JP2003171540A - Polyester resin composition for profile extrusion molding and molded article using the same - Google Patents

Abstract

(57) [Summary] [PROBLEMS] To prevent resin dripping during processing, and to provide a molded article having good transparency and solvent resistance,
An object of the present invention is to provide a polyester resin composition capable of processing a profile extrusion molded article having excellent detergent resistance. SOLUTION: A polyester resin composition for irregular extrusion molding comprising (a) 30 to 97 parts by weight of an amorphous polyester and at least one of (a) a crystalline polyester and (c) a crystal nucleating agent. Preferably, both (a) the crystalline polyester and (c) the crystal nucleating agent are contained.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyester resin composition suitable for profile extrusion processing. More specifically, the present invention relates to a polyester resin composition which does not cause resin sagging during molding, maintains the transparency of the molded product, and gives a profile extrusion molded product having sufficient mechanical properties.

[0002]

2. Description of the Related Art Conventionally, a profile extrusion process has been employed in manufacturing window frames, rain gutters and the like as building material products from plastics. As a resin suitable for this profile extrusion molding, a vinyl chloride resin (hereinafter referred to as vinyl chloride) or a polyolefin resin is generally used, although it is required to follow the complicated shape of the die and have a characteristic that the dimensional accuracy is good. Particularly in applications requiring transparency, it is difficult to use a polyolefin that is whitened due to crystallization, and thus vinyl chloride is the main resin material. However, in recent years, there is a movement to replace the vinyl chloride resin with another material because of the problem of generation of dioxin during incineration of vinyl chloride and the problem of restraining use of a plasticizer due to endocrine disrupting substances. Among the many alternative materials, polyester is a powerful material because of its physical properties, environmental suitability, and price. However, there are two major problems in replacing the vinyl chloride used for profile extrusion processing with polyester.

Generally, the process of the profile extrusion molding process starts from the kneading extrusion process, and proceeds in the order of the profile mold process, the sizing process, the cooling process, the cutting process, and the secondary processing process. When a polyester resin is applied to those processes, the resin sagging occurs on the way from the irregular mold to the sizing process, so that the process cannot proceed to the next process or the proper shape cannot be maintained.

The second problem is that when an amorphous polyester or a highly transparent crystalline polyester is used to obtain a transparent molded product, when dirt is attached in the assembly process after commercialization. It has poor resistance to being wiped off by chemicals such as solvents and detergents, and may cause whitening or swelling when rubbed.

[0005]

SUMMARY OF THE INVENTION In view of the above circumstances, the present invention is a polyester resin composition for profile extrusion molding which does not cause resin sagging during profile extrusion processing and is excellent in transparency, solvent resistance and detergent resistance after processing. The purpose is to provide things.

[0006]

Means for Solving the Problems As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that by adding an amorphous polyester resin, a crystalline polyester resin and a crystal nucleating agent, it is possible to carry out a profile extrusion process. The inventors have found that a polyester resin composition for profile extrusion molding, which does not cause resin sagging and is excellent in transparency, solvent resistance, and detergent resistance after processing, can be obtained, and completed the present invention.

That is, the present invention has the following features. (1) at least one of (a) an amorphous polyester and (a) a crystalline polyester and (c) a crystal nucleating agent,
A polyester resin composition for profile extrusion molding, which comprises:

(2) (a) The amorphous polyester is characterized in that it contains an aromatic dicarboxylic acid having 8 to 14 carbon atoms and an aliphatic or alicyclic glycol having 2 to 10 carbon atoms as main components ( 1) The polyester resin composition for profile extrusion molding according to 1).

(3) (a) The polyester resin composition for profile extrusion molding according to (2), wherein the aromatic dicarboxylic acid having 8 to 14 carbon atoms of the amorphous polyester is terephthalic acid or isophthalic acid. object.

(4) (a) Acrylic or alicyclic glycol having 2 to 10 carbon atoms in the amorphous polyester is ethylene glycol, diethylene glycol, neopentyl glycol, cyclohexanedimethanol, 1,3-propanediol, 2- The polyester resin composition for profile extrusion molding according to (2) or (3), which is methyl-1,3-propanediol.

(5) (a) The crystalline polyester resin has a melting point of 90 to 220 ° C. (1) to
(4) A polyester resin composition for profile extrusion molding according to the above.

(6) (a) When the total glycol component of the crystalline polyester is 100 mol%, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol and cyclohexanediene. The polyester resin composition for profile extrusion molding according to (1) to (5), characterized in that at least one of methanol is contained in an amount of 50 mol% or more.

(7) The storage elastic modulus in the tensile mode at 25 ° C. is 1 × 10 ⁷ Pa or more, and the storage elastic modulus in the tensile mode is from 1 × 10 ⁷ Pa to 1 × 10 ⁶ Pa. The width of the temperature range shown is 60 ° C. or more, and the polyester resin composition for profile extrusion molding processing according to the above (1) to (6).

