JP2002020592A - Polyester resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition which has good crystallinity and ultraviolet-cutting property, and has a high compatibility. SOLUTION: Polyethylene terephthalate (A) 9
9.5 to 70 parts by weight, and 95 to 100 mol% of the acid component are 2,6-naphthalenedicarboxylic acid units and terephthalic acid and / or isophthalic acid units, and
A polyester resin composition comprising 0.5 to 30 parts by weight of a thermoplastic polyester (B) in which 0 to 100 mol% is tetramethylene glycol.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to polyethylene terephthalate (hereinafter sometimes abbreviated as "PET").
And a thermoplastic polyester (hereinafter abbreviated as "PBNT") having 2,6-naphthalenedicarboxylic acid unit, terephthalic acid and / or isophthalic acid unit as an acid component, and tetramethylene glycol as a main glycol component. The present invention relates to a polyester resin composition comprising: More specifically, the present invention relates to a PET / PBNT composition which has improved crystallinity and ultraviolet cut properties of PET and has a high compatibility.

[0002]

2. Description of the Related Art A composition comprising polytetramethylene naphthalate (hereinafter sometimes abbreviated as "PBN") and PET has a PBN / PET = 0.02 / 99.98-1.
It is known in the range of 0/90 (weight ratio). JP-A-4-
No. 239625 discloses that PBN / PET = 0.2 / 9.
A polyester composition consisting of 9.8 to 10/90 parts by weight is described. JP-A-4-239528 describes a composition in which PBN is mixed with PET at a ratio of 0.02 to 0.2% by weight. These technologies are
The purpose is to improve the light fastness of PET.

[0003]

For use in fibers, films, sheets, resin molded articles, food packaging containers (bottles, containers, etc.) and non-food containers (pharmaceuticals, drinks, etc.), polyester is crystalline. In addition, when a blend of a plurality of polyesters is used, the compatibilizing rate of the polyester constituting the blend needs to be high. The present invention does not impair the gas barrier properties of polyester used for fibers, films, sheets, resin molded products, food packaging containers (bottles, containers, etc.), and non-food containers (pharmaceuticals, drinks, etc.), and provides heat resistance. It is another object of the present invention to provide a PET / PBNT composition having a high compatibilization rate, which is further provided with improved crystallinity and ultraviolet cut properties.

[0004]

That is, the present invention relates to 99.5 to 70 parts by weight of polyethylene terephthalate (A), wherein 95 to 100 mol% of the acid component is 2,6-naphthalenedicarboxylic acid unit and terephthalic acid. And / or isophthalic acid units, and the thermoplastic resin (B) is 0.5 to 30 parts by weight of a thermoplastic polyester (B) in which 70 to 100 mol% of a glycol component is tetramethylene glycol. Hereinafter, the present invention will be described in detail.

[Polyethylene terephthalate (A)] Polyethylene terephthalate (A) is a thermoplastic polyester having a terephthalic acid unit as an acid component and ethylene glycol as a glycol component. As the above components, it is preferable that ethylene glycol is a component of 90 mol% or more of the total glycol components.

[0006] Polyethylene terephthalate (A) includes
A dicarboxylic acid other than terephthalic acid may be contained as a copolymer component, and a glycol component other than ethylene glycol may be contained as a copolymer component. Further, an oxycarboxylic acid component and a compound having three or more functional groups may be copolymerized.

[0007] The intrinsic viscosity of polyethylene terephthalate (A) is preferably 0.6 to 1.2, more preferably
It is 0.6-1.0, more preferably 0.7-0.9. When the intrinsic viscosity is lower than 0.6, physical properties such as a decrease in impact strength and a decrease in stretch moldability are unfavorably caused. On the other hand, if the intrinsic viscosity is higher than 1.2, the productivity is poor and the stretch moldability is undesirably reduced.

