JP2003128773A - Flame-retardant polyester resin for calendering and resin composition, and sheet using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester resin composition whose sheet can easily be peeled from rolls when calendered, and can give the calendered sheet having good flame retardance in spite of a non-halogen resin and having excellent quality. SOLUTION: This flame-retardant polyester resin for calendering is characterized by containing phosphorus atoms in the molecular chain in an amount of >=0.3 wt.%, and containing an aromatic dicarboxylic acid in the acid component in an amount of >=60 mol.%. The polyester resin composition comprises the polyester resin and a lubricant in an amount of 0.01 to 5 pts.wt. per 100 pts.wt. of the polyester resin. The sheet uses the polyester resin composition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to various sheets and films, particularly industrial processing sheets, which have good roll releasability in the calendar processing of polyester, and the nonflammability of the calendered sheets is excellent.
The present invention relates to a polyester resin and a resin composition that are most suitable for calendering and that are useful for films.

[0002]

2. Description of the Related Art Conventionally, vinyl chloride sheets (films) have been widely used for certain purposes because they are inexpensive and have excellent transparency. Extrusion molding and calender molding are known as methods for processing this sheet, but in extrusion molding, the friction of the die lip affects the processability (moldability) of the resin, and the sheet (film) Accuracy is poor in terms of thickness, width, flow direction, etc.
It is also unsuitable for mass production. Therefore, the latter is more frequently used in terms of productivity and quality. However, in recent years, there is a movement to replace the vinyl chloride sheet (film) with another material due to the problem of dioxins generation during incineration of vinyl chloride and the problem of suppression of plasticizer use due to endocrine disrupting substances. Of the many alternative materials, polyester is a powerful material in terms of its physical properties and price. However, there are the following major problems in replacing with polyester.

That is, it is difficult to apply it to calender molding, which is widely used as a method for molding a vinyl chloride sheet.
Conventionally, a polyester resin has been mainly used in extrusion molding as a method for producing a sheet or film because of its ease of processing. However, when the polyester resin is subjected to calendering, the adhesive force to the roll when it is thermoplasticized is relatively strong, and it tends to adhere to the roll during the processing, which makes molding difficult. Therefore, it has been attempted to add various lubricants in order to prevent the adhesion to the rolls. Examples of such lubricants include hydrocarbon lubricants such as polyethylene wax and paraffin wax, higher fatty acid lubricants, higher alcohol lubricants, metal soaps with higher fatty acids, fatty acid amide lubricants, ester lubricants, and other types of lubricants. It is being appreciated. For example, JP-A-11-343353, JP-A-2000-136294, and JP-A-2000-18619.
1, JP 2000-302951, JP 2001-64.
496, JP 2001-4019, US-606891.
Amorphous polyethylene terephthalate copolymerized with cyclohexanedimethanol at 0 was calendered into sheets using various lubricants.

Although it is possible to form an amorphous polyethylene terephthalate copolymerized with cyclohexanedimethanol as described above into a sheet by calendering, it is important to substitute vinyl chloride resin with this polyester. There was a problem. That is, vinyl chloride resin retains a high degree of flame retardancy due to the action of chlorine atoms present in the molecule, but in the above polyester, due to the molecular design,
Since no consideration is given to imparting flame retardancy, it is difficult to expand to applications requiring flame retardancy, such as wallpaper for building materials, decorative panels for doors, and outer panels for electrical appliances.

[0005]

SUMMARY OF THE INVENTION In view of the above circumstances, the present invention provides good roll releasability for the purpose of imparting calenderability, and in particular, the calendered sheet has non-halogen flame retardancy. An object of the present invention is to provide an excellent flame-retardant polyester resin for calendar processing, a resin composition, and a sheet using the same.

