CN105102205A - Polyester film and method for producing same - Google Patents

Polyester film and method for producing same Download PDF

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Publication number
CN105102205A
CN105102205A CN201480018015.9A CN201480018015A CN105102205A CN 105102205 A CN105102205 A CN 105102205A CN 201480018015 A CN201480018015 A CN 201480018015A CN 105102205 A CN105102205 A CN 105102205A
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China
Prior art keywords
polyester film
film
polyester
width
thermal shrinkage
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Granted
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CN201480018015.9A
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Chinese (zh)
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CN105102205B (en
Inventor
中居真一
真木康之
铃木绅由
浜田保弘
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Fujifilm Corp
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Fujifilm Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
    • B29C55/14—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively
    • B29C55/143—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively firstly parallel to the direction of feed and then transversely thereto
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
    • B29C55/16—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial simultaneously
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)

Abstract

The invention provides a polyester film that satisfies formulas (1) to (4), and a method for producing the polyester film. W/1000<[(Ss1 - Ss2)/CS1/100]<2W (1) 0<(Ss1 - Ss2)<0.5 (2) -1<(Ss1 + Ss2 + SCT)/3<3 (3) 0<Cs1<0.2 (4) [Ss1 represents the machine direction thermal shrinkage rate (%) of the film at an edge having a large machine direction thermal shrinkage rate among the edges in the film width direction. Ss2 represents the machine direction thermal shrinkage rate (%) of the film at an edge having a small machine direction thermal shrinkage rate among the edges in the film width direction. SCT represents the machine direction thermal shrinkage rate (%) at the center of the film in the film width direction. CS1 represents the maximum value (m) of the magnitude of curvature at the edge having a large machine direction thermal shrinkage rate among the film edges in the film width direction. W represents the film width (m)].

Description

Polyester film and manufacture method thereof
Technical field
The present invention relates to polyester film and manufacture method thereof.
Background technology
Polyester is applicable to the various uses such as electric insulation purposes and optical applications.Wherein, as electric insulation purposes, in recent years, particularly the solar cell purposes such as back-protective sheet (so-called backboard) of solar cell gets most of the attention.
Carry out biaxial stretch-formed grade after melt extruding and the polyester film that obtains coating or paste functionality material on film sometimes, be utilized as functional membrane.Now, if manufactured with while the conveyance such as roller polyester film, then when heating conveyance due to a variety of causes, polyester film may occur sometimes fold or damage, or film bends.
As the technology relevant to above-mentioned condition, disclose, at heat setting temperature Tm-35 ~ 65 DEG C, thermal finalization is carried out to polyester film, hot wire-CVD process is carried out at 140 ~ 175 DEG C, thus, the thermal contraction of film is reduced, carry out homogenising, thus the faults such as the fold in operation are afterwards improved (such as, with reference to Japanese Unexamined Patent Publication 2012-094699 publication).
In addition, the conveyance direction (MD by reducing film is disclosed; MachineDirection, percent thermal shrinkage longitudinally) and the vertical direction (TD of MD; Percent thermal shrinkage TransverseDirection, laterally) than MD/TD percent thermal shrinkage, give the heating conveyance property (such as, with reference to Japanese Unexamined Patent Publication 2001-191406 publication) of film.
Prior art document
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2012-094699 publication
Patent document 2: Japanese Unexamined Patent Publication 2001-191406 publication
Summary of the invention
Invent problem to be solved
Although Japanese Unexamined Patent Publication 2012-094699 publication and Japanese Unexamined Patent Publication 2001-191406 publication all disclose the low thermal shrinkage of film and its homogenising is effective to the improvement of fold etc., insufficient to the suppression of fold and damage.
The present invention carries out in view of the foregoing, its object is to, and provides and is difficult to fold when producing heating conveyance and the polyester film of damage and manufacture method thereof, to realize this object as problem.
For the method for dealing with problems
The present invention obtains following opinion and realizes based on this opinion, that is: when heating conveyance polyester film, extend and the easy opinion producing fold and damage such as the position relaxed in polyester film local; And by making the percent thermal shrinkage of the length direction on the bending size of the end of film width and width in prescribed limit, even if the length of local then also can be suppressed uneven when heating conveyance, thus be difficult to the opinion producing fold and damage.
Concrete grammar for realizing above-mentioned problem is as follows.
<1> polyester film, it meets following formula (1) ~ (4),
W/1000＜[(S s1-S s2)/C S1/100]＜2W…(1)
0＜(S s1-S s2)＜0.5…(2)
-1＜(S s1+S s2+S CT)/3＜3…(3)
0＜C s1＜0.2…(4)
In formula (1) ~ (4),
S s1represent in the end of polyester film width, in the end of side that percent thermal shrinkage under 150 DEG C, 30 minutes of vertical with above-mentioned polyester film width direction is large, the percent thermal shrinkage [%] in vertical with above-mentioned polyester film width direction,
S s2represent in the end of polyester film width, in the end of side that percent thermal shrinkage under 150 DEG C, 30 minutes of vertical with above-mentioned polyester film width direction is little, the percent thermal shrinkage [%] in vertical with above-mentioned polyester film width direction.
S cTrepresent polyester film width central portion, percent thermal shrinkage [%] under 150 DEG C, 30 minutes of vertical with above-mentioned polyester film width direction.
C s1represent in the end of polyester film width, in the end of side that percent thermal shrinkage under 150 DEG C, 30 minutes of vertical with above-mentioned polyester film width direction is large, the maximum [m] that bends size.
W represents the film of polyester film wide [m].
The polyester film of <2> as described in <1>, it also meets following formula (5) ~ (7).
W/2000＜[{S CT-(S s1+S s2)/2}/C CT/100]＜W…(5)
-0.5＜{S CT-(S s1+S s2)/2}＜0.5…(6)
-0.2＜C CT＜0.2…(7)
In formula (5) ~ (7),
S s1with the S in formula (1) etc. s1implication is identical, represents the percent thermal shrinkage [%] in the end of the side that percent thermal shrinkage under 150 DEG C, 30 minutes of in the end of polyester film width, vertical with above-mentioned polyester film width direction is large, vertical with above-mentioned polyester film width direction.