[Thermoplastic polyester (B)] In the thermoplastic polyester (B), 95 to 100 mol% of the acid component is composed of 2,6-naphthalenedicarboxylic acid units and terephthalic acid and / or isophthalic acid units, 7 of the component
It is a thermoplastic polyester in which 0 to 100 mol% is tetramethylene glycol. Then, the ratio of the 2,6-naphthalenedicarboxylic acid unit to the terephthalic acid and / or isophthalic acid unit of the thermoplastic polyester (B) is preferably 90/10 to 50/50 (mol% / mol%),
More preferably, it is 90/20 to 60/40 (mol% / mol).

When the proportion of 2,6-naphthalenedicarboxylic acid units exceeds 90 mol%, the compatibilization with PET becomes slow, and when the proportion is less than 50 mol%, the gas barrier property and the UV cut property of PET are improved. The mixing ratio of PBNT increases, and the moldability decreases, which is not preferable. In addition, terephthalic acid and / or
If the proportion of isophthalic acid units is less than 10 mol%, the rate of compatibilization with PET decreases, and if it exceeds 50 mol%, the melting point and glass transition temperature of PBNT unfavorably decrease.

The thermoplastic polyester (B) contains 2,6
-A dicarboxylic acid other than naphthalenedicarboxylic acid may be contained as a copolymer component, and a glycol component other than tetramethylene glycol may be contained as a copolymer component. Further, an oxycarboxylic acid component and a compound having three or more functional groups may be copolymerized.

The intrinsic viscosity of the thermoplastic polyester (B) is preferably 0.5 to 1.5, more preferably 0.6.
To 1.3, more preferably 0.7 to 1.2. If the intrinsic viscosity is less than 0.5, physical properties such as impact strength decrease and stretch moldability decrease, which is not preferable.
If the intrinsic viscosity exceeds 1.5, the productivity is poor, which is not preferable. Solid-phase polymerization may be performed in order to keep the intrinsic viscosity within the range of the present invention.

The melting point of the thermoplastic polyester (B) is 1
The temperature is preferably from 65 ° C to 225 ° C. When the temperature is lower than 165 ° C., fusion occurs at the time of drying, and when the temperature is higher than 225 ° C., compatibilization by melt kneading with PET is unfavorably slow.

[Copolymer Component] The polyethylene terephthalate (A) and the thermoplastic polyester (B) may be used by copolymerizing a copolymer component. Examples of the acid component of the copolymer component include 2,7-, 1,5-, 1,7- and other isomers of naphthalenedicarboxylic acid; isophthalic acid;
Aromatic dicarboxylic acids such as diphenyl dicarboxylic acid, diphenoxyethane dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenyl sulfone dicarboxylic acid; alicyclic dicarboxylic acids such as hexahydroterephthalic acid and hexahydroisophthalic acid; adipic acid, sebacic acid;
Examples include aliphatic dicarboxylic acids such as azelaic acid; and difunctional carboxylic acids such as oxyacids such as p-β-hydroxyethoxybenzoic acid and ε-oxycaproic acid.

As the glycol component of the copolymer component, ethylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, decamethylene glycol, neopentyl glycol, diethylene glycol, 1,1-cyclohexanedimethanol,
Examples thereof include 1,4-cyclohexanedimethanol, 2,2-bis (4′-β-hydroxyphenyl) propane, and bis (4′-β-hydroxyethoxyphenyl) sulfonic acid.

[Composition ratio] The composition ratio between polyethylene terephthalate (A) and thermoplastic polyester (B) is as follows:
(A) 99.5 to 70 parts by weight, (B) 0.5 to 3 parts by weight
0 parts by weight, preferably (A) 99 to 80 parts by weight, (B) 1 to 20 parts by weight, more preferably (A) 98 to 8 parts by weight.
(B) 2 to 15 parts by weight with respect to 5 parts by weight. If the amount of polyethylene terephthalate (A) is less than 70 parts by weight, the intrinsic properties of PET such as moldability will be greatly impaired. When the amount of the thermoplastic polyester (B) is less than 0.5 part by weight, the effect of improving the crystallinity and ultraviolet ray cut property is low, and when the amount is more than 30 parts by weight, the moldability is largely reduced.

