CN102825773A - Manufacturing method of polyester resin, protective sheet used for solar cell and solar cell module - Google Patents

Abstract

Provided is a manufacturing method of polyester resin, a protective sheet used for solar cell and a solar cell module. A rotational speed N of a screw is adjusted in an area range represented by the following formulas in which an extrusion output per unit Y satisfies, so that Y changes continuously, and extrusion amount Q per unit time of melt-mixing polymer resin increases from Qmin to Qmax or decreases from Qmax to Qmin, and thus melt extrusion is carried out (Y : extrusion amount per unit Q/N, Yunder = 9.01 * 10<-7> * D3, Yover = 6.93 * 10 <-6> * D3, D : screw diameter, Q0 : extrusion amount of regular operation, Qmax and Qmin : maximum or minimum extrusion amount of increasing or decreasing). When 0 <= Q <= 0.5*Q0, (Y-Yunder) / Q <= (Yover - Y under) / (0.5 * Q0); when 0.5*Q0 < Q, Y <= Yover; Y >= Yunder; 0.6*Q0 <= Qmax <= 1.2*Q0; 0.15*Q0 <= Qmin <= 0.4*Q0.

Description

The method of making of mylar, used for solar batteries screening glass and solar module

Technical field

The present invention relates to manufacturing approach, used for solar batteries screening glass and the solar module of mylar.

Background technology

Polyester is applicable to various uses such as electric insulation purposes, optical applications.Wherein, as the electric insulation purposes, particularly the protection of the inner face of solar cell is gazed at sheet solar cell purposes such as (so-called backboards) in recent years.

On the other hand, polyester exists carboxyl and hydroxyl on its surface usually morely, causes hydrolysis under the environmental condition of moisture easily existing, and has the tendency of deterioration with time.For example using the environment that is provided with of solar module usually is that outdoor grade often exposes environment such in wind and rain to the open air, owing to expose to the open air under the condition of reaction that is hydrolyzed easily, therefore expectation is controlled at the water-disintegrable state that stably suppresses polyester.

Yet, for example, during startup when the switching of raw material and during the screw rod of extruder restarting after stopping etc.,, carry out the increase and decrease of extrusion capacity as effective method in order to remove the foreign matter that is attached to mould.In the past, under the situation of the increase and decrease of carrying out such extrusion capacity, through as the extrusion capacity Q/N [kg/hr/rpm] of the resin that is extruded carry out for the rotational speed N of setting screw rod under the constant condition with respect to extruding change.Yet; Under Q/N is constant condition; Exist to cause that easily the air vent that is described below overflows the problem of (Vent up), so-called air vent overflows for molten resin is full of (adverse current) and causes pipe arrangement obstruction etc. to the passage pipe arrangement that passage, perhaps further molten resin are sucked into the attraction usefulness that is connected with passage.

As preventing one of method that above-mentioned air vent overflows; Technology below for example disclosing: the output of the pressure sensor through being equipped on the degassing portion in the rotating cylinder; The omen that the inspection air vent overflows; Screw speed and quantity delivered are controlled at not the scope (for example, with reference to patent documentation 1) of can air vent overflowing.

In addition; When starting once more after the screw rod of extruder stops, proterties, heating and the mixing state of the resin that extruder is inner is different when turning round continuously, extrusion capacity change etc. when perhaps restarting; To this; Disclose the extrusion device that is described below: the mode of rotating speed is controlled gear when becoming the starting of confirming according to the screw rod dwell time, and appropriate change screw speed (for example, with reference to patent documentation 2).

The prior art document

Patent documentation

Patent documentation 1: japanese kokai publication hei 6-254945 communique

Patent documentation 2: TOHKEMY 2004-358695 communique

Summary of the invention

Invent problem to be solved

Yet, even if the fact is also not reach fully through above-mentioned prior art to solve: for example,, overflow and increase and decrease the air vent that causes easily when spray volume carries out intermittent working in order to remove extruder inner deterioration thing, retentate.If cause that air vent overflows, then cause quality to reduce easily, particularly under the situation of the weather resistance that the purposes of for example solar module etc. will be aspired for stability, the performance that can't guaranteeing of might existing stipulated.

The present invention accomplishes in view of the above fact; Its purpose is; The manufacturing approach of the mylar that is described below is provided; And to reach this purpose as problem, the air vent when wherein the manufacturing approach of mylar can suppress melting mixing (particularly intermittently melt extruding the intermittent working of mylar) overflows, and retained foreign body is few and realize the stabilisation of resin quality.

The method that is used to deal with problems

The concrete method that is used to reach above-mentioned problem is described below.

<1>A kind of manufacturing approach of mylar; It has the operation that melt extrudes that is described below; Promptly; Make the polyester raw material resin of putting into double screw extruder in rotating cylinder in the melting mixing, according to the relation of the extrusion capacity Y of unit [kg/hr/rpm] Yu the time per unit extrusion capacity Q [kg/h] of the mylar after the fusion, the rotating speed of the screw rod in the extrusion capacity Y of unit satisfies the above-mentioned rotating cylinder of range regulation in represented zone, following relational expression (1)～(5); Y is changed continuously, and the extrusion capacity Q that makes time per unit simultaneously is by Q _MinTo Q _MaxIncrease perhaps by Q _MaxTo Q _MinReduce, thereby melt extrude.

(1) 0≤Q≤0.5 * Q ₀The time,

(Y-Y _under)/Q≤(Y _over-Y _under)/(0.5×Q ₀)

(2) 0.5 * Q ₀During＜Q,

Y≤Y _over

(3)Y≥Y _under

(4)0.6×Q ₀≤Q _max≤1.2×Q ₀

(5)0.15×Q ₀≤Q _min≤0.4×Q ₀

In above-mentioned relation formula (1)～(5), Y representes the extrusion capacity Q/N of unit [kg/hr/rpm] of per 1 rotation of screw rod, Y _UnderAnd Y _OverBe Y _Under[kg/hr/rpm]=9.01 * 10 ^-7* D ³, Y _Over[kg/hr/rpm]=6.93 * 10 ^-6* D ³D representes screw rod footpath [mm].The extrusion capacity of the time per unit of the molten polyester resin when Q representes to turn round [kg/h], Q ₀Extrusion capacity when expression is not carried out increase and decrease or subtracted constant running that increases variation.Q _Max, Q _MinRepresent increase and decrease respectively or subtract maximum extrusion capacity, the minimum extrusion capacity that increases when changing.N representes the rotating speed [rpm] of screw rod.

In addition, represent N at N _MaxOr N _MinSituation under, N _MaxExpression Q _MaxThe time minimum speed, N _MinExpression Q _MinThe time minimum speed.

<2>According to above-mentioned<1>The manufacturing approach of described mylar, the extrusion capacity Y of unit is at Q _MaxThe time Y _MaxRatio with respect at Q _MinThe time Y _MinRatio satisfy following relational expression (6).

1.1≤Y _max/Y _min≤5.0…(6)

In the above-mentioned relation formula (6), Y _MinExpression Q _Min/ N _Min, Y _MaxExpression Q _Max/ N _Max

<3>According to above-mentioned<1>Or it is above-mentioned<2>The manufacturing approach of described mylar changes Y and by Q _MinTo Q _MaxIncrease perhaps by Q _MaxTo Q _MinIn the process that reduces, be to be made as in 5 seconds the constant time with Y.

<4>According to above-mentioned<1>～<3>The manufacturing approach of each described mylar above-mentionedly melt extrudes in the operation, if with the increase of the extrusion capacity Q of mylar or reduce the needed time and be made as t [hr], then makes extrusion capacity Q by Q _MinTo Q _MaxIncrease perhaps by Q _MaxTo Q _MinThe speed (Q/t, the unit: kg/hr that reduce ²) absolute value satisfy following relational expression (7).

0.50×D ²≤|Q/t|≤6.48×D ²…(7)

In the above-mentioned relation formula (7), Q is the negative value of expression under the situation that extrusion capacity reduces.

< 5>according to the manufacturing approach of each described mylar in above-mentioned < 1 >～above-mentioned < 4 >; To during being extruded in through rotating cylinder, make extrusion capacity Q increase and decrease or subtract the number of times that increases and be made as n until mylar; In increase and decrease or subtract that to increase above-mentioned frequency n when finishing be that n satisfies following relational expression (8) under 1 time the situation.

1＜n＜10…(8)

<6>According to above-mentioned<1>～above-mentioned<5>In the manufacturing approach of each described mylar, above-mentionedly melt extrude operation when intermittently melt extruding the intermittent working of mylar, Y is changed continuously, and by Q _MinTo Q _MaxIncrease perhaps by Q _MaxTo Q _MinReduce.

<7>A kind of polyester film, it is by above-mentioned to passing through<1>～above-mentioned<6>In the mylar made of the manufacturing approach of each described mylar stretch and obtain 1m ²In maximum length be 1 of the number less than of the above foreign matter of 50 μ m.

< 8>a kind of used for solar batteries screening glass, it has above-mentioned < 7>described polyester film.

< 9>a kind of solar module; It has: the substrate of the transparency of sunshine incident; Be disposed at the solar cell device of a side of aforesaid substrate; And, be disposed at above-mentioned < 8>described used for solar batteries screening glass this solar cell device and the side opposition side configuration aforesaid substrate.

The invention effect

According to the present invention, a kind of manufacturing approach of mylar can be provided, the air vent when it can suppress melting mixing (particularly intermittently melt extruding the intermittent working of mylar) overflows, and retained foreign body is few and realize the stabilisation of resin quality.

In addition, when carrying out intermittent working, realize the shorteningization of the time of intermittent working.

Description of drawings

Fig. 1 is the sectional view of the formation example of the summary of expression double screw extruder.

Fig. 2 is in the two-dimensional coordinate axle of the extrusion capacity Q that the extrusion capacity Y of the longitudinal axis unit of being made as, transverse axis is made as molten resin, by the figure of the scope of relation line (a)～(d) center on.

Fig. 3 is the figure of the condition of expression embodiment 1.

Fig. 4 is the figure of the condition of expression embodiment 2.

Fig. 5 is the figure of the condition of expression embodiment 3.

Fig. 6 is the figure of the condition of expression embodiment 4.

Fig. 7 is the figure of the condition of expression embodiment 5.

Fig. 8 is the figure of the condition of expression embodiment 6.

Fig. 9 is the figure of the condition of expression embodiment 7.

Figure 10 is the figure of the condition of expression embodiment 8.

Figure 11 is the figure of the condition of expression embodiment 9.

Figure 12 is the figure of the condition of expression embodiment 10.

Figure 13 is the figure of the condition of expression embodiment 11.

Figure 14 is the figure of the condition of expression embodiment 12.

Figure 15 is the figure of the condition of expression embodiment 13.

Figure 16 is the figure of the condition of expression embodiment 14.

Figure 17 is the figure of the condition of expression comparative example 1.

Figure 18 is the figure of the condition of expression comparative example 2.

Figure 19 is the figure of the condition of expression comparative example 3.

Figure 20 is the figure of the condition of expression comparative example 4.

Figure 21 is the figure of the condition of expression comparative example 5.

Figure 22 is the figure of the condition of expression comparative example 6.

Figure 23 is the figure of the condition of expression comparative example 7.

Figure 24 is the figure of the condition of expression comparative example 8.

Figure 25 is the figure of the condition of expression comparative example 9.

The Q of Figure 26 when melt extruding among expression (A) embodiment 1, (B) embodiment 2, (C) embodiment 3, (D) embodiment 4, N, and the chart of Q/N.

The Q of Figure 27 when melt extruding among expression (A) embodiment 5, (B) embodiment 6, (C) embodiment 7, (D) embodiment 8, N, and the chart of Q/N.

The Q of Figure 28 when melt extruding among expression (A) embodiment 9, (B) embodiment 10, (C) embodiment 11, N, and the chart of Q/N.

The Q of Figure 29 when melt extruding among expression (A) embodiment 12, (B) embodiment 13, (C) embodiment 14, N, and the chart of Q/N.

The Q of Figure 30 when melt extruding in expression (A) comparative example 1, (B) comparative example 2, (C) comparative example 3, (D) comparative example 4, N, and the chart of Q/N.

The Q of Figure 31 when melt extruding in expression (A) comparative example 5, (B) comparative example 6, (C) comparative example 7, (D) comparative example 8, N, and the chart of Q/N.

Q when Figure 32 melt extrudes in the comparative example 9 for expression, N, and the chart of Q/N.

The specific embodiment

Below, be elaborated for the manufacturing approach of mylar of the present invention.

The manufacturing approach of mylar of the present invention; It has the operation that melt extrudes that is described below; Promptly; Make the polyester raw material resin of putting into double screw extruder in rotating cylinder in the melting mixing, according to the relation of the extrusion capacity Y of unit [kg/hr/rpm] with the extrusion capacity Q [kg/h] of time per unit of the mylar after the fusion, so that the extrusion capacity Y of unit satisfies the rotating speed that the mode of the scope in represented zone, following relational expression (1)～(5) is regulated the screw rod in the rotating cylinder; Y is changed continuously, and the extrusion capacity Q of time per unit that makes the mylar after the fusion is by Q _MinTo Q _MaxIncrease perhaps by Q _MaxTo Q _MinReduce, melt extrude.

Here, the relation of unit extrusion capacity Y and extrusion capacity Q can be based on a axle (the for example longitudinal axis) the extrusion capacity Y of the unit of getting [kg/hr/rpm] on the two-dimensional coordinate axle, get extrusion capacity Q [kg/h] and the relation line of drawing at another axle (for example transverse axis).For example, following relational expression (1)～(5) can be illustrated in the extrusion capacity Y of the longitudinal axis unit of getting, transverse axis and get the relation when drawing relation line on the two-dimensional coordinate axle that extrusion capacity Q [kg/h] forms.

