JP2001200144A - Polyester resin composition and molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition composed of a thermoplastic polyester resin, an ultraviolet absorber and a dispersant, and a molding having excellent ultraviolet screening activity and transparency. SOLUTION: A resin composition obtained by compounding a thermoplastic polyester resin with an inorganic ultraviolet absorber and an organic dispersant. The amount of addition of the inorganic ultraviolet absorber is 0.01-50 pts.wt. based on 100 pts.wt. of the thermoplastic polyester resin, the ratio of the amount of addition of the organic dispersant to that of the inorganic ultraviolet absorber (R = the amount of addition of organic dispersant/the amount of addition of inorganic ultraviolet absorber) is 0.1<=R<=5. Further, a molding prepared from the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester resin composition having excellent ultraviolet blocking ability and transparency by blending an inorganic ultraviolet absorber and an organic dispersant in a thermoplastic polyester resin and this resin. The present invention relates to a molded article such as a package and a bottle using the composition.

[0002]

2. Description of the Related Art Conventionally, plastic molded products include packaging materials typified by containers for foods, beverages, toiletries and cosmetics, as well as mechanical materials, electric and electronic materials, optical materials, building materials, and the like. Used in a wide range of fields. Various additives are added to such a plastic molded article in order to impart functionality according to the purpose of use,
One example is an ultraviolet absorber.

[0003] Ultraviolet rays refer to electromagnetic waves having a wavelength of 100 to 400 nm, and UV-C having a wavelength of 100 to 280 nm.
-320 nm UV-B, 320-400 nm UV-
A is divided into three types. The energy of light in this area is
C, H, O binding energies 294-462 kJ / mo
1 (70 to 110 kcal / mol). Therefore, in a plastic molded product mainly composed of a bond of C, H, and O, the bond may be broken by the irradiation of ultraviolet rays, resulting in deterioration of the resin, discoloration, and reduction in mechanical strength. On the other hand, not only plastic molded articles, but also contents to be filled in packaging materials, particularly toiletries and cosmetics, may be accompanied by discoloration, deterioration, and decomposition of drugs due to irradiation of ultraviolet rays.

[0004] In order to solve such a problem, an ultraviolet absorber is blended into a plastic molded product. In general, organic ultraviolet absorbing materials are often used as the ultraviolet absorbing material. Representative examples thereof include phenyl salicylate, 2-hydroxy-4-methoxybenzophenone, and 2- (2'-hydroxy-5-methylphenyl) benzo. And triazole. The organic ultraviolet absorbing material can impart transparency and ultraviolet absorbing ability by being kneaded into a plastic molded product.

[0005] However, such an organic ultraviolet absorbing material has a problem that a molded article is colored due to its ultraviolet absorbing mechanism. In a plastic molded article, this coloring problem is accompanied by poor appearance. Therefore, I want to avoid it as much as possible.

Further, the organic ultraviolet absorbing material is a component having a relatively low molecular weight, and when such an ultraviolet absorbing material is kneaded into a molded article made of plastic, the organic ultraviolet absorbing material is eluted into the contents. Therefore, there is a need for room for improvement in consideration of deterioration of the contents and consumers who use the contents.

Further, recent organic UV absorbing materials include:
In order to expand the UV absorption region of the UV absorbing material, there are many types in which chlorine is introduced into the structure of this organic UV absorbing material, but considering the dioxin problem in recent years, such UV absorbing material The flow of dehalogenation is becoming stronger.

Therefore, instead of these organic ultraviolet absorbing materials, attempts have been made to use inorganic ultraviolet absorbing materials corresponding to non-elution, safety, hygiene, environmental issues, and dehalogenation. I have. Typical examples thereof include zinc oxide, titanium oxide, cerium oxide, iron oxide and the like.

However, while these inorganic ultraviolet absorbing materials have the advantage of being excellent in thermal stability, they have the following problems. Generally, when an inorganic ultraviolet absorbing material, particularly titanium oxide or zinc oxide, is irradiated with ultraviolet light, electrons are generated in the conduction band of the inorganic compound and holes are generated in the valence band when absorbing the ultraviolet light. . Some of these move to the surface of the inorganic compound and form radicals such as .OH and .OOH by oxygen, moisture, heat and the like. These radicals cause decomposition and deterioration of the resin (photocatalytic activity). The photocatalytic activity of the inorganic ultraviolet absorber acts disadvantageously in processing (melt kneading) of the resin composition to which the inorganic ultraviolet absorber is added.

For this reason, even if a small amount of an inorganic ultraviolet absorbing material is added to a resin and kneaded in a molten state, the decomposition and deterioration of the resin are caused by the photocatalytic activity of the inorganic ultraviolet absorbing material. ) Or a significant decrease in mechanical properties due to a decrease in the molecular weight of the resin.

Therefore, in order to reduce the photocatalytic activity as much as possible, an extremely small amount of the ultraviolet absorber (less than 0.01 part by weight of the ultraviolet absorber per 100 parts by weight of the resin) is melt-kneaded with the resin. When the stable supply of the ultraviolet absorbing material becomes difficult, the dispersion of the concentration of the ultraviolet absorbing agent becomes large, and the necessary and sufficient ultraviolet absorbing effect cannot be obtained.

Further, in order to solve these problems, even if an attempt is made to prepare a high-concentration dispersion (master batch) in which an inorganic ultraviolet absorbent is dispersed at a high concentration, the photocatalytic activity is too strong and the resin deteriorates. Melt kneading becomes impossible.

In general, the surface tension of an inorganic ultraviolet absorber is smaller than that of a plastic, and the interaction between the inorganic compound and the plastic is originally low. Therefore, when the inorganic compound fine particles are added at the time of plasticizing and kneading the plastic, the following is obtained. Problems arise.

Generally, the particle size of primary particles of an inorganic compound called ultrafine particles is on the order of several nm, and the size is smaller than the wavelength of visible light. If this inorganic compound is dispersed in the form of primary particles in plastic, there is no problem of lowering the transparency of the plastic molded article. However, such an inorganic compound is usually added to plastic in a state of secondary particles in which primary particles are aggregated, and is melt-kneaded. In addition, if the inorganic compound fine particles are added during plasticization and kneading of the plastic, the dispersibility of the inorganic compound particles in the plastic is reduced due to the interaction between the particles during kneading, and the primary particles or the secondary particles are aggregated. In addition, secondary particles having a dispersed particle diameter of several μm to several tens μm are generated.

Since the secondary particles have a large particle size, not only the appearance of the plastic molded product is poor, but also the mechanical strength of the molded product may be reduced. Further, when the particle size of the inorganic compound dispersed in the molded body is on the order of μm,
Visible light is scattered by the inorganic compound, and as a result, there is a problem that the transparency of the plastic molded article is significantly reduced. Also, 2
Dispersion of the sub-agglomerated particles means that a larger amount of the inorganic compound is added than the amount at which the effect of adding the inorganic compound is obtained, resulting in an increase in cost.

