JP2001040197A - Polyester resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester resin composition having excellent roll peeling properties, long run properties and heat stability, and the most suitable for calender processing by compounding an aliphatic phosphate compound into a polyester resin. SOLUTION: A polyester resin composition comprises compounding an aliphatic phosphate compound into a polyester resin. Further, the aliphatic phosphate compound is combined with at least one selected from a different organic phosphate compound, and/or a phenolic antioxidant and an organic phosphite compound. The aliphatic phosphate compound is a mono-, di-, or triphosphate compound of a 6-30C saturated or unsaturated higher aliphatic alcohol or a metal salt of the compound. The polyester resin composition usually comprises compounding per 100 pts.wt. of the polyester resin, 0.05-5.0 pts.wt. of the aliphatic phosphate compound, 0.01-1.0 pts.wt. of the phenolic antioxidant, 0.01-3.0 pts.wt. of the phosphite compound and 0.05-5.0 pts.wt. of the organic phosphate compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to calendering of polyester resin, and more particularly, to roll releasability.
To provide polyester resin that is excellent in long run property and heat stability, is useful for various sheets and films, such as shrink labels for food, cosmetics and beverages, heat-sealable films with fragrance retention, oil-resistant multilayer sheets, and is most suitable for calendering. It is in.

[0002]

2. Description of the Related Art Conventionally, extrusion molding of a polyester resin has been mainly used as a method for producing a sheet or a film because of its easy processing. However, extrusion molding is less sensitive to film thickness, width, direction, flow direction, etc. because it is affected by the friction of the die lip compared to calendar molding, and it is not suitable for mass production. There is a demand for a polyester resin that is capable of performing the following.

[0003] However, since polyester resin has a strong adhesive force to a roll when it is thermoplasticized, various lubricants have been studied. For example, various lubricants such as hydrocarbon lubricants such as polyethylene wax and paraffin wax, higher fatty acid lubricants, higher alcohol lubricants, metal soaps using higher fatty acids, aliphatic amide lubricants, and ester lubricants have been studied. It was not possible to obtain sufficient roll releasability and long run time.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to solve the conventional problems and to provide a polyester resin which is excellent in roll releasability, long run property and heat stability and is most suitable for calendering.

[0005]

Means for solving the above problems are as follows. One or more aliphatic phosphate ester compounds are blended with the polyester resin, and a different organic phosphate ester compound, phenolic antioxidant and / or organic phosphite compound is used in combination. Thereby, it is possible to obtain a polyester resin which is optimal for calendering with excellent roll releasability, long run property and thermal stability.

In the present invention, the polyester resin is
Polyethylene terephthalate, polybutylene terephthalate, a polymer of a mixed alcohol of ethylene glycol and 1,4-dihydroxymethylcyclohexane and terephthalic acid, poly-1,4-cyclohexane dimethylene terephthalate, polybutylene naphthalate, and a polyester resin Mixture of two or more, or, mainly polyester resin, polycarbonate, ABS,
Any mixture of other thermoplastic resins, such as polypropylene, polyethylene, polystyrene, nylon, rubber, etc., can be used.

The aliphatic phosphate compound in the present invention is a mono-, di- or tri-phosphate compound with a saturated or unsaturated higher aliphatic alcohol having 6 to 30 carbon atoms and a metal salt thereof. is there. The representative examples are fisted, but not limited to them. Examples of the aliphatic phosphate ester-based compounds used include triisodecyl phosphate, tridodecyl phosphate, trihexadecyl phosphate, trioctadecyl phosphate, dihexyl octadecyl phosphate, decyl dodecyl tridecyl phosphate, and dinonyl 1-methylpentyl. Phosphate, bis (2-methylhexadecyl) pentadecyl phosphate, eicosyl bis (12-tridecenyl) phosphate, tris (cis-9-octadecenyl) phosphate, cis-
9-octadecenyl dioctadecyl phosphate, ditetradecyl phosphate, diheptyl phosphate,
Dioctadecyl phosphate, didodecyl phosphate, nonyl tetradecyl phosphate, cis-9-octadecenyl octadecyl phosphate, hexadecyl decyl phosphate, diicosyl phosphate,
Bis (cis-9-octadecenyl) phosphate, dodecyl phosphate, octadecyl phosphate, eicosyl phosphate and octyl phosphate and their lithium, sodium, potassium, magnesium,
Metal salts of calcium, barium, zinc and aluminum are mentioned. The amount of addition of these aliphatic phosphate ester compounds is 0.05 to 5.0 parts by weight, preferably 0.1 to 2.0 parts by weight, based on 100 parts by weight of the polyester resin.
Parts by weight. If the addition amount is less than 0.05 part by weight, the roll lubricity is insufficient, and if it is more than 5.0 parts by weight, it may undesirably emerge on the surface.