The manufacturing approach of mylar of the present invention can also be provided with following operation except setting melt extrudes operation: make the mylar that is extruded be shaped to sheet, the sheet molding procedure of for example on the casting drum, cooling off; Other operations such as stretching process that the mylar of sheet is stretched.

Among the present invention, with the mylar after the fusion (below, also abbreviate molten resin as) when extruding, according to Y is changed continuously and Q by Q _MinTo Q _MaxIncrease or by Q _MaxTo Q _MinThe mode that reduces; Setting makes the extrusion capacity Q increase and decrease of the time per unit of molten resin perhaps subtract the process that increases variation; In said process; Be not carry out Y (=Q/N) for constant control, but below the extrusion capacity Y of unit of per 1 rotation of screw rod satisfies the rotating speed of the scope control screw rod in represented zone, relational expression (1)～(5) of expression, the extrusion capacity Q increase and decrease of the mylar of extruding is perhaps subtracted increases variation.Thus; Prevent the generation that the air vent of mylar when melting mixing (particularly intermittently melt extruding the intermittent working of mylar) overflows; No matter whether switch material resin etc. according to change of kind etc.; Can both carry out the manufacturing of stabilized resins, reduce the retained foreign body in the resin, realize the stabilisation of resin quality.

-melt extrude operation-

Melt extruding in the operation among the present invention; Make the polyester raw material resin of putting into double screw extruder in rotating cylinder in the melting mixing; According to the relation of the extrusion capacity Y of unit [kg/hr/rpm] with extrusion capacity Q [kg/h]; The rotating speed of the screw rod in the extrusion capacity Y of unit satisfies the range regulation rotating cylinder in represented zone, relational expression (1)～(5), Y is changed continuously and make fusion after the extrusion capacity Q of time per unit of mylar by Q _MinTo Q _MaxIncrease or by Q _MaxTo Q _MinReduce, melt extrude.

Basically the known in the past double screw extruder with twin shaft screw rod that is used for resin melt extrusion is set the necessary condition of the mylar be used to obtain to expect, can carry out the melting mixing based on used double screw extruder.Double screw extruder can use small-sized or large-scale any device.

Fig. 1 illustrates the formation example that is fit to double screw extruder of the present invention.The summary sectional view of the formation example of the double screw extruder that uses during the manufacturing approach of the polyester film that Fig. 1 can relate in embodiment of the present invention for expression roughly.

Under through the situation that melt extrudes the manufactured polyester film, normally used extruder has single shaft and multiaxis substantially.As multiaxis, double screw extruder (twin shaft screw extruder) is widely used.As double screw extruder, for example shown in Figure 1, can be double screw extruder 100, it has: rotating cylinder 10 (cylinder), this rotating cylinder have the supply port 12 of base feed resin and the outlet of extruder 14 of resin melt extrusion; 2 screw rod 20A that have above external diameter of 140mm and rotation in rotating cylinder 10 respectively, 20B; And, be disposed at rotating cylinder 10 around and the temperature control unit 30 of the temperature in the control rotating cylinder 10.In addition, can before next-door neighbour's supply port 12, raw material feed device be set, be provided with filter 42 and mould 40 in addition in the front of outlet of extruder 14.In addition, can also not shown gear pump further be set in the front of outlet of extruder 14.

< rotating cylinder >

Resin extruded outlet of extruder 14 after rotating cylinder 10 has the supply port 12 that is used for the base feed resin and makes heating and melting.

That the internal face of rotating cylinder 10 uses is heat-resisting, abrasion performance, and excellent corrosion resistance and can guarantee the material with the friction of resin.Usually the nitrated steel that uses the inner face via nitride to handle also can carry out nitrogen treatment and use chrome-molybdenum steel, nickel chromium molybdenum steel, stainless steel.Particularly in the purposes that requires antifriction consumption, corrosion resistance; Use through centre spinning at the internal face liner of rotating cylinder 10 the bimetallic rotating cylinder of corrosion resistances such as nickel, cobalt, chromium, tungsten, abrasion performance material alloy lining, or the spraying plating epithelium that forms pottery is effective.

Rotating cylinder 10 is provided with passage 16A, the 16B that is used to vacuumize.Vacuumize through passage 16A, 16B, thereby can remove the volatile ingredients such as moisture in the resin in the rotating cylinder 10 effectively.Through suitable configuration passage 16A, 16B, the pulverizing bits (puff) etc. of the film of output in the raw material of drying regime (particle, powder, sheet etc.) not, the film forming way are directly used as material resin.

From considering that with the relation of degassing efficiency passage 16A, 16B require suitable opening area and ventilation hole count.Double screw extruder 100 expectations have 1 place above passage 16A, 16B.In addition, if the number of passage 16A, 16B is too much, then have possibility that passage overflows, the worry of being detained the increase of deterioration foreign matter, thereby passage preferably is provided with 1 place or 2 places.

In addition,, then there is possibility, should be noted that as foreign matter remarkableization on goods if the resin that is trapped near the wall the passage and the volatile ingredient of separating out drop to the inside of extruder 100 (rotating cylinder 10).For delay, the suitable selection of suitableization of the shape of vent cap, top passage, side passage is effectively, and the common use of separating out of volatile ingredient utilizes the heating of pipe arrangement etc. to prevent the method for separating out.

For example, extruding under the situation of PET, the inhibition of hydrolysis, thermal decomposition, oxidation Decomposition produces big influence to the quality of goods (film).For example, purge, can suppress oxidation Decomposition through making resin supply port 12 evacuation or nitrogen.

In addition, through passage 16A, 16B are set in many places,, also can carry out and extrude identical the extruding of situation that is dried to the resin below the 50ppm with single shaft even be under the situation about 2000ppm at the raw water component.

In addition, for the resin that suppresses to be caused by shear heat evolution decomposes, preferably parts such as kneading portion are not set as far as possible can taking into account the scope of extruding and outgasing.

In addition since the pressure of screw rod outlet (outlet of extruder) 14 more greatly then shear heat evolution is big more, thereby preferred in the scope of the stability of guaranteeing to utilize the degassing efficiency of passage 16A, 16B and extruding, the pressure of outlet of extruder 14 is low as far as possible.

< twin shaft screw rod >

In rotating cylinder 10, be provided with screw rod footpath (external diameter) D and the utilization that have more than the φ 140mm and comprise 2 screw rod 20A that the driver part 21 of motor and gear is rotated, 20B.D is in the large-scale double screw extruder more than the φ 140mm in the screw rod footpath, can produce in a large number, on the other hand, is easy to generate air vent and overflows, and causes the reduction of quality after the generation fusion inequality easily.Yet; Among the present invention; Even use under the situation of large-scale double screw extruder with the above screw rod of external diameter 140mm, also can be when preventing that air vent from overflowing, suppressing the fusion inequality, can suppress production of foreign matters and the increase of the terminal COOH that causes by heating.

Double screw extruder is divided into occlusal pattern and the non-occlusal pattern of 2 screw rod 20A, 20B substantially, and than non-occlusal pattern, the melting effect of occlusal pattern is bigger.Among the present invention, can be any type in occlusal pattern and the non-occlusal pattern, suppress the uneven viewpoint of fusion from abundant compounding raw materials resin, preferably use occlusal pattern.

The direction of rotation of 2 screw rod 20A, 20B also is divided into equidirectional and different direction respectively.Than equidirectional rotary-type, the melting effect of different direction rotary screw 20A, 20B is higher, and equidirectional rotary-typely have from cleaning effect, thereby for preventing that the delay in the extruder from being effective.

Further, direction of principal axis also has parallel and oblique, also has in the shape that applies the circular cone type of using under the situation of strong shearing.

In the double screw extruder that uses among the present invention, use the screw portion of different shape.As the shape of screw rod 20A, 20B, can use 1 oblique rail of the helical form (Japanese: 22 complete tiltedly rail screw rod Off ラ イ ト) that for example is provided with uniform pitch.

Through use kneading disk, rotor etc. to implement the part of shearing in heating and melting portion, can more positively make the material resin fusion.In addition,, can stop resin, melting sealed when forming traction passage 16A, 16B through using contrary screw rod or seal.For example, as shown in Figure 1, kneading part (kneading disk) 24A, the 24B of the fusion of aforesaid promotion material resin can be set near passage 16A, 16B.

It is effective that the temperature that is provided for cooling off molten resin in the resin extruded direction downstream of extruder 100 is transferred the mode in district's (cooling end).Comparing shear heat evolution, under the higher situation of the heat transfer efficiency of rotating cylinder 10, the short screw rod 28 of pitch be set through transfer district's (cooling end) in temperature, can improve rotating cylinder 10 walls the resin translational speed, and improve temperature and transfer efficient.From improving the viewpoint of cooling effect, with respect to screw rod footpath D, the pitch that is positioned at the screw rod 28 of cooling end is preferably 0.5D～0.8D.

< temperature control unit >

Around rotating cylinder 10, be provided with temperature control unit 30.In the extruder 100 shown in Figure 1, be divided into heating/cooling device C1～C9 of 9 by raw material supplying mouth 12 to outlet of extruder 14 at length direction and constitute temperature control unit 30.Thus, through cut apart be configured in rotating cylinder 10 around heating/cooling device C1～C9, can be divided into for example each zone (district) of the C1～C7 of heating and melting portion and cooling end C8, C9, and make rotating cylinder 10 interior each Region control in desired temperatures.

Usually band heater heating or armored cable aluminum casting heater (Japanese: Season line ア Hikaru Shin a mini Cast Ru Eyes Hiroshi a Tatari one), but is not limited to these, you can also use such as heat medium circulation heating method.On the other hand, cooling is generally the air cooling that utilizes air blast, also oriented be wound on rotating cylinder 10 around pipe in flow into the method for water or oil.

< mould >

Be provided with at the outlet of extruder 14 of rotating cylinder 10 and be used to make the molten resin extruded by outlet of extruder 14 mould 40 with membranaceous (band shape) ejection.In addition, between the outlet of extruder 14 of rotating cylinder 10 and mould 40, be provided with and be used to prevent that molten resin not or foreign matter from sneaking into the filter 42 of film.

< gear pump >

In order to improve thickness and precision, importantly reduce the change of extrusion capacity as far as possible.In order to reduce the change of extrusion capacity as far as possible, can also between extruder 100 and mould 40, gear pump be set.Through supply with a certain amount of resin by gear pump, can improve thickness and precision.Particularly under the situation of using the twin shaft screw extruder,, thereby preferably utilize gear pump to realize extruding stabilisation because the boost capability of extruder self is low.

Through using gear pump, the pressure oscillation that can make 2 sides of gear pump is below 1/5 of 1 side, and can make the resin pressure amplitude of fluctuation is in ± 1%.As other advantages, can not improve the pressure of screw tip portion and utilize filter to filter, thereby can expect the preventing of rising of resin temperature, the raising and the shortening of the holdup time in the extruder of transfer efficiency.The filter that in addition, can also prevent filter presses the amount of resin of being supplied with by screw rod that is upgraded to reason and changes in time.Wherein, if gear pump is set, then should be noted that owing to the equipments choice method causes the length of equipment elongated, the holdup time of resin is elongated, caused the cut-out of strand by the shear stress of gear pump portion.

If 1 pressure of gear pump (going into to press) is excessive with the difference of 2 pressure (going out to press), then the load of gear pump becomes big, and it is big that shear heat evolution becomes.Therefore, the differential pressure during running be 20MPa with interior, be preferably 15MPa, further be preferably in the 10MPa.In addition, it is constant that a pressure of gear pump is become, and the screw rod rotation or the working pressure control valve of control extruder are effective.

The double screw extruder and the polyester raw material resin of formation as shown in Figure 1 are prepared in melt extruding in the operation among the present invention, when heating through 30 pairs of rotating cylinders 10 of temperature control unit, make screw rod 20A, and the 20B rotation is by supply port 12 base feed resins.In addition, for the particle of heating raw resin etc. and screw drive equipment such as not welding and protection motor, supply port 12 preferably cools off with the form that prevents to conduct heat.

Supply to material resin in the rotating cylinder except through the heating that utilizes temperature control unit 30 fusion; Also follow heat release and the fusion of friction between friction, resin and screw rod 20A, 20B or the rotating cylinder 10 between the resin of rotation of screw rod 20A, 20B etc. through utilization; Meanwhile, follow the rotation of screw rod and slowly move to outlet of extruder 14.

Though supply to material resin in the rotating cylinder be heated to fusing point Tm (℃) above temperature; But if resin temperature is crossed the fusion deficiency of hanging down when then melt extruding; Might be difficult to by mould 40 ejections; On the contrary, then might be if resin temperature is too high because thermal decomposition and terminal COOH significantly increases causes the reduction of hydrolytic resistance.From these viewpoints, utilize heating-up temperature and the screw rod 20A of temperature control unit 30, the rotating speed of 20B through adjustment, preferably with the maximum resin temperature (Tmax of the length direction in the double screw extruder (resin extruded direction); [℃]) be made as (Tm+40) ℃～(Tm+60) ℃, more preferably be made as (Tm+40) ℃～(Tm+55) ℃, further preferably be made as (Tm+45) ℃～(Tm+50) ℃.

The maximum resin temperature T max of the length direction (resin extruded direction) in the double screw extruder is the temperature of heated material resin in the rotating cylinder that is equipped with screw rod 20A, 20B 10 of double screw extruder 100; When having shear heat evolution, be the temperature that comprises the portion of localized hyperthermia that causes by above-mentioned heat release.Tmax obtains through the mensuration of the resin temperature in the rotating cylinder.From the viewpoint of the increase that suppresses terminal COOH, above-mentioned Tmax [℃] be preferably below 290 ℃, more preferably below 280 ℃.In addition, from the not enough viewpoint of fusion that prevents resin, the lower limit temperature expectation of Tmax is 260 ℃.