[0006]

Means for Solving the Problems As a result of intensive studies aimed at achieving the above-mentioned problems, the present inventors have found that a polyester resin containing a phosphorus atom in the molecular chain, a lubricant, and a flame retardant if necessary are added. The present invention has been completed by finding that not only the roll releasability at the time of calendar processing is good, but also excellent flame retardancy can be achieved without halogen. That is, the present invention has the following features. (1) A flame-retardant polyester resin for calendering, characterized in that the phosphorus atom contained in the molecular chain is 0.3 wt% or more and the aromatic dicarboxylic acid is contained in 60 mol% or more of the acid component. (2) 30 mol% or more of terephthalic acid per total carboxylic acid component, 30 mol% or more of ethylene glycol per total diol component, and 5 to 70 mol% of isophthalic acid per total dicarboxylic acid component, and / or
1,2-propanediol per total diol component, 1,
3-propanediol, 1,4-butanediol, 2-
For calendering according to (1), which contains at least 5 mol% of at least one diol component selected from the group consisting of methyl-1,3-propanediol, neopentyl glycol, diethylene glycol and cyclohexanedimethanol. Flame-retardant polyester resin. (3) The flame-retardant polyester resin for calendar processing according to (1) or (2), which is obtained by copolymerizing the phosphorus-containing carboxylic acid represented by the general formula I or the general formula II and its ester compound.

[0007]

[Chemical 3] R ¹ , R ² : hydrogen atom or hydrocarbon group R ³ , R ⁴ : hydrogen atom, hydrocarbon group or hydroxy-substituted hydrocarbon group 1, m: integer from 0 to 4

[Chemical 4] R ⁵ : Hydrogen atom or hydrocarbon group R ⁶ , R ⁷ : Hydrogen atom, hydrocarbon group or hydroxy-substituted hydrocarbon group

(4) A flame-retardant polyester resin composition for calendering, which comprises blending the polyester resin described in (1) to (3) with a lubricant in an amount of 0.01 to 5 parts by weight per 100 parts by weight of the polyester resin.

(5) The flame-retardant polyester resin composition for calendering according to (4), wherein the lubricant is a polyolefin wax and / or a metal salt of an organic phosphate.

(6) 0.5 to 80 parts by weight of a flame retardant in 100 parts by weight of polyester in the polyester resin described in (1) to (3) or the polyester resin composition described in (4) and (5). A flame-retardant polyester resin composition for calendaring, which is added.

(7) A sheet obtained by calendering the polyester resin described in (1) to (3) or the resin composition described in (4) to (6).

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The polyester resin for calendering of the present invention has a phosphorus atom contained in the molecular chain of 0.3 wt% or more and an aromatic dicarboxylic acid of 60 mol% or more in the acid component. Required. 0.3w of phosphorus atom
If it is less than t%, sufficient flame retardancy may not be obtained. The upper limit is not particularly limited, but considering economic efficiency and polymerizability, it is preferably 8 wt% or less, more preferably 5 wt% or less. Further, if 60 mol% or more, preferably 65 mol% or more, more preferably 70 mol% or more of the acid component is not an aromatic dicarboxylic acid, the mechanical properties when processed into a sheet are poor and the hydrolyzability is poor. Since the molecular weight decreases with time, the physical properties of the sheet decrease. Further, if the aromatic ring concentration is increased, it can be expected that the flame retardant effect is further improved. This is because the polyester resin is an aromatic condensation resin, especially an oxygen-containing condensation resin,
This itself has the ability to form a carbonized film, exhibits self-extinguishing properties, and is further copolymerized with a phosphorus-containing compound, which becomes phosphoric acid or polyphosphoric acid in the solid phase during combustion, and acts as a dehydrating agent. By doing so, the formation of the carbonized film is promoted.

The polyester resin for calendering used in the present invention preferably contains 30 mol% or more of terephthalic acid based on all carboxylic acid components. More preferably 3
It is 5 mol% or more, and most preferably 40 mol% or more.
If terephthalic acid is not contained in an amount of 30 mol% or more, the mechanical properties of the sheet become poor, which is not preferable.

The polyester resin for calendering used in the present invention preferably contains 30 mol% or more of an ethylene glycol component based on all diol components. It is more preferably 35 mol% or more, and most preferably 40 mol% or more. If ethylene glycol is not contained in an amount of 30 mol% or more, the mechanical properties of the sheet are inferior, which is not preferable.