Next, the phenolic antioxidants used in the present invention are described, but are not limited thereto. 2,6-di-tert-butylphenol, 2,6
-Di-tert-butyl-4-methylphenol, 2,
6-di-tert-butyl-4-ethylphenol, 2
-Tert-butyl-4,6-dimethylphenol,
2,4,6-tri-tert-butylphenol, 2-
tert-butyl-4-methoxyphenol, 3-methyl-4-isopropylphenol, 2,6-di-ter
t-butyl-4-hydroxymethylphenol, 2,2
-Bis (4-hydroxyphenyl) propane, bis (5
-Tert-butyl-4-hydroxy-2-methylphenyl) sulfide, 2,5-di-tert-amylhydroquinone, 2,5-di-tert-butylhydroquinone, 1,1-bis (3-tert-butyl- 4-hydroxy-5-methylphenyl) butane, bis (3-ter
t-butyl-2-hydroxy-5-methylphenyl) methane, 2,6-bis (2-hydroxy-3-tert-
Butyl-5-methylbenzyl) -4-methylphenol, bis (3-tert-butyl-4-hydroxy-5)
-Methylbenzyl) sulfide, bis (3-tert-
Butyl-5-ethyl-2-hydroxyphenyl) methane, bis (3,5-di-tert-butyl-4-hydroxyphenyl) methane, bis (3-tert-butyl-
2-hydroxy-5-methylphenyl) sulfide,
1,1-bis (4-hydroxyphenyl) cyclohexane, ethylenebis [3,3-bis (3-tert-butyl-4-hydroxyphenyl) butyrate], bis [2
-(2-hydroxy-3-tert-butyl-5-methylbenzyl) -4-methyl-6-tert-butylphenyl] terephthalate, 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -2 -Methyl propane,
4-methoxyphenol, cyclohexylphenol,
p-phenylphenol, catechol, hydroquinone, 4-tert-butylpyrocatechol, ethyl gallate, propyl gallate, octyl gallate, lauryl gallate, cetyl gallate, β-naphthol, 2,4
5-trihydroxybutyrophenone, tris (3,5-
Di-tert-butyl-4-hydroxyphenyl) isocyanate, 1,3,5-tri-methyl-2,4,6-
Tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 1,6-bis [2- (3,5-
Di-tert-butyl-4-hydroxyphenyl) propionyloxy] hexane, tetrakis [3- (3,5
-Di-tert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane, bis (3-cyclohexyl-2-hydroxy-5-methylphenyl) methane, bis [3- (3,5-di-tert-butyl-) 4-
Hydroxyphenyl) propionyloxyethyl] sulfide, n-octadecyl-3- (3,5-di-ter
t-butyl-4-hydroxyphenyl) propionate, bis [3- (3,5-di-tert-butyl-4-
Hydroxyphenyl) propionylamino] hexane,
2,6-bis (3-tert-butyl-2-hydroxy-5-methylphenyl) -4-methylphenol, bis [S- (4-tert-butyl-3-hydroxy-2,
6-di-methylbenzyl)] thioterephthalate, tris [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, 1,1,3-tris (3-tert- Butyl-
4-hydroxy-6-methylphenyl) butane and the like. These phenolic antioxidants are added in an amount of 0.01 to 1: 1 based on 100 parts by weight of the polyester resin.
0 parts by weight, preferably 0.02 to 0.8 parts by weight. If the addition amount is less than 0.01 parts by weight, the thermal stability at the time of molding processing becomes incongruous. Adhesion to occurs. Further, even if it is added in an amount of 1.0 part by weight or more, the effect of the present invention is saturated and it is not economical.