[0016]

SUMMARY OF THE INVENTION The object of the present invention is to provide a polyester resin composition comprising a thermoplastic polyester resin, an inorganic ultraviolet absorber and an organic dispersant in view of the above situation. By improving the dispersibility of an ultraviolet absorber, it is possible to provide a polyester resin composition having excellent ultraviolet blocking ability and transparency, and a molded article such as a package and a bottle using the polyester resin composition. It is an issue.

[0017]

SUMMARY OF THE INVENTION The present invention has been conceived in order to solve the above-mentioned problems, and the invention according to claim 1 comprises an inorganic ultraviolet absorber and a thermoplastic polyester resin in a thermoplastic polyester resin. In the resin composition containing the organic dispersant, the amount of the inorganic UV absorber is 0.01 to 50 parts by weight based on 100 parts by weight of the thermoplastic polyester resin, and the amount of the organic dispersant added. A polyester resin composition characterized in that the ratio of the amount of the inorganic ultraviolet absorber added (R = the amount of the organic dispersant added / the amount of the inorganic ultraviolet absorber) is 0.1 ≦ R ≦ 5.

Further, the invention according to claim 2 is characterized in that the inorganic ultraviolet absorber comprises zinc oxide, titanium oxide, cerium oxide,
The polyester resin composition according to claim 1, wherein the polyester resin composition is a metal compound of any of iron oxides or a mixture thereof.

The invention according to claim 3 is characterized in that the metal compound is a metal compound which is an inorganic ultraviolet absorber and is doped with a metal different from the metal species. Item 10. A polyester resin composition according to item 2.

Further, according to a fourth aspect of the present invention, the metal doped in the metal compound is a transition metal element or
The polyester resin composition according to claim 3, wherein the polyester resin composition contains at least one of Li, Mg, Al, Ga, In, Sn, and Sb.

The absorption edge of ultraviolet absorption of a metal compound of zinc oxide, titanium oxide, cerium oxide, iron oxide, or a mixture thereof is about 385 nm, and U near 400 nm.
VA cannot be blocked. Therefore, a transition metal element or Li, Mg, Al, Ga, In, Sn,
By doping a metal such as Sb, the absorption edge can be shifted to the longer wavelength side. As a result, ultraviolet rays close to the visible light range can be blocked, and contents that are sensitive to light, such as foods, cosmetics, and medicines, can be protected.

The invention according to claim 5 is characterized in that the acid component of the thermoplastic polyester resin is at least one of terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, succinic acid, adipic acid, succinic acid and sebacic acid. 5. A method according to claim 1, wherein the material is selected from one or more.
The polyester resin composition according to any one of the above.

Further, in the invention according to claim 6, the diol component of the thermoplastic polyester resin is ethylene glycol, propylene glycol, brene glycol,
The glycol according to claim 1, wherein the glycol is selected from at least one of glycols such as 1,4-cyclohexanedimethanol and polyoxyalkylene glycols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol. 7. Any one
It is a polyester-type resin composition of item.

According to a seventh aspect of the present invention, the thermoplastic polyester resin comprises a polymer of an oxyacid or a copolymer of an oxyacid. The polyester-based resin composition described in the above.

The invention according to claim 8 is characterized in that the organic dispersant has an average molecular weight of 500 to 10,000 based on a viscosity method.
Polyethylene, polypropylene, low molecular weight polyolefin-based wax such as ethylene-propylene copolymer or a carboxylic acid-modified product thereof or a carboxylic acid-modified product of a copolymer thereof, or a higher fatty acid or a metal salt, ester, amide, Is a polyester-based resin composition containing at least one of the following.

Since the organic dispersant has low compatibility with the base polyester resin, it has a matrix-domain structure (sea-island structure), and light may be scattered and opaque due to the difference in the refractive index between the matrix and the domain. There is. Therefore, the average molecular weight is 500 to 100 as measured by the viscosity method.
It is preferred to use one of 00.

The invention according to claim 9 is the first invention.
9. A molded article such as a packaging bag or a bottle, which is molded with a resin layer using the polyester-based resin composition according to any one of items 1 to 8.

According to a tenth aspect of the present invention, a polyester resin composition using a doped metal compound is used as an ultraviolet absorber according to the third or fourth aspect as a master patch and contains no metal compound. Diluted with thermoplastic polyester, and with respect to 100 parts by weight of the thermoplastic polyester-based resin, the metal layer excluding the metal used for the dope is a resin layer using a polyester-based resin composition that is 0.01 to 20 parts by weight. A molded product such as a packaging bag or a bottle, which is characterized by being molded.

[0029] Further, the invention according to claim 11 provides a multilayer resin composition comprising at least one or more polyester resin compositions according to any one of claims 1 to 8 as a resin layer constituting a molded article. A molded article such as a package or a bottle is molded with the resin layer.

Further, according to the twelfth aspect, the wavelength 7
At the light transmittance at 00 nm, the light transmittance (A) of the resin layer of the molded article composed of the polyester resin alone
And a ratio (A / A) of a light transmittance (B) of a resin layer composed of a polyester resin composition comprising the inorganic ultraviolet absorbent and the organic dispersant according to any one of claims 1 to 8.
The molded product such as a package or a bottle according to any one of claims 9 to 11, wherein B) is 1 to 2. The wavelength of 700 nm is in the visible light region, and the higher the transmittance, the more visually transparent.

According to a thirteenth aspect of the present invention, the resin layer constituting the molded body has a thickness of 0.3 mm or more and a wavelength of 36 mm.
The molded product such as a package or a bottle according to any one of claims 9 to 12, wherein a light transmittance at 0 nm is 10% or less. The wavelength of 360 nm is ultraviolet light, and the lower the transmittance, the more the ultraviolet light is absorbed by the resin layer, and the more the content can be protected from the ultraviolet light.

The invention according to claim 14 is characterized in that the resin layer having a thickness of 0.3 mm or more has a haze (cloudiness) value of 20% or less. 1
And molded articles such as bottles.

[0033]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. As the inorganic compound having an ultraviolet absorbing ability in the present invention, zinc oxide, titanium oxide, cerium oxide, iron oxide and the like can be used, and any one kind or a mixture of two or more kinds is used. Of these, zinc oxide is particularly preferred because zinc oxide has a better ultraviolet absorbing effect than titanium oxide. The average primary particle diameter of the metal compound represented by zinc oxide is 10 to 100 nm, more preferably 10 to 100 nm, in consideration of the ultraviolet absorbing ability and dispersibility when blended with the thermoplastic resin.
30 nm fine particles.

