evaluations were performed (see Table 6). After that, a container was manufactured by vacuum forming, and it was confirmed that both transparency and appearance were good.

Example 3-6
The same as in Example 3-1 except that 0.7 part of the polyester masterbatch (M-6) was used instead of 1 part of the polyester masterbatch (M-1) charged in the above "pot mixer PM-01". A single-layer sheet (S6) was manufactured and various evaluations were performed (see Table 6). After that, a container was manufactured by vacuum forming, and it was confirmed that both transparency and appearance were good.

Example 3-7
The same as in Example 3-1 except that 1.0 part of the polyester masterbatch (M-7) was used instead of 1 part of the polyester masterbatch (M-1) charged in the above "pot mixer PM-01". A single-layer sheet (S7) was manufactured and various evaluations were performed (see Table 6). After that, a container was manufactured by vacuum forming, and it was confirmed that both transparency and appearance were good.

Example 3-8
100 parts of the PETG resin "Easter GN001" and 1.3 parts of the copolymerized polyester masterbatch (M-8) were put into the above "pot mixer PM-01" and stirred for 10 minutes to make a coaxial twin-screw kneading extruder. It was transferred to the arranged raw material hopper. Then, the resin raw material contained in the raw material hopper was transferred to the raw material hopper disposed in the coaxial twin-screw kneading extruder. After that, the resin raw material stored in the raw material hopper is supplied to the coaxial twin-screw kneading extruder, melt-kneaded at 240 to 260 ° C., and then the supply amount of the molten resin and the screw rotation speed are adjusted from the multi-manifold T-die. While doing so, it was wound on a cooling roll whose temperature was adjusted to 30 ° C. to obtain a single-layer sheet (S8) having a thickness of 200 μm. Then, various evaluations were performed on this single-layer sheet (S8) (see Table 6).
Next, this single-layer sheet (S8) was put into a vacuum forming machine equipped with a mold having an opening of 110 mm × 110 mm, a bottom of 95 mm × 95 mm and a depth of 20 mm, and the heater temperature was 400 ° C. and the mold temperature was 50 ° C. Under the above conditions, vacuum forming was performed with the single layer temperature in the preheating step set to 100 ° C. to obtain a container-shaped molded product. It was confirmed that the obtained molded product had good transparency and appearance.

Example 3-9
The same as in Example 3-1 except that 1.8 parts of the polyester masterbatch (M-9) was used instead of 1 part of the polyester masterbatch (M-1) charged in the above "pot mixer PM-01". A single-layer sheet (S9) was manufactured and various evaluations were performed (see Table 6). After that, a container was manufactured by vacuum forming, and it was confirmed that both transparency and appearance were good.

Example 3-10
The same as in Example 3-1 except that 1.1 parts of the polyester masterbatch (M-10) was used instead of 1 part of the polyester masterbatch (M-1) charged in the above "pot mixer PM-01". A single-layer sheet (S10) was manufactured and various evaluations were performed (see Table 6). After that, a container was manufactured by vacuum forming, and it was confirmed that both transparency and appearance were good.

Example 3-11
The same as in Example 3-1 except that 3.0 parts of the polyester masterbatch (M-11) was used instead of 1 part of the polyester masterbatch (M-1) charged in the above "pot mixer PM-01". A single-layer sheet (S11) was manufactured and various evaluations were performed (see Table 6). After that, a container was manufactured by vacuum forming, and it was confirmed that both transparency and appearance were good.

Example 3-12
The same as in Example 3-1 except that 2.5 parts of the polyester masterbatch (M-12) was used instead of 1 part of the polyester masterbatch (M-1) charged in the above "pot mixer PM-01". A single-layer sheet (S12) was manufactured and various evaluations were performed (see Table 6). After that, a container was manufactured by vacuum forming, and it was confirmed that both transparency and appearance were good.

Example 3-13
The same as in Example 3-1 except that 0.3 part of the polyester masterbatch (M-13) was used instead of 1 part of the polyester masterbatch (M-1) charged in the above "pot mixer PM-01". A single-layer sheet (S13) was manufactured and various evaluations were performed (see Table 6). After that, a container was manufactured by vacuum forming, and it was confirmed that both transparency and appearance were good.

Example 3-14
The same as in Example 3-1 except that 4.0 parts of the polyester masterbatch (M-14) was used instead of 1 part of the polyester masterbatch (M-1) charged in the above "pot mixer PM-01". A single-layer sheet (S14) was manufactured and various evaluations were performed (see Table 6). After that, a container was manufactured by vacuum forming, and it was confirmed that both transparency and appearance were good.