(8) A molded product obtained by subjecting the resin composition of the above (1) to (7) to a profile extrusion process.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The polyester resin composition for atypical extrusion molding of the present invention comprises (a) an amorphous polyester and (b) at least one of a crystalline polyester and (c) a crystal nucleating agent. is there.

The term "amorphous" as used herein is defined as follows. That is, using a differential scanning calorimeter (DSC), -10
After heating from 0 ° C to 300 ° C at a rate of 20 ° C / min,
Cool from 300 ℃ to -100 ℃ at 50 ℃ / min,
Next, the temperature is raised again from -100 ° C to 300 ° C at a rate of 20 ° C / min. It shows that neither of the two heating processes has a clear melting peak. On the contrary, crystallinity means that when DSC is measured under the same conditions, a clear melting peak is shown.

Amorphous polyester is generally poor in solvent resistance, and its surface is roughened due to contact with a solvent or the like, and even if it is an amorphous resin, it is crystallized by contact with a solvent. By adopting the above-mentioned constitution, the present invention can improve solvent resistance. This is because the crystalline polyester or crystal nucleating agent present in the finished molded product is present, so that when it comes into contact with a solvent, it becomes a crystal with a wavelength of light or less, which does not impair transparency in appearance and is further crystallized. It is considered that the resin does not swell even if the solvent adheres to the surface of the molded product, and the molecular motion is hindered, but this is not due to any reason.

It is preferable that both (a) the crystalline polyester and (c) the crystal nucleating agent are used. It is considered that this is because the crystalline resin is crystallized promptly under the influence of the crystal nucleating agent so that the transparency of the molded article itself is not impaired.

In the polyester resin composition of the present invention, when the crystalline polyester is added, when the total amount of the polyesters (a) and (a) is 100 parts by weight,
(A) The blending lower limit of the amorphous polyester is preferably 30.
Parts by weight, more preferably 50 parts by weight, still more preferably 65 parts by weight, and the upper limit of compounding is preferably 97 parts by weight,
It is more preferably 90 parts by weight. (I) The lower limit of the blending of the crystalline polyester is preferably 3 parts by weight, more preferably 5 parts by weight, and the upper limit of the blending is preferably 70 parts by weight,
It is more preferably 50 parts by weight, still more preferably 35 parts by weight. If the amount of the amorphous polyester is less than 30 parts by weight, it is difficult to adjust the viscoelasticity at the processing temperature in order to prevent resin sagging during the profile extrusion process, and the crystallinity of the finished molded product Is noticeable, which may cause whitening of the appearance, which is not preferable. On the other hand, if the blending amount of the amorphous polyester exceeds 97 parts by weight, the effect of the crystalline resin is not sufficiently exhibited, and very high solvent resistance and detergent resistance of the molded product may not be exhibited.

The amorphous polyester resin (a) used in the present invention preferably contains an aromatic dicarboxylic acid having 8 to 14 carbon atoms and an aliphatic or alicyclic glycol having 2 to 10 carbon atoms as main components. When the total acid component and glycol component are 100 mol%,
Each of both components is 50 mol% or more, preferably 60 mol%, more preferably 65 mol% or more. If the content of both components is less than 50 mol%, the elongation and mechanical properties of the molded product obtained by the profile extrusion process may deteriorate.

Among the (a) amorphous polyester resins used in the present invention, the aromatic dicarboxylic acid having 8 to 14 carbon atoms is preferably terephthalic acid or isophthalic acid. The use of these dicarboxylic acids further improves the elongation and mechanical properties of the molded product obtained by the profile extrusion process. It is preferable that terephthalic acid is contained in an amount of 50 mol% or more, and further 60 mol% or more, and it is also preferable to include both terephthalic acid and isophthalic acid.

The (a) amorphous polyester resin of the present invention may be copolymerized with a polyvalent carboxylic acid other than the above-mentioned terephthalic acid and isophthalic acid, for example, orthophthalic acid, naphthalenedicarboxylic acid, succinic acid, Adipic acid,
Known compounds such as azelaic acid, sebacic acid, decanoic acid, dimer acid, cyclohexanedicarboxylic acid and trimellitic acid can be used.

Among the (a) amorphous polyesters used in the present invention, the aliphatic or alicyclic glycol having 2 to 10 carbon atoms is ethylene glycol, diethylene glycol, neopentyl glycol, cyclohexanedimethanol,
It is preferably 1,3-propanediol and 2-methyl-1,3-propanediol. Further, those containing 50 mol% or more, and further 60 mol% or more of ethylene glycol are preferable.