An inorganic compound such as silica or an organic substance such as stearic acid may be used, if necessary, for the purpose of suppressing the photocatalytic activity of the inorganic ultraviolet absorbing compound and improving the dispersibility in plastics. Although surface treatment may be performed, in the present invention, even if an inorganic compound not subjected to such surface treatment is used, the photocatalytic activity is suppressed by the effect of a dispersant described below, and an inorganic ultraviolet absorbing metal compound is used. Can be improved.

The amount of the inorganic ultraviolet absorber added to the thermoplastic polyester resin is determined by the amount of the thermoplastic polyester resin 1
It is preferable that the amount is 0.01 to 50 parts by weight with respect to 00 parts by weight, and further, the ratio of the amount of the organic dispersant to the amount of the inorganic ultraviolet absorber (R = organic dispersant) Additive amount / inorganic ultraviolet absorber addition amount) 0.1 ≦ R ≦
5 range. That is, the amount of the inorganic ultraviolet absorber is set to be equal to or less than one fifth of the organic dispersant as long as the dispersibility and the transparency are not impaired.

As described above, the absorption edge of ultraviolet absorption of a metal compound such as zinc oxide and titanium oxide is about 385 nm, and UV-A near 400 nm cannot be cut off. Therefore, by doping these metal compounds with a metal, the absorption edge can be shifted to the longer wavelength side. Thereby, by blending a metal compound doped with a metal into a thermoplastic polyester resin, a resin composition capable of shielding ultraviolet rays close to the visible light region is obtained,
It can be applied to cosmetics, medicines, etc. that are sensitive to ultraviolet rays.

The metal (ion) to be doped into the metal compound in the present invention is preferably a metal different from the metal species of the metal compound having an ultraviolet absorbing ability. Such metals include transition metal elements, Li, M
It is preferable to use at least one of g, Al, Ga, In, Sn, and Sb, and particularly preferable is a transition metal element such as Cr, V, Fe, and Co.

In the case of doping a metal with a chemical method such as a sol-gel method or an ion exchange method, a new absorption band other than a metal compound appears in the visible light region, but the photoactivity under visible light irradiation is low. Also, the activity under ultraviolet irradiation is greatly reduced. This is presumed to be because the doped metal becomes a recombination center. On the other hand, when a metal is doped by a physical method such as an ion implantation method, the entire absorption band shifts to a longer wavelength side. Therefore, as a metal doping method, an ion implantation method is preferably used. The shift of the absorption band to the higher wavelength region is proportional to the doping amount,
If the absorption is at least nm, coloring is unavoidable even with excellent transparency. Therefore, it is preferable to determine the absorption band and the corresponding metal doping amount in accordance with the required quality such as light resistance of the contents. However, when the content is required to block visible light in food or the like, it is preferable to increase the amount of metal dope.

The thermoplastic polyester resin of the present invention comprises at least one of terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, succinic acid, adipic acid, succinic acid, and sebacic acid. As the component, at least one kind of glycols such as ethylene glycol, propylene glycol, butylene glycol and 1,4-cyclohexanedimethanol, or polyoxyalkylene glycols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol is polymerized. It is constituted by doing.

As other acid components, diphenylsulfonedicarboxylic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, azelaic acid and the like can be selected, and the diol component is neopentyl glycol, diethylene glycol, 1,4-cyclohexane. Examples include dimethylol, 2,2-bis (4-β-hydroxyethoxyphenyl) propane, and 1,4-bis (β-hydroxyethoxy) benzene.

Further, the thermoplastic polyester resin is
A polyester resin composition comprising a polymer of an oxyacid or a copolymer of an oxyacid may be used, and various oxyacids such as lactic acid, ε-caprolactone, p-oxybenzoic acid, p-β-hydroxyethoxybenzoic acid, etc. You can choose.

Representative examples of the above-mentioned thermoplastic polyester resin include polyethylene terephthalate resin (hereinafter PET) and polyethylene naphthalate resin (hereinafter PE).
N) and other aromatic polyester resins; aliphatic polyester resins such as polyethylene succinate resin and polybutylene succinate resin; polymers of oxyacids such as polylactic acid resin and polycaprolactone resin; Polyester elastomers obtained by copolymerizing oxyalkylene glycol can be used, and blends of two or more of these can be used. However, they have excellent mechanical properties, chemical resistance, heat resistance, etc., and are stretched and heat-set. In particular, PET is preferably used because rigidity and dimensional stability can be improved.

There are various forms such as films, sheets, bottles, plates, trays, cups, etc. as molded articles made of the resin composition.
The addition amount of the inorganic ultraviolet absorbing metal compound is, as described above, based on 100 parts by weight of the thermoplastic polyester resin.
It is preferable to be blended so as to be 0.01 to 50 parts by weight.

If the amount is less than 0.01 part by weight, the transparency as compared with the blank is almost the same, but the ultraviolet absorbing ability is inferior. On the other hand, when the amount is more than 50 parts by weight, the ultraviolet absorbing ability is excellent, but the transparency as compared with the blank is significantly reduced. From this, when the inorganic ultraviolet absorption with respect to 100 parts by weight of the thermoplastic polyester resin is a metal compound, the addition amount is 0.01 to 50 parts by weight, more preferably 0.01 to 20 parts by weight, The amount of the metal compound to be added is adjusted according to the required ultraviolet absorbing ability and the thickness of the sample. If the amount is less than 0.01 part by weight, the ultraviolet ray absorbing effect may not be obtained,
If it exceeds 50 parts by weight, the transparency may be reduced.
Further, as described later, it is possible to prepare a high-concentration dispersion of 5 to 50 parts by weight of an inorganic ultraviolet absorber in advance, and to dilute the dispersion in a subsequent bottle molding process to adjust the concentration to a desired concentration. is there.

The particle size of the inorganic ultraviolet absorbent in the present invention is preferably as small as possible, and is preferably on the order of nm. Furthermore, if it is intended to maintain the transparency of the resin to which the metal compound is not added, the maximum particle size is 400 nm or less, and the average particle size is 10 to 10 in consideration of the blending with the thermoplastic resin and the ultraviolet absorbing effect. 100
nm, more preferably 10 to 30 nm.
However, since the decrease in transparency due to the addition of the inorganic metal compound is caused by light scattering by the inorganic metal compound, the amount of the metal compound added depends on the actual thickness of the container and the required physical properties. Can be suppressed, and the transparency can be improved.

The dispersant of the present invention is compounded to improve the dispersibility of the inorganic metal compound having an ultraviolet absorbing ability in a thermoplastic resin and to suppress the photocatalytic activity of the metal compound. As such a dispersant, it is possible to use at least one kind of higher fatty acid or its metal salt, ester, amide, or low molecular weight polyolefin-based wax or its acid-modified product or copolymer. Agents are preferably used.