Example 3-15
The same as in Example 3-1 except that 2.5 parts of the polyester masterbatch (M-15) was used instead of 1 part of the polyester masterbatch (M-1) charged in the above "pot mixer PM-01". A single-layer sheet (S15) was manufactured and various evaluations were performed (see Table 6). After that, a container was manufactured by vacuum forming, and it was confirmed that both transparency and appearance were good.

Example 3-16
The same as in Example 3-1 except that 2.7 parts of the polyester masterbatch (M-16) was used instead of 1 part of the polyester masterbatch (M-1) charged in the above "pot mixer PM-01". A single-layer sheet (S16) was manufactured and various evaluations were performed (see Table 6). After that, a container was manufactured by vacuum forming, and it was confirmed that both transparency and appearance were good.

Comparative Example 3-1
The same as in Example 3-1 except that 0.8 part of the polyester masterbatch (m-1) was used instead of 1 part of the polyester masterbatch (M-1) charged in the above "pot mixer PM-01". A single-layer sheet (SS1) was manufactured and various evaluations were performed (see Table 6). After that, when the container was manufactured by vacuum forming, the slipperiness and smoke generation resistance were insufficient.

Comparative Example 3-2
The same as in Example 3-1 except that 0.3 part of the polyester masterbatch (m-2) was used instead of 1 part of the polyester masterbatch (M-1) charged in the above "pot mixer PM-01". A single-layer sheet (SS2) was manufactured and various evaluations were performed (see Table 6). After that, when the container was manufactured by vacuum forming, the slipperiness and smoke generation resistance were insufficient.

Comparative Example 3-3
The same as in Example 3-1 except that 4.5 parts of the polyester masterbatch (m-3) was used instead of 1 part of the polyester masterbatch (M-1) charged in the above "pot mixer PM-01". A single-layer sheet (SS3) was manufactured and various evaluations were performed (see Table 6). After that, when the container was manufactured by vacuum forming, the transparency was insufficient.

Comparative Example 3-4
The same as in Example 3-1 except that 4.5 parts of the polyester masterbatch (m-4) was used instead of 1 part of the polyester masterbatch (M-1) charged in the above "pot mixer PM-01". A single-layer sheet (SS4) was manufactured and various evaluations were performed (see Table 6). After that, when the container was manufactured by vacuum forming, the smoke generation resistance was insufficient.

Comparative Example 3-5
The same as in Example 3-1 except that 4.5 parts of the polyester masterbatch (m-5) was used instead of 1 part of the polyester masterbatch (M-1) charged in the above "pot mixer PM-01". A single-layer sheet (SS5) was manufactured and various evaluations were performed (see Table 6). After that, when the container was manufactured by vacuum forming, the transparency was insufficient.
Comparative Example 3-6
Same as Reference Example 3-1 except that 4.7 parts of the polyester masterbatch (m-6) was used instead of 1 part of the polyester masterbatch (M-1) charged in the above "pot mixer PM-01". A single-layer sheet (SS6) was manufactured and various evaluations were performed (see Table 6). After that, a container was manufactured by vacuum forming, and it was confirmed that both transparency and appearance were good.

Example 4-1
100 parts of the PET resin "BG-80" and 1.0 part of the polyester masterbatch (M-1) are charged in the "pot mixer PM-01", stirred for 10 minutes, and placed in a coaxial twin-screw kneading extruder. The raw material hopper No. Moved to 1. On the other hand, only the PET resin "BG-80" was used in the raw material hopper No. 1 disposed in another coaxial twin-screw kneading extruder. Moved to 2. After that, the raw material hopper No. 1 and No. The resin raw material contained in 2 is supplied to each coaxial twin-screw kneading extruder, and both are melt-kneaded at 260 to 280 ° C., and then the supply amount of the molten resin and the screw rotation speed are adjusted from the multi-manifold T-die. While doing so, the raw material hopper No. The layer made of the resin raw material of No. 1 was co-extruded so as to be a skin layer on both sides and wound on a cooling roll whose temperature was adjusted to 30 ° C., and the thickness of the skin layer, the core layer and the skin layer was 30 μm, respectively. Two-kind, three-layer laminated sheets (L1) having a size of 240 μm and 30 μm were obtained (see Table 7).

The obtained laminated sheet (L1) was evaluated for slipperiness, transparency and smoke generation resistance by the following methods, and the results are also shown in Table 7.