The preferred amorphous polyester combination in the present invention is specifically terephthalic acid / isophthalic acid // ethylene glycol = 90 to 70/10 to 30.
/// 100 mol%, terephthalic acid // ethylene glycol / 1,2-propylene glycol = 100 // 80-
50/20 to 50 mol%, terephthalic acid / isophthalic acid // ethylene glycol / 1,3-propylene glycol = 95 to 80/5 to 20 // 90 to 70/10 to 30
Mol%, terephthalic acid / isophthalic acid // ethylene glycol / 1,4-butanediol = 95 to 70/5 to 3
0 // 90 to 50/10 to 50 mol%, terephthalic acid /
/ Ethylene glycol / 2-methyl-1,3-propanediol = 100 // 60-80 / 4.0-20 mol%, terephthalic acid / isophthalic acid // ethylene glycol / 2-methyl-1,3-propanediol = 95-8
0/5 to 20 // 70 to 90/30 to 10 mol%, terephthalic acid // ethylene glycol / neopentyl glycol = 100 // 85 to 60/15 to 40 mol%, terephthalic acid / isophthalic acid // ethylene glycol / Neopentyl glycol = 95-80 / 5-20 // 90-
70/10 to 30 mol%, terephthalic acid // ethylene glycol / diethylene glycol = 100 // 75 to 5
0/25 to 50 mol%, terephthalic acid / isophthalic acid /
/ Ethylene glycol / diethylene glycol = 95-
80/5 to 20 // 90 to 75/10 to 25 mol%, terephthalic acid / ethylene glycol / 1,4-cyclohexanedimethanol = 100 // 80 to 60/20 to 4
0 mol% is mentioned.

Furthermore, terephthalic acid // ethylene glycol / neopentyl glycol = 100 // 85-6
0 / 15-40 mol%, terephthalic acid / isophthalic acid /
/ Ethylene glycol / neopentyl glycol = 95
~ 80/5 to 20 // 90 to 70/10 to 30 mol%,
Terephthalic acid // ethylene glycol / diethylene glycol = 100 // 75 to 50/25 to 50 mol%, terephthalic acid / isophthalic acid // ethylene glycol / diethylene glycol = 95 to 80/5 to 20 // 90 to
75/10 to 25 mol%, terephthalic acid // ethylene glycol / 1,4-cyclohexanedimethanol = 10
It is more preferably 0 // 80 to 60/20 to 40 mol%.

Among these, ethylene glycol and neopentyl glycol (60/40 to 90/10 (molar ratio)), ethylene glycol and 1,4-cyclohexanedimethanol (60/40 to 90/10 (molar ratio))
The combination of is easy to achieve both the profile extrusion processability and the transparency of the molded product, and is most preferably the combination of ethylene glycol and neopentyl glycol.

The (a) amorphous polyester resin of the present invention is the above-mentioned ethylene glycol, diethylene glycol, neopentyl glycol, cyclohexanedimethanol, 1,3-propanediol, 2-methyl-1,3.
-A polyhydric alcohol component other than propanediol may be copolymerized, for example, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, and 3 -Methyl-1,5-
Pentanediol, hexanediol, nonanediol, dimerdiol, ethylene oxide adduct of bisphenol A and propylene oxide adduct, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, 2-butyl-2-ethyl-
1,3-propanediol, tricyclodecane dimethanol, neopentyl hydroxypivalate ester,
2,2,4-trimethyl-1,5-pentanediol,
Trimethylolpropane or the like can be used.

The crystalline polyester resin (a) used in the present invention preferably has a melting point of 90 to 220 ° C. A more preferable lower limit is 100 ° C., and further preferable is 1
It is 10 ° C. On the other hand, the more preferable upper limit is 200 ° C, and more preferably 190 ° C. When the melting point is lower than 90 ° C., the crystallinity decreases, so that the solvent resistance and the detergent resistance decrease. On the other hand, if the melting point exceeds 220 ° C, it is necessary to set the extruder barrel temperature at the time of the profile extrusion process to a high value, and the hydrolysis causes the molecular weight to decrease, causing resin sag during processing, and molding machine There is a decrease in physical strength.

The (a) crystalline polyester used in the present invention is ethylene glycol, 1,3-propanediol, when the total glycol component is 100 mol%.
1,4-butanediol, 1,6-hexanediol,
At least one of cyclohexanedimethanol is 5
It is preferable to contain 0 mol% or more. More preferably 55
It is at least mol%, more preferably at least 60 mol%.
In order to exert solvent resistance, it is important to rapidly crystallize the crystalline polyester present in the molded product, but in order to impart sufficient crystallinity, it is preferable that the above components are contained in an amount of 50 mol% or more. preferable. On the other hand, if it is less than 50 mol%, the solvent resistance is lowered. Among the above components, the use of ethylene glycol, 1,3-propanediol, and 1,4-butanediol is particularly preferable from the viewpoint of solvent resistance because crystallization proceeds relatively quickly.