Particularly preferred is a carboxylic acid-modified product of a low-molecular-weight polyolefin wax which is a resin-based dispersant. Such a carboxylic acid-modified polyolefin-based dispersant has a molecular weight of 10,000 or less in a viscosity method, and A resin-based dispersant containing a main chain copolymer or a graft copolymer obtained by modifying any of polyethylene, polypropylene, and ethylene-propylene copolymer with a carboxylic acid having at least one carboxyl group.

Various carboxylic acids such as monocarboxylic acids such as acrylic acid and methacrylic acid, and dicarboxylic acids such as maleic anhydride and itaconic acid can be used as the carboxylic acid for modifying the polyolefin wax. Further, the amount of modification with these carboxylic acids can be determined by an acid value (KOHmg /
g) is 20 to 60, and the weight fraction of the acid component is 1 to 10% by weight.
It is preferable that it is above. The low molecular weight polyolefin-based wax copolymer has a molecular weight of 10,000 or less in a viscosity method, and may be either a main chain copolymer or a graft copolymer.
g-polyethylene copolymer and the like.

The above-mentioned polyolefin wax of polyethylene, polypropylene and ethylene-polypropylene copolymer modified with a carboxylic acid is melt-kneaded with a polyester resin and an inorganic ultraviolet absorber, so that the surface of the inorganic ultraviolet absorber becomes The group reacts with the group to give a surface treatment effect of the inorganic ultraviolet absorber. In other words, the polyethylene, polypropylene, and ethylene-propylene copolymers modified with the carboxylic acid can provide the function of a dispersant and the function of suppressing photocatalytic activity. Even if an ultraviolet absorber is blended, it is possible to obtain a polyester resin composition and a molded article of a polyester-based resin made of the polyester resin composition, with good dispersibility and without deterioration of the resin accompanying photocatalytic activity.

As described above, a resin dispersant having a molecular weight of 500 to 10,000 as measured by a viscosity method is used. Since the resin-based dispersant of the above-described component has low compatibility with the base polyester, the resin-based dispersant forms a sea-island structure in which the domains of the resin-based dispersant are dispersed in a sea-island shape in the polyester matrix, and the refractive index of the matrix and the domain is high Differences can scatter light and become opaque. When a compound having a molecular weight of more than 10,000 is blended, the resin-based dispersant may be dispersed in the polyester-based resin in a state where the domain is large, and the transparency may be impaired. From such a viewpoint, it is preferable to add a resin dispersant having a relatively low molecular weight (low viscosity).

As described above, the ratio of the added amount of the organic dispersant to the added amount of the inorganic metal compound (R = the added amount of the organic dispersant /
(Inorganic metal compound addition amount) is 0.1 ≦ R ≦ 5.
If the ratio of the dispersant is large (R> 5), the mechanical strength may be reduced or the processability may be reduced. Conversely, if the ratio of the dispersant is small (R <0.1), the dispersion state of the metal compound may be reduced. And the transparency of the molded article made of the resin composition may be reduced. In particular, when set in the range of 0.5 ≦ R ≦ 1, the dispersion state of the inorganic ultraviolet absorber is also good, and the transparency is good.
A resin composition having excellent processability can be obtained.

The average primary particle diameter of the inorganic ultraviolet absorbent is 10 to 30 nm as described above, and the average primary particle diameter of the inorganic ultraviolet absorbent dispersed in the polyester resin composition is 2 nm. The secondary particle diameter is preferably 5 μm
The thickness is more preferably set to 1 μm or less.

The average primary particle diameter is determined in consideration of the dispersibility in plastics and the effect of absorbing ultraviolet rays. The average secondary particle diameter is determined by the poor appearance of the polyester resin bottle due to poor dispersion and the bottle due to poor dispersion. The above range is set for the purpose of suppressing a decrease in mechanical strength of the above.

Normally, when an inorganic metal compound not subjected to a surface treatment is blended with a thermoplastic polyester resin or the like, phenomena such as deterioration of the resin, discoloration and reduction in mechanical strength due to the photocatalytic activity of the metal compound are observed. . This phenomenon becomes a problem after processing and is called chalking, but when the amount of the metal compound added is large, it is remarkable even during processing, and in terms of improving processability, it is effective to use the dispersant of the present invention. is there.

The light transmission characteristic of the molded article made of the thermoplastic polyester resin composition of the present invention depends on molding conditions, but when the thickness of the molded article is 2 mm, the wavelength is 700 nm.
Has a light transmittance of 75% or more and a wavelength of 400 nm to 360
The average light transmittance between nm is 35% or less, and the wavelength is 360 nm.
Is preferably 10% or less. However, the evaluation method in the case of the thickness of 2 mm is not limited, and it is preferable to maintain the light absorbing ability and the high transparency regardless of the thickness.

As an index of transparency, in addition to the above-mentioned light transmittance, a haze value (cloudiness) represented by the ratio of the total light transmittance to the diffuse transmittance is also representative. However, the haze value varies greatly depending not only on the dispersed particle diameter of the metal compound, but also on the sample thickness, the sample surface state, and the crystallinity (crystallinity, spherulite size, orientation, etc.) of the base resin, If transparency is required, when the thickness of the thermoplastic polyester resin molded article of the present invention is 2 mm, the haze value is 30% or less, and a resin having good transparency such as PET is used. 20 when the thickness is 0.3mm
% Or less, more preferably 10% or less.

As a method for producing a molded article comprising the thermoplastic polyester resin composition of the present invention, first, a blend of an ultraviolet absorbent and a dispersant is dry-blended with a thermoplastic polyester resin and melt-kneaded. To obtain a resin composition. When performing this melt-kneading,
Various kneaders such as a single screw extruder, a twin screw extruder, and a Brabender type kneader can be used. Second, a molded article made of the resin composition is obtained by injection molding, blow molding, or injection molding and stretch blow molding, and various molding methods such as sheet molding and vacuum molding can be used.

The above-mentioned polyester resin composition may be used as a compound as it is as a molded product. However, a masterbatch in which an inorganic ultraviolet absorbent and an organic dispersant are previously blended is prepared using the above kneading machine. It is preferable to form a molded product by diluting the ultraviolet-ray absorbing agent and the organic dispersing agent so as to have a concentration in the above-mentioned range by using these molding methods. The amount of the inorganic ultraviolet absorber in such a masterbatch is 0.01 to 50 parts by weight, preferably 5 to 20 parts by weight.

In particular, a polyester resin composition using a doped metal compound as an ultraviolet absorber is used as a master patch, diluted with a thermoplastic polyester resin containing no metal compound, and a thermoplastic polyester resin 1
A polyester resin composition is used in which the metal compound excluding the metal used for the dope is 0.01 to 20 parts by weight with respect to 00 parts by weight. When the amount is less than 0.01 part by weight, the transparency as compared with the blank is almost the same, but the ultraviolet absorbing ability is inferior. When the amount is more than 20 parts by weight, the ultraviolet absorbing ability is excellent, but the transparency is remarkably reduced.