[Production Method of Polyester Resin Composition] Polyethylene terephthalate (A) and thermoplastic polyester (B) are melt-mixed using, for example, a single screw extruder, a twin screw extruder, an injection molding machine, and a film forming machine. Thereby, the polyester resin composition of the present invention can be obtained. In the melt mixing, it is preferable that the components are uniformly micro-dispersed, but the components may be partially reacted to perform block copolymerization.
Therefore, the temperature at the time of melt-kneading differs depending on the kneading equipment and the mixing ratio of the polyethylene terephthalate (A) and the thermoplastic polyester (B), etc.
C is preferable, and 280C to 330C is preferable.

When the polyethylene terephthalate (A) and the thermoplastic polyester (B) are melt-kneaded, it is preferable that conditions satisfying a relationship represented by the following formula (1) are satisfied. k ≧ 0.90 (1) (where k = [100% − (haze value of blend obtained after melt kneading (%))] ÷ (residence time (second) during melt kneading) (Compatibilization rates and haze values are for 300 μm thick bottle pieces of the blend; these values are at 295 ° C.)

[Haze, Crystallization Temperature from Solid State, Glass Transition Temperature] The transparency of the polyester resin composition of the present invention, as a haze value, is preferably 10% or less, more preferably 5% or less, more preferably 5% or less. Preferably it is 2% or less.
If the haze value exceeds 10%, it is not preferable for applications requiring transparency. The crystallization temperature from the solid state is preferably from 120 ° C to 150 ° C, more preferably from 120 ° C to 1 ° C.
The temperature is 40 ° C, more preferably 125 ° C to 140 ° C. 1
If the temperature is lower than 20 ° C., crystallization is fast,
It is not preferable because the transparency is lowered. The glass transition temperature is preferably from 65C to 85C, more preferably from 70C to 85C. If the glass transition temperature is lower than 65 ° C., the heat treatment after filling the contents for the purpose of sterilization in a packaging container or the like, or the filling of high-temperature contents that have been subjected to a heat sterilization treatment is large, which is not preferable. Further, when a resin molded product is used, it is difficult to use it in a state where a certain temperature is applied, which is not preferable.

[Additives] The polyester resin composition includes:
Fillers, lubricants, colorants, light stabilizers, heat stabilizers, ultraviolet absorbers, fluorescent brighteners, and other various additives may be added. Examples of the ultraviolet absorber include a benzotriazole compound, a triazine compound, a benzophenone compound, a cyanoacrylate compound, and a benzoxazine compound.

As the benzotriazole compound, 2
-(2H-benzotriazol-2-yl) -4-methylphenol, 2- (2H-benzotriazol-2-yl)
Yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazole-2)
-Yl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2- (2H-benzotriazole-2)
-Yl) 4,6-bis (1,1-dimethylethyl) phenol, 2- (5-chloro-2H-benzotriazol-2-yl) -6- (1,1-dimethylethyl-4-methyl) phenol , 2- (2H-benzotriazole-
2-yl) -4,6-bis (1,1-dimethylpropyl) phenol, 2,2′-methylenebis [6- (2H
-Benzotriazol-2-yl) -4- (1,1,
3,3-tetramethylbutyl) phenol, 2- (2H
-Benzotriazol-2-yl) -6-dodecyl-4
-Methylphenol, among which 2- (2H
-Benzotriazol-2-yl) -4-methylphenol, 2- (2H-benzotriazol-2-yl)-
4,6-bis (1-methyl-1-phenylethyl) phenol is preferably used.

As the triazine compound, 2- (4,4
6-diphenyl-1,3,5-triazin-2-yl)
-5- (hexyloxy) phenol, 2- [4,6-
Bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol, 1,5,8,12-tetrakis [4,6-bis (N
-Butyl-N-1,2,2,6,6-pentamethyl-4
-Piperidylamino) -1,3,5-triazine-2-
Yl] -1,5,8,12-tetraazododecane, among which 2- (4,6-diphenyl-1,3,3
5-triazin-2-yl) -5- (hexyloxy)
Phenol is preferably used.