S s2with the S in formula (1) etc. s2implication is identical, represents the percent thermal shrinkage [%] in the end of the side that percent thermal shrinkage under 150 DEG C, 30 minutes of in the end of polyester film width, vertical with above-mentioned polyester film width direction is little, vertical with above-mentioned polyester film width direction.
S cTwith the S in formula (3) cTimplication is identical, represent polyester film width central portion, percent thermal shrinkage [%] under 150 DEG C, 30 minutes of vertical with above-mentioned polyester film width direction.
C cTrepresent that the maximum of the half bending size of cutting out in the end of the width of polyester film obtained by the line cutting polyester film of the central authorities along the film width in the both ends connecting polyester film length direction is added the value [m] obtained divided by 2.
W is identical with the W implication in formula (1), represents the film wide [m] of polyester film.
The polyester film of <3> as described in <1> or <2>, wherein, film wide (W) is for more than 0.3m and below 8m.
The polyester film of <4> according to any one of <1> ~ <3>, wherein, film width, measure (DSC) pre-peak temperature deviation of measuring by means of differential scanning calorimetry and be more than 0.5 DEG C and less than 10 DEG C.
The polyester film of <5> according to any one of <1> ~ <4>, wherein, the inherent viscosity of polyester film is more than 0.55dL/g and below 0.90dL/g.
The polyester film of <6> according to any one of <1> ~ <5>, wherein, the amount of the terminal carboxyl group of polyester film is more than 5eq/ ton and below 35eq/ ton.
The polyester film of <7> according to any one of <1> ~ <6>, wherein, from 3 officials can above polyfunctional monomer Component units be more than 0.005 % by mole and less than 2.5 % by mole containing ratio relative to whole Component units of the polyester in polyester film.
The manufacture method of a <8> polyester film, it comprises:
Film forming process, melt extrudes slabbing by polyester feed stock resin, and cooling on curtain coating drum, makes polyester film be shaped;
Longitudinal stretching operation, by the polyester film longitudinal stretching along its length after shaping;
Cross directional stretch operation, polyester film is transported to following portion successively, by the polyester film after longitudinal stretching along the width cross directional stretch vertical with length direction, wherein, described each portion is: the preheating part polyester film after longitudinal stretching being preheated to the temperature that can stretch; Polyester film after preheating is applied along the width vertical with length direction the extension section that tension force carries out cross directional stretch; Polyester film after longitudinal stretching and cross directional stretch are carried out in heating makes its crystallization to carry out the thermal finalization portion of thermal finalization; The tension force of the polyester film after heat hot sizing, lax polyester film removes the hot wire-CVD portion of the residual strain of striping; And by the cooling end of the polyester film cooling after hot wire-CVD,
In at least one in thermal finalization portion and hot wire-CVD portion, selective radiation heating is carried out by heater in the end of the polyester film of width, makes the beeline on the surface of heater and the surface of polyester film be more than 10mm and below 300mm.
The manufacture method of the polyester film of <9> as described in <8>, wherein, radiation heating is undertaken by pottery heater processed.
The manufacture method of the polyester film of <10> as described in <9>, wherein, the surface temperature of at least one in pottery heater processed is more than 300 DEG C and less than 700 DEG C.
The manufacture method of the polyester film of <11> as described in <9> or <10>, wherein, pottery heater processed at least one cover with cancellate crown cap.
The manufacture method of the polyester film of <12> according to any one of <8> ~ <11>, wherein, cross directional stretch operation uses biaxial stretch-formed device, this biaxial stretch-formed device has preheating part, extension section, thermal finalization portion, hot wire-CVD portion and cooling end, at least two holding components are used to hold the both ends of the width of polyester film at preheating part to an end, by polyester film from preheating part conveyance to cooling end
Polyester film is made to be 40 DEG C ~ 140 DEG C from the surface temperature of the polyester film held when component departs from.
The manufacture method of the polyester film of <13> as described in <12>, wherein, for the surface temperature of polyester film from the polyester film held when component departs from, relative to the surface temperature of the central portion of the width of polyester film, make width apart from the surface temperature of polyester film of the position holding component 200mm low 1 DEG C ~ 20 DEG C.
Invention effect
According to the present invention, even if the polyester film and the manufacture method thereof that are also difficult to produce damage and fold when heating conveyance on the surface can be provided.
Accompanying drawing explanation
Fig. 1 is for illustration of the S in the present invention s1, S s2, S cT, C s1and the polyester film schematic diagram of the definition of W.
Fig. 2 is for illustration of the C in the present invention c1, C c2and C cTdefinition half cut out polyester film schematic diagram.
Fig. 3 is the top view of the example that biaxial stretcher is shown from upper surface.
Detailed description of the invention
< polyester film >
Polyester film stacked multiple polyester film or realize multifunction or Composite at polyester film upper strata azido functional layer sometimes.Add man-hour at such polyester film, usually, while utilizing the conveyances such as roller, carry out the heating of film and stretching etc.
The fold produced when heating conveyance polyester film and damage, tend to be caused by the inequality that there is flatness on film (lax or contraction).On film, the position of partial relaxation is departed from and forms damage on roller, or the bending and form fold of relaxing in conveyance.
About the inequality of the flatness of polyester film, if be also from heating film before the film do not heated situation about existing, then also sometimes produce due to the thermal contraction inequality (certain position contraction phase compared with other positions reduce over the ground and produce lax etc.) during heating.
Although attempt percent thermal shrinkage deviation during flatness and the heating improveing the film do not heated respectively, and insufficient.
Be directed to this, it is the film meeting formula described later (1) ~ (4) by making polyester film, specifically, by increasing the percent thermal shrinkage at the lax position of non-heating film, reducing the percent thermal shrinkage at contraction position, when can form heating conveyance, damage and bend the film that fold is inhibited.