The molded article made of the thermoplastic polyester resin composition of the present invention can be obtained by adding a thermoplastic polyester resin to
Although it may be a single-layer molded article made of a resin composition obtained by blending an inorganic ultraviolet absorber and an organic dispersant, a multilayer molded article having at least one polyester resin composition layer may be used. Is also preferably performed. The polyester resin composition layer may be present at any position in the multilayer molded article, or may be two or more layers, depending on the purpose. For example, it may be the outermost layer or the innermost layer,
It may be an intermediate layer.

Examples of the resin to be multilayered include natural thermoplastic polyester resin containing no metal compound and dispersant, polyamide, saponified ethylene-vinyl acetate copolymer, polyvinylidene chloride, polyolefin and the like. When the adhesiveness with the polyester resin composition layer is poor, it is preferable to provide an adhesive layer between them.

As described above, the thickness of the polyester-based resin composition layer is set so as to satisfy the ultraviolet absorbing ability and the high transparency, and the thickness of the other resin layers is determined for transparency, barrier property and the like. Determined according to required quality. The light absorbing ability of the multilayer molded article reflects the ultraviolet absorbing ability of the resin composition layer, and the transparency is multi-layered. By forming a multilayer with a highly transparent resin, high transparency can be maintained.

As an example of a method for molding a bottle using these thermoplastic polyester-based resin compositions, the following methods are mainly mentioned.

<Bottle Molding Method-1> The above-mentioned polyester-based resin and the inorganic ultraviolet absorbent and the organic dispersant adjusted to a predetermined compounding ratio in advance were mixed with a tumbler-type mixer, a ribbon mixer, a Henschel mixer or the like. A dry blended product of the composition is prepared, and put into hoppers of various molding machines such as direct blow, stretch blow, injection and stretch blow molding, and then various bottles are formed.

<Bottle Molding Method-2> A dry blend of the above-mentioned polyester resin composition is prepared using the above-mentioned polyester resin and inorganic ultraviolet absorber in advance using a tumbler type mixer, ribbon mixer, Henschel mixer or the like. In advance, these polyester resin compositions are melt-kneaded using a Banbury mixer, a kneader, a twin-screw extruder or the like, and a compound of the polyester-based resin composition is prepared in advance. Thereafter, these compounds are put into hoppers of the above-described various bottle forming machines, and then each molding is performed. When preparing the compound, besides dry blending the polyester resin and the inorganic UV compound, a powder feeder is used to separately supply a mixture of the inorganic UV compound and the organic dispersant to various kneaders. It does not matter.

The above two methods correspond to a method for producing a large polyester resin bottle. As the production method, the <bottle molding method-2> is more advantageous in terms of kneadability and dispersibility of an inorganic compound having an ultraviolet absorbing ability. Highly preferred, furthermore, a high concentration dispersion is prepared in advance with an inorganic ultraviolet absorber in a range of 50 parts by weight or less based on 100 parts by weight of the polyester resin (master batch),
When forming a bottle, it is very preferable to dilute the masterbatch and form it in terms of cost and work efficiency.

In the molding, not only a single-layer bottle of the polyester resin composition to which the above-mentioned inorganic ultraviolet absorbent is added, but also a co-extrusion multilayer molding with various resins is performed. At least one layer of the constitution may be a layer of a polyester resin composition to which an inorganic ultraviolet absorbing material is added.

Representative examples of the layer structure of these polyester resin bottles are shown below. In the following constitutional examples, a polyester resin containing an ultraviolet absorber is referred to as a polyester resin composition layer. (1) Polyester resin composition layer (single layer) (2) Polyester resin composition layer / recycled polyester resin layer / polyester resin layer or polyester resin composition layer (multilayer)

As described above, various bottle configurations are conceivable, including not only a single layer but also a recycled polyester resin layer as an intermediate layer. However, the present invention is not limited to these configurations. The polyester resin composition layer can be formed in a polyester resin bottle. Further, the thickness of these polyester resin composition layers is preferably at least 0.3 mm or more from the viewpoint of transparency and the effect of absorbing ultraviolet light.

In addition to the bottles described above, the molded article can be developed in various forms such as films, sheets and trays, and additives such as coloring agents may be added as necessary. .

[0071]

EXAMPLES Examples of the present invention will be described below, but the technical scope of the present invention is not limited to these examples.

<Example 1> Polyethylene terephthalate (PET) was used as a thermoplastic polyester resin, and the average primary particle diameter was 20 as a metal compound having an ultraviolet absorbing ability.
A Cr-doped zinc oxide having a thickness of nm was used (the Cr-doping method was an ion implantation method), and a carboxylic acid-modified low-molecular-weight polyolefin wax was used as a dispersant. At this time, the addition amount of zinc oxide was set to 0.3 parts by weight and the dispersant was set to 0.225 parts by weight (R = addition amount of dispersant / addition amount of metal compound = 0.75) based on 100 parts by weight of PET. Using a twin screw extruder,
The mixture of the metal compound and the dispersant is mixed with a molten PET.
After adding and kneading, the extruded molten resin was cooled with water and then pelletized to obtain dried pellets of a resin composition comprising PET, zinc oxide and a dispersant. Next, using the pellets, a square plate of Example 1 having a thickness of 2 mm and a size of 10 cm × 10 cm was obtained by injection molding.

Example 2 PET was used as a thermoplastic polyester resin, V-doped zinc oxide having an average primary particle diameter of 20 nm was used as a metal compound having an ultraviolet absorbing ability (the V-doping method was an ion implantation method), and a low-dispersion agent was used. A carboxylic acid modified product of a molecular weight polyolefin wax was used.
At this time, the addition amount of zinc oxide was set at 20.0 parts by weight and the dispersant was set at 15.0 parts by weight (R = addition amount of dispersant / addition amount of metal compound = 0.75) based on 100 parts by weight of PET. Using a twin screw extruder, the mixture of the metal compound and the dispersant is
After being added to and kneaded with the molten PET, the extruded molten resin was cooled with water and then pelletized to obtain dried pellets of a resin composition comprising PET, zinc oxide and a dispersant. Next, the pellets were blended with natural PET so that the zinc oxide concentration in the obtained molded article was 0.5 parts by weight, and injection molding was performed to obtain a 2 mm thick, 10 cm × 10 cm Example 2
Was obtained. Here, natural PET is PET that does not contain additives such as metal compounds and dispersants.