-passage pressure-

Carry out vacuum through passage 16A, 16B and take out and draw, thereby can effectively remove the volatile ingredients such as moisture in the resin in the cylinder.If the passage hypotony, then might spill into outside the rotating cylinder 10 by molten resin, as if the passage hypertonia then removing of volatile ingredient become insufficient, might be easy to generate the hydrolysis of the film of gained.From preventing that molten resin from optionally removing the viewpoint of volatile ingredient by passage 16A, when 16B overflows, passage pressure is preferably 1.333Pa～666.5Pa (0.01Torr～5Torr), 1.333Pa～533.2Pa (0.01Torr～4Torr) more preferably.

-mean residence time-

In rotating cylinder, material resin is carried out heating and melting, be preferably 10 minutes from outlet of extruder 14 output backs until being extruded into membranaceous mean residence time～20 minutes by mould 40.If material resin is carried out heating and melting; Is more than 10 minutes from the outlet of extruder 14 output backs of extruder 100 until the mean residence time of being extruded by mould 40; Then can molten resin not residual be suppressed to less, on the other hand, if this mean residence time is below 20 minutes; The increase of the terminal COOH amount that then can prevent to be caused by thermal decomposition obtains more excellent hydrolytic resistance.From such viewpoint, material resin is carried out heating and melting and mean residence time after being extruded by outlet of extruder 14 more preferably 10 minutes～15 minutes.

Here, mean residence time is defined by following formula.

Mean residence time (second)={ extruder downstream pipe arrangement volume [cm ³] * molten mass density [g/cm ³] * 3600/1000}/extrusion capacity [kg/h]

-cooling-

In rotating cylinder, material resin is carried out heating and melting as stated, on the other hand, through temperature control unit 30, with the inwall of outlet of extruder 14 sides of rotating cylinder 10 become mylar (material resin) fusing point Tm (℃) below the mode of cooling end control.If with the inwall of outlet of extruder 14 sides of rotating cylinder 10 be controlled at as cooling end material resin fusing point Tm (℃) below, then can suppress the terminal COOH amount that resin caused by superheated increases.From the viewpoint of the increase that positively suppresses terminal COOH amount, the temperature of this cooling end is preferably in (Tm-100) ℃～Tm ℃ the scope, in the scope of more preferably (Tm-50) ℃～(Tm-10) ℃.

With respect to screw rod footpath D, the length of cooling end is preferably 4D～11D.If the length of cooling end is more than the 4D, then make the effectively cooling and suppress the increase of terminal COOH of resin that is melted heating.On the other hand, if the length of cooling end is below the 11D, then can prevents the resin sub-cooled and solidify, thereby melt extrude smoothly.

In addition, the resin temperature Tout at outlet of extruder 14 is preferably below Tm+30 ℃.Wherein, If it is low excessively at the resin temperature Tout of outlet of extruder 14; Part that then might molten resin is solidified, thereby is preferably below Tm～(Tm+25) ℃ at the resin temperature Tout of outlet of extruder 14, further is preferably (Tm+10) ℃～(Tm+20) ℃.

Mylar by the outlet of extruder 14 of rotating cylinder 10 is extruded is extruded by mould 40 (for example waiting chill roll to the casting drum) through filter 42, is shaped to sheet, and cools off.

Behind mould 40 melt extrusions (molten resin), in the interval that for example contacts (space), preferably humidity is adjusted into 5%RH～60%RH with chill roll, more preferably be adjusted into 15%RH～50%RH.Through the humidity that makes the space is above-mentioned scope, can regulate the COOH amount and the OH amount on film surface.In addition, through being adjusted to low humidity, can reduce the carboxylic acid amount on film surface.

In addition, after once improving resin temperature, cool off, when can suppress the increase of terminal COOH amount, suppress not fusion production of foreign matters.And then, to suppress to be shaped to the effect that the mist degree of the mylar of sheet rises.Particularly under the situation that is shaped to abundant sheet, though the deficiency of cooling velocity causes mist degree to rise easily, the rising of this moment is inhibited.

In addition, the thickness of film be preferably 2mm～8mm, more preferably 2.5mm～7mm, further be preferably 3mm～6mm.Through making the thickness thickening, can prolong until the melt that is extruded and be cooled to the required time below the glass transition temperature (Tg).During this, the COOH base on film surface is diffused into polyester inside, can reduce surface C OOH amount.

Among the present invention, the terminal COOH of polyester raw material amount is preferably below the 3eq/t with poor (Δ AV) through the terminal COOH amount of the mylar of the sheet that melt extrudes.For example, obtain terminal COOH amount and be the polyester sheet below the 25eq/t (ton).If terminal COOH amount is for below the 25eq/ ton, then hydrolytic resistance is excellent, and obtains long durability.Viewpoint from hydrolysis; Expect that terminal COOH amount is low; But the viewpoint of the adaptation when raising makes by the sheet of moulding and adherend driving fit, the lower limit of the AV of the mylar that is formed as sheet after extruding is preferably the 2eq/ ton, and the scope of preferred AV is 10～20eq/ ton.

The mensuration of terminal COOH amount can likewise be carried out with above-mentioned method.

In addition, the per 1 ton molar equivalent of " eq/t " expression.

Then, the increase and decrease process for extrusion capacity Q is elaborated.

Under the situation about melt extruding through double screw extruder among the present invention, setting makes the extrusion capacity Q of the time per unit of the mylar after the fusion carry out increase and decrease or subtracts the process (in this specification, being referred to as " increase and decrease process ") that increases variation.Through making extrusion capacity Q carry out increase and decrease or subtracting and increase variation, for example can suppress when the switching of different raw materials such as rerum naturas such as kind or melt viscosity etc., (also comprising the situation that makes screw rod and restart) or the air vent that is easy to generate when intermittently extruding the intermittent working of mylar overflow during the running starting of double screw extruder.

Particularly in the switching of the polyester kind of material resin, under situation such as inherent viscosity (IV) different raw materials resin switching, can effectively suppress the generation that air vent overflows.

At this moment, the rotating speed of the screw rod in the scope in the zone that relational expression (1)～(5) of expression below satisfying through the extrusion capacity Y of unit in per 1 rotation of screw rod are represented in the adjusting rotating cylinder, the increase and decrease that carries out extrusion capacity Q perhaps subtracts and increases variation.

(1) 0≤Q≤0.5 * Q ₀The time,

(Y-Y _under)/Q≤(Y _over-Y _under)/(0.5×Q ₀)

(2) 0.5 * Q ₀During＜Q,

Y≤Y _over

(3)Y≥Y _under

(4)0.6×Q ₀≤Q _max≤1.2×Q ₀

(5)0.15×Q ₀≤Q _min≤0.4×Q ₀

In above-mentioned relation formula (1)～(5), Y representes the extrusion capacity Q/N of unit [kg/hr/rpm] of per 1 rotation of screw rod.In addition, the Y in the formula _UnderAnd Y _Over[kg/hr/rpm] is respectively Y _Under=9.01 * 10 ^-7* D ³, Y _Over=6.93 * 10 ^-6* D ³, D representes screw rod footpath [mm].

The extrusion capacity of the time per unit of the molten polyester resin when Q representes to turn round [kg/h], Q ₀Extrusion capacity when expression is not carried out increase and decrease or subtracted constant running that increases variation, Q _Max, Q _MinRepresent increase and decrease respectively or subtract maximum extrusion capacity, the minimum extrusion capacity that increases when changing.

N representes the rotating speed [rpm] of screw rod.Here, represent maximum (top) speed N at N _MaxOr minimum speed N _MinSituation under, N _MaxExpression Q _MaxThe time minimum speed, N _MinExpression Q _MinThe time minimum speed.

For above-mentioned relation formula (1)～(5), describe with reference to Fig. 2.

Fig. 2 is at the extrusion capacity Y of the longitudinal axis unit of getting (=Q/N; Unit: [kg/hr/rpm]), transverse axis is got in the two-dimensional coordinate axle of extrusion capacity Q (unit: [kg/h]) of molten resin, by the figure of relation line (1)～scope that (5) center on.

The extrusion capacity Q of the mylar that at first, will be extruded by double screw extruder is defined as relational expression (4), (5) represented Q _MinAnd Q _MaxScope.

At this moment, (=the scope that Q/N) satisfies above-mentioned relation formula (1)～(2) carries out the increase and decrease of extrusion capacity Q or subtracts increasing variation at the extrusion capacity Y of unit.That is,

The extrusion capacity Y of unit is the scope below the Y value on the line segment (a) and (b) among Fig. 2.If Y is for surpassing the Y value on the line segment (a) or surpassing Y _Over(=6.93 * 10 ^-6* D ³[kg/hr/rpm]) scope (zone that surpasses the Y value on the line segment (b) among Fig. 2), then per extrusion capacity that rotates for 1 time of screw rod is excessive, thereby is easy to generate air vent and overflows.

Among the present invention, can pass through the quantity delivered of consideration resin viscosity and material resin etc., and regulate rotational speed N, be adjusted into the scope that satisfies relational expression (1)～(2).

In addition, the extrusion capacity Y of unit (=Q/N) satisfy the scope of above-mentioned relation formula (3), carry out the increase and decrease of extrusion capacity Q or subtract increasing variation.That is,

The minimum of a value of the extrusion capacity Y of unit is Y _Under(=9.01 * 10 ^-7* D ³[kg/hr/rpm]) be the represented above scope of Y value of line segment (c) among Fig. 2.If Y is not enough Y _UnderScope (being lower than the zone of the Y value on the line segment (c) among Fig. 2), then because the rotating speed of screw rod is excessive, the resin deterioration forms retained foreign body easily.If retained foreign body increases, then bring the reduction of the weatherability of mylar, the reduction of membrane property.

Wherein, Y _UnderThe value of the scope that is preferably the vacuum do not destroyed in the passage and can air vent overflow.

Among the present invention, consider the quantity delivered of resin viscosity and material resin etc.,, can be adjusted to the scope that satisfies relational expression (3) through regulating rotational speed N.

Therefore; Among the present invention; Through with the extrusion capacity Y of unit (=Q/N) include in above-mentioned relation formula (1)～(3), promptly by the mode in the zone of the trapezoidal expression among Fig. 2, make extrusion capacity Q carry out increase and decrease or subtract the control that increases variation, the air vent in the time of can preventing melting mixing overflows.Thus, the quality that stably keeps mylar.

By Q _MinTo Q _MaxSubtract to increase and change perhaps by Q _MaxTo Q _MinCarry out in the process of increase and decrease, the represented Q/N of Y is changed continuously.Thus, increase and decrease perhaps subtracts to increase to change rapidly becomes possibility, and can carry out removing of the shortening of intermittent working time, effective foreign matter.

At this moment, Q/N is in constant preferred 5 seconds of time.

Above-mentioned Q _Min, Q _MaxBe the extrusion capacity Q when not carrying out constant running that increase and decrease or subtract increases variation ₀Carry out increase and decrease or subtract minimum of a value, the maximum that increases when changing, the maximum extrusion capacity Q of mylar _MaxSatisfy above-mentioned relation formula (4), minimum extrusion capacity Q _MinSatisfy above-mentioned relation formula (5).Q ₀Behind the expression increase and decrease or subtract increase after the variation, the setting extrusion capacity [kg/h] when not carrying out increase and decrease or subtracting the constant running that increases variation.

Q _Min, Q _MaxFor improving the essential factor of removing effect of deterioration thing.Making extrusion capacity Q carry out increase and decrease or subtracting in above-mentioned relation formula (1)～(5) in the process that increases variation, if be conceived to Q _Max, then it is the more zone of extrusion capacity of comparing constant when running, therefore, and Q _MaxThe following 0.6Q that is limited to ₀If Q _MaxNot enough 0.6Q ₀, then the effect of removing of deterioration thing reduces.On the other hand, if Q _MaxSurpass 1.2Q ₀, then pressure rises rapidly, might can't avoid air vent to overflow.

In addition, if be conceived to Q _Min, then it is the extrusion capacity zone still less when comparing constant the running, therefore, and Q _MinThe following 0.15Q that is limited to ₀If Q _MinNot enough 0.15Q ₀, then might can't keep vacuum and the foreign matter increase, perhaps might overflow by air vent.On the other hand, if Q _MinFor surpassing 0.4Q ₀Scope, then can't increase the increase and decrease amplitude of spray volume, the effect that can not expect from resin, to remove foreign matter.

Wherein, above-mentioned Q _MaxPreferred satisfied 0.6 * Q ₀≤Q _Max≤1.05 * Q ₀, more preferably satisfy 0.6 * Q ₀≤Q _Max≤0.8 * Q ₀

Among the present invention, as minimum of a value Y with respect to the extrusion capacity Y of unit _MinMaximum Y _MaxRatio, be preferably the scope that satisfies following relational expression (6).

1.1≤Y _max/Y _min≤5.0…(6)

In the above-mentioned relation formula (6), Y _MinExpression Q _Min/ N _Min, Y _MaxExpression Q _Max/ N _Max

Making extrusion capacity Q carry out increase and decrease or subtracting in the process that increases variation, through the Y of the extrusion capacity Y of the unit of making _Max/ Y _MinRatio be more than 1.1, can suppress the generation of the not fused mass of extrusion capacity hour, prevent that air vent from overflowing.In addition, through making Y _Max/ Y _MinRatio be below 5.0, can suppress the rotating speed of screw rod and not make it excessive, and prevent the deterioration of resin and reduce retained foreign body.

Wherein, Y _Max/ Y _MinRatio be preferably more than 1.5 below 3.0, more preferably more than 1.5 below 2.2.