The (a) crystalline polyester resin used in the present invention is other than the above-mentioned ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol and cyclohexanedimethanol. Polyvalent carboxylic acid component, polyhydric alcohol component may be copolymerized, for example, as the polyvalent carboxylic acid component, terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, succinic acid, adipic acid, azelaic acid,
Known compounds such as sebacic acid, decanoic acid, dimer acid, cyclohexanedicarboxylic acid and trimellitic acid can be used. On the other hand, as the polyhydric alcohol component, 1,2-butanediol, 1,3-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-
Methyl-1,3-propanediol, nonanediol,
Dimer diol, ethylene oxide adduct of bisphenol A and propylene oxide adduct, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, 2-butyl-2-ethyl-1,3
-Propanediol, tricyclodecanedimethanol,
Neopentyl hydroxypivalate ester, 2,2
4-trimethyl-1,5-pentanediol, trimethylolpropane, etc. can be used.

The number average molecular weight of the (a) amorphous polyester resin and (a) crystalline polyester resin used in the present invention is preferably 15,000 to 40,000, more preferably 18,000 to 35,000, and further preferably 20.
000-35,000. Number average molecular weight is 15,000
If it is less than the above range, the strength and elongation of the molded product will be insufficient due to insufficient resin cohesive force, and the molded product will become brittle and cannot be used. On the other hand, 40,000
If the above is exceeded, the melt viscosity will increase too much, and the optimum temperature for the profile extrusion process will also increase, resulting in a poorer result.

The acid value of the (a) amorphous polyester resin and (a) crystalline polyester resin used in the present invention is
Preferably 100 equivalents / 10 ⁶ g or less, more preferably 50 equivalents / 10 ⁶ g or less, further preferably 40 equivalents /
It is 10 ⁶ g or less. When the acid value exceeds 100 equivalent / 10 ⁶ g, hydrolysis is further promoted when the resin is heated during the profile extrusion process, and the mechanical strength of the finished molded product is lowered. Further, as the resin is decomposed, the resin sag during processing is deteriorated.

The melt viscosity of the polyester resin composition used in the present invention at 220 ° C. and a shear rate of 100 sec ⁻¹ is preferably 6000 to 600,000 dPa · s.
ec, more preferably 7,000 to 100,000 dPa ·
sec, more preferably 8000-50000 dPa
・ It is sec. If the melt viscosity is less than 6000 dPa · sec, the resin sag during processing deteriorates. Meanwhile, 600,000
If it exceeds dPa · sec, the melt viscosity is too high and the productivity is lowered, which is not practical.

The polyester resin composition of the present invention comprises
(C) A crystal nucleating agent can be added. In this case, the lower limit of compounding of the crystal nucleating agent is preferably 0.1 part by weight, and the upper limit of compounding is preferably 10 parts by weight. More preferably, the lower limit is 0.5 parts by weight and the upper limit is 5 parts by weight. If the blending amount is less than 0.1 part by weight, it has no effect on microcrystallization and the solvent resistance effect may be weakened. On the other hand, if it exceeds 10 parts by weight, the fluidity at the time of profile extrusion and the mechanical properties of the molded product may deteriorate, which is not preferable. The crystal nucleating agent accelerates the crystallization rate of the crystalline polyester and the orientation of the amorphous polyester to quickly complete the crystallization and orientation, and the size of the spherulites can be controlled by adjusting the number of crystal nuclei. . If the diameter of the generated spherulites is extremely fine crystals below the wavelength of visible light, transparency will not be lost even after resin crystallization, and it will be easy to achieve both transparency and solvent resistance of the molded product. . The diameter of the spherulites is 300 nm.
Hereafter, it is preferably 200 nm or less, and particularly preferably 100 nm or less. Specific examples of the crystal nucleating agent include inorganic fine particles such as talc, silica, graphite, carbon powder, pyroferrite, gypsum and neutral clay, and metal oxides such as magnesium oxide, aluminum oxide and titanium dioxide, sulfates and phosphoric acid. Salts, silicates, oxalates, stearates, benzoates, salicylates, tartrates, sulfonates, montanic acid wax salts, montanic acid wax ester salts, terephthalates, carboxylates, α-olefins And α, β
An ionic copolymer or the like composed of an unsaturated carboxylic acid may be mentioned. Among them, particularly effective ones are oxalates, stearates, benzoates, salicylates, tartrates, sulfonates, montan wax salts, montan wax ester salts, terephthalates and carboxylates. , Α-olefins.