Example 3 PET was used as a thermoplastic polyester resin, Cr-doped titanium oxide having an average primary particle diameter of 20 nm was used as a metal compound having an ultraviolet absorbing ability (Cr-doping method was an ion implantation method), and a low-dispersion agent was used. A carboxylic acid modified product of a molecular weight polyolefin wax was used. At this time, the addition amount of zinc oxide was 0.3 parts by weight with respect to 100 parts by weight of PET, and the dispersant was 0.225 parts by weight (R
= Addition amount of dispersant / addition amount of metal compound = 0.75). Using a twin-screw extruder, the mixture of the metal compound and the dispersant is added to the molten PET, kneaded, and the extruded molten resin is water-cooled and pelletized to form a resin composition comprising PET, titanium oxide, and a dispersant. A dry pellet of the product was obtained.
Next, using the pellets, a thickness of 2 m is formed by injection molding.
Thus, a square plate of Example 3 having a size of 10 cm × 10 cm was obtained. Here, natural PET is PET that does not contain additives such as metal compounds and dispersants.

Example 4 PET was used as a thermoplastic polyester resin, and V-doped titanium oxide having an average primary particle diameter of 20 nm was used as a metal compound having an ultraviolet absorbing ability (V).
The doping method was an ion implantation method), and a carboxylic acid-modified low-molecular-weight polyolefin wax was used as a dispersant. At this time, the addition amount of zinc oxide was set at 20.0 parts by weight and the dispersant was set at 15.0 parts by weight (R = addition amount of dispersant / addition amount of metal compound = 0.75) based on 100 parts by weight of PET. Using a twin-screw extruder, the mixture of the metal compound and the dispersant is added to the molten PET, kneaded, and the extruded molten resin is water-cooled and pelletized to form a resin composition comprising PET, titanium oxide, and a dispersant. A dry pellet of the product was obtained. Next, the pellets were blended with natural PET so that the titanium oxide concentration in the obtained molded article was 0.5 parts by weight, and the thickness was 2 mm, 10 cm × 10 cm by injection molding.
Of Example 4 was obtained. Here, natural PET is PET that does not contain additives such as metal compounds and dispersants.

Example 5 PET was used as a thermoplastic polyester resin, and Cr-doped zinc oxide having an average primary particle diameter of 20 nm was used as a metal compound having an ultraviolet absorbing ability (C).
The r-doping method was an ion implantation method), and a carboxylic acid-modified low-molecular-weight polyolefin wax was used as a dispersant. At this time, the addition amount of zinc oxide was set at 20.0 parts by weight and the dispersant was set at 15.0 parts by weight (R = addition amount of dispersant / addition amount of metal compound = 0.75) based on 100 parts by weight of PET. Using a twin-screw extruder, the mixture of the metal compound and the dispersant is added to the molten PET, kneaded, and the extruded molten resin is water-cooled and pelletized to form a resin composition comprising PET, zinc oxide, and a dispersant. A dry pellet of the product was obtained. Next, the pellets were blended with natural PET so that the zinc oxide concentration in the obtained molded article was 0.5 parts by weight, and a preform was obtained by injection molding, and then the body was averaged by stretch blow molding. A bottle of Example 5 having a wall thickness of 0.8 mm and a capacity of 220 ml was obtained.

Example 6 PET was used as a thermoplastic polyester resin, V-doped zinc oxide having an average primary particle diameter of 20 nm was used as a metal compound having an ultraviolet absorbing ability (the V-doping method was an ion implantation method), and a low-dispersion agent was used. A carboxylic acid modified product of a molecular weight polyolefin wax was used.
At this time, the addition amount of zinc oxide was set at 20.0 parts by weight and the dispersant was set at 15.0 parts by weight (R = addition amount of dispersant / addition amount of metal compound = 0.75) based on 100 parts by weight of PET. Using a twin screw extruder, the mixture of the metal compound and the dispersant is
After being added to and kneaded with the molten PET, the extruded molten resin was cooled with water and then pelletized to obtain dried pellets of a resin composition comprising PET, zinc oxide and a dispersant. Next, the pellets were blended with natural PET so that the zinc oxide concentration in the obtained molded article was 0.8 parts by weight, and a preform was obtained by injection molding. Example 6 having a wall thickness of 0.8 mm and a capacity of 220 ml
Got a bottle.

Example 7 PET was used as a thermoplastic polyester resin, and Cr-doped zinc oxide having an average primary particle diameter of 20 nm was used as a metal compound having an ultraviolet absorbing ability (C).
The r-doping method was an ion implantation method), and a carboxylic acid-modified low-molecular-weight polyolefin wax was used as a dispersant. At this time, the addition amount of zinc oxide was set to 2.0 parts by weight and the dispersant to 2.0 parts by weight (R = addition amount of dispersant / addition amount of metal compound = 1) based on 100 parts by weight of PET. Using a twin-screw extruder, the mixture of the metal compound and the dispersant is added to the molten PET, kneaded, and the extruded molten resin is water-cooled and pelletized to form a resin composition comprising PET, zinc oxide, and a dispersant. A dry pellet of the product was obtained. Next, after using the dried pellets of this resin composition for the intermediate layer to obtain a multilayer preform of natural PET / resin composition / natural PET by injection molding, natural PET (thickness 200 μm) / Resin composition (thickness 4
A multilayer bottle of Example 7 having an average body thickness of 0.8 mm and a capacity of 220 ml of (00 μm) / natural PET (200 μm in thickness) was obtained.

Comparative Example 1 An injection-molded square plate of Comparative Example 1 was obtained in the same manner as in Example 1, except that the metal compound and the dispersant were not added.

Comparative Example 2 An injection molded plate of Comparative Example 2 was obtained in the same manner as in Example 1, except that no dispersant was added.

<Comparative Example 3> PET as a thermoplastic resin
Was used as a metal compound having an ultraviolet absorbing ability by using Cr-doped zinc oxide having an average primary particle diameter of 20 nm (the Cr-doping method was an ion implantation method), and no dispersant was used. At this time, the addition amount of zinc oxide was set to 20.0 parts by weight based on 100 parts by weight of PET. Using a twin-screw extruder, after adding and kneading this metal compound to PET in a molten state,
The extruded molten resin was water-cooled and pelletized to obtain pellets of a resin composition comprising PET and zinc oxide. However, PET was significantly deteriorated due to the photocatalytic activity of zinc oxide, and processing was impossible.

Comparative Example 4 An injection molded plate of Comparative Example 4 was obtained in the same manner as in Example 3, except that no dispersant was used.

Comparative Example 5 An injection molded plate of Comparative Example 5 was obtained in the same manner as in Example 3, except that titanium oxide not doped with metal was added.