In addition; Under the situation that the extrusion capacity Q that makes mylar increases or reduces; Be made as t [hr] if will begin to increase or be reduced to the required time of accomplishing increase or reducing to desired amount from it, then perhaps subtracting the speed (Q/t) that increases preferably satisfies following relational expression (7) in extrusion capacity Q increase and decrease.

0.50×D ²≤|Q/t|≤6.48×D ²…(7)

In the above-mentioned relation formula (7), D representes that screw rod footpath [mm], the Q when extrusion capacity reduces represent the value of bearing.In addition, || the expression absolute value.

Make extrusion capacity Q carry out increase and decrease or subtracting in the process that increases variation, through making its speed | Q/t| is 0.50 * D ²More than, can appropriateness keep speed of increasing and decrease or subtract the speedup degree, thereby can shorten total run time and significant loss is suppressed to less.In addition, through making increase and decrease or subtracting the speed that increases | Q/t| is 6.48 * D ²Below, the speed that extrusion capacity increases can not become too fast, thereby can prevent that air vent from overflowing.

Wherein, above-mentioned | Q/t| is preferably 0.57 * D ²More than 5.04 * D ²Below, 0.85 * D more preferably ²More than 4.37 * D ²Below, further be preferably 1.34 * D ²More than 4.23 * D ²Below.

Make extrusion capacity Q carry out increase and decrease or subtracting in the process that increases variation; With mylar during being extruded in through rotating cylinder from supply ports such as funnel or filters extrusion capacity Q increase and decrease or subtract the number of times that increases and be made as n; In increase and decrease or subtract that to increase frequency n counting when finishing be that preferably its n satisfies the represented scope of following relational expression (8) under 1 time the situation.

1＜n＜10…(8)

According to above-mentioned relation formula (8), make n be more than 2 times, be about to be made as more than 2 times until making extrusion capacity Q completion increase minimizing or accomplishing the operation that reduces increase, can prevent effectively that thus air vent from overflowing.In addition, being below 9 times, being that aforesaid operations is below 9 times through n, can shorten the used time of intermittent working, is being favourable aspect the raising productivity.

Wherein, n is preferably the situation that satisfies 2＜n＜6.

Making extrusion capacity Q carry out increase and decrease or subtracting in the process that increases variation, can carry out through the rotating speed of regulating the screw rod in the rotating cylinder.The adjusting of rotating speed can utilize the motor that is connected with screw rod and the driver part 21 of gear of comprising for example shown in Figure 1 to carry out.Driver part 21 is electrically connected with and is used to control the control assembly (not shown) to its output signal.

Melt extruding in the operation among the present invention is not intermittently to carry out but the increase and decrease or subtract of carrying out the extrusion capacity Q of mylar continuously increases, is above-mentioned the making " by Q among the present invention _MinTo Q _MaxIncrease perhaps by Q _MaxTo Q _MinReduce " operation.If intermittently carrying out the increase and decrease or subtract of the extrusion capacity of mylar increases; Then total run time is elongated, causes significant loss, but the increase and decrease through carrying out extrusion capacity continuously or subtract increases; Can realize shortening, the reduction significant loss of total run time, and improve the stability of quality simultaneously.

Then, for the polyester raw material resin that in the manufacturing of mylar, uses (below, also abbreviate material resin as.) describe.

(polyester raw material resin)

The polyester raw material resin is the raw material of polyester film, and the material of polyester is then not special to be limited so long as comprise, and except polyester, can also comprise the slurry of inorganic particulate or organic filler.In addition, the polyester raw material resin can also comprise the titanium elements from catalyst.

The kind of contained polyester is not special in the polyester raw material resin limits, can dicarboxylic acids composition and glycol component synthesize the polyester that forms in order for example to use, also can use commercially available polyester.

As material resin, preferred characteristics viscosity (IV) is 0.7～0.9 mylar.

IV through material resin is more than 0.7, can the terminal COOH of raw material be suppressed to lessly, and keeps film quality well.In addition, if IV is below 0.9, then the increase of terminal COOH tails off, film quality is good.The IV of material resin is preferably 0.70～0.85, and more preferably 0.70～0.80.

The IV of material resin can adjust according to polymerization methods and polymerizing condition.For example, can inherent viscosity be adjusted into above-mentioned scope through after liquid phase polymerization, carrying out solid phase.

The terminal COOH amount (AV) of material resin is preferably below the 25eq/t (equivalent/ton), more preferably below the 15eq/t.In addition, from the for example viewpoint of the adaptation between acquisition and the adherend, the terminal COOH amount expectation of material resin is for more than the 2eq/t.

The value of terminal COOH amount for measuring through following method.That is,

After material resin 0.1g is dissolved into benzyl alcohol 10ml, further add chloroform, obtain mixed solution, to wherein dripping phenol red indicator.With benchmark liquid (0.01N, KOH-benzyl alcohol mixed solution) this solution is carried out titration, obtain the terminal carboxyl group amount by dripping quantity.

In addition, the per 1 ton molar equivalent of " eq/t " expression.

In addition, under the situation of mixing the various kinds of resin use, the terminal COOH scale of material resin shows the amount under the admixture.For example; As PETG (PET); Mix more than a kind or 2 kinds or under the situation such as chip material as the pulverizing of PET film bits of its particle, terminal COOH amount is total metering of terminal COOH amount with the terminal COOH amount of smear metal of the total amount of the terminal COOH amount of particle or particle.

In addition, the fusing point of material resin (Tm) is preferably 250 ℃～260 ℃ scope.The value of above-mentioned fusing point Tm for obtaining through the differential scanning calorimetry.During for the mixing of a plurality of resins, the mean value of fusing point is preferably in above-mentioned scope.

The bulk specific gravity of material resin is preferably 0.6～0.8 scope.If bulk specific gravity is more than 0.6, then can more stably extrude, if proportion is below 0.8, then can suppress localized heat release effectively.

The bulk specific gravity of material resin is meant; Powder is put into the container or the additive method of certain volume with certain state; With the proportion (quality of per unit volume) that the quality of the powder that forms the regulation shape is obtained divided by the volume of this moment, the more little then volume of bulk specific gravity is big more.

In the middle of above-mentioned, the heat release when suppressing to extrude more effectively suppress terminal COOH increase aspect, the bulk specific gravity of material resin is preferably 0.7～0.75 scope especially.

As the mylar that constitutes material resin, can be through utilizing known method to make dicarboxylic acids or its ester derivant and diatomic alcohol compounds carry out esterification and/or ester exchange reaction obtains.

As above-mentioned dicarboxylic acids or its ester derivant; For example can enumerate out; Aliphatic dicarboxylic acid classes such as malonic acid, butanedioic acid, glutaric acid, adipic acid, suberic acid, decanedioic acid, dodecanedioic acid, dimeric dibasic acid, eicosane diacid, pimelic acid, azelaic acid, methylmalonic acid, ethyl malonic acid; Alicyclic dicarboxylic acids such as adamantane dicarboxylic acids, norbornene dicarboxylic acids, isobide, cyclohexane dicarboxylic acid, decahydronaphthalene dicarboxylic acids, terephthalic acid (TPA), M-phthalic acid, phthalic acid, 1,4-naphthalene dicarboxylic acids, 1; 5-naphthalene dicarboxylic acids, 2; 6-naphthalene dicarboxylic acids, 1,8-naphthalene dicarboxylic acids, 4,4'-diphenyldicarboxylic acids, 4; 4 '-diphenyl ether dicarboxylic acids, 5-sodium sulfo isophthalate, phenylindan dicarboxylic acids, anthracene dicarboxylic acids, luxuriant and rich with fragrance dicarboxylic acids, 9, dicarboxylic acids or its ester derivants such as aromatic binary carboxylic acid such as 9 '-two (4-carboxyl phenyl) fluorenic acid.

As above-mentioned diatomic alcohol compounds, for example can enumerate out ethylene glycol, 1,2-propane diols, 1; Ammediol, 1,4-butanediol, 1,2-butanediol, 1, glycols such as 3-butanediol; 1, ester ring type di-alcohols such as 4-cyclohexanedimethanol, the spiroglycol, isobide, bisphenol-A, 1; 3-benzene dimethanol, 1,4-benzene dimethanol, 9,9 '-two (4-hydroxy phenyl) fluorenes, etc. aromatic dicarboxylic alcohols etc.

Esterification and/or ester exchange reaction can be used known in the past catalysts.As catalysts, can enumerate out alkali metal compound, alkaline earth metal compound, zinc compound, lead compound, manganese compound, cobalt compound, aluminium compound, antimonial, titanium compound, phosphorus compound etc.Usually in the stage arbitrarily before the manufacturing approach of polyester finishes, preferably add antimonial, germanium compound, titanium compound as polymerization catalyst.As such method, for example, as if being that example is enumerated with the germanium compound, the then preferred germanium compound powder that directly adds.

Preferred polyester is PETG (PET), polyethylene-2,6-naphthalate (PEN), has 1, the poly terephthalic acid cyclohexanedimethanoester ester (PCT) of 4-cyclohexanedimethanol structure, more preferably PET.

Have 1; Under poly terephthalic acid cyclohexanedimethanoester ester (PCT) situation (PCT) of 4-cyclohexanedimethanol structure; From 1, the ratio that contains of the structure of 4-cyclohexanedimethanol (CHDM) is the scope of 0.1～100 mole of % with respect to the total amount (all in the glycol) from the structure of diol component preferably.Especially particularly from the scope that ratio is preferably 0.1～20 mole of % or 80～100 moles of % that contains of the structure of CHDM; The scope of 0.5～16 mole of % or 83～98 moles of % more preferably is preferably the scope of 1～12 mole of % or 86～96 moles of % especially.Existence is from two zones in the few zone of the structure of CHDM (0.1～20 mole of %) and high zone (80～100 moles of %), this be because be easy to generate in these zones crystallization, form that the amorphous that is taken between crystallization carries out bridge joint easily fasten chain (tie chain).In the zone of CHDM above 20 moles of % and less than 80%, can mix and have CHDM and EG, regularity reduces, and is difficult for generating crystallization.

In addition, for containing the detailed description of composition that CHDM is the polyester layer of polyester, of the back.

PET is preferably use and is selected from germanium (Ge) series catalysts, antimony (Sb) series catalysts, aluminium (Al) series catalysts, reaches the PET that is polymerized more than a kind or 2 kinds in titanium (Ti) series catalysts, more preferably Ti series catalysts.

The reactivity of above-mentioned Ti series catalysts is high, can reduce polymerization temperature.Therefore, can be suppressed at particularly that PET carries out thermal decomposition and produces COOH in the polymerisation.Among the present invention, be fit to the terminal COOH amount of polyester film is adjusted into the scope below the 30eq/ ton.

The Ti catalyst that obtains through the polymerization of using the Ti series catalysts is that the manufacturing of PET for example can be used the polymerization of record in TOHKEMY 2005-340616 communique, TOHKEMY 2005-239940 communique, TOHKEMY 2004-319444 communique, No. 3436268 communiques of japanese, No. 3979866 communiques of japanese, No. 3780137, japanese, the TOHKEMY 2007-204538 communique etc.

Using as the Ti series catalysts under the situation of titanium sub-group compound; Preferably as the use amount of titanium sub-group compound; The scope that below in the above 30ppm of titanium elements scaled value 1ppm, more preferably below the above 20ppm of 2ppm, further is preferably below the above 15ppm of 3ppm is used, and carries out polymerization.In the case, polyester film preferably comprises the titanium below the above 30ppm of 1ppm.

If the amount of titanium sub-group compound is more than the 1ppm, then can obtain preferred IV, if below the 30ppm, then can terminal COOH be suppressed to lowlyer, be favourable for the raising of hydrolytic resistance.

In addition, the crushing piece of the preferred hybrid resin film of material resin prepares.

As above-mentioned resin molding, suitable is polyester film, preferably with material resin in mylar be the film of polyester of the same race.The crushing piece of resin molding can improve volume height for for example unwanted film being pulverized the crushed material of processing small pieces (so-called smear metal) or bits sheet etc., and the situation that bulk specific gravity is compared for example be merely particle reduces.

As the size of this crushing piece, the scope of Volume Changes is then not special to be limited if apply, and preferred thickness is 20～5000 μ m.Wherein, excessively reduce fullness rate in order not make bulk specific gravity become excessive,, be preferably the scope of 100～1000 μ m, the scope of 100～500 μ m more preferably from avoiding the not enough viewpoint of fusion.

In addition, further reducing by aspect the terminal COOH amount of the polyester film of system film, the deviation of the size of preferred powder fragment is little, for example the preferred deviation of the thickness of crushing piece in ± 100%, more preferably ± 50% in, further be preferably ± 10% in.Using under the situation of crushing piece, be suppressed to lessly through deviation, can make the change of terminal COOH amount of the polyester film of gained be suppressed to lower the size of thickness etc.

As the quality ratio of crushing piece in material resin, preferably the gross mass with respect to material resin is below the 50 quality %, and the expectation of the lower limit of its quality ratio is 10 quality %.Through the ratio that makes crushing piece is below the 50 quality %, can be suppressed to the amplitude of fluctuation of the terminal COOH amount of the polyester film of gained lower.Wherein, for the same reason, the quality ratio of crushing piece more preferably 10～30 quality %, be preferably 20～30 quality % especially.

As the bulk specific gravity of crushing piece, satisfy in the scope of above-mentioned scope at the bulk specific gravity of material resin, be preferably 0.3～0.7 scope.Bulk specific gravity is identical with the bulk specific gravity meaning of above-mentioned material resin, likewise measures with said method.