Next, examples of the organic phosphite compound used in the present invention will be described, but the present invention is not limited to these compounds. Triphenyl phosphite, tris (methylphenyl) phosphite, triisooctyl phosphite, tridecyl phosphite, tris (2-ethylhexyl) phosphite, tris (nonylphenyl) phosphite, tris (octyl phenyl) phosphite, tris [Decyl poly (oxyethylene) phosphite, tris (cyclohexylphenyl) phosphite, tricyclohexyl phosphite, tri (decyl)
Thiophosphite, triisodecylthiophosphite,
Phenyl bis (2-ethylhexyl) phosphite,
Phenyl diisodecyl phosphite, tetradecyl poly (oxyethylene) bis (ethylphenyl) phosphite, phenyl dicyclohexyl phosphite, phenyl diisooctyl phosphite, phenyl di (tridecyl) phosphite, diphenyl cyclohexyl phosphite, Diphenyl isooctyl phosphite, diphenyl 2-ethylhexyl phosphite, diphenyl isodecyl phosphite, diphenyl cyclohexyl phenyl phosphite, diphenyl (tridecyl) thiophosphite, nonylphenyl ditridecyl phosphite, phenyl p- tert-butylphenyl dodecyl phosphite, diisopropyl phosphite, bis [octadecyl poly (oxyethylene)]
Phosphite, octyl poly (oxypropylene) / tridecyl poly (oxypropylene) phosphite, monoisopropyl phosphite, diisodecyl phosphite, diisooctyl phosphite, monoisooctyl phosphite, didodecyl phosphite, monododecyl phosphite, dicyclohexyl phosphite Phyte, monocyclohexyl phosphite, monododecyl poly (oxyethylene) phosphite, bis (cyclohexyl phenyl) phosphite, monocyclohexyl phenyl phosphite, bis (p-tert-butyl phenyl) phosphite, tetratridecyl 4,4 4'-isopropylidene diphenyl diphosphite, tetratridecyl.
4,4'-butylidenebis (2-tert-butyl-5
-Methylphenyl) diphosphite, tetraisooctyl-4,4'-thiobis (2-tert-butyl-5-
Methylphenyl) diphosphite, tetrakis (nonylphenyl) poly (propyleneoxy) isopropyl diphosphite, tetratridecyl propyleneoxypropyl diphosphite, tetratridecyl 4,4'-
Isopropylidene dicyclohexyl diphosphite, pentakis (nonylphenyl) bis [poly (propyleneoxy) isopropyl] triphosphite, heptaquis (nonylphenyl) tetrakis [poly (propyleneoxy) isopropyl] pentaphosphite, heptakis (nonylphenyl) Tetrakis (4,4'-isopropylidenediphenyl) pentaphosphite, decaquis (nonylphenyl) heptakis (propyleneoxyisopropyl) octaphosphite, decaphenylheptakis (propyleneoxyisopropyl) octaphosphite, bis (butoxycarboethyl)・ 2,2-dimethylene-trimethylenedithiophosphite, bis (isooctoxycarbomethyl) ・ 2,2-dimethylenetrimethylenedithiophosphite , Tetradodecyl-ethylenedithiophosphite, tetradodecylhexamethylenedithiophosphite, tetradodecyl-2,2'-oxydiethylenedithiophosphite, pentadodecyldi (hexamethylene) trithiophosphite, diphenylphosphite, 4,4'-isopropylidene-dicyclohexyl phosphite, 4,4'-isopropylidene diphenyl alkyl (C12-C15) phosphite,
2-tert-butyl-4- [1- (3-tert-butyl-4-hydroxyphenyl) isopropyl] phenyldi (p-nonylphenyl) phosphite, ditridecyl-4,4'-butylidenebis (3-methyl-6 te
rt-butylphenyl) phosphite, dioctadecyl-2,2-dimethylenetrimethylenediphosphite, tris (cyclohexylphenyl) phosphite, hexatridecyl / 4,4 ', 4 "-1,1,3-butanetriyl -Tris (2-tert-butyl-5-methylphenyl) triphosphite, tridodecylthiophosphite, decaphenyl hepakis (propyleneoxyisopropyl) octaphosphite, dibutylpentakis (2,2-dimethylenetrimethylene) diphosphite ,
Dioctyl pentakis (2,2-dimethylenetrimethylene) diphosphite, didecyl-2,2-dimethylenetrimethylenediphosphite and lithium thereof;
Metal salts of sodium, potassium, magnesium, calcium, barium, zinc and aluminum.
The addition amount of these organic phosphite compounds is 0.01 to 3.
0 parts by weight, preferably 0.02 to 2.0 parts by weight. If the addition amount is less than 0.01 parts by weight, the thermal stability during the molding process will be unsatisfactory in this case as well, and coloring of the resin due to thermal deterioration and adhesion to the roll will occur. Further, even if it is added in an amount of 3.0 parts by weight or more, the effect of the present invention is saturated and it is not economical. These phenolic antioxidants and organic phosphite compounds may be used alone, but when two or more of them are used in combination, the effect is further exhibited.