The polyester resin of the present invention has a composition containing an antioxidant in order to suppress thermal deterioration of the polyester resin during processing (prevents coloring of the resin and generation of resin sag due to thermal deterioration). It is desirable to use. Preferable examples of the antioxidant include phenolic antioxidants and organic phosphite ester compounds.

Specific examples of the phenolic antioxidant used in the present invention include, for example, 2,6-di-tert-butylphenol and 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-tert-butyl-4-hydroxymethylphenol, 2,2-bis (4-hydroxydiphenyl)
Propane, bis (5-tert-butyl-4-hydroxy-2-methylphenyl) sulfide, 2,5-di-t
ert-amylhydroquinone, 2,5-di-tert-
Butylhydroquinone, 1,1-bis (3-tert-butyl-4-hydroxy-5-methylphenyl) butane,
Bis (3-tert-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-hydroxydiphenyl) methane, bis (3,5-di-tert-butyl 4-hydrodiphenyl) methane, bis (3-tert
-Butyl-2-hydroxy-5-methylphenyl) sulfide, 1,1-bis (4-hydroxyphenyl) cyclohexane, ethylenebis [3,3-bis (3-ter)
t-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-methylpropane, 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 (3,3
5-di-tert-butyl-4-hydroxyphenyl)
Isocyanate, 1,3,5-trimethyl-2,4,6
-Tris (3,5-di-tert-butyl-4-hydroxydibenzyl) benzene, 1,6-bis [2- (3,5
-Di-tert-butyl-4-hydroxyphenyl) propionyloxy] hexane, tetrakis [3- (3,3
5-di-tert-butyl-4-hydroxydiphenyl)
Propionyloxymethyl] methane, bis (3-cyclohexyl-2-hydroxy-5-methylphenyl) methane, bis [3- (3,5-di-tert-butyl-4-]
Hydroxyphenyl) propionyloxyethyl] sulfide, n-otatadecyl-3- (3,5-di-ter
t-butyl-4-hydroxyphenyl) propionate, bis [3- (3,5-di-tert-butyl 4-hydroxydiphenyl) propionylamino] hexane,
2,6-bis (3-tert-butyl-2-hydroxy-5-methylphenyl) -4-methylphenol, bis [S- (4-tert-butyl-3-hydroxy-2,
6-Dimethylbenzyl)] thioterephthalate, tris [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tris (3,5-di-tert-butyl-4-). Hydroxybenzyl) isocyanurate, 1,1,3-tris (3-tert-butyl-4-hydroxy-6-methylphenyl) butane and the like can be mentioned. These compounds may be used alone or in combination of two or more.

The upper limit of the amount of the phenolic antioxidant compounded is preferably 1.0 part by weight or less, particularly preferably 0.8.
Parts by weight or less, while the preferred lower limit is 0.01 parts by weight or more,
It is particularly preferably 0.02 part by weight or more. If the amount is less than 0.01 parts by weight, it is difficult to obtain the effect of suppressing thermal deterioration during processing, and if it exceeds 1.0 part by weight, the effect of suppressing thermal deterioration is saturated and uneconomical.