It should be noted that, in the present invention, the state that the flatness of film refers to the lax of polyester film and shrinks, when referring to the contraction of the lax or part of not part in film, flatness is good.In addition, in the TD direction of film, have to membrane portions lax shrink or both it when, also referred to as " flatness there are differences " or " flatness exists uneven ".
Below, polyester of the present invention is described in detail.
Polyester film of the present invention meets following formula (1) ~ (4).
W/1000＜[(S s1-S s2)/C S1/100]＜2W…(1)
0＜(S s1-S s2)＜0.5…(2)
-1＜(S s1+S s2+S CT)/3＜3…(3)
0＜C s1＜0.2…(4)
In formula (1) ~ (4),
S s1represent the percent thermal shrinkage [%] in the direction vertical with film width of the polyester film of the side that the percent thermal shrinkage (150 DEG C, 30 minutes) in direction in the end of film width, vertical with film width is large, S s2represent the percent thermal shrinkage [%] in the direction vertical with film width of the polyester film of the side that the percent thermal shrinkage (150 DEG C, 30 minutes) in direction in the end of film width, vertical with film width is little.
S cTrepresent the percent thermal shrinkage (150 DEG C, 30 minutes) [%] in the direction vertical with film width of the polyester film of the film central portion of film width.
C s1represent the maximum [m] of the bending size in the end of the side that the percent thermal shrinkage (150 DEG C, 30 minutes) in direction in the film end of film width, vertical with film width is large.
W represents the film of polyester film wide [m].
It should be noted that, in the present invention, " end of film width " not only refers to the edge of the width of polyester film, and refers to the region from edge to 10% of the total length of the width of polyester film (that is, width).
In addition, describe in detail after the manufacture method of polyester film, polyester film uses roller etc. to carry out transporting, stretching and obtain usually.Now, by the conveyance direction of film also referred to as MD (MachineDirection) direction.In addition, the MD direction of film is also referred to as the length direction of film.In addition, film width is the direction vertical with length direction.Also referred to as TD (TransverseDirection) direction in the film that film width manufactures while conveyance film.
In the present invention, film width is called TD or TD direction, the direction vertical with film width is called MD or MD direction.In addition, by the thermal contraction in MD direction also referred to as MD thermal contraction, its ratio is called MD percent thermal shrinkage.Therefore, the percent thermal shrinkage in vertical with film width direction is also expressed as MD percent thermal shrinkage.
In addition, in the present invention, percent thermal shrinkage (150 DEG C, 30 minutes) is as given a definition.
The coupons M of polyester film being cut into 30mm, MD direction, TD direction 120mm introduces 2 foundation directrixes with the interval of 100mm in advance in the MD direction.Coupons M to be positioned under no-station pole canopy in the heated oven of 150 DEG C after 30 minutes, to carry out process coupons M being cooled to room temperature, measure the interval of 2 foundation directrixes.Interval after the process now measured is set to A [mm].The numerical value [%] using the formula of " 100 × (100-A)/100 " to be calculated by the interval Amm after interval 100mm before treatment and process is called the MD percent thermal shrinkage (S) of coupons M.
Below, percent thermal shrinkage (150 DEG C, 30 minutes) is simply called percent thermal shrinkage.
In the present invention, the kind of polyester is not particularly limited, the kind of the polyester that can use in the present invention as described later, but particularly PETG (Polyethyleneterephthalate; PET) be well used.PETG is referred to hereinafter referred to as during PET.
Therefore, about S s1, S s2and S cT, in other words as described below.
S s1and S s2be the MD percent thermal shrinkage of the end in the TD direction of polyester film, S s1represent the MD percent thermal shrinkage [%] of the side that MD percent thermal shrinkage is large, S s2represent the MD percent thermal shrinkage [%] of the side that MD percent thermal shrinkage is little.
S cTrepresent the MD percent thermal shrinkage [%] of the central portion in the TD direction of polyester film.
First, about S s1, S s2, S cT, C s1, C cTand the relation of W, use Fig. 1 and Fig. 2 to be described.
The polyester film after bending is respectively illustrated in (A) and (B) of Fig. 1.
Usually, by polyester feed stock resin melting mixing, stretching and reclaim polyester film, when in the end in the MD direction by film, an end winding support hangs aloft, the edge tending to the end in TD direction bends.
Schematically illustrate in Fig. 1 like this from high-altitude suspension, the state of polyester film that makes film loosely not strain.
In the present invention, when the MD percent thermal shrinkage in the one end in TD direction measuring polyester film and the MD percent thermal shrinkage in the other end, end large for measured value is set to S1, the MD percent thermal shrinkage in S1 is set to S s1.On the other hand, end little for measured value is set to S2, the MD percent thermal shrinkage in S2 is set to S s2.In addition, the MD percent thermal shrinkage of the central portion in the TD direction of polyester film is set to SCT.
Shown in (A) of Fig. 1 from high-altitude suspension polyester film time, S1 side (high MD percent thermal shrinkage side) expand into the film of arc-shaped, S2 side shown in (B) (low MD percent thermal shrinkage side) expand into the film of arc-shaped.
Wide for film in the end, MD direction of film (the film total length in TD direction) is set to W and illustrates by (A) of Fig. 1 and the polyester film shown in (B).In addition, in Fig. 1, the position of the central authorities of the wide W of film in the end, MD direction of film is set to C w, by the C be fixed in the end, MD direction of film in the side of eminence wbe expressed as C wu, another side C wbe expressed as C wd.
In addition, in Fig. 1, the total length in the MD direction of polyester film is set to L.But L is not the length at the edge of the end, TD direction of polyester film, but the distance of end to another end from the MD direction of the polyester film of high-altitude suspension.Connect C wuwith C wdand the straight line Y1 obtained (straight line in Fig. 1, vertical direction is shown in broken lines) from C wuto C wddistance be L.