Examples of the benzophenone compound include 2-hydroxy-4-methoxy-5-sulfobenzophenone,
2-hydroxy-4-n-octoxybenzophenone,
2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone are exemplified.

As the cyanoacrylate compound, 2
-Ethylhexyl-2-cyano-3,3'-diphenyl acrylate and 2-ethyl-2-cyano-3,3'-diphenyl acrylate.

As the benzoxazine-based compound, 2-
p-methoxyphenyl (3,1-benzoxazine-4
-One), 2-α-naphthyl (3,1-benzoxazin-4-one), 2-β-naphthyl (3,1-benzoxazin-4-one), 2-p-phthalimidophenyl (3,1 -Benzoxazin-4-one), 2,2'-
Bis (3,1-benzoxazin-4-one), 2,
2'-p-phenylenebis (3,1-benzoxazin-4-one), 2,2 '-(4,4'-diphenylene)
Bis (3,1-benzoxazin-4-one), 2,
2 ′-(2,6- or 1,5-naphthalene) bis (3,
1-benzoxazin-4-one) and 1,3,5-tri (3,1-benzoxazin-4-one-2-yl) benzene, among which 2,2′-bis (3
1-benzoxazin-4-one), 2,2'-p-phenylenebis (3,1-benzoxazin-4-one)
Is preferably used.

Examples of the colorant include oxide pigments, ferrocyanide pigments, silicate pigments, phosphate pigments, carbon black, condensed polycyclic pigments, and phthalocyanine pigments.

Examples of oxide pigments include titanium dioxide, ferric oxide (bengara), chromium oxide, cobalt blue (cobalt oxide / aluminum oxide composite oxide pigment), zinc oxide (zinc white), and lead tetroxide ( Lead red), cuprous oxide (cuprous oxide), and titanium nickel yellow. As the ferrocyanide pigment, navy blue can be exemplified. Manganese violet can be exemplified as the phosphate pigment. An example of the condensed polycyclic pigment is an anthraquinone pigment. Examples of the phthalocyanine pigment include phthalocyanine blue, metal-free phthalocyanine, phthalocyanine green, and fast sky blue. Examples of the silicate pigment include ultramarine blue, talc, and white carbon. Preferred examples of the white carbon include anhydrous silicic acid, hydrous silicic acid, hydrous magnesium silicate, hydrous calcium silicate, and hydrous aluminum silicate.

Examples of the heat stabilizer (antioxidant) include monophenol-based, bisphenol-based, polymer-type phenol-based, and phosphorus-based ones.

As the monophenols, 2,6-di-
t-butyl-p-cresol, butylhydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, stearyl-β- (3,5-di-tert-butyl-4-
(Hydroxyphenyl) propionate. Among them, stearyl-β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate is preferred.

The bisphenols include 2,2'-methylenebis (4-methyl-6-t-butylphenol) and 2,2'-methylenebis (4-ethyl-6-t-
Butylphenol), 4,4′-thiobis (3-methyl-6-t-butylphenol) and 4,4′-butylidenebis (3-methyl-6-t-butylphenol).

As the polymer type phenol, 1,1,1
3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,
4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3-
(3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane and α-tricolor. Among them, tetrakis- [methylene-3-
(3 ′, 5′-Di-tert-butyl-4′-hydroxyphenyl) propionate] methane is preferred.

Examples of the phosphorus system include triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, 4,4'-butylidene-bis (3-methyl-6-t-butylphenyl ditridecyl) phosphite, and cyclic. Neopentanetetraylbis (octadecylphosphite), tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis (2,4-di-t) -Butylphenyl)
Phosphite and cyclic neopentanetetraylbis (2,6-di-t-butyl-4-methylphenyl) phosphite. Among them, cyclic neopentanetetraylbis (octadecylphosphite), tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis ( 2,4-di-
(t-Butylphenyl) phosphite is preferred.