In the present invention, the use of an aliphatic phosphate ester compound alone is notable for its effectiveness. However, when an organic phosphate ester compound different from these compounds is used in combination with these compounds, the use of an aliphatic phosphate ester compound is further increased. The effect is dramatically improved. Thus, these organic phosphate ester compounds are organic phosphate ester compounds obtained by using an alcohol containing an ether group as a raw material, at least one of which is esterified using the alcohol as a component. As an alcohol component, an alcohol or phenolic compound having no ether group may be contained as one component, and further, a free hydroxyl group directly linked to phosphoric acid may not react with the alcohol. Representative examples of these are given below, but are not limited thereto. Examples of the organic phosphate compound used include tris [methyldi (oxyethylene)] phosphate, tris [butyldi (oxyethylene)] phosphate, and tris (2-methoxypropyl).
Phosphate, tris (hexoxyethyl) phosphate, tris [ethyldi (oxypropylene)] phosphate, tris [butylpoly (oxypropylene)] phosphate, tris [octylpoly (oxypropylene)] phosphate, tris [phenylpoly (oxypropylene)] phosphate, tris [Dodecylpoly (oxyethylene)] phosphate, tris [propylpoly (oxyethylene)] phosphate, tris [2- (2
-Hydroxyethoxy) ethyl] phosphate, bis [ethyldi (oxyethylene)]-2- (2-hydroxypropoxy) propyl phosphate, bis [methyldi (oxyethylene)] butyl poly (oxypropylene) phosphate, didodecylethyldi (oxypropylene) ) Phosphate, tridecyl-2-methoxypropyl-2-hydroxyethyldi (oxyethylene) phosphate, bis [methyldi (oxyethylene)] tolylphosphate, octylethyldi (oxyethylene) nonylphenylphosphate, tetrakis (2-
Methoxyethyl) .2,2'-oxydiethyldiphosphate, tetrakis [ethyldi (oxyethylene)].
2,2'-oxybis (1-methylethyl)) diphosphate, tetrakis [acetyldi (oxyethylene)]
.5,5'-oxybis (3-oxapentamethylene)
Diphosphate, bis [methyltri (oxyethylene)]. Bis (2-methoxyethyl) .O, O'-propylenedi (oxypropylene) diphosphate, methyldi (oxyethylene) .ethyltri (oxypropylene) .2,2 ' -Dimethylenetrimethylene) diphosphate, tri (octadecyl) -2-octoxyethyl.
Trimethylene diphosphate, bis [methyldi (oxypropylene) .bis [ethyltri (oxyethylene)]
• 4,4'-methylenediphenyl diphosphate, bis [tetradecyl poly (oxyethylene)] phosphate, bis [methyldi (oxyethylene)] phosphate bis (phenoxyethyl) phosphate, bis [2-hydroxypropyl poly (oxypropylene) Phosphate, hexadecyl 2-hydroxyethoxyethyl phosphate, cyclohexylphenyl propyldi (oxyethylene) phosphate, bis [hexylpoly (oxyethylene)] ethylenepoly (oxyethylene) diphosphate, propyldi (oxypropylene) -2-
Hydroxypropyl di (oxypropylene) phosphate, bis [2-hydroxypropyl poly (oxypropylene)] phosphate, dodecyl 2-hydroxyethyl poly (oxyethylene) / 4,4'-thiodiphenyl diphosphate, methyl di (oxyethylene) Phosphate, 2-hydroxypropyldi (oxypropylene)
Phosphate, 2-hydroxypropyl poly (oxypropylene) phosphate, octadecyl poly (oxyethylene) phosphate, and the like, and lithium, sodium, potassium, magnesium, calcium, barium, zinc, and aluminum metal salt compounds thereof are included. The amount of the organic phosphate compound to be added is 0.05 to 100 parts by weight of the polyester resin.
It is 5.0 parts by weight, preferably 0.1 to 3.0 parts by weight. When the amount is less than 0.05 part by weight, a sufficient combination effect cannot be obtained when used in combination with the aliphatic phosphate ester-based compound, and when the amount exceeds 5.0 parts by weight, the performance / cost balance is deteriorated.