Specific examples of the organic phosphite ester compound used in the present invention include triphenyl phosphite, tris (methylphenyl) phosphite, triisooctyl phosphite, tridecyl phosphite,
Tris (2-ethylhexyl) phosphite, tris (nonylphenyl) phosphite, tris (octylphenyl) phosphite, tris [decylpoly (oxyethylene)] phosphite, tris (cyclohexylphenyl) phosphite, tricyclohexylphosphite, tri (Decyl) thiophosphite, triisodecyl thiophosphite, phenyl bis (2-ethylhexyl) phosphite, phenyl diisodecyl phosphite, tetradecyl poly (oxyethylene) bis (ethylphenyl) phosphato, phenyl dicyclohexyl phosphite Fight, phenyl diisooctyl phosphite, phenyl di (tridecyl) phosphite, diphenyl cyclohexyl phosphite, diphenyl isooctyl phosphite, Phenyl-2-ethylhexyl phosphite, diphenyl isodecyl phosphite, diphenyl cyclohexylphenyl phosphite, diphenyl (tridecyl) thio phosphite, nonylphenyl-ditridecylphosphite, phenyl
p-tert-butylphenyl dodecyl phosphite, diisopropyl phosphite, bis [otadecyl poly (oxyethylene)] phosphite, octyl poly (oxypropylene) / tridecyl poly (oxypropylene) phosphite, monoisopropyl phosphite,
Diisodecyl phosphite, diisooctyl phosphite, monoisooctyl phosphite, didodecyl phosphite, monododecyl phosphite, dicyclohexyl phosphite, monocyclohexyl phosphite, monododecyl poly (oxyethylene) phosphite, bis (cyclohexylphenyl) Phosphite, monocyclohexyl phenyl phosphite, bis (p-tert)
-Butylphenyl) phosphite, tetratridecyl
4,4'-isopropylidene diphenyl diphosphite, tetratridecyl 4,4'-butylidene bis (2
-Tert-butyl-5-methylphenyl) diphosphite, tetraisooctyl.4,4'-thiobis (2-
tert-butyl-5-methylphenyl) diphosphite, tetrakis (nonylphenyl) .poly (propyleneoxy) isopropyldiphosphite, tetratridecyl-propyleneoxypropyldiphosphite, tetratridecyl.4,4'-isopropylidenedicyclohexyl Diphosphite, pentakis (nonylphenyl)
Bis [poly (propyleneoxy) isopropyl] triphosphite, heptakis (nonylphenyl) .tetrakis [poly (propyleneoxy) isopropyl] pentaphosphite, heptakis (nonylphenyl) .tetrakis (4,4'-isopropylidenediphenyl) pentaphos Fight, decaquis (nonylphenyl) / heptaquis (propyleneoxyisopropyl) octaphosphite, decaphenyl / heptaquis (propyleneoxyisopropyl) octaphosphite, bis (butoxycarboethyl) / 2,2-dimethylene-trimethylenedithiophosphite, Bis (isooctoxycarbomethyl)
2,2-dimethylene trimethylene dithiophosphite,
Tetradodecyl / ethylenedithiophosphite, tetradodecyl / hexamethylenedithiophosphite, tetradodecyl / 2,2'-oxydiethylenedithiophosphite, pentadodecyl / di (hexamethylene) trithiophosphite, diphenylphosphite, 4,4 '-Isopropylidene-dicyclohexylphosphite, 4,
4'-isopropylidenediphenyl alkyl (C12
To C15) phosphite, 2-tert-butyl-4-
[1- (3-tert-Butyl-4-hydroxydiphenyl) isopropyl] phenyldi (p-nonylphenyl)
Phosphite, ditridecyl 4,4'-butylidene bis (3-methyl-6-tert-butylphenyl) phosphite, dioctadecyl 2,2-dimethylene trimethylene diphosphite, tris (cyclohexylphenyl) phosphite, hexa Tridecyl 4,4 ', 4 "
-1,1,3-butanetriyl-tris (2-tert
-Butyl-5-methylphenyl) triphosphite, tridodecylthiophosphite, decaphenyl heptakis (propyleneoxyisopropyl) octabosphite, dibutyl pentakis (2,2-dimethylene trimethylene) diphosphite, dioctyl pentakis (2 , 2-dimethylenetrimethylene) diphosphite,
Didecyl-2,2-dimethylene trimethylene diphosphite and lithium, sodium, potassium thereof,
Mention may be made of metal salts of magnesium, caldium, barium, zinc and aluminum. These compounds may be used alone or in combination of two or more.

With respect to the amount of the organic phosphite ester compound, the preferable upper limit is 3.0 parts by weight or less, particularly preferably 2.0 parts by weight or less, and the preferable lower limit is 0.01 parts by weight or more, particularly preferably It is 0.02 parts by weight or more. If the amount is less than 0.01 parts by weight, it is difficult to obtain the effect of suppressing thermal deterioration during processing, and if it exceeds 3.0 parts by weight, the effect of suppressing thermal deterioration is saturated and uneconomical.

The combined use of a phenolic antioxidant and an organic phosphite ester compound is preferable because the effect of suppressing thermal deterioration is further improved.

In the present invention, the polyester resin composition
Tensile mode storage modulus of 10⁷ Pa
Above, and at a temperature lower than 180 ℃ 10⁷ Below Pa
It is preferable that Furthermore, in the region of 250 ℃ or less,
10⁷ Pa to 10⁶The width of the temperature region showing up to Pa is 6
It is preferably 0 ° C. or higher. 10 at 25 ° C ⁷ 
If it is less than Pa, the price of the vinyl chloride molded product targeted by this patent
Not suitable for replacement. In addition, the width of the temperature region is 60
By having the temperature above ℃, the profile extrusion during profile extrusion processing
Maintains viscoelasticity suitable for fluctuations and distribution of temperature control
Can have. A viscoelastic material suitable for this profile extrusion
In order to make it crystalline, crystalline polyester is used
This can be achieved by adding an appropriate amount to the tell. Also, the crystal nucleus
It can also be adjusted by the addition amount of the agent.