The polyester resin for calendering used in the present invention contains 5 to 70 mol% of isophthalic acid based on all dicarboxylic acid components, and / or 1,2-propanediol, 1,3-propanediol based on all diol components. 1,4-butanediol, 2-methyl-1,3-
5-70 at least one diol component selected from the group consisting of propanediol, neopentyl glycol, diethylene glycol, cyclohexanedimethanol
It is preferable to contain mol%. A more preferable upper limit is 65 mol%, and a most preferable upper limit is 60 mol%. A more preferred lower limit is 9 mol%, and a most preferred lower limit is 12 mol%. The calendering suitability can be improved by appropriately introducing these copolymerization components into the molecular chain and appropriately adjusting the glass transition temperature, melting point and softening point of the polyester resin. Among these, isophthalic acid, neopentyl glycol, diethylene glycol, and cyclohexanedimethanol are preferable from the economical point of view, and in consideration of compatibility with the lubricant added for imparting calender processability, neopentyl glycol is 5 to 70 mol%. Most preferably, it is copolymerized.

In the polyester resin for calendering used in the present invention, it is essential to introduce a phosphorus atom into the molecular chain.
From the viewpoint of versatility, it is preferable to copolymerize the phosphorus-containing carboxylic acid represented by II or its ester compound.

[0017]

[Chemical 5]

[0018]

[Chemical 6]

Specific examples of R ¹ and R ² are a hydrogen atom and a hydrocarbon group such as methyl, ethyl, propyl and phenyl. R ¹ and R ² may be the same or different. R ³ and R ⁴ are hydrogen atoms, carbonized such as methyl, ethyl, propyl, butyl, phenyl, benzyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydrsoxybutyl and 2-hydroxyethyloxyethyl. Examples thereof include a hydrogen group or a hydroxy group-substituted hydrocarbon group. Specific examples of R ⁵ are a hydrogen atom and a hydrocarbon group such as methyl, ethyl, propyl and phenyl. R ⁶ and R ⁷ are hydrogen atom, methyl, ethyl, propyl,
Butyl, phenyl, benzyl, 2-hydroxyethyl,
2-hydroxypropyl, 3-hydroxypropyl, 4
A hydrocarbon group such as hydrosoxybutyl, 2-hydroxyethyloxyethyl, or a hydroxy group-substituted hydrocarbon group. Of these, the compound represented by the formula III is preferable in terms of economy.

[0020]

[Chemical 7]

The polyester resin for calendering of the present invention is the above-mentioned terephthalic acid, isophthalic acid, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2-methyl-
1,3-propanediol, neopentyl glycol,
Other than diethylene glycol and cyclohexanedimethanol, polyvalent carboxylic acid and polyhydric alcohol components may be copolymerized. For example, as polyvalent carboxylic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6
-Naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 2,2'-diphenyldicarboxylic acid, 4,
Aromatic dibasic acids such as 4'-diphenyl ether dicarboxylic acid, adipic acid, azelaic acid, sebacic acid, 1,4
-Aliphatic or alicyclic compounds such as cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid, dimer acid and trimellitic acid Can be mentioned. On the other hand, 1,2 as polyhydric alcohol
-Butanediol, 1,3-butanediol, 1,4-
Butanediol, 1,5-pentanediol, 1,6-
Hexanediol, 3-methyl-1,5-pentanediol, dipropylene glycol, 2,2,4-trimethyl-1,5-pentanediol, neopentyl hydroxypivalate ester, ethylene of bisphenol A Oxide adduct and propylene oxide adduct, ethylene oxide adduct of hydrogenated bisphenol A and propylene oxide adduct, 1,9-nonanediol, 2-methyloctanediol, 1,10-decanediol, 2-butyl 2-Ethyl-1,3-propanediol, tricyclodecane dimethanol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol and the like can be mentioned.

The number average molecular weight of the polyester resin for calendering used in the present invention is preferably 15,000.
-40,000, more preferably 18,000-3500
It is 0, more preferably 20000 to 35000.
If the number average molecular weight is less than 15,000, the strength and elongation of the sheet are insufficient due to insufficient resin cohesive force, and the sheet becomes brittle and cannot be used. On the other hand, when it is 40,000 or more, the melt viscosity increases, so that the optimum temperature for calendering also increases, and as a result, the releasability of the sheet from the roll deteriorates.

The acid value of the polyester resin for calendering used in the present invention is preferably 60 equivalents / 10 ⁶ g.
The amount is preferably 50 equivalents / 10 ⁶ g or less, more preferably 40 equivalents / 10 ⁶ g or less. Acid value is 60
When it exceeds the equivalent / 10 ⁶ g, hydrolysis is further promoted when the resin is heated during calendering, and the mechanical strength of the finished sheet is lowered. Further, as the resin is decomposed, the releasability of the sheet from the roll is also reduced.