A polyhydric alcohol can be added to the polyester resin of the present invention, if necessary. Examples of the polyhydric alcohol used in the present invention include pentaerythritol, dipentaerythritol, trimethylolpropane, ditrimethylolpropane, dipentaerythritol adipate and the like.

Other components can be appropriately added to the polyester resin of the present invention depending on the application. For example, a filler, an ultraviolet absorber, a light stabilizer, a pigment, an antistatic agent, an antibacterial agent, an ethoxy compound, a crosslinking agent, a sulfur-based antioxidant and the like can be mentioned.

Hereinafter, the present invention will be described in more detail with reference to examples.

Examples 1 to 17 and Comparative Example 1 shown in Table 1
6 were mixed, the sheet thickness was set to 0.3 mm with a 6-inch chilled roll set at 180 ° C. and 190 ° C., and the adhesion time to the roll was measured.
It was noted in.

[0015]

[Table 1]

[0016]

[Table 2]

In Table 1, A is a polyester resin,
er PETG6763 (Eastman Chemi
cal), B is tris (octadecyl) phosphate, C is bis (dioctadecylphosphate) zinc salt,
D is calcium dodecyl phosphate, E is butylated hydroxytoluene, F is tetrakis [methylene-3-
(3,5-tert-4-hydroxyphenyl) propionate] methane, G is decyldiphenylphosphite, H is dioctadecyl.2,2'-dimethylenetrimethylenediphosphite, I is dodecylpoly (oxypropylene) phosphite Zinc salt, J is tris [butyltri (oxypropylene)] phosphate, K is didodecyloctyldi (oxyethyl) phosphate, L is bis [tetradecylpoly (oxyethylene) phosphate,
M is dodecyl poly (oxyethylene) phosphate, N
Is a zinc salt of decyl poly (oxyethylene) phosphate,
O is ethylene bis (stearyl amide) and P is zinc stearate.

[0018]

As described above, the polyester resin composition of the present invention is a composition in which a specific phosphate compound is blended. It facilitates and enables products of excellent quality.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // B29C 43/24 B29C 43/24 B29K 67:00 B29L 7:00 (72) Inventor Taira Nakayama Yokohama City 1186 Nakayama-cho Midori-ku E-Shin Kasei Co., Ltd.F-term (reference) CF081 CG002 CL002 EJ017 EJ027 EJ037 EJ047 EW046 EW049 EW060 EW068 FD070 FD077 GC00 GG00

Claims (4)

[Claims] 1. A polyester resin composition for calender molding, wherein at least one selected from aliphatic phosphate ester compounds is blended with a polyester resin. 2. The polyester resin composition for calender molding according to claim 1, wherein at least one selected from a phenolic antioxidant and an organic phosphite compound is further used in combination with said composition. 3. The polyester resin composition for calender molding according to claim 1, wherein the resin composition according to claim 1 is further used in combination with at least one selected from organic phosphoric ester compounds. 4. The polyester for calender molding according to claim 3, wherein the resin composition according to claim 3 is further used in combination with at least one selected from a phenolic antioxidant and an organic phosphite compound. Resin composition.