(1) Sliding laminated sheet (L1) was subjected to 20 ° C. and 65% R. H. After adjusting the humidity for 24 hours, the static friction coefficient was measured in the same atmosphere using a friction measuring machine "TR-2" (model name) manufactured by Toyo Seiki Co., Ltd. in accordance with JIS K7125. The measurement was performed on an arbitrary surface of three laminated sheets, and the average value of a total of three points was adopted to evaluate the slipperiness according to the following criteria.
⊚: 0.40 or less 〇: Over 0.40 to 0.60 or less ×: Over 0.60

(2) Transparency The HAZE of the laminated sheet (L1) was measured using a haze meter "NDH5000" (model name) manufactured by Nippon Denshoku Kogyo Co., Ltd. in accordance with JIS K7136. The measurement was performed on an arbitrary position of five laminated sheets, an average value of a total of five points was adopted, and transparency was evaluated according to the following criteria.
◎: 5% or less 〇: Over 5% to 10% or less ×: Over 10%

(3) Smoke resistance No. 1 of the above raw material hopper. A predetermined amount of the resin raw material of No. 1 was supplied to a coaxial twin-screw kneading extruder, and the time during which continuous operation was possible without causing contamination of the manufacturing equipment derived from smoke-generating components during the process of melt-kneading at 290 ° C. was measured. , Smoke resistance was evaluated according to the following criteria.
◎: Over 20 hours 〇: Over 4 hours to under 20 hours ×: Over 4 hours

Next, this laminated sheet (L1) was put into a vacuum forming machine equipped with a mold having an opening of 110 mm × 110 mm, a bottom of 95 mm × 95 mm and a depth of 20 mm, and the heater temperature was 400 ° C. and the mold temperature was 55 ° C. Under the conditions, vacuum forming was performed with the laminate temperature in the preheating step set to 110 ° C. to obtain a container-shaped molded product. When the obtained molded product was visually observed, the transparency was good, and no defects in appearance such as breakage, cracks, and bubbles were observed.

Example 4-2
Laminated sheet (L2) in the same manner as in Example 4-1 except that the polyester masterbatch (M-2) was used instead of the polyester masterbatch (M-1) charged in the above "pot mixer PM-01". Was manufactured and various evaluations were performed (see Table 7). After that, a container was manufactured by vacuum forming, and it was confirmed that both transparency and appearance were good.

Example 4-3
Same as Example 4-1 except that 0.9 part of polyester masterbatch (M-3) was used instead of 1 part of polyester masterbatch (M-1) charged in the above "pot mixer PM-01". Laminated sheet (L3) was manufactured and various evaluations were performed (see Table 7). After that, a container was manufactured by vacuum forming, and it was confirmed that both transparency and appearance were good.

Example 4-4
The same as in Example 4-1 except that 1.2 parts of the polyester masterbatch (M-4) was used instead of 1 part of the polyester masterbatch (M-1) charged in the above "pot mixer PM-01". A laminated sheet (L4) was manufactured and various evaluations were performed (see Table 7). After that, a container was manufactured by vacuum forming, and it was confirmed that both transparency and appearance were good.

Example 4-5
The same as in Example 4-1 except that 1.2 parts of the polyester masterbatch (M-5) was used instead of 1 part of the polyester masterbatch (M-1) charged in the above "pot mixer PM-01". A laminated sheet (L5) was manufactured and various evaluations were performed (see Table 7). After that, a container was manufactured by vacuum forming, and it was confirmed that both transparency and appearance were good.

Example 4-6
The same as in Example 4-1 except that 0.5 part of the polyester masterbatch (M-6) was used instead of 1 part of the polyester masterbatch (M-1) charged in the above "pot mixer PM-01". A laminated sheet (L6) was manufactured and various evaluations were performed (see Table 7). After that, a container was manufactured by vacuum forming, and it was confirmed that both transparency and appearance were good.

Example 4-7
Same as Example 4-1 except that 1.0 part of polyester masterbatch (M-7) was used instead of 1 part of polyester masterbatch (M-1) charged in the above "pot mixer PM-01". A laminated sheet (L7) was manufactured and various evaluations were performed (see Table 7). After that, a container was manufactured by vacuum forming, and it was confirmed that both transparency and appearance were good.