The melt viscosity of the polyester resin for calendering used in the present invention at 220 ° C. and a shear rate of 100 sec ⁻¹ is preferably 3000 to 60000 d.
Pa · sec, more preferably 4000-50000d
Pa · sec, more preferably 5000 to 40,000
dPa · sec. Melt viscosity is 3000 dPa · s
When it is less than ec, the release property of the sheet from the roll deteriorates because the tackiness of the resin increases. Meanwhile, 60,000 dPa · se
When it exceeds c, the melt viscosity is too high and the productivity is lowered, which is not practical.

When a sheet is produced by calendering using the polyester resin of the present invention, it is necessary to add a lubricant to the polyester resin in order to enhance the releasability of the molten sheet from the roll.

The amount of the lubricant used in the present invention is 0.0
1 to 5 parts by weight. A more preferred lower limit is 0.05 part by weight, a still more preferred lower limit is 0.1 part by weight, and a most preferred lower limit is 0.2 part by weight. A more preferable upper limit is 4.5 parts by weight, a still more preferable upper limit is 4 parts by weight, and a most preferable upper limit is 3.5 parts by weight. The amount of lubricant is 0.01
If it is less than 5 parts by weight, the effect of improving the roll releasability is difficult to obtain, and if it exceeds 5 parts by weight, the transparency and coloring of the sheet obtained by the processing,
Printability tends to decrease.

As the lubricant used in the present invention, a polyolefin wax, a metal salt of an organic phosphoric acid ester, an organic phosphoric acid ester, an ester compound of adipic acid or azelaic acid and a higher aliphatic alcohol, ethylenebisstearoammite, Methylenebis stearoamites, glycerin higher fatty acid ester compounds, pentaerythritol higher fatty acid ester compounds, higher aliphatic alcohols, higher fatty acids, paraffins derived from petroleum or coal, waxes, natural or synthetic polymer ester waxes, higher fatty acids Metallic soap and the like.
These may be used alone or in combination of two or more. In particular, it is preferable to use a polyolefin wax and / or a metal salt of an organic phosphoric acid ester because the releasability of the sheet from the roll and the transparency of the finished sheet are easily compatible.

Examples of the polyolefin wax used as a lubricant in the present invention include polyethylene wax, polypropylene wax and derivatives thereof, and the derivatives include those with other monomers such as acrylic acid, vinyl acetate, styrene and maleic acid. There are copolymers and partially oxidized degradation forms.

The metal salt of an organic phosphate ester used as a lubricant in the present invention is, for example, a metal salt of an organic phosphate ester represented by the following general formula (IV) and / or a metal salt of the following general formula (V). The metal salts of organic phosphoric acid esters can be mentioned.

[0030] Formula (IV): [{RO ( C f H 2f O) n} 3-ao PO (O) a (O
H) _e ] _d {M (OH) _b } _c [In the formula, R represents a hydrocarbon group having 4 to 30 carbon atoms, M represents an alkali metal, alkaline earth metal, Zn or A1, and a is 1 Or 2, e represents 0 or 1 (provided that a is 1, 0 or 1 and a is 2, 0), b represents 0 to 2, and c represents 1 or 2. And d
Represents 1 to 3, f represents 2 or 3, and n represents 0 to 60
In addition, a, b, c, and d have the following relationship with the valence of the metal (M) (hereinafter referred to as m). m = 1
, B = 0, d = 1, a = c, m = 2, b =
0, c = 1, a × d = 2, or b = 1, d = 1, a
= C, m = 3, b = 0, d = 3, a = c, b =
1, c = 1, a × d = 2, or b = 2, d = 1, a
= C, and when m≥2, different phosphate ion groups may be bound to the metal (M), and in this case, d = 2 or 3 is the total number of different phosphate ion groups. Is. Also, d is 2 or 3
In this case, the structure in each [] may be the same or different from each other. ]