Examples of the light stabilizer include hindered amine-based light stabilizers. Tin stabilizers of Tinba Specialty Chemical Co., Ltd.
uvin-622, ADK STAB LA of Asahi Denka
-57, LA77, LA67 and the like.

[Molded Article] The polyester resin composition of the present invention can be used as a molded article. Examples of the molded article include a hollow molded article, a film, a sheet, and a resin molded article. These compacts may be a single-layer compact or a multilayer compact. In the case of a multilayer, the composition of the present invention can be used as a material constituting a surface layer or an intermediate layer. That is, according to the present invention, there is provided a multilayer molded article comprising a surface layer and an intermediate layer, wherein at least one of the surface layers comprises the polyester resin composition of the present invention, and a multilayer molded article comprising the surface layer and the intermediate layer A multilayer molded article is provided wherein at least one of the intermediate layers comprises the polyester resin composition of the present invention.

[Method of Manufacturing Molded Body] As a method of manufacturing a hollow molded body, a hot parison method in which an injection unit and a blow unit are integrated, a cold parison method in which an injection unit and a blow unit are separate facilities, and a direct blow method Method, injection blow method, extrusion blow method,
Alternatively, a method of processing once into a sheet and a film and then thermoforming can be used. As a method for producing a film and a sheet, a method for forming an unstretched film and a sheet by a single-screw or twin-screw extruder can be used, and further, a method for uniaxially or biaxially stretching and a method for inflation molding can be used. it can. Injection molding, gas injection molding, extrusion molding, compression molding, and the like can be used as a method for molding the resin molded body.

[0035]

The present invention will be described below in more detail with reference to examples. The characteristics in the examples were measured by the following methods. (1) A sample having a thickness of 300 μm is cut out from an arbitrary portion of the body of the haze bottle, and Color and c manufactured by Nippon Denshoku Industries Co., Ltd.
color difference meter (MODE
L1001DP). (2) Glass transition temperature (Tg), crystallinity (Tci), melting point (Tm), intrinsic viscosity (IV), acetaldehyde (A
A) Content In case of bottle, cut out sample from mouth and DuPo
nt DSC (MODEL2200) with a heating rate of 5
° C / min. Was measured. IV was measured at 25 ° C. with tetrachloroethane: phenol = 4: 6 (weight ratio). The AA content was determined by freeze-crushing a sample, charging the sample in a vial bottle, holding at 150 ° C. × 60 minutes, and using headspace gas chromatography manufactured by Hitachi. (3) Ultraviolet ray cutability A sample having a thickness of 300 μm (bottle) is cut out from an arbitrary part of the body of the bottle, and ultraviolet is used.
and visible spectrum
The light transmittance was measured with a ter. (4) Polyethylene terephthalate (A) Polyethylene terephthalate (A) was prepared by the method of the following reference example.

Reference Example 1 A polyethylene terephthalate (trade name: TR8550T) manufactured by Teijin was prepared. (5) Production of thermoplastic polyester (B) Thermoplastic polyester (B) was produced by the method of the following reference example.

REFERENCE EXAMPLE 2 80 parts by weight of dimethyl 2,6-naphthalenedicarboxylate, 17 parts by weight of dimethyl terephthalate and 65 parts by weight of tetramethylene glycol were used as a by-product of methanol by using tetra-t-butoxytitanium as a catalyst. Is removed from the system and transesterified while heating to 210 ° C., and then the reaction product is subjected to a polycondensation reaction under high temperature and high vacuum to obtain an intrinsic viscosity (2 parts by weight of tetrachloroethane and 3 parts by weight of phenol). , A mixed solvent of 25 ° C.) 0.80 (Reference Example 2).

Reference Example 3 60 parts by weight of 2,6-naphthalenedicarboxylic acid dimethyl ester, 32 parts by weight of dimethyl terephthalate and 65 parts by weight of tetramethylene glycol were used as a catalyst to produce methanol as a by-product using tetra-t-butoxytitanium as a catalyst. Is removed from the system and transesterified while heating to 210 ° C., and then the reaction product is subjected to a polycondensation reaction under high temperature and high vacuum to obtain an intrinsic viscosity (2 parts by weight of tetrachloroethane and 3 parts by weight of phenol). , A mixed solvent of 25 ° C.) and 0.85 (Reference Example 3).