In addition, branching can also be achieved by introducing a small amount of an isocyanate curing agent such as a dimer of TDI or an epoxy curing agent of bisphenol A type or phenol novolac type to cause a reaction. Especially TDI dimer (“Desmodule TT” from BASF as a product example)
Has high reactivity and is suitable for introducing a branched group into polyester having a hydroxyl group. The addition amount is preferably 0.05 part or more and less than 10 parts with respect to 100 parts of polyester. More preferably, it is 0.2 parts or more and less than 2 parts. Further, it can be achieved by compounding and kneading an ultra-high molecular weight acrylic polymer or an acrylic polymer obtained by copolymerizing a fluoropolymer. In particular, an acrylic polymer copolymerized with a fluorine-based polymer (as an example of a product, "Metabrene A-3000" manufactured by Mitsubishi Rayon Co., Ltd.)
Since the viscoelasticity can be easily adjusted with a very small amount,
Suitable for profile extrusion. Polyester 1 added
It is preferably 0.01 part or more and less than 1 part with respect to 00 parts. More preferably, it is 0.02 part or more and less than 0.5 part.

The storage elastic modulus in the tensile mode is obtained by applying a sheet-like resin to a dynamic viscoelasticity measuring device. The size of the sample sheet is, for example, length 15
mm (excluding the grip), width 4 mm, thickness about 1 mm, the measurement conditions were fixed at a frequency of 10 Hz, and a temperature rising rate of 20 ° C./minute from -20 ° C. until measurement became impossible (maximum 250).
(° C) scan. Regarding the method of preparing the sample sheet, for example, from the softening point of the polyester resin,
By heat pressing or the like set to a high temperature as described above, the polyester resin is sandwiched between films having high heat resistance such as a polyimide film and pressed to obtain a smooth sheet.

Other components can be appropriately added to the polyester resin composition of the present invention depending on the application. For example, impact resistance improver, filler, UV absorber, surface treatment agent, lubricant, light stabilizer, pigment, antistatic agent, antibacterial agent, epoxy compound, crosslinking agent, sulfur-based antioxidant, flame retardant, Examples include plasticizers, processing aids, and foaming agents.

[0045]

EXAMPLES The following examples are given to explain the present invention in more detail, but the present invention is not limited to these examples.

The measured values described in the synthesis examples are measured by the following method.

Polyester composition: The resin was dissolved in deuterated chloroform and quantified by H-NMR.

Glass transition temperature, melting point: Using a differential scanning calorimeter, 10 mg of a measurement sample was placed in an aluminum pan, the lid was pressed and sealed, and the temperature was measured at a heating rate of 20 ° C./min.

Number average molecular weight: Determined as a polystyrene conversion value by gel permeation chromatography using hexafluoroisopropanol as a solvent.

Acid value: 1 g of resin was dissolved in 30 ml of chloroform and titrated with a 0.1N potassium hydroxide ethanol solution. Phenolphthalein was used as the indicator.

Storage elastic modulus: A sample of the polyester resin composition was placed on a tabletop heat press (manufactured by Tester Sangyo Co., Ltd.) adjusted to 200 ° C. via a polyimide film (“Kapton” manufactured by Toray DuPont) and 2N. / Mm
The pressure of ² was maintained for 20 seconds to obtain a sheet sample having a thickness of 1 mm. This is 15 mm long (excluding grip), width 4
The sample was cut into mm, set in a dynamic viscoelasticity measuring device "DVA-200" manufactured by IT Measurement and Control Co., Ltd., and measured in a tensile mode. The measurement condition is frequency 1
It was fixed at 0 Hz, and the scan was performed from -20 ° C to the point where measurement became impossible (maximum 250 ° C) at a heating rate of 20 ° C / min.

<Synthesis Example of Amorphous Polyester (A)> 960 parts by weight of dimethyl terephthalate and 5 parts of ethylene glycol are placed in a reaction can equipped with a stirrer, a thermometer, and an outflow cooler.
27 parts by weight, 156 parts by weight of neopentyl glycol, 0.34 parts by weight of tetrabutyl titanate, 170-2
The transesterification reaction was performed at 20 ° C. for 2 hours. After the transesterification reaction was completed, the temperature of the reaction system was raised from 220 ° C. to 270 ° C., while the pressure inside the system was gradually reduced to 500 Pa over 60 minutes. And 55 below 130 Pa
A polycondensation reaction was performed for a minute to obtain an amorphous polyester (A).

As a result of NMR analysis of the amorphous polyester (A), the dicarboxylic acid component was 100 mol% of terephthalic acid,
The diol component had a composition of 80 mol% ethylene glycol and 20 mol% neopentyl glycol. The glass transition temperature is 78 ° C., the number average molecular weight is 28,000,
The acid value was 30 equivalents / 10 ⁶ g.