Among the present invention, preferably further contain end-capping reagent.Through having the structure that makes molecule crosslinked between crystallizing polyester (fastening chain), become firm structure, have excellent weather resistance.Contain end-capping reagent through polyester film, can make and fasten excessively prosperity of chain, can suppress embrittlement and improve hear resistance.Thus, the worry to the evils that are easy to generate when the film forming also diminishes.

End-capping reagent in polyester, is more than the 0.1 quality % with the gross mass with respect to polyester preferably and the scope below the 10 quality % contains.The content of end-blocking material is the above and scope below the 5 quality % of 0.2 quality % more preferably, further is preferably the above and scope below the 2 quality % of 0.3 quality %.Through end-capping reagent and carboxylic acid end reaction (end-blocking), terminal polarity reduces, and forms the chain of fastening that the amorphous that is taken between crystallization carries out bridge joint easily.If the amount of end-capping reagent is then to obtain above-mentioned effect more than the 0.1 quality % easily, in addition through being below the 10 quality %, can in polyester, not forming impurity ground and promote crystallization to generate, form easily and fasten chain.

End-capping reagent is meant, with the carboxyl reaction of the end of polyester, and the additive that the terminal carboxyl group amount of polyester is reduced.

As end-capping reagent, can enumerate out carbon imide compound 、 oxazoline compound, epoxide, carbonate products etc.Among the present invention, preferably contain in isocyanate compound, carbon imide compound and the epoxide a kind and multiple, more preferably contain the carbon imide compound.End-capping reagent can a kind of independent use, also can make up use.

If end-capping reagent adds then better effects if with mylar when the system film.In addition, also can contain end-capping reagent with implementing solid phase.Specifically; End-capping reagent can be before the raw material supplying mouth that supplies to double screw extruder and the polyester raw material mixed with resin; Also can with double screw extruder melting mixing polyester the time, mix, also can after double screw extruder is discharged molten resin, be mixed into the molten resin.

The carbon imide compound that preferably in molecule, has circulus in the end-capping reagent.This is because have reactive high, the territory polyester end reaction more effectively of carbon imidodicarbonic diamide of the carbon imide compound of circulus.

Preferably contain first nitrogen with 1 carbon imidodicarbonic diamide base and carbon imidodicarbonic diamide base and second nitrogen ring-type carbon imide compound in the end-capping reagent through the circulus that combines base and combine.

-ring-type carbon imide compound-

Ring-type carbon imide compound is to contain first nitrogen with 1 carbon imidodicarbonic diamide base and carbon imidodicarbonic diamide base and second the nitrogen compound through the circulus that combines base and combine.

Here, first nitrogen is meant that (nitrogen-atoms in 2 nitrogen-atoms that N=C=N-) have, second nitrogen is meant another nitrogen-atoms to carbon imidodicarbonic diamide base.

Ring-type carbon imide compound carries out end-blocking as end-capping reagent to the terminal carboxyl group of polyester, thereby polyester film of the present invention can improve the weatherability of polyester film, particularly damp and hot durability through containing ring-type carbon imide compound.

Through using ring-type carbon imide compound to improve the weatherability of polyester film, it is considered to because following reason.

Through making the carbon imide compound is circulus, can be described below, and promotes on polyester, further to form to fasten chain.

The cracking of ring-type carbon imidodicarbonic diamide is with the terminal carboxylic acid reaction of polyester (being called PET-1).

The other end of the carbon imidodicarbonic diamide of cracking is a NCO, with the terminal hydroxyl reaction of other polyester (being called PET-2).

Ring-type carbon imide compound is a circulus, thus with the position of hydroxyl reaction be connected with the position of carboxylic acid reaction.Consequently, form the fasten chain structure of two PET strands (PET-1 and PET-2) by the connection of ring-type carbon imidodicarbonic diamide.

Ring-type carbon imide compound is preferably with respect to the polyester raw material resin to be the ratio use of 0.05 quality %～20 quality %.

Below, be elaborated for ring-type carbon imide compound.

Ring-type carbon imide compound preferable weight-average molecular weight (Mw) is more than 400, more preferably 500～1500.

In addition, ring-type carbon imide compound can have a plurality of circuluses.

Specifically, the circulus of ring-type carbon imide compound have 1 carbon imidodicarbonic diamide base (N=C=N-) and its first nitrogen combine through combining base with second nitrogen.In 1 circulus; Only has 1 carbon imidodicarbonic diamide base; But for example in volution etc., molecule, have under the situation of a plurality of circuluses,, then can have a plurality of carbon imidodicarbonic diamide bases as compound certainly if having 1 carbon imidodicarbonic diamide base in each circulus that combines with spiro-atom.Atomicity in the circulus is preferably 8～50, more preferably 10～30, further is preferably 10～20, is preferably 10～15 especially.

Here, the atomicity in the circulus is meant the number of the atom of direct formation circulus, for example, if if 8 yuan of rings then are that 8 50 yuan of rings then are 50.This be because if the atomicity in the circulus less than 8, then the stability of ring-type carbon imide compound reduces, and has keeping, uses the situation of difficult that becomes.In addition, this be because, the higher limit of the first number that on reactive viewpoint, encircles has no particular limits, the difficulty but the ring-type carbon imide compound that surpasses 50 atomicity becomes on synthetic produces the situation that cost significantly rises.On above-mentioned viewpoint, the atomicity in the circulus preferably selects 10～30, more preferably select 10～20, especially preferably select 10～15 scope.

Circulus is preferably the represented structure of following formula (1).

[changing 1]

In the formula (1); Q (below, be also referred to as combine basic Q) for the combination base that is selected from 2～4 any 1 valencys in fatty group, alicyclic group and the aromatic series base, or be selected from the combination base of 2～4 valencys of the combination of 2 above groups in fatty group, alicyclic group and the aromatic series base.In addition, the combination of 2 above groups can be the form like the combination group of the same race of aromatic series base and aromatic series Kina appearance.

The fatty group, alicyclic group and the aromatic series base that constitute Q can contain the substituting group of hetero atom or 1 valency independently of one another.Hetero atom is meant O, N, S, P in this case.2 valencys in conjunction with in the valency of base are used to form circulus.Be that circulus combines with polymer or other circuluses by singly-bound, two key, atom or atomic group under the situation of combination base of 3 valencys or 4 valencys at Q.

Be preferably in conjunction with basic Q the carbon number 1～20 that is selected from 2～4 valencys fatty group, 2～4 valencys carbon number 3～20 alicyclic group, or the aromatic series base of the carbon number 5～15 of the alicyclic group of the carbon number 3～20 of the fatty group of the carbon number 1～20 of the aromatic series base of the carbon number 5～15 of 2～4 valencys or 2～4 valencys, 2～4 valencys and 2～4 valencys in the combination of the group more than 2.

As the example of the combination that is selected from the group more than 2 in fatty group, alicyclic group and the aromatic series base that constitute to combine basic Q, can enumerate out that alkylidene combines with arlydene, the structure as alkylidene-arlydene etc.

Be preferably the combination base of 2～4 represented valencys of following formula (1-1), formula (1-2) or formula (1-3) in conjunction with basic Q.

[changing 2]

In the formula (1-1), Ar ¹And Ar ²Be the aromatic series base of the carbon number 5～15 of 2～4 valencys independently of one another.Ar ¹And Ar ²The substituting group that can further contain hetero atom or 1 valency independently of one another.

As by Ar ¹Or Ar ²The aromatic series base of expression can be enumerated out the arlydene of carbon number 5～15, aromatic hydrocarbons three bases of carbon number 5～15, aromatic hydrocarbons four bases of carbon number 5～15.As arlydene (divalent), can enumerate out phenylene, naphthylene etc.As aromatic hydrocarbons three bases (3 valency), can enumerate out benzene three bases, naphthalene three bases etc.As aromatic hydrocarbons four bases (4 valency), can enumerate out benzene four bases, naphthalene four bases etc.These aromatic series bases can be substituted.

The substituting group of 1 valency that can have as the aromatic series base can be enumerated out aryl, halogen atom, nitro, amide groups, hydroxyl, ester group, ether, aldehyde radical of alkyl, the carbon number 6～15 of carbon number 1～20 etc.

In the formula (1-2), R ¹And R ²Be fatty group, or the combination of the alicyclic group of the carbon number 3～20 of the fatty group of the carbon number 1～20 of the alicyclic group of the carbon number 3～20 of 2～4 valencys or 2～4 valencys and 2～4 valencys, perhaps of the carbon number 1～20 of 2～4 valencys independently of one another, be selected from the combination of the group more than 2 in the aromatic series base of carbon number 5～15 of alicyclic group and 2～4 valencys of carbon number 3～20 of fatty group, 2～4 valencys of the carbon number 1～20 of 2～4 valencys.Constitute R ¹And R ²Fatty group, alicyclic group and aromatic series base can further contain the substituting group of hetero atom or 1 valency independently of one another.

As by R ¹Or R ²The fatty group of expression can be enumerated out the alkylidene of carbon number 1～20, alkane three bases of carbon number 1～20, alkane four bases of carbon number 1～20 etc.As alkylidene, can enumerate out methylene, ethylidene, propylidene, butylidene, pentylidene, hexylidene, inferior heptyl, Ya Xinji, inferior nonyl, inferior decyl, inferior dodecyl, inferior cetyl etc.As alkane three bases, can enumerate out methane three bases, ethane three bases, propane three bases, butane three bases, pentane three bases, hexane three bases, heptane three bases, octane three bases, nonane three bases, decane three bases, dodecane three bases, hexadecane three bases etc.As alkane four bases, can enumerate out methane four bases, ethane four bases, propane four bases, butane four bases, pentane four bases, hexane four bases, heptane four bases, octane four bases, nonane four bases, decane four bases, dodecane four bases, hexadecane four bases etc.These fatty groups can be substituted.

The substituting group of 1 valency that can have as fatty group can be enumerated out aryl, halogen atom, nitro, amide groups, hydroxyl, ester group, ether, aldehyde radical of alkyl, the carbon number 6～15 of carbon number 1～20 etc.

As alicyclic group, can enumerate out the cycloalkylidene of carbon number 3～20, cycloalkane three bases of carbon number 3～20, cycloalkane four bases of carbon number 3～20.As cycloalkylidene, can enumerate out cyclopropylidene, inferior cyclobutyl, cyclopentylene, cyclohexylidene, inferior suberyl, inferior ring octyl group, inferior ring nonyl, inferior ring decyl, inferior cyclo-dodecyl, inferior ring cetyl etc.As cycloalkane three bases, can enumerate out cyclopropane three bases, cyclobutane three bases, pentamethylene three bases, cyclohexane three bases, cycloheptane three bases, cyclooctane three bases, cyclononane three bases, cyclodecane three bases, cyclododecane three bases, ring hexadecane three bases etc.As cycloalkane four bases, can enumerate out cyclopropane four bases, cyclobutane four bases, pentamethylene four bases, cyclohexane four bases, cycloheptane four bases, cyclooctane four bases, cyclononane four bases, cyclodecane four bases, cyclododecane four bases, ring hexadecane four bases etc.These alicyclic groups can be substituted.

The substituting group of 1 valency that can have as fatty group can be enumerated out aryl, halogen atom, nitro, amide groups, hydroxyl, ester group, ether, aldehyde radical of alkyl, the carbon number 6～15 of carbon number 1～20 etc.

As the aromatic series base, can enumerate out and can contain hetero atom respectively and have aromatic hydrocarbons three bases of arlydene heterocycle structure, carbon number 5～15, carbon number 5～15, aromatic hydrocarbons four bases of carbon number 5～15.As arlydene, can enumerate out phenylene, naphthylene etc.As aromatic hydrocarbons three bases (3 valency), can enumerate out benzene three bases, naphthalene three bases etc.As aromatic hydrocarbons four bases (4 valency), can enumerate out benzene four bases, naphthalene four bases etc.These aromatic series bases can be substituted.

The substituting group of 1 valency that can have as the aromatic series base can be enumerated out aryl, halogen atom, nitro, amide groups, hydroxyl, ester group, ether, aldehyde radical of alkyl, the carbon number 6～15 of carbon number 1～20 etc.

In above-mentioned formula (1-1) and the formula (1-2), X ¹And X ²Be independently of one another the carbon number 1～20 of 2～4 valencys fatty group, 2～4 valencys carbon number 3～20 alicyclic group or 2～4 valencys carbon number 5～15 the aromatic series base, or be selected from the combination of the group more than 2 in the aromatic series base of carbon number 5～15 of alicyclic group and 2～4 valencys of carbon number 3～20 of fatty group, 2～4 valencys of the carbon number 1～20 of 2～4 valencys.Constitute X ¹And X ²Fatty group, alicyclic group and aromatic series base can further contain the substituting group of hetero atom or 1 valency independently of one another.

As fatty group, can enumerate out the alkylidene of carbon number 1～20, alkane three bases of carbon number 1～20, alkane four bases of carbon number 1～20 etc.As alkylidene, can enumerate out methylene, ethylidene, propylidene, butylidene, pentylidene, hexylidene, inferior heptyl, Ya Xinji, inferior nonyl, inferior decyl, inferior dodecyl, inferior cetyl etc.As alkane three bases, can enumerate out methane three bases, ethane three bases, propane three bases, butane three bases, pentane three bases, hexane three bases, heptane three bases, octane three bases, nonane three bases, decane three bases, dodecane three bases, hexadecane three bases etc.As alkane four bases, can enumerate out methane four bases, ethane four bases, propane four bases, butane four bases, pentane four bases, hexane four bases, heptane four bases, octane four bases, nonane four bases, decane four bases, dodecane four bases, hexadecane four bases etc.These fatty groups can be substituted.

The substituting group of 1 valency that can have as fatty group can be enumerated out aryl, halogen atom, nitro, amide groups, hydroxyl, ester group, ether, aldehyde radical of alkyl, the carbon number 6～15 of carbon number 1～20 etc.