Reference Example 4 60 parts by weight of 2,6-naphthalenedicarboxylic acid dimethyl ester, 32 parts by weight of dimethyl isophthalate and 65 parts by weight of tetramethylene glycol are by-produced using tetra-t-butoxytitanium as a catalyst. Methanol is distilled out of the system and transesterification is performed while heating to 210 ° C., and then the reaction product is subjected to a polycondensation reaction under high temperature and high vacuum to obtain an intrinsic viscosity (2 parts by weight of tetrachloroethane and 3 parts by weight of phenol). Of a mixed solvent (25 ° C.) of 0.87 (Reference Example 4).

Reference Example 5 100 parts by weight of 2,6-naphthalenedicarboxylic acid dimethyl ester and 65 parts by weight of tetramethylene glycol were used as a catalyst, using tetra-t-butoxytitanium as a catalyst, and by-produced methanol was distilled out of the system. The reaction product is subjected to a transesterification reaction while heating to 210 ° C., and then the reaction product is subjected to a polycondensation reaction under high temperature and high vacuum to obtain an intrinsic viscosity (a mixed solvent of 2 parts by weight of tetrachloroethane and 3 parts by weight of phenol, 25 ° C.) ) A polymer of 0.80 (Reference Example 5) was obtained.

Example 1 95 parts by weight of the polyethylene terephthalate (A) of Reference Example 1 and 5 parts by weight of the thermoplastic polyester (B) obtained in Reference Example 3 were mixed with an injection molding machine (M-100DM) manufactured by Meiki Seisakusho Co., Ltd. ) (Cylinder setting 295
° C, screw rotation speed 160 rpm, molding cycle 36
sec, residence time 100 sec) melt kneading, weight 55
g of preform was obtained. Table 1 shows the results. Subsequently, this preform was transferred to KRUPP CORPOPLA.
The bottle was blow-molded with LB01 manufactured by ST, and the bottle had an inner volume of about 1.5 L (liter) and an average body thickness of about 300 μm. In addition, the obtained bottle was evaluated. Table 1 shows the results
Shown in

[Examples 2 to 5, Comparative Examples 1 and 2]
Similarly to the above, the polyethylene terephthalate (A) of Reference Example 1 and the thermoplastic polyester (B) obtained in Reference Example were used in the proportions shown in Table 1 to form a bottle. evaluated. Table 1 shows the results.

[0043]

[Table 1]

[0044]

According to the present invention, it is possible to provide a resin composition which has good crystallinity and ultraviolet-cutting properties, and has a high compatibility.

Claims (6)

[Claims] 1. Polyethylene terephthalate (A) 9
9.5 to 70 parts by weight, and 95 to 100 mol% of the acid component are 2,6-naphthalenedicarboxylic acid units and terephthalic acid and / or isophthalic acid units, and
A polyester resin composition comprising 0.5 to 30 parts by weight of a thermoplastic polyester (B) in which 0 to 100 mol% is tetramethylene glycol. 2. The 2,6-form of the thermoplastic polyester (B)
The ratio of naphthalenedicarboxylic acid units to terephthalic acid and / or isophthalic acid units is 90/10 to 50/50
The polyester resin composition according to claim 1, which is (mol% / mol%). 3. The thermoplastic polyester (B) has a melting point of:
The polyester resin composition according to claim 1, wherein the temperature is 165C to 225C. 4. The method according to claim 1, wherein the haze is 10% or less.
The polyester resin composition according to any one of the above. 5. A crystallization temperature from a solid state of 120 ° C. or more.
The polyester resin composition according to any one of claims 1 to 3, which is at 150C. 6. The polyester resin composition according to claim 1, wherein the glass transition temperature is from 65 ° C. to 85 ° C.