Formula (V): [{R ¹ O (C _f H _2f O) _n } _3-ae PO (O) _a (O
H) _e ] _d {M (OCOR ² ) _s (OH) _x } _t [In the formula, R ¹ represents a hydrocarbon group having 4 to 30 carbon atoms, and R ²
Represents an alkyl group having 1 to 25 carbon atoms, M represents an alkali metal, an alkaline earth metal, Zn or A1, and a represents 1
Or 2 and e represents 0 or 1 (where a is 1
Is 0 or 1 when a is 2, and 0 when a is 2. ), D
Represents 1 or 2, s represents 1 or 2, x represents 0 or 1, t represents 1 or 2, and f represents 2 or 3.
And n represents 0 to 60. Also, s + x = 1 or 2, and a, d, s, and t are valences of the metal (M) (hereinafter,
(described as m) has the following relationship. When m = 2, s = 1, d = 1, a = t, and when m = 3, s
= 1, t = 1, axd = 2, or s = 2, d = 1,
When a = t and m = 3, different phosphate ion groups may be bound to the metal (M), and in that case, d = 2 is the total number of various phosphate ion groups. means. When d is 2, the structures in [] may be the same or different. ]

As the hydrocarbon group having 4 to 30 carbon atoms represented by R in the above general formula (IV) and the hydrocarbon group having 4 to 30 carbon atoms represented by R ¹ in the general formula (V), , An alkyl group, a phenyl group, an arylalkyl group, an argenyl group or an alkylphenyl group is preferable. In addition, the general formula (I
The alkali metal represented by V) and M in the general formula (V) is preferably Li, Na, K or the like, and the alkaline earth metal is preferably Mg, Ca, Ba or the like.

The metal salt of the organic phosphoric acid ester represented by the general formula (IV) and the metal salt of the organic phosphoric acid ester represented by the general formula (V) can be produced by a conventional method. The method is not particularly limited.

Preferable examples of the metal salt of the organic phosphoric acid ester represented by the general formula (IV) include, for example, compounds (1) to (13) shown in Table 1 below and compounds (14) shown in Table 2 below. ) To compound (16) and the like, and preferable examples of the metal salt of the organic phosphoric acid ester represented by the general formula (V) include, for example, compound (15) shown in Table 2 below.
-Compound (26) is mentioned. These are 1 or 2
One or more species can be used in combination. It should be noted that these compounds (compound (1) to compound (26)) may be used alone or as a polyamine as shown by the number of repeating oxyethylene units or oxytrimethylene units in the polyether alcohol component including decimals. ether alcohols repetition number of oxyethylene units or oxytrimethylene units in component (in the formula (C _l H _2l O) _n number of repetitions (n)) is a mixture of different phosphoric acid ester metal salt.

[0035]

[Table 1]

[0036]

[Table 2]

The polyester resin and resin composition used in the present invention are phosphorus-based, nitrogen-based, hydrated metal-based, inorganic-based,
By using the silicon-based flame retardant together, the flame-retardant effect of the phosphorus-containing polyester resin can be further enhanced. For example, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, triethyl phosphate, cresyl diphenyl phosphate,
Xylenyl diphenyl phosphate, cresyl bis (2,6-xylenyl) phosphate, 2-ethylhexyl phosphate, dimethyl methyl phosphate, resorcinol bis (diphenyl) phosphate, bisphenol A bis (diphenyl) phosphate, bisphenol A bis ( Dicresyl) phosphate, diethyl-N, N-bis (2-hydroxyethyl)
Phosphorus flame retardants such as aminomethyl phosphate, phosphoric acid amide, organic phosphine oxide, red phosphorus, ammonium polyphosphate, phosphazene, cyclophosphazene, triazine, melamine cyanurate, succinoguanamine, ethylene dimelamine, triguanamine. , Cyanuric acid triazinyl salt, melem, melam, tris (β-cyanoethyl) isocyanurate, acetoguanamine, guanylmelamine sulfate, melem sulfate, nitrogen flame retardants such as melam sulfate, potassium diphenylsulfone-3-sulfonate, aromatic sulfone Metal salt flame retardants such as imide metal salts and polystyrene sulfonic acid alkali metal salts, aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, barium hydroxide, basic magnesium carbonate, zirco hydroxide. Um, hydrated metal-based flame retardants such as tin oxide, silica, aluminum oxide, iron oxide, titanium oxide,
Manganese oxide, magnesium oxide, zirconium oxide,
Zinc oxide, molybdenum oxide, cobalt oxide, bismuth oxide, chromium oxide, tin oxide, antimony oxide, nickel oxide, copper oxide, tungsten oxide, zinc borate, zinc metaborate, barium metaborate, zinc carbonate, magnesium carbonate, calcium carbonate , Inorganic flame retardants such as barium zinc stannate, and silicon flame retardants such as silicone powder. A higher flame retardant effect can be obtained from the combined effect of the flame retardant mechanism of the phosphorus compound-containing resin itself and the flame retardant. From the viewpoint of mechanical properties of the finished sheet, the compounding amount is preferably 200 parts by weight with respect to 100 parts by weight of the polyester resin, and more preferably 180 parts by weight.
The most preferable upper limit is 150 parts by weight. On the other hand, the lower limit is 0.5 part by weight.