<Comparative Example 6> PET as a thermoplastic resin
And a Cr-doped titanium oxide having an average primary particle diameter of 20 nm as a metal compound having an ultraviolet absorbing ability (the Cr-doping method is an ion implantation method). At this time, the addition amount of zinc oxide was set to 20.0 parts by weight based on 100 parts by weight of PET. Using a twin-screw extruder, this metal compound was added to PET in a molten state, kneaded, and then the extruded molten resin was water-cooled and pelletized to obtain pellets of a resin composition composed of PET and titanium oxide. However, PET was significantly deteriorated due to the photocatalytic activity of titanium oxide, and processing was impossible.

Comparative Example 7 A stretch blow bottle of Comparative Example 7 was obtained in the same manner as in Example 5, except that the metal compound and the dispersant were not added.

With respect to the body portions of the plates and bottles obtained in Examples 1 to 7 and Comparative Examples 1 to 7, the light transmittance was evaluated using a spectrophotometer and the transparency was evaluated using a haze meter. Table 1 shows the results.

[0087]

[Table 1]

The following can be said from these results. The above-mentioned molded article has excellent ultraviolet absorbing ability and can maintain high transparency by improving the dispersibility of the inorganic ultraviolet absorber (metal compound). Furthermore, by suppressing the photocatalytic activity of the inorganic ultraviolet absorber, there is no fear of deterioration during processing and after molding.

In Examples 1 to 7, carboxylic acid modification of PET, which is a thermoplastic polyester resin, with zinc oxide or titanium oxide doped with Cr or V as a metal compound, and a low molecular weight polyolefin wax as an organic dispersant. In a range of 0.1 ≦ R ≦ 5 in a ratio R of a dispersant addition amount / a metal compound addition amount R of 0.01 to 5 parts by weight of the metal compound and 100 parts by weight of the thermoplastic polyester resin. It is to set in.

Further, from Comparative Examples 1 and 7, it can be seen that when no metal compound is added, the ultraviolet absorbing ability is inferior. From Comparative Examples 2 and 4, it can be seen that when no dispersant is added, the dispersibility of the metal compound is reduced, so that the transparency is reduced. From Comparative Example 5, it can be seen that when only titanium oxide is added, its absorption edge is around 350 nm, so that ultraviolet rays in a high wavelength region cannot be blocked.

From Comparative Examples 3 and 6, without adding a dispersant,
When attempting to disperse a high concentration of a metal compound in PET, the photocatalytic activity of the metal compound cannot be suppressed.
It can be seen that T deteriorates during processing.

Next, a plastic bottle was formed by the method described below in addition to the above embodiment.

<Materials> (A) Polyester resin A-1 Polyethylene terephthalate (PET) A-2 Copolymer ester obtained by copolymerizing polyethylene terephthalate with 1,4-cyclohexanedimethanol A-3 Polylactic acid A-4 Polyethylene Phthalate (PEN) (B) Inorganic ultraviolet absorber B-1 Untreated zinc oxide (average particle size 20 nm) (C) Organic dispersant C-1 Maleic anhydride-modified ethylene propylene copolymer wax (molecular weight 1600)

<Method of preparing a master batch> A master batch of an inorganic UV absorber was prepared using the polyester resin (A) and the inorganic UV absorber (B).
The addition amount of the inorganic ultraviolet absorbent (A) in the master batch was set to 10 parts by weight based on 100 parts by weight of the polyester resin (A). The organic dispersant (C)
The ratio of the amount of the organic dispersant added / the amount of the inorganic ultraviolet absorber was unified to 0.75. A twin-screw extruder is used to create a masterbatch. The polyester resin is used in the hopper of the twin-screw extruder, and the inorganic UV absorber and the organic dispersion are dispersed using a powder feeder from the resin supply unit. The blend of agents was added. After adjusting the feeder so as to have a predetermined compounding ratio, the mixture was melt-kneaded at a processing temperature of 265 ° C. and a rotation number of 100 rotations. The compound in the molten state was extruded into strands, and then used as a master batch after water cooling, pelletizing, dehumidifying and drying.

<Bottle Molding Method> Using an injection / stretch blow molding machine and partly a direct blow molding machine, bottles were molded for each polyester resin. The molding temperature was set at 230 to 290 ° C. in accordance with the molding temperature of each resin. At this time, a masterbatch was prepared for each resin, and the amount of the inorganic ultraviolet absorber contained in those bottles was reduced to 100% of the polyester resin.
It diluted so that it might become 0.5 weight part with respect to weight part. At this time, the average thickness of the bottle is 0.8 mm.

<Evaluation Items> The processing conditions in twin-screw extrusion and bottle molding were summarized. Furthermore, the light transmittance of the obtained molded article was measured, and the light transmittance at 360 nm and the light transmittance ratio at 700 nm (containing no inorganic compound /
Inorganic compound). Further, as another index of transparency, the haze of the molded article was measured by a haze meter. In addition, 14
The sample was irradiated with a xenon lamp for 4 hours, and the presence or absence of functional discoloration was examined. Furthermore, the dispersion state of the inorganic ultraviolet absorbent secondary particles dispersed in the bottle and the laminated film was examined by a scanning electron microscope (SEM).

<Example 1> The above-mentioned polyethylene terephthalate resin (PET) (A-1) and untreated zinc oxide (B-
1) A maleic anhydride-modified ethylene propylene copolymer wax having a molecular weight of 1600 as an organic dispersant (C-
A bottle was molded using 1).

Comparative Example 1 Maleic anhydride-modified ethylene propylene copolymer wax having a molecular weight of 1600 (C-
The same as Example 1 except that the dispersant of 1) was not used.

Comparative Example 2 The same as Example 1 except that the ratio of the amount of the organic dispersant / the amount of the inorganic ultraviolet absorber was set to 10.

Comparative Example 3 The same as Example 1 except that the ratio of the amount of the organic dispersant / the amount of the inorganic ultraviolet absorber was 0.05.

<Comparative Example 4> An inorganic UV absorber and a polyethylene terephthalate resin (A-1) were directly stirred with a dry blend without adding a dispersant and without forming a master batch, and molding was performed directly. Other than the above, it is the same as the first embodiment. The inorganic UV absorber is 0.5 part by weight based on 100 parts by weight of the polyethylene terephthalate resin.

Example 2 Example 2 was the same as Example 1 except that the polyester resin was a copolymer ester (A-2) obtained by copolymerizing polyethylene terephthalate with 1,4-cyclohexanedimethanol.

Example 3 The same as Example 1 except that the polyester resin was polylactic acid (A-3).

Example 4 Example 4 was the same as Example 1 except that the polyester resin was polyethylene naphthalate (PEN) (A-4).

Table 2 shows the evaluation results of the above molded article bottles.

[0106]

[Table 2]

The following can be said from these results.