Example 4-8
100 parts of the PETG resin "Easter GN001" and 1.3 parts of the copolymerized polyester masterbatch (M-8) were put into the above "pot mixer PM-01" and stirred for 10 minutes to make a coaxial twin-screw kneading extruder. Arranged raw material hopper No. Moved to 1. On the other hand, only the above PETG resin "Easter GN001" was used in the raw material hopper No. 1 disposed in another coaxial twin-screw kneading extruder. Moved to 2. After that, the raw material hopper No. 1 and No. The resin raw material contained in 2 is supplied to each coaxial twin-screw kneading extruder, and both are melt-kneaded at 240 to 260 ° C., and then the supply amount of the molten resin and the screw rotation speed are adjusted from the multi-manifold T-die. While doing so, the raw material hopper No. The layer made of the resin raw material of No. 1 was co-extruded so as to be a skin layer on both sides and wound on a cooling roll whose temperature was adjusted to 30 ° C., and the thickness of the skin layer, the core layer and the skin layer was 30 μm, respectively. Two-kind, three-layer laminated sheets (L8) having a size of 240 μm and 30 μm were obtained. Then, various evaluations were performed on this laminated sheet (L8) (see Table 7).
Next, this laminated sheet (L8) is put into a vacuum forming machine equipped with a mold having an opening of 110 mm × 110 mm, a bottom of 95 mm × 95 mm and a depth of 20 mm, and has a heater temperature of 400 ° C. and a mold temperature of 50 ° C. Under the conditions, vacuum forming was performed with the laminate temperature in the preheating step set to 100 ° C. to obtain a container-shaped molded product. It was confirmed that the obtained molded product had good transparency and appearance.

Example 4-9
The same as in Example 4-1 except that 2.5 parts of the polyester masterbatch (M-9) was used instead of 1 part of the polyester masterbatch (M-1) charged in the above "pot mixer PM-01". A laminated sheet (L9) was manufactured and various evaluations were performed (see Table 7). After that, a container was manufactured by vacuum forming, and it was confirmed that both transparency and appearance were good.

Example 4-10
The same as in Example 4-1 except that 1.1 parts of the polyester masterbatch (M-10) was used instead of 1 part of the polyester masterbatch (M-1) charged in the above "pot mixer PM-01". A laminated sheet (L10) was manufactured and various evaluations were performed (see Table 7). After that, a container was manufactured by vacuum forming, and it was confirmed that both transparency and appearance were good.

Example 4-11
The same as in Example 4-1 except that 3.5 parts of the polyester masterbatch (M-11) was used instead of 1 part of the polyester masterbatch (M-1) charged in the above "pot mixer PM-01". A laminated sheet (L11) was manufactured and various evaluations were performed (see Table 7). After that, a container was manufactured by vacuum forming, and it was confirmed that both transparency and appearance were good.

Example 4-12
The same as in Example 4-1 except that 5.0 parts of the polyester masterbatch (M-12) was used instead of 1 part of the polyester masterbatch (M-1) charged in the above "pot mixer PM-01". A laminated sheet (L12) was manufactured and various evaluations were performed (see Table 7). After that, a container was manufactured by vacuum forming, and it was confirmed that both transparency and appearance were good.

Example 4-13
The same as in Example 4-1 except that 0.3 part of the polyester masterbatch (M-13) was used instead of 1 part of the polyester masterbatch (M-1) charged in the above "pot mixer PM-01". A laminated sheet (L13) was manufactured and various evaluations were performed (see Table 7). After that, a container was manufactured by vacuum forming, and it was confirmed that both transparency and appearance were good.

Example 4-14
The same as in Example 4-1 except that 5.0 parts of the polyester masterbatch (M-14) was used instead of 1 part of the polyester masterbatch (M-1) charged in the above "pot mixer PM-01". A laminated sheet (L14) was manufactured and various evaluations were performed (see Table 7). After that, a container was manufactured by vacuum forming, and it was confirmed that both transparency and appearance were good.

Example 4-15
The same as in Example 4-1 except that 2.5 parts of the polyester masterbatch (M-15) was used instead of 1 part of the polyester masterbatch (M-1) charged in the above "pot mixer PM-01". A laminated sheet (L15) was manufactured and various evaluations were performed (see Table 7). After that, a container was manufactured by vacuum forming, and it was confirmed that both transparency and appearance were good.

Example 4-16
The same as in Example 4-1 except that 2.7 parts of the polyester masterbatch (M-16) was used instead of 1 part of the polyester masterbatch (M-1) charged in the above "pot mixer PM-01". A laminated sheet (L16) was manufactured and various evaluations were performed (see Table 7). After that, a container was manufactured by vacuum forming, and it was confirmed that both transparency and appearance were good.

Comparative Example 4-1
The same as in Example 4-1 except that 0.8 part of the polyester masterbatch (m-1) was used instead of 1 part of the polyester masterbatch (M-1) charged in the above "pot mixer PM-01". A laminated sheet (LL1) was manufactured and various evaluations were performed (see Table 7). After that, when the container was manufactured by vacuum forming, the slipperiness and smoke generation resistance were insufficient.