Other components may be appropriately added to the polyester resin composition of the present invention depending on the application. Examples thereof include fillers, fillers, ultraviolet absorbers, light stabilizers, pigments, antistatic agents, antibacterial agents, epoxy compounds, crosslinking agents and the like.

[0039]

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 value described in the synthesis example is measured by the following method.

Resin composition: The resin was dissolved in deuterated chloroform and quantified by H-NMR. Glass transition temperature: using a differential scanning calorimeter, measurement sample 10
Place mg in an aluminum pan, press the lid to seal, and seal at 20 ℃ /
It was measured at a temperature rising rate of 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,
It was determined by titration with a 1N potassium hydroxide ethanol solution.
Phenolphthalein was used as the indicator.

Phosphorus atom content: (Determination of phosphorus by wet decomposition / molybdenum blue colorimetric method) The sample was weighed in an Erlenmeyer flask according to the phosphorus concentration in the sample, and 3 ml of sulfuric acid, 0.5 ml of perchloric acid and 3.5 ml of nitric acid. Was added and gradually decomposed by heating in an electric heater over half a day. When the solution became clear, it was further heated to generate sulfuric acid white smoke, allowed to cool to room temperature, and this decomposition solution was transferred to a 50 ml volumetric flask.
5% 2% ammonium molybdate solution and 0.2%
2 ml of a hydrazine sulfate solution was added, the volume was adjusted with pure water, and the contents were mixed well. Place the flask in a boiling water bath for 10 minutes to heat and develop the color, then cool with water to room temperature, degas with ultrasonic waves, take the solution into an absorption cell 10 mm, and control the blank test solution with a spectrophotometer (wavelength 830 nm). And the absorbance was measured. The phosphorus content was determined from the calibration curve previously prepared, and the phosphorus concentration in the sample was calculated.

<Polyester Synthesis Example 1> 4,250 parts by weight of dimethyl terephthalate and 1930 of dimethyl isophthalate were placed in a reaction vessel equipped with a stirrer, a thermometer, and an outflow cooler.
Parts by weight, 820 parts by weight of ethylene glycol, 4290 parts by weight of neopentyl glycol and 2.7 parts by weight of tetrabutyl titanate were added, and transesterification was carried out at 170 to 220 ° C. for 2 hours. After the transesterification reaction is completed, the reaction system is fed with an ethylene glycol solution of formula III (solid content concentration 50%,
Add 6920 parts by weight of GHM-1 manufactured by Sanko Co., Ltd., and reheat to 220 ° C. with stirring for 10 minutes. When the temperature reached 220 ° C., the temperature was raised from 220 ° C. to 270 ° C., while the pressure inside the system was gradually reduced to 500 Pa over 60 minutes. And 5 at below 130Pa
Polycondensation reaction was carried out for 5 minutes to prepare a copolyester synthesis example 1.
Got

[0043]

[Chemical 8]

As a result of NMR analysis in Polyester Synthesis Example 1, the dicarboxylic acid component was 55 mol% terephthalic acid, 25 mol% isophthalic acid, 20 mol% of the component of formula VI (formula VI was represented as a dicarboxylic acid for convenience), and the diol component. Had a composition of 51 mol% ethylene glycol and 49 mol% neopentyl glycol. The glass transition temperature is 68 ° C, the number average molecular weight is 28,000, and the acid value is 30 equivalents / 1.
It was 0 ⁶ g and the phosphorus content was 2.9 wt%.