As alicyclic group, can enumerate out the cycloalkylidene of carbon number 3～20, cycloalkane three bases of carbon number 3～20, cycloalkane four bases of carbon number 3～20.As cycloalkylidene, can enumerate out cyclopropylidene, inferior cyclobutyl, cyclopentylene, cyclohexylidene, inferior suberyl, inferior ring octyl group, inferior ring nonyl, inferior ring decyl, inferior cyclo-dodecyl, inferior ring cetyl etc.As cycloalkane three bases, can enumerate out cyclopropane three bases, cyclobutane three bases, pentamethylene three bases, cyclohexane three bases, cycloheptane three bases, cyclooctane three bases, cyclononane three bases, cyclodecane three bases, cyclododecane three bases, ring hexadecane three bases etc.As cycloalkane four bases, can enumerate out cyclopropane four bases, cyclobutane four bases, pentamethylene four bases, cyclohexane four bases, cycloheptane four bases, cyclooctane four bases, cyclononane four bases, cyclodecane four bases, cyclododecane four bases, ring hexadecane four bases etc.These alicyclic groups can be substituted.

The substituting group of 1 valency that can have as alicyclic group can be enumerated out aryl, halogen atom, nitro, amide groups, hydroxyl, ester group, ether, aldehyde radical of alkyl, the carbon number 6～15 of carbon number 1～20 etc.

As the aromatic series base, can enumerate out and can contain hetero atom respectively and have aromatic hydrocarbons three bases of arlydene heterocycle structure, carbon number 5～15, carbon number 5～15, aromatic hydrocarbons four bases of carbon number 5～15.As arlydene, can enumerate out phenylene, naphthylene etc.As aromatic hydrocarbons three bases (3 valency), can enumerate out benzene three bases, naphthalene three bases etc.As aromatic hydrocarbons four bases (4 valency), can enumerate out benzene four bases, naphthalene four bases etc.These aromatic series bases can be substituted.

The substituting group of 1 valency that can have as the aromatic series base can be enumerated out aryl, halogen atom, nitro, amide groups, hydroxyl, ester group, ether, aldehyde radical of alkyl, the carbon number 6～15 of carbon number 1～20 etc.

S and k are 0～10 integer independently of one another, are preferably 0～3 integer, 0～1 integer more preferably in above-mentioned formula (1-1) and the formula (1-2).

This is because if s and k surpass 10, then ring-type carbon imide compound becomes difficult on synthetic, produces the situation that cost significantly rises.From this viewpoint, integer is preferably selected 0～3 scope.In addition, be 2 when above, at s or k as the X of repetitive ¹, or X ²Can with other X ¹, or X ²Different.

X in the above-mentioned formula (1-3) ³Be aromatic series base or their combination of carbon number 5～15 of alicyclic group or 2～4 valencys of carbon number 3～20 of fatty group, 2～4 valencys of the carbon number 1～20 of 2～4 valencys.

Constitute X ³Fatty group, alicyclic group and aromatic series base can further contain the substituting group of hetero atom or 1 valency independently of one another.

As fatty group, can enumerate out the alkylidene of carbon number 1～20, alkane three bases of carbon number 1～20, alkane four bases of carbon number 1～20 etc.As alkylidene, can enumerate out methylene, ethylidene, propylidene, butylidene, pentylidene, hexylidene, inferior heptyl, Ya Xinji, inferior nonyl, inferior decyl, inferior dodecyl, inferior cetyl etc.As alkane three bases, can enumerate out methane three bases, ethane three bases, propane three bases, butane three bases, pentane three bases, hexane three bases, heptane three bases, octane three bases, nonane three bases, decane three bases, dodecane three bases, hexadecane three bases etc.As alkane four bases, can enumerate out methane four bases, ethane four bases, propane four bases, butane four bases, pentane four bases, hexane four bases, heptane four bases, octane four bases, nonane four bases, decane four bases, dodecane four bases, hexadecane four bases etc.These fatty groups can contain the substituting group of 1 valency.

The substituting group of 1 valency that can have as fatty group can be enumerated out aryl, halogen atom, nitro, amide groups, hydroxyl, ester group, ether, aldehyde radical of alkyl, the carbon number 6～15 of carbon number 1～20 etc.

As alicyclic group, can enumerate out the cycloalkylidene of carbon number 3～20, cycloalkane three bases of carbon number 3～20, cycloalkane four bases of carbon number 3～20.As cycloalkylidene, can enumerate out cyclopropylidene, inferior cyclobutyl, cyclopentylene, cyclohexylidene, inferior suberyl, inferior ring octyl group, inferior ring nonyl, inferior ring decyl, inferior cyclo-dodecyl, inferior ring cetyl etc.As cycloalkane three bases, can enumerate out cyclopropane three bases, cyclobutane three bases, pentamethylene three bases, cyclohexane three bases, cycloheptane three bases, cyclooctane three bases, cyclononane three bases, cyclodecane three bases, cyclododecane three bases, ring hexadecane three bases etc.As cycloalkane four bases, can enumerate out cyclopropane four bases, cyclobutane four bases, pentamethylene four bases, cyclohexane four bases, cycloheptane four bases, cyclooctane four bases, cyclononane four bases, cyclodecane four bases, cyclododecane four bases, ring hexadecane four bases etc.These alicyclic groups can contain the substituting group of 1 valency.

The substituting group of 1 valency that can have as alicyclic group can be enumerated out arlydene, halogen atom, nitro, amide groups, hydroxyl, ester group, ether, aldehyde radical of alkyl, the carbon number 6～15 of carbon number 1～20 etc.

As the aromatic series base, can enumerate out and can contain hetero atom respectively and have aromatic hydrocarbons three bases of arlydene heterocycle structure, carbon number 5～15, carbon number 5～15, aromatic hydrocarbons four bases of carbon number 5～15.As arlydene, can enumerate out phenylene, naphthylene etc.As aromatic hydrocarbons three bases (3 valency), can enumerate out benzene three bases, naphthalene three bases etc.As aromatic hydrocarbons four bases (4 valency), can enumerate out benzene four bases, naphthalene four bases etc.These aromatic series bases can be substituted.

The substituting group of 1 valency that can have as the aromatic series base can be enumerated out aryl, halogen atom, nitro, amide groups, hydroxyl, ester group, ether, aldehyde radical of alkyl, the carbon number 6～15 of carbon number 1～20 etc.

In addition, Ar ¹, Ar ², R ¹, R ², X ¹, X ²And X ³Can contain hetero atom, in addition, when Q is the combination base of divalent, Ar ¹, Ar ², R ¹, R ², X ¹, X ²And X ³It all is the base of divalent.When Q is the combination base of 3 valencys, Ar ¹, Ar ², R ¹, R ², X ¹, X ²And X ³In 1 be the group of 3 valencys.When Q is the combination base of 4 valencys, Ar ¹, Ar ², R ¹, R ², X ¹, X ²And X ³In 1 be the group of 4 valencys, perhaps 2 is the group of 3 valencys.

As ring-type carbon imide compound, can enumerate out following ring-type carbon imide compound (a)～(c).

[ring-type carbon imide compound (a)]

Ring-type carbon imide compound (a) is the represented compound of following formula (2).

[changing 3]

In the formula (2), Q _aCombination base for the divalent of the combination base that is selected from any 1 divalent in fatty group, alicyclic group and the aromatic series base or the combination that is selected from the group more than 2 in fatty group, alicyclic group and the aromatic series base further can contain hetero atom.Fatty group, alicyclic group and aromatic series base are identical with the middle explanation of formula (1).Wherein, in the compound of formula (2), fatty group, alicyclic group and aromatic series base all are divalent.Q _aBe preferably the combination base of the represented divalent of following formula (2-1), formula (2-2) or formula (2-3).

[changing 4]

In formula (2-1)～formula (2-3), Ar _a ¹, Ar _a ², R _a ¹, R _a ², X _a ¹, X _a ², X _a ³, s and k respectively with formula (1-1)～formula (1-3) in Ar ¹, Ar ², R ¹, R ², X ¹, X ², X ³, s and k be identical.Wherein, they all are divalent.

As above-mentioned ring-type carbon imide compound (a), can enumerate out following compound.

[changing 5]

[ring-type carbon imide compound (b)]

Ring-type carbon imide compound (b) is the represented compound of following formula (3).

[changing 6]

In the formula (3), Q _bCombination base for 3 valencys of the combination base that is selected from 3 any 1 valencys in fatty group, alicyclic group and the aromatic series base or the combination that is selected from the group more than 2 in fatty group, alicyclic group and the aromatic series base can further contain hetero atom.Fatty group, alicyclic group and aromatic series base are identical with the middle explanation of formula (1).Wherein, in the compound of formula (3), constitute Q _bGroup in 1 be 3 valencys.

In the formula (3), Y is the carrier of the circulus of carrying ring-type carbon imide compound.

Q _bBe preferably the combination base of 3 represented valencys of following formula (3-1), formula (3-2) or formula (3-3).

[changing 7]

In formula (3-1)～formula (3-3), Ar _b ¹, Ar _b ², R _b ¹, R _b ², X _b ¹, X _b ², X _b ³, s and k respectively with the Ar of formula (1-1)～formula (1-3) ¹, Ar ², R ¹, R ², X ¹, X ², X ³, s and k be identical.Wherein, 1 in these is the base of 3 valencys.

Y is preferably singly-bound, two key, atom, atomic group or polymer.Y is the joint portion, and a plurality of circuluses combine by Y, form the represented structure of formula (3).

As above-mentioned ring-type carbon imide compound (b), can enumerate out following compound.

[changing 8]

[ring-type carbon imide compound (c)]

Ring-type carbon imide compound (c) is the represented compound of following formula (4).

[changing 9]

In the formula, Q _cCombination base for 4 valencys of the combination base that is selected from 4 any 1 valencys in fatty group, alicyclic group and the aromatic series base or the combination that is selected from the group more than 2 in fatty group, alicyclic group and the aromatic series base further can contain hetero atom.Z ¹And Z ²For carrying the carrier of circulus.Z ¹And Z ²Can mutually combine and form circulus.

Fatty group, alicyclic group and aromatic series base are identical with the middle explanation of formula (1).Wherein, in the compound of formula (4), Q _cBe 4 valencys.Therefore, 1 in these groups is the group of 4 valencys, and perhaps 2 is the group of 3 valencys.

Q _cBe preferably the combination base of 4 represented valencys of following formula (4-1), formula (4-2) or formula (4-3).

[changing 10]

In formula (4-1)～formula (4-3), Ar _c ¹, Ar _c ², R _c ¹, R _c ², X _c ¹, X _c ², X _c ³, s and k respectively with formula (1-1)～formula (1-3), Ar ¹, Ar ², R ¹, R ², X ¹, X ², X ³, s and k be identical.Wherein, for Ar _c ¹, Ar _c ², R _c ¹, R _c ², X _c ¹, X _c ²And X _c ³, in these 1 is that group or 2 of 4 valencys are the group of 3 valencys.Z ¹And Z ²Preferably be singly-bound, two key, atom, atomic group or polymer independently of one another.Z ¹And Z ²Be the joint portion, a plurality of circuluses are by Z ¹And Z ²In conjunction with and form the represented structure of formula (4).

As above-mentioned ring-type carbon imide compound (c), can enumerate out following compound.

[changing 11]

(manufacturing approach of ring-type carbon imide compound)

Ring-type carbon imide compound can synthesize based on the method for record in the paragraph sequence number [0075] of TOHKEMY 2011-256337 communique etc.

Mylar among the present invention can further contain additives such as Photostabilised dose, anti-oxidant.

If contain Photostabilised dose, then can prevent uv degradation.As Photostabilised dose, can enumerate out light such as absorption ultraviolet ray and convert into heat energy compound, catch resin carry out light absorption and decompose generation free radical, and suppress to decompose the material etc. of chain reaction.As Photostabilised dose, preferably absorb light such as ultraviolet ray and convert the compound of heat energy into.Through containing such Photostabilised dose, even accept ultraviolet irradiation for a long time continuously, also can guarantee the raising effect of higher partial discharge voltage for a long time, the tone variations that perhaps prevents to cause, strength deterioration etc. by the ultraviolet ray in the resin.

For example as long as ultra-violet absorber is in the scope of other characteristics of not damaging polyester, then can be fit to not especially to use with limiting the organic system ultra-violet absorber, inorganic be ultra-violet absorber, and these and with in arbitrarily.On the other hand, the humidity resistance of expectation ultra-violet absorber excellent, can in resin, evenly disperse.

As the example of ultra-violet absorber,, can enumerate out ultra-violet stabilizers such as ultra-violet absorbers such as salicylic acid system, benzophenone series, BTA system, cyanoacrylate system and hindered amine system etc. as the ultra-violet absorber of organic system.Specifically, for example can enumerate out, salicylic acid system to 2 of tert-butyl-phenyl salicylate, OPS p octylphenyl salicylate, benzophenone series; 4-dihydroxy benaophenonel, 2-hydroxyl-4-methoxy benzophenone, 2-hydroxyl-4-methoxyl group-5-diphenylsulfone ketone, 2,2 ', 4; 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) BTA, 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) BTA, 2 of 4 '-tetrahydroxybenzophenone, two (2-methoxyl group-4-hydroxyl-5-benzoyl phenyl) methane, BTA system, [4-(1,1 for 2 '-di-2-ethylhexylphosphine oxide; 3,3-tetramethyl butyl)-6-(2H BTA-2-yl) phenol], the ethyl=alpha-cyano-β of cyanoacrylate system, β-diphenylacrylate ester, as the 2-(4 of triazine system; 6-diphenyl-1,3,5-triazines-2-yl)-5-[(hexyl) oxygen base]-phenol, hindered amine system two (2; 2,6,6-tetramethyl-4-piperidyl) sebacate, butanedioic acid dimethyl-1-(2-hydroxyethyl)-4-hydroxyl-2; 2,6,6-tetramethyl piperidine condensation polymer and two (octyl phenyl) nickel sulfide, and 2; 4-di-tert-butyl-phenyl-3 ', 5 '-di-t-butyl-4 '-hydroxybenzoate etc.