Comparative Example 4-2
The same as in Example 4-1 except that 0.3 part of the polyester masterbatch (m-2) was used instead of 1 part of the polyester masterbatch (M-1) charged in the above "pot mixer PM-01". A laminated sheet (LL2) was manufactured and various evaluations were performed (see Table 7). After that, when the container was manufactured by vacuum forming, the slipperiness and smoke generation resistance were insufficient.

Comparative Example 4-3
The same as in Example 4-1 except that 4.5 parts of the polyester masterbatch (m-3) was used instead of 1 part of the polyester masterbatch (M-1) charged in the above "pot mixer PM-01". A laminated sheet (LL3) was manufactured and various evaluations were performed (see Table 7). After that, when the container was manufactured by vacuum forming, the transparency was insufficient.

Comparative Example 4-4
The same as in Example 4-1 except that 4.5 parts of the polyester masterbatch (m-4) was used instead of 1 part of the polyester masterbatch (M-1) charged in the above "pot mixer PM-01". A laminated sheet (LL4) was manufactured and various evaluations were performed (see Table 7). After that, when the container was manufactured by vacuum forming, the smoke generation resistance was insufficient.

Comparative Example 4-5
The same as in Example 4-1 except that 4.5 parts of the polyester masterbatch (m-5) was used instead of 1 part of the polyester masterbatch (M-1) charged in the above "pot mixer PM-01". A laminated sheet (LL5) was manufactured and various evaluations were performed (see Table 7). After that, when the container was manufactured by vacuum forming, the transparency was insufficient.
Comparative Example 4-6
Same as Reference Example 4-1 except that 4.7 parts of the polyester masterbatch (m-6) was used instead of 1 part of the polyester masterbatch (M-1) charged in the above "pot mixer PM-01". A laminated sheet (LL6) was manufactured and various evaluations were performed (see Table 7). After that, a container was manufactured by vacuum forming, and it was confirmed that both transparency and appearance were good.

As is clear from the results in Table 7, according to Examples 4-1 to 4-16 , the resin molded body exhibits excellent slipperiness while maintaining high transparency, and the molded body such as a sheet or a film is exhibited. It is possible to provide a method for manufacturing a thermoplastic polyester resin masterbatch, a thermoplastic polyester resin sheet, a thermoplastic polyester resin molded body, and a polyester resin container, which emits less smoke from a resin modifier during melt processing and is less likely to cause manufacturing defects.

The masterbatch of the present invention has excellent transparency and is suitable as a raw material for producing a polyester resin molded product having a smooth surface. In addition, when a molded product is manufactured using this masterbatch, contamination of the manufacturing equipment by the fuming substance derived from the modifier contained therein is suppressed, and the productivity is improved.
The polyester resin molded product of the present invention is suitable for films, sheets, lids, containers, bag-shaped objects for accommodating articles inside, and the like. Since the surface of this molded product is smooth, when the molded products are overlapped with each other, it can be easily taken out one by one or one by one without causing blocking.

Claims (6)

A masterbatch used to manufacture polyester resin molded products in combination with polyester resin.
Contains a polyester resin, a modifier, and an inorganic filler,
The modifier is
(A) A complete esterified product of a 3- to hexavalent polyhydric alcohol and a fatty acid having an alkyl group having 12 to 22 carbon atoms, and
(B) A partial esterified product of a trihydric polyhydric alcohol and a fatty acid having an alkyl group having 12 to 22 carbon atoms, which contains a partially esterified product having a hydroxy group.
The content ratios of the component (A) and the component (B) are 45 to 85% by mass and 15 to 55% by mass, respectively, when the total of these is 100% by mass.
The ratio of the total amount of the component (A) and the component (B) is 5 to 30 parts by mass when the content of the polyester resin is 100 parts by mass.
The master batch is characterized in that the content ratio of the inorganic filler is 5 to 35 parts by mass when the polyester resin is 100 parts by mass. The masterbatch according to claim 1, wherein the polyhydric alcohol used for forming the component (A) and the component (B) both contains pentaerythritol or glycerin. The masterbatch according to claim 1 or 2, wherein the polyhydric alcohol used for forming the component (A) and the component (B) is pentaerythritol. The aspect according to any one of claims 1 to 3, wherein the fatty acid used for forming the component (A) and the component (B) both contains a saturated fatty acid having an alkyl group having 16 to 18 carbon atoms. Master Badge. The masterbatch according to any one of claims 1 to 4, wherein the inorganic filler is at least one selected from silica, zeolite and talc. A method for producing a polyester resin molded product, which comprises subjecting a molding material containing the polyester resin and the masterbatch according to any one of claims 1 to 4 to a molding process.