[0045]

[Chemical 9]

Polyester Synthesis Examples 2 to 6 and Comparative Synthesis Examples 1 to 3 were manufactured in the same manner as in Polyester Synthesis Example 1. Table 3 shows the composition and the measurement results. (Numbers are mol% in resin)

[0047]

[Table 3]

The polyester shown in Table 3 was mixed with each component shown in Tables 4 and 5 in a beaker, and the mixture was heated at 180 ° C.
The mixture was kneaded on two 6-inch chilled rolls set to.
The resin adhering to the chilled roll is occasionally peeled off and mixed, and after kneading for 5 minutes, the roll interval is set to 0.3 mm (sheet thickness is set to 0.3 mm) to improve the peelability when peeling the molten sheet from the roll. evaluated. The evaluation criteria are as follows. The results are shown in Tables 4 and 5.

Sheet releasability: Good-Releasability from roll, good adhesiveness to roll, difficult to peel, normal sheet cannot be collected Flame retardancy: Limit according to JIS K7201 oxygen index method The oxygen index (LOI) was used for evaluation. This is the minimum oxygen concentration required for the sample to burn. The larger the oxygen index, the higher the flame retardancy. The lubricants and flame retardants listed in Tables 4 and 5 mean the following compounds. a: tridecyl poly (oxyethylene) phosphate zinc salt b: styrene-modified polyethylene wax c: aluminum hydroxide d: ammonium polyphosphate Also, the numerical values for the amount of polyester, the amount of lubricant, and the amount of flame retardant in the table are parts by weight.

[0050]

[Table 4]

[0051]

[Table 5]

[0052]

As described above, the polyester resin and the composition thereof of the present invention are a composition in which a polyester containing a phosphorus atom in the molecular chain, a lubricant, and optionally a flame retardant are combined. Because of this, it is possible to improve the sheet releasability from the roll when calendering a polyester resin composition, which was difficult in the past, and it is also possible to process calender sheets of excellent quality, which has good flame retardancy despite being non-halogen. can do.

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Claims (7)

[Claims] 1. The phosphorus atom contained in the molecular chain is 0.3 wt.
% Or more, and of the acid components, aromatic dicarboxylic acid is 60
A flame-retardant polyester resin for calendering, characterized by containing at least mol%. 2. Containing 30 mol% or more of terephthalic acid based on all carboxylic acid components, 30 mol% or more based on all diol components, and 5 to 70 mol% of isophthalic acid based on all dicarboxylic acid components, and / or
Alternatively, a group consisting of 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, neopentyl glycol, diethylene glycol and cyclohexanedimethanol per all diol components. The flame-retardant polyester resin for calendering according to claim 1, which contains 5-70 mol% of at least one diol component selected from the following. 3. The flame-retardant polyester resin for calendering according to claim 1, which is obtained by copolymerizing a phosphorus-containing carboxylic acid represented by the general formula I or general formula II or an ester compound thereof. [Chemical 1] R ¹ , R ² : hydrogen atom or hydrocarbon group R ³ , R ⁴ : hydrogen atom, hydrocarbon group or hydroxy-substituted hydrocarbon group 1, m: an integer of 0 to 4 R ⁵ : Hydrogen atom or hydrocarbon group R ⁶ , R ⁷ : Hydrogen atom, hydrocarbon group or hydroxy-substituted hydrocarbon group 4. A flame-retardant polyester resin composition for calendering, comprising the polyester resin according to claim 1 and a lubricant mixed in an amount of 0.01 to 5 parts by weight per 100 parts by weight of the polyester resin. 5. The flame-retardant polyester resin composition for calendar processing according to claim 4, wherein the lubricant is a polyolefin wax and / or a metal salt of an organic phosphoric acid ester. 6. A flame retardant is added to the polyester resin according to any one of claims 1 to 3 or the polyester resin composition according to any one of claims 4 and 5 as polyester 1
A flame-retardant polyester resin composition for calendaring, which is added in an amount of 0.5 to 200 parts by weight with respect to 00 parts by weight. 7. A sheet obtained by calendering the polyester resin according to any one of claims 1 to 3 or the resin composition according to any one of claims 4 to 6.