The amorphous polyesters (B) to (E) were manufactured in the same manner as the amorphous polyester (A). The composition and the measurement results are shown in Table 1. (Numbers are mol% in resin)

The crystalline polyesters (a) to (e) were produced in the same manner as the amorphous polyester (A). Table 3 shows the composition and the measurement results. (Numbers are mol% in resin)

[0056]

[Table 1]

The polyesters shown in Table 1 were mixed with the respective components shown in Tables 4 and 5 in a beaker, and the mixture was set to an extruder (Toyo Seiki Seisakusho Co., Ltd.) with a rotation speed of 30 rpm and a barrel temperature of 180 ° C. Made "Laboplast Mill", L
/ D = 30, screw diameter = 20mm, full flight,
The mixture was kneaded at a compression ratio of 2.0). The kneaded resin is attached to the extruder by ASTM Extrusion Die N
o. 1 The resin sag of the molded product was evaluated by atypical extrusion processing from Garvey Type. At this time, the molded product was picked up as follows: ○: "There was no resin sagging and it was smooth." ×: "Resin sagging occurred and the sizing process could not be performed." Table 2 and 3 together with the storage elastic modulus of the obtained sheet.

The crystal nucleating agents, stabilizers, curing agents and additives shown in Tables 2 and 3 mean the following compounds. I: Sodium stearate II: Tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate III: "Desmodur TT" manufactured by BASF IV: "Metabrene A-3000" manufactured by Mitsubishi Rayon

The numerical values in the table for the amount of polyester, crystal nucleating agent, amount of stabilizer, amount of curing agent and amount of additive are parts by weight.

[0060]

[Table 2]

[0061]

[Table 3]

The methods for evaluating transparency and solvent resistance in the table are as follows.

Transparency: The molded products were visually compared and evaluated according to the following criteria. (5: extremely transparent, 4: good transparency,
3: transparent, 2: slightly opaque, 1: slightly opaque. )

Solvent resistance: The molded product was immersed in methyl ethyl ketone for 10 minutes, and then visually checked for whitening and swelling, and evaluated according to the following criteria. (5: no change, 4: slightly swelled but no big change, 3: whitening occurs, 2: whitening occurs, and the surface swells a little,
1: Whitening occurs and the surface melts)

In the column of evaluation of transparency and solvent resistance, "-" in Comparative Example means that the product could not be formed into a molded product due to adhesion.

[0066]

As described above, the polyester resin composition of the present invention is a composition in which an amorphous polyester, a crystalline polyester and a crystal nucleating agent are combined, and therefore, the polyester resin composition which has been difficult in the past. Not only facilitates atypical extrusion of products (in particular, prevents resin sagging), but also makes finished molded products have good transparency and excellent solvent resistance and detergent resistance. Can be enabled.

Continued front page    F-term (reference) 4F071 AA44 AA45 AB03 AB18 AB24                       AB25 AB26 AB30 AC09 AE22                       BB06 BC07                 4F207 AA24 AB08 AM32 KA01 KA20                       KF01                 4J002 CF03X CF04W DA016 DA026                       DE076 DE136 DE146 DG056                       DJ006 DJ016 DJ046 EG016                       EG056 EG076 EG106 EV256                       FD206

Claims (8)

[Claims] 1. (a) Amorphous polyester, and
A polyester resin composition for profile extrusion molding, comprising at least one of (a) a crystalline polyester and (c) a crystal nucleating agent. 2. The (a) amorphous polyester has 8 carbon atoms.
The polyester resin composition for profile extrusion molding according to claim 1, which comprises an aromatic dicarboxylic acid having 14 to 14 and an aliphatic or alicyclic glycol having 2 to 10 carbon atoms as main components. 3. (a) Amorphous polyester having 8 to 8 carbon atoms
The polyester resin composition for profile extrusion molding according to claim 2, wherein the aromatic dicarboxylic acid of 14 is terephthalic acid or isophthalic acid. 4. The (a) amorphous polyester having 2 to 2 carbon atoms
The aliphatic or alicyclic glycol of 10 is at least one selected from ethylene glycol, diethylene glycol, neopentyl glycol, cyclohexanedimethanol, 1,3-propanediol and 2-methyl-1,3-propanediol. The polyester resin composition for profile extrusion molding according to claim 2 or 3. 5. The polyester resin composition for profile extrusion molding according to any one of claims 1 to 4, wherein the crystalline polyester resin (a) has a melting point of 90 to 220 ° C. 6. (a) When the total glycol component of the crystalline polyester is 100 mol%, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, cyclohexanedimethanol. The polyester resin composition for profile extrusion molding according to any one of claims 1 to 5, wherein at least one of them is contained in an amount of 50 mol% or more. 7. The storage elastic modulus in the tensile mode at 25 ° C. is 1 × 10 ⁷ Pa or more, and the storage elastic modulus in the tensile mode is from 1 × 10 ⁷ Pa to 1 × 10 ⁶ Pa. The polyester resin composition for profile extrusion molding according to any one of claims 1 to 6, wherein the width of the temperature range is 60 ° C or more. 8. A molded product obtained by profile extrusion of the resin composition according to claim 1.