At this, to make connection C wuwith C wdstraight line (straight line Y1) mode parallel with gravity direction overlap.
In addition, C will be passed through in the S1 side of polyester film wuthe end in the film TD direction on limit, place, the straight line Z1 parallel with gravity direction (in Fig. 1, the straight line represented by chain-dotted line) sign on polyester film.Then, the position of the half (L/2) of straight line Y1 draws the straight line C vertical with straight line Y1 l.
In polyester film shown in (A) of the Fig. 1 expanded in the S1 side of polyester film, straight line C lon distance, distance namely from the end, TD direction of the S1 side of polyester film to straight line Z1 be called C s1.
Usually, the TD direction bend at end of film becomes the polyester film of arc-shaped (to draw straight line C in 1/2 distance in the MD direction of film lposition) the bending size at place is maximum." in the film end of film width, the maximum [m] of the bending size in the end of the side that the percent thermal shrinkage (150 DEG C, 30 minutes) in the direction vertical with film width is large " in formula (1) and (4) is as the C of Fig. 1 (A), (B) s1and the numerical value obtained.
In polyester film shown in (B) of the Fig. 1 inserted in the S1 side of polyester film, C s1for straight line C lon distance, represent with the form of the end, TD direction of the S1 side from polyester film to the distance of straight line Z1.
Below, by width be the maximum of bending size of polyester film and the C of W s1also referred to as " overall with circular arc ".
It should be noted that, when the S1 side of polyester film being expand into arc-shaped, the circular arc of (when drawing straight line Z1 in the inner side of polyester film) is called positive circular arc, and the circular arc that will insert (when the outside of polyester film picture straight line Z1) during S1 side is called negative circular arc.
Then, Fig. 2 is described.
Fig. 2 shows the polyester film shown in Fig. 1 along connecting C wuwith C wdand the straight line Y1 cutting obtained and obtain partly cut out polyester film.The fragment of cutting out S1 side in polyester film at half of the polyester film shown in (B) of Fig. 1 has been shown in (A) of Fig. 2.The fragment of cutting out S2 side in polyester film at half of the polyester film shown in (A) of Fig. 1 has been shown in (B) of Fig. 2.
In the film shown in (A) of Fig. 1, be positioned at the C of the central authorities in film TD direction wdby the cutting of film, in fig. 2, the end in TD direction is positioned at.
By C wdposition in (A) of Fig. 2, be called C1, in (B) of Fig. 2, be called C2.
Fig. 2 also schematically illustrate half sanction polyester film as the polyester film of Fig. 1 by an end winding support in the end in the MD direction of film in eminence and hang time state.
Usually, cutting C in bending film wu-C wdtime straight line (straight line Y1), lose tension force, there is the tendency bent in the same manner as original film.
Half film wide (total length in TD direction) cut out in the end, MD direction of polyester film shown in (A) and (B) of Fig. 2 is W/2.In the present invention, the half position of the W/2 in the end, MD direction of film is called C w2.In the end, MD direction of film, the C in the side of eminence will be fixed on w2be called C w2u, by the C in another end w2be called C w2d.
In Fig. 2, from connection C w2uwith C w2dand the C of the straight line Y2 obtained (straight line in Fig. 2, vertical direction is illustrated by the broken lines) w2uto C w2ddistance be L.
Make connection C w2uwith C w2dstraight line (straight line Y2) overlap in the mode parallel with gravity direction.
In addition, by the C1 side of cutting out polyester film half, signed on half sanction polyester film by C1, the straight line Z2 parallel with gravity direction (in Fig. 2, the straight line represented by chain-dotted line).Then, the straight line C vertical with straight line Y2 is drawn in the position of the half (L/2) of straight line Y2 l.
Shown in (A) of Fig. 2 of the C1 side expansion of half sanction polyester film half cuts out in polyester film, by straight line C lon distance, be namely called C from half end, TD direction of cutting out the C1 side of polyester film to the distance of straight line Z2 c1.
Shown in (B) of Fig. 2 of the C2 side expansion of half sanction polyester film half cuts out in polyester film, by straight line C lon distance, be namely called C from half end, TD direction of cutting out the C2 side of polyester film to the distance of straight line Z2 c2.
As mentioned above, usually, the TD direction bend at end of film becomes the polyester film of arc-shaped (to draw straight line C in 1/2 distance in the MD direction of film lposition) bending size maximum." maximum of 2 half that are obtained by the line cutting polyester film of the central authorities along the polyester film width in the both ends connecting polyester film length direction bending sizes of cutting out in the end of the width of polyester films is added the value [m] obtained divided by 2 " in formula (5) and (7) is by the C of Fig. 2 (A), (B) c1and C c2as " (C c1+ C c2)/2 " and the numerical value C obtained cT.
Half-and-half cut out polyester film when further illustrating, 2 the half line cutting polyester films cut out between mid point that polyester film connects along the limit of film width in 2 ends of the length direction at polyester film obtain.
To represent that width is the C that half of W/2 cuts out the bending size of polyester film cTalso referred to as " partly cutting out circular arc ".In addition, the circular arc that the C1 side of polyester film expand into the situation of arc-shaped is called positive circular arc, the circular arc of situation about being expanded C2 side is called negative circular arc.
Then, about formula (1) ~ (7), be described successively.
[formula (1)]
Formula (1) represents with the following sign of inequality.
W/1000＜[(S s1-S s2)/C S1/100]＜2W…(1)
Below, by MD thermal contraction rate variance " S s1-S s2" be expressed as Δ S.
Formula (1) represent MD thermal contraction rate variance Δ S-phase wide for the film of the end in MD direction be the overall with circular arc C of the polyester film of W s1ratio [(S s1-S s2)/C s1/ 100 [%]] be greater than 1/1000th of the wide W of film and be less than 2 times of the wide W of film.