By mixing an inorganic UV absorber with various polyester resins and using a carboxylic acid-modified olefin copolymer as an organic dispersant, not only can the photocatalytic activity of zinc oxide be suppressed, but also the zinc oxide It is possible to obtain a polyester resin bottle having an ultraviolet absorbing effect while significantly improving the dispersibility and maintaining substantially the same transparency as the blank.

Further, it can be seen that when no dispersant is added, a hydrolysis reaction of the polyester resin is induced due to the remarkable influence of the photocatalytic activity, and a master batch cannot be obtained. Furthermore, when the mixing ratio of the dispersant greatly changes, the transparency is remarkably reduced. When the amount of the dispersant is large, the transparency is reduced due to the compatibility problem with the polyester resin. A decrease in transparency due to poor dispersion of the agent is observed. Further, as shown in an example in which a bottle was molded without adding a dispersant (Comparative Example 4), when a dispersant was not used, the dispersion of zinc oxide was very poor, and the dispersion became considerably large secondary particles. This results in poor appearance.

In some cases, an organic ultraviolet absorber is used for the polyester resin in order to minimize the transparency of the resin itself. However, as described above, at present, it is desirable to refrain from using an organic ultraviolet absorber as much as possible due to problems of hygiene, safety, dissolution, and halogen. The polyester resin bottle of the present invention has no hygiene, safety, or dissolution problems,
In addition, it is an interesting bottle because it is possible to suppress the decrease in transparency, which has been a problem in the past, as much as possible.

[0111]

According to the present invention, the photocatalytic activity of the inorganic ultraviolet absorber can be suppressed, the resin can be prevented from deteriorating, and it has ultraviolet absorbing ability, that is, ultraviolet shielding property. A molded article in which the original transparency of the resin is maintained can be produced. This effect is particularly remarkable when a compound obtained by modifying a low molecular weight polyolefin wax with a carboxylic acid is used as the organic dispersant.

Further, by using an inorganic ultraviolet absorber in which a metal compound is doped with a different kind of metal, the absorption edge of the ultraviolet wavelength is shifted to a longer wavelength side, thereby protecting contents which are modified or decomposed by ultraviolet light. It is possible.

Further, it is possible to solve the problem that the organic ultraviolet absorbent elutes into the contents and alters the contents, and that chlorine is introduced into the structure to shift the ultraviolet absorption end to the longer wavelength side. It is possible to obtain a molded article excellent in hygiene, heat resistance, light resistance and the like.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 3/22 C08K 5/09 5/09 5/10 5/10 5/20 5/20 C08L 23/02 C08L 23/02 B65D 1/00 A F term (reference) 3E033 BA15 BA16 BA17 CA20 FA03 3E064 BA54 BB03 BC13 BC14 EA04 EA05 EA07 4F070 AA47 AC14 AC15 AE23 AE28 FB03 4F071 AA15 AA20 AA30 BB07 BB13 BC01 BC04 BC12 4J002 AE052 BB032 BB122 BB152 BB202 BB212 CF031 CF061 CF081 CF101 CF191 DE096 DE106 DE116 DE136 FB076 FD056 GF00 GG01 GG02

Claims (14)

[Claims] 1. A resin composition in which an inorganic UV absorber and an organic dispersant are mixed in a thermoplastic polyester resin, wherein the amount of the inorganic UV absorber added is 0 to 100 parts by weight of the thermoplastic polyester resin. 0.01 to 50 parts by weight,
The ratio of the amount of the organic dispersant added to the amount of the inorganic UV absorber (R = the amount of the organic dispersant added / the amount of the inorganic UV absorber) is 0.1 ≦ R ≦ 5. Polyester-based resin composition. 2. The method according to claim 1, wherein the inorganic ultraviolet absorber is a metal compound of zinc oxide, titanium oxide, cerium oxide, iron oxide, or a mixture thereof.
The polyester-based resin composition according to item 1. 3. The polyester resin composition according to claim 2, wherein the metal compound is a metal compound which is doped with a metal different from the metal species. object. 4. The method according to claim 1, wherein the metal doped in the metal compound is a transition metal element or Li, Mg, Al, Ga, In,
The polyester-based resin composition according to claim 3, wherein at least one of Sn and Sb is contained. 5. The method according to claim 1, wherein the acid component of the thermoplastic polyester resin is
The terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, succinic acid, adipic acid, succinic acid, sebacic acid, or at least one selected from the group consisting of: Polyester resin composition. 6. The diol component of the thermoplastic polyester resin is a glycol such as ethylene glycol, propylene glycol, brene glycol, 1,4-cyclohexanedimethanol, or a polyethylene glycol, polypropylene glycol, polytetramethylene glycol, or the like. The polyester-based resin composition according to any one of claims 1 to 5, wherein the polyester-based resin composition is selected from at least one of polyoxyalkylene glycols. 7. The polyester resin composition according to claim 1, wherein the thermoplastic polyester resin comprises a polymer of oxyacid or a copolymer of oxyacid. 8. A low-molecular-weight polyolefin wax of polyethylene, polypropylene or ethylene-propylene copolymer, or a carboxylic acid-modified or copolymer thereof, wherein the organic dispersant has an average molecular weight in the range of 500 to 10,000 according to a viscosity method. A polyester resin composition comprising at least one of a carboxylic acid-modified product or a higher fatty acid or a metal salt, ester or amide thereof. 9. A molded article such as a packaging bag or a bottle, which is molded with a resin layer using the polyester resin composition according to any one of claims 1 to 8. 10. The polyester resin composition using a doped metal compound as a master patch as the ultraviolet absorber according to claim 3 or 4, which is diluted with a thermoplastic polyester containing no metal compound. Packaging characterized by being formed of a resin layer using a polyester resin composition in which a metal compound excluding a metal used for dope is 0.01 to 20 parts by weight with respect to 100 parts by weight of a plastic polyether resin. Molded articles such as bags and bottles. 11. A package formed by a multilayer resin layer containing the polyester resin composition according to any one of claims 1 to 8 as at least one layer as a resin layer constituting a molded article. And molded articles such as bottles. 12. A light transmittance at a wavelength of 700 nm, a light transmittance (A) of a resin layer of a molded article made of a polyester-based resin alone, and an inorganic ultraviolet absorption according to any one of claims 1 to 8. The ratio (A / B) of the light transmittance (B) of the resin layer composed of the polyester resin composition composed of the agent and the organic dispersant to 1 to 2 is 1 to 2. A molded article such as the package and the bottle according to any one of the preceding claims. 13. The resin layer constituting the molded product has a thickness of 0.3.
mm or more, the light transmittance at a wavelength of 360 nm is 10
% Or less, and the molded article such as a package and a bottle according to any one of claims 9 to 12. 14. The resin layer having a thickness of 0.3 mm or more has a haze value of 20% or less.
The molded article such as the package and the bottle according to any one of the above.