In these ultra-violet absorbers, from the high viewpoint of patience of tackling ultraviolet radiation absorption repeatedly, more preferably triazine is a ultra-violet absorber.In addition, these ultra-violet absorbers can add film to above-mentioned ultra-violet absorber monomeric form, also can be so that have the monomer and the importing of the form after organic system conductive material or the non-water-soluble resin copolymerization of ultra-violet absorber ability.

With respect to the gross mass of polyester film, Photostabilised dose of content in polyester film is preferably more than the 0.1 quality % below the 10 quality %, more preferably more than the 0.3 quality % below the 7 quality %, further be preferably more than the 0.7 quality % below the 4 quality %.Thus, the molecular weight of the polyester that can suppress to be caused by long light deterioration reduces, and its result can suppress to destroy the closing force that causes by the aggegation in the film that produces and reduce.

Further, polyester film of the present invention can also contain for example lubricant (particulate), ultra-violet absorber, colouring agent, nucleator (crystallization agent), fire-retardantization agent etc. as additive except containing above-mentioned Photostabilised dose.

Except above-mentioned, contain 1, the poly terephthalic acid cyclohexanedimethanoester ester (PCT) of 4-cyclohexanedimethanol (CHDM) structure also can preferably use the method for record in the paragraph sequence number 0089～0090,0120～0121 of WO2009/125701 for example.In addition, the manufacturing that gathers 2,6 (ethylene naphthalate)s (PEN) also can reference example such as the paragraph sequence number 0046 and 0060 of the paragraph sequence number 0170 of TOHKEMY 2011-153209, TOHKEMY 2008-39803 in the method for record.

< polyester film and used for solar batteries screening glass >

Polyester film of the present invention is to be shaped to the polyester sheet that does not stretch that sheet forms through the mylar that the manufacturing approach of the mylar of the invention described above is made indulge the polyester film that stretching and/or horizontal stretching get.In addition, used for solar batteries screening glass of the present invention has the polyester film of the mylar acquisition of being made by the manufacturing approach of the mylar that passes through the invention described above.

Owing to use the mylar of making through the manufacturing approach of mylar of the present invention, thus stretched and polyester film (used for solar batteries screening glass) that obtain has stable good quality, so have the hydrolytic resistance of expectation, and then have excellent weather resistance.

In addition, the mylar moulding that polyester film of the present invention is made by the manufacturing approach of the mylar through the invention described above gets, thereby stable quality is sneaked into less, had to the foreign matter when membranization.Foreign matter in the film is sneaked into the reduction that brings weatherability, thereby expectation does not have foreign matter to sneak into.Specifically, preferred 1m ²In maximum length be 1 of the number less than of the above foreign matter of 50 μ m.Specifically, through microscopic examination film 1m ²In the above foreign matter number of 50 μ m that exists, try to achieve this foreign matter number for many places, whether judge " 1 of the number deficiency of foreign matter " by this mean value.

Vertical stretching is carried out as follows: for example, in 1 pair of carry-over pinch rolls of stretched polyester sheet film is passed through in clamping, in the time of along length direction (MD direction) the conveyance film of film, between the carry-over pinch rolls more than 2 couple who arranges along the conveyance direction of film, apply tension.In the vertical stretching process, vertical stretching ratio is preferably 2～5 times, more preferably 2.5～4.5 times, further is preferably 2.8～4 times.

In addition, horizontal stretching can be carried out applied tension by the polyester of preheating through the edge width (TD direction) vertical with length direction (MD direction).

Polyester film after the stretching can further be provided with following operation: through heating and make its crystallization carry out the heat fixation operation of heat fixation having implemented polyester after vertical stretching and the horizontal stretching; The polyester film that in the heat fixation operation, is fixed is heated and the lax operation of heat that the tension of polyester film relaxed and remove residual strain.

Polyester sheet of the present invention is through after the stretch processing of implementing expectation; Be provided with at least 1 layer raising and battery side substrate cementability easy-adhesion layer, UV-absorbing layer, comprise Chinese white etc. and constitute the functional layer of the white layer such as reflecting layer (dyed layer) etc. of light reflective, can constitute the used for solar batteries screening glass.For example, can on the polyester film behind the uniaxial tension and/or after biaxial stretch-formed, be coated with the formation functional layer.Coating forms the known coating technique that can use rolling method, blade (knife edge) rubbing method, intaglio plate rubbing method, curtain Tu Fa etc.

In addition, can, these implement surface treatment (fiery scorching processing, corona treatment, plasma treatment, UV treatment etc.) before being coated with.Further preferred use adhesive is fitted.

Polyester film of the present invention has and contains the polyester layer that CHDM is a polyester, and said CHDM is that polyester uses 1, and 4-cyclohexanedimethanol (CHDM) contains the structure from CHDM as diol component in resin.In the case, polyester film can be only is that the CHDM of polyester is that polyester layer constitutes by containing CHDM, also can constitute to comprise the sandwich construction more than two layers or three layers that this CHDM is polyester layer and other resin beds (for example PETG (PET)).Specifically, can constitute for example to contain and have 1, the poly terephthalic acid cyclohexanedimethanoester ester (PCT) of 4-cyclohexanedimethanol structure and the sandwich construction of PET (sandwich construction of example: PCT/PET or the sandwich construction of PCT/PET/PCT etc.).

Containing CHDM is the composition of the polyester layer of polyester

(1) CHDM is a polyester

CHDM be polyester preferably diol component (all glycol in) contain 0.1～20 mole of % or 80～100 moles of % from 1; The structure of 4-cyclohexanedimethanol; It is above and below 16 moles of % or 83 moles of % are above and 98 moles below the % more preferably to contain 0.5 mole of %, and it is above and below 12 moles of % or 86 moles of % are above and 96 moles below the % especially preferably to contain 1 mole of %.Thus, have two zones from the low zone of the structure of CHDM (0.1～20 mole of %), high zone (80～100 moles of %), this is because polyester is obtained crystalline texture easily in this zone, brings into play high mechanical strength, hear resistance easily.

Through using these CHDM is polyester, improves hear resistance, to suppress foreign matter residual, obtains to make the effect of resin stay in gradeization thus.

As be used to form CHDM be polyester from 1, the material of the unit beyond the structure of 4-cyclohexanedimethanol is as glycol component; Can enumerate out as 1 of typical example 2-propane diols, 1, ammediol, 1; 4-butanediol, 1,2-butanediol, 1, ester ring type glycols, bisphenol-As, 1 such as aliphatic diol class, the spiroglycol, isobide such as 3-butanediol; The 3-benzene dimethanol, 1,4-benzene dimethanol, 9; Dihydroxylic alcohols such as aromatic diol class such as 9 '-two (4-hydroxy phenyl) fluorenes etc., but be not limited to this.Wherein preferably make spent glycol.

As be used to form CHDM be polyester from 1; The material of the unit beyond the structure of 4-cyclohexanedimethanol; As the dicarboxylic acids composition; Can enumerate out alicyclic dicarboxylic acid, M-phthalic acid, phthalic acids, 1 such as aliphatic dicarboxylic acid class, adamantane dicarboxylic acids, norbornene dicarboxylic acids, isobide, cyclohexane dicarboxylic acid, decahydronaphthalene dicarboxylic acids such as malonic acid as typical example, butanedioic acid, glutaric acid, adipic acid, suberic acid, decanedioic acid, dodecanedioic acid, dimeric dibasic acid, eicosane diacid, pimelic acid, azelaic acid, methylmalonic acid, ethyl malonic acid, 4-naphthalene dicarboxylic acids, 1,5-naphthalene dicarboxylic acids, 2; 6-naphthalene dicarboxylic acids, 1; 8-naphthalene dicarboxylic acids, 4,4'-diphenyldicarboxylic acids, 4,4 '-diphenyl ether dicarboxylic acids, 5-sodium sulfo-M-phthalic acid, phenylindan dicarboxylic acids, anthracene dicarboxylic acids, luxuriant and rich with fragrance dicarboxylic acids, 9; Dicarboxylic acids such as aromatic dicarboxylic acids such as 9 '-two (4-carboxyl phenyl) fluorenic acid or its ester derivant etc., but be not limited to this.

As CHDM is the dicarboxylic acids composition of polyester, preferably contains the structure from terephthalic acid (TPA) at least.

CHDM is that the dicarboxylic acids composition of polyester can also add M-phthalic acid (IPA) except adding terephthalic acid (TPA) acid among the present invention.Preferred IPA amount is 0 mole more than the % and 15 moles below the % in whole dicarboxylic acids, and more preferably 0 mole of % is above and 12 moles below the %, and it is above and 9 moles below the % further to be preferably 0 mole of %.

～stepped construction～

Polyester film of the present invention can have at least 1 layer and contain the polyester layer that CHDM is a polyester as stated, also can be for having by containing polyester layer and other the folded layer by layer stepped constructions that forms that CHDM is a polyester.When particularly shared ratio is 80～100 moles of % in polyester from the structure of CHDM, preferably constitute stepped construction.This is because if uprise from the structure proportion of CHDM, then uprise easily with respect to PETG (PET) weatherability (the anti-water decomposition property that adds), but mechanical strength dies down easily.Therefore, can be through range upon range of with other resin beds (for example PETG (PET)) and complementary mutually, so preferred.

Polyester film of the present invention is also preferably by to contain CHDM be polyester layer (below be called the P1 layer) and contain with PETG as the range upon range of form of the polyester layer of the polyester of main component (below be called the P2 layer).

The P2 layer is meant, the ratio of terephthalic acid units in the dicarboxylic acids unit is 95 moles more than the %, and the ratio of ethylene glycol unit in glycol unit is 95 moles more than the %.

In addition, the IV of P2 layer be preferably more than 0.7 and 0.9 below, more preferably 0.72 or more and 0.85 following, further be preferably more than 0.74 and below 0.82.Through improving IV, can suppress the decomposition (molecular weight reduction) in the low wet environment (dry thermal condition) of hygrothermal environment (wet thermal condition) and high temperature thus.

The number of plies sum of P1 layer and P2 layer is preferably more than 2 layers, more preferably more than 2 layers and below 5 layers, further is preferably more than 2 layers and below 4 layers in the polyester film of the present invention.Especially preferred is to be clamped the 3-tier architecture of P2 layer or clamped the 3-tier architecture of P1 layer, 2 layers of structure that P2 layer and P1 are folded layer by layer by 2 layers of P2 layer by 2 layers of P1 layer.

Constitute under the situation more than 2 layers at polyester film of the present invention, the summation of the preferred P1 layer of thickness be more than 5% and below 40% of gross thickness, more preferably 7% or more and 38% following, further be preferably more than 10% and below 35%.Through summation is more than 5%, can show high-weatherability, is below 40% through summation, shows high mechanical strength easily.

Such stepped construction can be through general method manufacturing.Specifically; Stepped construction is made through the mode that is described below, that is, and and through using branch manifold mould (multi manifold die), feed block mould (feed block die); So that extrude, thereby make by the range upon range of mode of melt (melt of resin) of a plurality of extruders supplies.

The thickness of each of polyester film layer can be measured the cross section of film through using secondary ion mass spectrometry meter (SIMS), is carried out to picture with the characteristic of P1 layer and the characteristic of P2 layer, thereby tries to achieve.

< solar module >

It is the solar cell device of electric energy that solar module constitutes the transform light energy that between the substrate of the transparency of sunshine incident and the polyester film of the invention described above (used for solar batteries backboard), disposes sunshine usually.As concrete embodiment; Can be the form that is described below and constitutes; Said form is for sealing the generating element (solar cell device) that is connected by the lead-in conductor (not shown) that takes out electricity with sealants such as ethylene-vinyl acetate copolymerization system (EVA system) resins, it is clamped between transparency carrier such as glass and the polyester film of the present invention (backboard) and mutual applying.

As the example of solar cell device, can be suitable for silicon systems such as monocrystalline silicon, polysilicon, amorphous silicon, various known solar cell devices such as III-V families such as copper-indium-gallium-selenium, copper-indium-selenium, cadmium-tellurium, gallium-arsenic, II-VI compound semiconductor system.For example can using between substrate and the polyester film, resin (so-called encapsulant) such as ethylene-vinyl acetate copolymer seals and constitutes.

Embodiment

Below, further specify the present invention through embodiment, but only otherwise exceed purport of the present invention, then be not limited to following examples.In addition, not special the qualification, then " part " is quality criteria.

(embodiment 1～embodiment 11, comparative example 1～9)

-double screw extruder-

As melt extruding machine; Prepare double screw extruder 100; Above-mentioned double screw extruder is as shown in Figure 1; The screw rod that in 2 places are provided with the cylinder of passage, has following formation, and around rotating cylinder, have along the direction of extruding of resin and be divided into 9 district (C1～C9) can carry out temperature controlled heater 30.The concrete condition of double screw extruder below is shown.