In polyester film, be usually difficult to make MD thermal contraction rate variance Δ S be 0, MD thermal contraction rate variance Δ S more than 0 when easily there is problem of the present invention.Particularly relative MD thermal contraction rate variance Δ S-phase is for overall with circular arc C s1ratio be greater than the polyester film of W/1000, effect of the present invention increases.
But in polyester film, bending degree is large, overall with circular arc C s1time large, even if reduce MD thermal contraction rate variance Δ S, fold when heating conveyance and damage also cannot be prevented.Its limit is the value more than W/1000.
On the other hand, in polyester film, MD thermal contraction rate variance Δ S-phase is for overall with circular arc C s1ratio increase refer to that bending degree is little, Δ S increases.That is, overall with circular arc C is supposed s1little, Δ S is large, then deviation appears in the MD thermal contraction when heating conveyance in TD direction, and the flatness of film also there are differences, and occurs lax etc., therefore, cannot prevent fold when heating conveyance and damage.If MD thermal contraction rate variance Δ S-phase is for overall with circular arc C s1ratio exceed 2 times of the wide W of film, then cannot prevent fold when heating conveyance and damage.
MD thermal contraction rate variance Δ S-phase is for overall with circular arc C s1ratio [(S s1-S s2)/C s1/ 100] be less than W/2 preferably greater than W/700, be less than W/4 more preferably above W/500, be less than W/8 preferably greater than W/400 further.
[formula (2)]
Formula (2) represents with the following sign of inequality.
0＜(S s1-S s2)＜0.5…(2)
That is, to represent that Δ S is less than 0.5 more than 0.Illustrated by (1), usually, the MD thermal contraction rate variance Δ S being difficult to make polyester film is 0, has the different tendency of MD percent thermal shrinkage at one end and the other end in the TD direction of film.In addition, in formula (1), regulation MD thermal contraction rate variance Δ S-phase is for overall with circular arc C s1ratio be less than 2W, even if but C s1little, if Δ S becomes excessive, then the flatness when heating of film also cannot be made to transport improves.
Δ S is 0.02 < Δ S < 0.4 preferably, more preferably 0.03 < Δ S < 0.3.
[formula (3)]
Formula (3) represents with the following sign of inequality.
-1＜(S s1+S s2+S CT)/3＜3…(3)
" (S s1+ S s2+ S cT)/3 " be S s1with S s2with S cTaverage, below, by " (S s1+ S s2+ S cT)/3 " be also expressed as S aV.
About the MD percent thermal shrinkage on the TD direction of polyester film, not only the balance of S1 side and S2 side is very important, S s1and S s2, with the MD percent thermal shrinkage S of the film central portion in TD direction cTbalance also very important.
At this, " the film central portion of film width (TD direction) " refers to, when the position at an end in the TD direction by polyester film and the center of another end is set to CT, using CT as center, TD direction and MD direction reach respectively the total length in the TD direction of polyester film ± region of 10%.
If S s1with S s2with S cTaverage S aVbe not less than 3, then the MD percent thermal shrinkage as film entirety becomes excessive, and the flatness of film cannot be made to improve.
S aVpreferably-0.5 < S aV< 2, more preferably-0.2 < S aV< 1.5.
[formula (4)]
Formula (4) represents with the following sign of inequality.
0＜C s1＜0.2…(4)
Formula (4) defines the scope of the maximum (overall with circular arc) that width is the bending size of the polyester film of W.By polyester feed stock resin melting mixing, stretching and the polyester film obtained, the curved edge in usual film TD direction, is difficult to make overall with circular arc be 0.If overall with circular arc reaches more than 0.2, then producing large lax before the heating conveyance of film on film, when heating conveyance film, the generation of fold and damage cannot have been suppressed.
Overall with circular arc C s1preferably 0.001 < C s1< 0.1, more preferably 0.002 < C s1< 0.05.
[formula (5) ~ formula (7)]
Polyester film of the present invention, except meeting formula (1) ~ (4), preferably meets formula (5) ~ (7) further.
Formula (5) ~ formula (7) be about by wide for the film polyester film for W along the C shown in Fig. 1 wu-C wdstraight line (straight line Y1) cutting and half regulation of cutting out polyester film that obtains.
About film wide for W/2 partly cut out polyester film, wide with film is that the polyester film of W is same, relaxed (in end, TD direction lax) by the end of controlling diaphragm and in lax (TD direction central portion lax), fold when easily suppressing heating conveyance and damage.
-Shi (5)-
Formula (5) represents with the following sign of inequality.
W/2000＜[{S CT-(S s1+S s2)/2}/C CT/100]＜W…(5)
" { S cT-(S s1+ S s2)/2}/C cT/ 100 " by above-mentioned scope, be difficult to produce difference in central authorities and end plane during heating conveyance, suppress lax etc. generation, therefore, be difficult to produce fold and damage.
" { S cT-(S s1+ S s2)/2}/C cT/ 100 " be less than 0.4 more preferably above-0.4, be less than 0.3 preferably greater than-0.3 further.
-Shi (6)-
Formula (6) represents with the following sign of inequality.
-0.5＜{S CT-(S s1+S s2)/2}＜0.5…(6)
" { S cT-(S s1+ S s2)/2} " by above-mentioned scope, be difficult to produce difference in central authorities and end plane during heating conveyance, suppress lax etc. generation, therefore, be difficult to produce fold and damage.
" { S cT-(S s1+ S s2)/2} " be less than 0.4 more preferably above-0.4, be less than 0.3 preferably greater than-0.3 further.
-Shi (7)-
Formula (7) represents with the following sign of inequality.
-0.2＜C CT＜0.2…(7)
C cTby in above-mentioned scope, be difficult to relaxing of the stage before occurring in heating conveyance, suppress the generation of fold and damage.
C cTmore preferably-0.1 < C cT< 0.1, further preferred-0.05 < C cT< 0.05.
Be suitable for formula (1) ~ (7) as long as polyester film by polyester feed stock resin melting mixing, carry out longitudinal stretching or cross directional stretch or both it after polyester film, be then not particularly limited.Such as, formula (1) ~ (7) can be applicable to after stretching the film of winding, the polyester film of the later half sanction processing that also goes for reeling, off-line through hot wire-CVD operation film, on film, form the film etc. of coating layer through primary coat operation.In addition, when making polyester film commercialization, the end in the TD direction of cutting film in order to prune, goes for the polyester film before this cutting, also goes for the polyester film after cutting sometimes.
Below, the preferred embodiment beyond formula (1) ~ (7) in polyester film of the present invention is described.
Film wide (total length in the TD direction of the film) W of polyester film of the present invention is preferably more than 0.3m and below 8m.That is, 0.3m≤W≤8m is preferably.Film is wide when being more than 0.3m, and productivity ratio is difficult to reduce.On the other hand, the wide film for below 8m of film easily operates, by size, fold when easily suppressing heating to transport and the generation of damage of controls MD percent thermal shrinkage and overall with circular arc.
The wide W of film of polyester film is more preferably more than 0.5m and below 5m, more preferably more than 0.7m and below 3m, most preferably is more than 0.8m and below 2m.
Polyester film make further TD direction, measure (DSC) pre-peak temperature deviation of measuring by means of differential scanning calorimetry and be more than 0.5 DEG C and less than 10 DEG C, thereby, it is possible to fold when suppressing heating to transport further and damage.
At this, DSC is that means of differential scanning calorimetry measures (Differentialscanningcalorimetry), and " the pre-peak temperature " of DSC is the temperature of polyester film being carried out to the peak occurred at first when DSC measures.
The pre-peak temperature of DSC usually be up to that to reach film surface temperature (heat setting temperature) suitable by polyester film during thermal finalization in the biaxial stretch-formed cross directional stretch operation of carrying out of polyester film.
It should be noted that, the pre-peak temperature of DSC is the value utilizing conventional method to obtain by means of differential scanning calorimetry mensuration (DSC).
In addition, the diaphragm of first-class for the TD direction of polyester film spaced 11 position P1 ~ P11 samples by pre-peak temperature deviation.DSC mensuration is carried out to the diaphragm in P1 ~ P11, measures each pre-peak temperature Tppl ~ Tppll, using the pre-peak temperature deviation of the difference of the maxima and minima in Tppl ~ Tppll as the DSC in TD direction.Below, by " the pre-peak temperature deviation of the DSC in TD direction " also referred to as Δ Tpp.
The pre-peak temperature deviation (Δ Tpp) of the DSC on the TD direction of polyester film is 0.5 DEG C ~ 10 DEG C, and polyester film easily meets above-mentioned formula (1) ~ (7).
Δ Tpp is more preferably more than 0.5 DEG C and less than 7 DEG C, more preferably more than 0.5 DEG C and less than 5 DEG C, most preferably is more than 0.5 DEG C and less than 4 DEG C.
From the view point of the hydrolytic resistance improving polyester film, weatherability is improved, the inherent viscosity (IV of polyester film; IntrinsicViscosity) more than 0.55dL/g and below 0.90dL/g is preferably, be more preferably more than 0.60dL/g and below 0.80dL/g, more preferably more than 0.62dL/g and below 0.78dL/g, most preferably is more than 0.63dL/g and below 0.75dL/g.
[end COOH measures (also referred to as acid number), AV to the amount of the terminal carboxyl group of polyester film; AcidValue] to be preferably more than 5eq/ ton and below 35eq/ ton.End COOH amount is more preferably more than 6eq/ ton and below 30eq/ ton, more preferably more than 7eq/ ton and below 28eq/ ton.
It should be noted that, in this description, " eq/ ton " represents the molar equivalent of every 1 ton.
AV is for making polyester at phenmethylol/chloroform (=2/3; Volume ratio) mixed solution in completely dissolve, as indicator use value that is phenol red, that carry out titration with titer (0.025NKOH-methyl alcohol mixed solution), calculated by this titer.
Polyester film makes dicarboxylic acid component and diol component copolymerization synthesize.About dicarboxylic acid component and diol component details as described later.In addition, the polyester film of the present invention total (a+b) preferably comprised from the number (a) of carboxylic acid group and the number (b) of hydroxyl is that the polyfunctional monomer of more than 3 is (hereinafter referred to as " 3 officials can polyfunctional monomer " above or be called simply " polyfunctional monomer ".) Component units.
Polyester film of the present invention as described later, can obtain by making such as (A) dicarboxylic acid component and (B) diol component utilize well-known method to carry out esterification and/or ester exchange reaction, preferably making itself and 3 officials can above polyfunctional monomer copolymerization and obtaining further.About the details of the illustration and preferred embodiment etc. of dicarboxylic acid component, diol component and polyfunctional monomer etc., as described later.
~ from polyfunctional monomer Component units ~
As the Component units from the number (a) of carboxylic acid group and the total (a+b) of the number (b) of hydroxyl being the polyfunctional monomer of more than 3, as described later, the polyfunctional monomer that the carboxylic acid that the number (a) that can list carboxylic acid group is more than 3 and their ester derivant or acid anhydrides etc., hydroxyl value (b) are more than 3 and " there is in a part both hydroxyl and carboxylic acid group and the number (a) of carboxylic acid group and the total (a+b) of the number (b) of hydroxyl are the hydroxyl acids of more than 3 " etc.About the details of their illustration and preferred embodiment etc., as described later.
In addition, the compound obtained at the carboxyl terminal of carboxylic acid or the hydroxyl acids such as carboxyl terminal addition 1-lactide, d-lactide, hydroxybenzoic acid of " there is in a part the polyfunctional monomer of both hydroxyl and carboxylic acid group " and derivative, the multiple compounds linked of this hydroxyl acids etc. is also preferably.
These can be used alone one, as required, also can be used together multiple.