< double screw extruder >

The equidirectional rotating clutch type of bilateral pore formula double screw extruder

Length L [mm]/screw rod footpath D [mm]: 31.5 (1 district of rotating cylinder is 3.5D)

Size: 180mm

Spray volume: 3000kg/h

Screw speed: 60rpm

Bowl temperature-C1:70 ℃, C2:270 ℃, C3:270 ℃, C4:270 ℃, C5:270 ℃, C6:270 ℃, C7:270 ℃, C8:270 ℃, C9:250 ℃

Screw rod shape: neutral kneader (neutral kneading) 2D, contrary screw rod 1D are set in the place ahead near the 1st passage

Neutral kneader 2D is set in the place ahead near the 2nd passage

In the direction of extruding of the resin of double screw extruder 100, as shown in Figure 1, be connected with metal fiber filter 42 and mould 40, further between screw rod and metal fiber filter, have not shown gear pump.The design temperature of the heater of heating mould is 280 ℃, and mean residence time is 10 minutes.

Gear pump: 2 gear-types

Filter: metallic fiber sintered filter (aperture 20 μ m)

Mould: die lip is 4mm at interval

-raw material-

As material resin, use the particle (below, also become the PET particle) of PETG (fusing point Tm:257 ℃, inherent viscosity IV:0.78, terminal COOH amount: 10 equivalents/t, Henschel mixer are carrying out crystallization under 160 ℃).

The PET particle uses the particle of the size of average major diameter: 4.5mm, average minor axis: 1.8mm, average length: 4.0mm.

-melt extrude-

Use the double screw extruder of preparing, heating and melting carries out melting mixing by supply port 12 base feed resins, meanwhile under the condition shown in the below table 1, melt extrudes (melt extruding operation).Here, each condition for embodiment shown in the below table 1 and comparative example is shown in Fig. 3～Figure 25.The Q, N of this moment, and Q/N be shown in Figure 26～Figure 32.

The melt of extruding by outlet of extruder (molten resin) through gear pump, metal fiber filter (aperture 20 μ m) after, be expressed into 20 ℃ chill roll (casting drum) by mould, use static to apply method and make its driving fit to chill roll., cool off when making melt forming be sheet to chill roll through driving fit.Chill roll uses the chill roller of hollow.Above-mentioned chill roller can carry out the temperature accent through the water that feeds to inside as thermal medium.

In addition, for conveyance territory (space), through around above-mentioned conveyance territory, and to wherein importing the damping air, thereby be 30%RH with humidity regulation from mould outlet to chill roll.The adjustment of the extrusion capacity through double screw extruder and the slit width of mould, making melt thickness is 3000 μ m.

As implied above, obtain the PET sheet (amorphism sheet) that does not stretch.

-vertical stretching and horizontal stretching-

Through using two pairs of nip roll, poor to giving peripheral speed between a side of nip roll and the opposing party, thus the PET sheet that does not stretch of gained is indulged stretching.The temperature of the stretching starting point that begins to stretch is made as 90 ℃, vertical stretching ratio is made as 3.5 times.After vertical the stretching, under 100 ℃, carry out horizontally being stretched to 4.2 times.

-thermal finalization and hot relaxing-

Then, make mean temperature be 200 ℃ and carry out thermal finalization, carry out 5% mitigation during thermal finalization at width.

Thus, make the twin-screw stretching PET film of expectation.

-estimate-

(1) air vent overflows

What the air vent in the process that in melt extruding operation, melt extrudes through visualization overflowed has or not, and estimates based on following metewand.Evaluation result is shown in below table 1.

< metewand >

A: unconfirmedly overflow to air vent.

B: confirm to overflow to air vent.

C: significantly produce air vent and overflow.

(2) quality stability

1m with the biaxial stretch-formed PET film of the above-mentioned making of microscopic examination ²In the above foreign matter of residual 50 μ m, 3 times (n=3) tries to achieve the operation of foreign matter number repeatedly, obtains the mean value of the foreign matter number of gained.Be the basis with this mean value, estimate according to following metewand evaluation.Evaluation result is shown in below table 1.Whether the size of foreign matter is to judge more than the 50 μ m with the maximum length of each particle.

< metewand >

A: do not have the above foreign matter of 50 μ m fully

B: at casting 1m ²The middle above foreign matter of 50 μ m that produces 1～5

C: at casting 1m ²The middle above foreign matter of 50 μ m that produces more than 6

(embodiment 12～13)

-CHDM be polyester preparation-

[the 1st operation]

Supply is as the M-phthalic acid (IPA) of dicarboxylic acids composition and terephthalic acid (TPA) (TPA) and as the cyclohexanedimethanol (CHDM) and the ethylene glycol (EG) of glycol component; Further supply with magnesium acetate and antimony trioxide, fusion under 150 ℃ nitrogen atmosphere as catalyst.Then, be warming up to 230 ℃ with 3 hours while stirring, methyl alcohol is distillated and finish ester exchange reaction.At this moment, through change the quantity delivered of IPA, CHDM according to the amount shown in the below table 2, obtaining 2 kinds of CHDM is polyester.

[the 2nd operation]

After ester exchange reaction finishes, in above-mentioned two kinds of polyester, be added on the ethylene glycol solution that has dissolved phosphoric acid in the ethylene glycol and got.

[the 3rd operation]

Arrive under 285 ℃ of temperature, the vacuum 0.1Torr final, the esterification reaction product of gained is carried out polycondensation reaction, obtaining CHDM is polyester (CHDM-2).And, make each polyester granulateization respectively.

[the 4th operation]

Then, take out the part of the polyester granulate of gained, under 160 ℃, make its dry 6 hours, implement crystallization and handle.Then, in stream of nitrogen gas, carried out solid phase with 24 hours down at 210 ℃, obtaining CHDM is polyester (CHDM-1).

-melt extrude-

In " melt extruding " of embodiment 1,, likewise obtain the PET sheet (amorphism sheet) that do not stretch with embodiment 1, and estimate except the CHDM-1 that material resin replaced with above-mentioned acquisition or the CHDM-2 (CHDM is a polyester).Evaluation result is shown in below table 1.

In addition, be polyester for the CHDM of above-mentioned acquisition, according to following method measure cyclohexanedimethanol in the glycol component contain rate, and the dicarboxylic acids composition in M-phthalic acid contain rate.

< composition measuring >

After dissolving CHDM is the particle of polyester (CHDM-1, CHDM-2) in hexafluoroisopropanol (HFIP) respectively, through ¹H-NMR carries out quantitatively.Working sample (CHDM, terephthalic acid (TPA), EG, M-phthalic acid) uses its identification signal in advance.

The amount of the amount of the isophthalic acid residues of gained and CHDM residue is shown in below table 2.In addition, terephthalic acid (TPA) contains rate and EG to contain rate as follows.

Terephthalic acid (TPA) contains rate (mole %)=" 100 moles of %-M-phthalic acids contain rate (mole %) "

EG contains rate (mole %)=" 100 (mole %)-CHDM lead (mole %) "

In addition, in below table 2, CHDM is that IV, the AV of polyester (CHDM-1, CHDM-2) uses said method to measure, and record as follows.

A) inherent viscosity (IV; Unit: dL/g):

Make the polyester of gained be dissolved in 1,1,2, in 2-tetrachloroethanes/phenol (=2/3 [mass ratio]) mixed solvent, try to achieve by the solution viscosity under 25 ℃ in this mixed solvent.

B) terminal COOH amount (AV; Unit: eq (equivalent)/ton):

Make the polyester of gained be dissolved in benzyl alcohol/chloroform (=2/3 fully; Volume ratio) in the mixed solution, phenol red as the indicator use, carry out titration with benchmark liquid (0.025N KOH-methanol mixed solution), calculate by this titer.

(embodiment 14)

In " melt extruding " of embodiment 1, in the supply port (hopper) 12 of double screw extruder, with main feeder base feed resin; Supply with following ring-type carbon imidodicarbonic diamide (1) with secondary feeder, supply, under 280 ℃, melt extrude in melting mixing; In addition; With embodiment 1 likewise, when obtaining the PET sheet (amorphism sheet) that does not stretch, estimate.At this moment, the quantity delivered of ring-type carbon imidodicarbonic diamide (1) is for being the ratio of 1.0 quality % with respect to material resin.Below table 1 illustrates evaluation result.

In addition, ring-type carbon imidodicarbonic diamide (1) is the compound of molecular weight 516, synthesizes based on the synthetic method of record in the reference example 2 of TOHKEMY 2011-258641 communique.

[changing 12]

[table 1]

In addition, in the record of table 1, for the " (Y-Y of operating condition _Under)/Q≤(Y _Over-Y _Under)/(0.5 * Q ₀) ", " Y≤Y _Over", " Y>=Y _Under", " 0.6 * Q ₀≤Q _Max≤1.2 * Q ₀" and " 0.15 * Q ₀≤Q _Min≤0.4 * Q ₀", this condition is satisfied in symbol " zero " expression in this hurdle of embodiment and comparative example, under the situation that does not satisfy this condition, is recited as " bad ".

Table 2

Shown in above-mentioned table 1, among the embodiment, prevented that air vent from overflowing, the mylar of manufacturing obtains stabilized resins on the quality.With respect to this, in the comparative example, fail to prevent that air vent from overflowing, overflow also relatively poor aspect the stabilisation of quality even if perhaps suppressed air vent.

Claims (11)

1. the manufacturing approach of a mylar, it has the operation that melt extrudes that is described below:

Make the polyester raw material resin of putting into double screw extruder in rotating cylinder in the melting mixing; According to the extrusion capacity Y of unit [kg/hr/rpm] of the mylar after the fusion relation with the extrusion capacity Q [kg/h] of time per unit; The rotating speed of the screw rod in the extrusion capacity Y of unit satisfies the said rotating cylinder of range regulation in represented zone, following relational expression (1)～(5); Y is changed continuously, and the extrusion capacity Q that makes time per unit simultaneously is by Q _MinTo Q _MaxIncrease perhaps by Q _MaxTo Q _MinReduce, thereby melt extrude,

(1) 0≤Q≤0.5 * Q ₀The time,

(Y-Y _under)/Q≤(Y _over-Y _under)/(0.5×Q ₀)

(2) 0.5 * Q ₀During＜Q,

Y≤Y _over

(3)Y≥Y _under

(4)0.6×Q ₀≤Q _max≤1.2×Q ₀

(5)0.15×Q ₀≤Q _min≤0.4×Q ₀

In the formula, Y representes the extrusion capacity Q/N of unit [kg/hr/rpm] of per 1 rotation of screw rod, Y _UnderAnd Y _OverBe Y _Under[kg/hr/rpm]=9.01 * 10 ^-7* D ³, Y _Over[kg/hr/rpm]=6.93 * 10 ^-6* D ³, D representes screw rod footpath [mm], the extrusion capacity of the time per unit of the molten polyester resin when Q representes to turn round [kg/h], Q ₀Extrusion capacity when expression is not carried out increase and decrease or subtracted constant running that increases variation, Q _Max, Q _MinRepresent increase and decrease respectively or subtract maximum extrusion capacity, the minimum extrusion capacity that increases when changing, N representes the rotating speed [rpm] of screw rod.

2. the manufacturing approach of mylar according to claim 1, the extrusion capacity Y of unit is at Q _MaxThe time Y _MaxWith respect at Q _MinThe time Y _MinRatio satisfy following relational expression (6),

1.1≤Y _max/Y _min≤5.0…(6)

Y _MinExpression Q _Min/ N _Min, Y _MaxExpression Q _Max/ N _Max, N _MaxExpression Q _MaxThe time minimum speed, N _MinExpression Q _MinThe time minimum speed.

3. the manufacturing approach of mylar according to claim 2 changes Y and by Q _MinTo Q _MaxIncrease perhaps by Q _MaxTo Q _MinIn the process that reduces, be to be made as in 5 seconds the constant time with Y.

4. the manufacturing approach of mylar according to claim 3 saidly melt extrudes in the operation, if with the increase of the extrusion capacity Q of mylar or reduce the needed time and be made as t [hr], then makes extrusion capacity Q by Q _MinTo Q _MaxIncrease perhaps by Q _MaxTo Q _MinThe speed (Q/t, the unit: kg/hr that reduce ²) absolute value satisfy following relational expression (7),

0.50×D ²≤|Q/t|≤6.48×D ²…(7)

Q is the negative value of expression under the situation that extrusion capacity reduces.

5. the manufacturing approach of mylar according to claim 3; To during being extruded in through rotating cylinder, make extrusion capacity Q increase and decrease or subtract the number of times that increases and be made as n until mylar; In increase and decrease or subtract that to increase said frequency n when finishing be that n satisfies following relational expression (8) under 1 time the situation

1＜n＜10…(8)。

6. the manufacturing approach of mylar according to claim 4; To during being extruded in through rotating cylinder, make extrusion capacity Q increase and decrease or subtract the number of times that increases and be made as n until mylar; In increase and decrease or subtract that to increase said frequency n when finishing be that n satisfies following relational expression (8) under 1 time the situation

1＜n＜10…(8)。

7. the manufacturing approach of mylar according to claim 5 saidly melt extrudes operation when intermittently melt extruding the intermittent working of mylar, and Y is changed continuously, and by Q _MinTo Q _MaxIncrease perhaps by Q _MaxTo Q _MinReduce.

8. the manufacturing approach of mylar according to claim 6 saidly melt extrudes operation when intermittently melt extruding the intermittent working of mylar, and Y is changed continuously, and by Q _MinTo Q _MaxIncrease perhaps by Q _MaxTo Q _MinReduce.

9. polyester film, it obtains 1m by the mylar of making through the manufacturing approach of claim 2 or 3 described mylar is stretched ²In maximum length be 1 of the number less than of the above foreign matter of 50 μ m.

10. used for solar batteries screening glass, it has the described polyester film of claim 9.

11. a solar module, it has:

The substrate of the transparency of sunshine incident,

Be disposed at the solar cell device of a side of said substrate, and

Be disposed at the described used for solar batteries screening glass of claim 10 this solar cell device and a side opposition side said substrate of configuration.

Images