In polyester film of the present invention, from 3 officials can above polyfunctional monomer Component units containing ratio, be preferably more than 0.005 % by mole and less than 2.5 % by mole relative to whole Component units of the polyester in polyester film.The ratio that contains from the Component units of polyfunctional monomer is more preferably more than 0.020 % by mole and less than 1 % by mole, more preferably more than 0.025 % by mole and less than 1 % by mole, more preferably more than 0.035 % by mole and less than 0.5 % by mole, be particularly preferably more than 0.05 % by mole and less than 0.5 % by mole, most preferably be more than 0.1 % by mole and less than 0.25 % by mole.
Can the Component units of above polyfunctional monomer from 3 officials by existing in polyester film, the Component units of above polyfunctional monomer can obtain the structure making polyester molecule chain component by from 3 officials, thus the complexing between polyester molecule can be promoted.Its result, even if polyester molecule is hydrolyzed under being exposed to hot and humid environment, molecular weight reduces, between polyester molecule, also form complexing, thus, suppresses the embrittlement of polyester film, obtains more excellent weatherability.In addition, such complexing is also effective to suppression thermal contraction.This can infer that the motility due to the complexing polyester molecule by above-mentioned polyester molecule reduces, and therefore, even if will shrink due to thermo-molecular, also cannot shrink, the thermal contraction of polyester film is inhibited.
In addition, by containing 3 officials can above polyfunctional monomer as Component units, the functional group used and the composition be coated with on polyester film in the coating layer of formation is not had to form hydrogen bond, covalent bond in polycondensation after esterification, thus, keep the adhesiveness of coating layer and polyester film more well, effectively can prevent the generation of peeling off.For the polyester film of solar cell backboard, adheres to the sealant such as EVA after coating forms the coating layer such as easy adhesive layer, though be exposed to outdoor wait the environment of wind and rain under long-time place when, also obtain the good adhesiveness being difficult to stripping.
Therefore, by from 3 officials can above polyfunctional monomer Component units be more than 0.005 % by mole containing ratio, weatherability, low thermal shrinkage behavior and with polyester film on be coated with the coating layer of formation adhesion easily improve further.In addition, by from 3 officials can above polyfunctional monomer Component units be less than 2.5 % by mole containing ratio, from 3 officials can the volume of Component units of above polyfunctional monomer large, therefore, be difficult to form crystallization and be inhibited.Its result, is promoted the formation of the low mobile composition formed by crystallization, can suppress water-disintegrable reduction.In addition, due to from 3 officials can the volume of Component units of above polyfunctional monomer large, the micro concavo-convex amount on film surface increases, and therefore, easily demonstrates anchoring effect, and polyester film improves with the adhesion of the coating layer being coated with formation on this film.In addition, due to this large volume, suppress the free volume (intermolecular gap) increased, thus the thermal contraction that produces because polyester molecule in large free volume can skid off (The り pulls out け ゐ) can be suppressed.In addition, the glass transition temperature (Tg) of excessive interpolation of Component units of above polyfunctional monomer can reduce and be also inhibited with from 3 officials, also effective to preventing the reduction of weatherability.
~ from end-capping reagent structure division ~
Polyester film of the present invention also preferably has the structure division of the free end-capping reagent from oxazoline based compound, carbodiimide compound and epoxide.It should be noted that, " structure division from end-capping reagent " refer to end-capping reagent and polyester end carboxylic acid reaction and in the structure of end bonding.
When comprising end-capping reagent in polyester film, the carboxylic acid reaction of end-capping reagent and polyester end, because bonding exists on polyester end, therefore, easily measures end COOH the value that (AV value) stably maintains the expectations such as above-mentioned preferred scope.That is, suppress the poly-ester hydrolysis promoted by terminal carboxylic, weatherability can be kept higher.In addition, bonding on polyester end, the end section volume of strand increases, and the micro concavo-convex amount on film surface increases, and therefore, easily demonstrates anchoring effect, and polyester film improves with the adhesion of the coating layer being coated with formation on this film.In addition, the volume of end-capping reagent is large, suppresses polyester molecule skid off from free volume and move.Its result, also has the effect of the thermal contraction suppressed with molecule movement.
It should be noted that, end-capping reagent is and the carboxyl reaction of the end of polyester, additive that the carboxyl terminal amount of polyester is reduced.
End-capping reagent can be used singly or in combination of two or more.
End-capping reagent, relative to the quality of polyester film, preferably contains in the scope of below 5 quality % at more than 0.1 quality %, is more preferably more than 0.3 quality % and below 4 quality %, more preferably more than 0.5 quality % and below 2 quality %.
Is more than 0.1 quality % by the end-capping reagent in polyester film containing ratio, becomes well with the adhesion of coating layer, can realize the weatherability raising that AV reduction effect causes simultaneously, and can give low thermal shrinkage behavior.In addition, end-capping reagent in polyester film containing ratio be below 5 quality % time, become good with the adhesion of coating layer, suppress the glass transition temperature (Tg) adding the polyester that end-capping reagent causes to reduce simultaneously, thus the reduction of the weatherability caused thus and the increase of thermal contraction can be suppressed.This is because, Tg reduces, relatively suppress to be increased and the water-disintegrable increase of generation by the reactivity of polyester, or the thermal contraction suppressing the motility of the polyester molecule increased by being reduced by Tg easily to increase and produce.
As the end-capping reagent in the present invention, preferably there is the compound of carbodiimide, epoxy radicals, Huo oxazolinyl.As the concrete example of end-capping reagent, carbodiimide compound, epoxide, oxazoline based compound etc. suitably can be listed.
The carbodiimide compound with carbodiimide has a functionality carbodiimide and multi-functional carbodiimide.As a functionality carbodiimide, can list: such as, dicyclohexylcarbodiimide, DIC, dimethyl carbodiimide, diisobutyl carbodiimide, dioctyl carbodiimide, ter /-butylisopropyl carbodiimide, diphenyl carbodiimide, di-t-butyl carbodiimide and two betanaphthyl carbodiimides etc., be preferably dicyclohexylcarbodiimide and DIC.
In addition, as multi-functional carbodiimide, be preferably the poly-carbodiimide of the degree of polymerization 3 ~ 15.Poly-carbodiimide has the repetitive represented by "-R-N=C=N-" etc. usually, and R represents the link group of the divalent such as alkylidene, arlydene.As such repetitive, can list: such as, 1, 5-naphthylene carbodiimide, 4, 4 '-diphenyl methane carbodiimide, 4, 4 '-diphenyldimethyhnethane carbodiimide, 1, 3-phenylene carbodiimide, 2, 4-xylene carbodiimide, 2, 6-xylene carbodiimide, 2, 4-xylene carbodiimide and 2, the mixture of 6-xylene carbodiimide, hexa-methylene carbodiimide, cyclohexane-1, 4-carbodiimide, phenylenedimethylidyne carbodiimide, isophorone carbodiimide, dicyclohexyl methyl hydride-4, 4 '-carbodiimide, hexahydrotoluene carbodiimide, tetramethylxylene carbodiimide, 2, 6-diisopropyl phenyl carbodiimide and 1, 3, 5-triisopropylbenzene-2, 4-carbodiimide etc.
From the view point of the generation of the isocyanate-based gas suppressing thermal decomposition to cause, carbodiimide compound is preferably the high carbodiimide compound of heat resistance.In order to improve heat resistance, molecular weight (degree of polymerization) is more high more preferred, more preferably makes the end of carbodiimide compound form the high structure of heat resistance.In addition, by reducing the temperature melt extruded by polyester feed stock resin, more effectively obtain the raising effect of weatherability and the reduction effect of thermal contraction of carbodiimide compound generation.
The generation of isocyanate-based gas when using the polyester film of carbodiimide compound preferably to keep 30 minutes at temperature 300 DEG C is 0 quality % ~ 0.02 quality %.When the generation of isocyanate-based gas is below 0.02 quality %, be difficult to generate bubble (space) in polyester film, therefore, be difficult to form the concentrated position of stress, thus, destruction and the stripping of easily generation in polyester film can be prevented.Thus, the adhesion and between adjacent material becomes good.
At this, isocyanate-based gas is the gas with NCO, can list: such as, diisopropyl benzene based isocyanate, 1,3,5-triisopropyl phenyl diisocyanate, 2-amino-1,3,5-triisopropyl phenyl-6-isocyanates, HMDI, IPDI and cyclohexyl isocyanate etc.
As the preferred example of epoxide with epoxy radicals, can list: epihydric alcohol ester compound and glycidyl etherified compound etc.
As the concrete example of epihydric alcohol ester compound, can list: glycidyl benzoate, t-butyl-benzoic acid ethylene oxidic ester, paratolunitrile ethylene oxidic ester, cyclohexane-carboxylic acid ethylene oxidic ester, n-nonanoic acid ethylene oxidic ester, stearic acid ethylene oxidic ester, laurate ethylene oxidic ester, palmitic acid ethylene oxidic ester, behenic acid ethylene oxidic ester, neodecanoic acid (versaticacid) ethylene oxidic ester, oleic acid ethylene oxidic ester, linoleic acid ethylene oxidic ester, mountain Yu acetylenic acid ethylene oxidic ester, stearolic acid ethylene oxidic ester, terephthalic acid diglycidyl ester, Diglycidyl M-phthalate, o-phthalic acid diglycidyl ester, naphthalenedicarboxylic acid 2-glycidyl ester, methylterephthalic acid's 2-glycidyl ester, hexahydrophthalic acid 2-glycidyl ester, tetrahydrophthalic acid 2-glycidyl ester, cyclohexane dicarboxylic acid 2-glycidyl ester, adipic acid 2-glycidyl ester, butanedioic acid 2-glycidyl ester, Diglycidyl Sebacate, dodecanedioic acid 2-glycidyl ester, octadecane dicarboxylic acids 2-glycidyl ester, trimellitic acid three-glycidyl ester and PMA tetra glycidyl ester etc.
In addition, as the concrete example of glycidyl etherified compound, can list: phenylglycidyl ether, adjacent phenylglycidyl ether, 1, two (the β of 4-, γ-glycidoxy) butane, 1, two (the β of 6-, γ-glycidoxy) hexane, 1, two (the β of 4-, γ-glycidoxy) benzene, 1-(β, γ-glycidoxy)-2-Ethoxyethane, 1-(β, γ-glycidoxy)-2-benzyloxy ethane, 2, 2-pair-[p-(β, γ-glycidoxy) phenyl] propane and 2, 2-pair-(4-hydroxy phenyl) propane, 2, 2-is two-the bisglycidyl base polyethers etc. that obtained by the reaction of bis-phenol and chloropropylene oxide such as (4-hydroxy phenyl) methane.
Zuo is oxazoline compound, can from the compound of Ju You oxazolinyl suitable choice for use, wherein, be preferably bisoxazoline compounds.
As bisoxazoline compounds, can illustrate: such as, 2,2 '-bis-(2-oxazoline), 2,2 '-bis-(4-methyl-2-oxazoline), 2,2 '-bis-(4,4-dimethyl-2-oxazoline), 2,2 '-bis-(4-ethyl-2-oxazoline), 2,2 '-bis-(4,4 '-diethyl-2-oxazoline), 2,2 '-bis-(4-propyl group-2-oxazoline), 2,2 '-bis-(4-butyl-2-oxazoline), 2,2 '-bis-(4-hexyl-2-oxazoline), 2,2 '-bis-(4-phenyl-2-oxazoline), 2,2 '-bis-(4-cyclohexyl-2-oxazoline), 2,2 '-bis-(4-benzyl-2-oxazoline), 2,2 '-p-phenylene two (2-oxazoline), 2,2 '-metaphenylene two (2-oxazoline), 2,2 '-adjacent phenylene two (2-oxazoline), 2,2 '-TOPOT 2,2′ p phenylenebis (4-methyl-2-oxazoline), 2,2 '-TOPOT 2,2′ p phenylenebis (4,4-dimethyl-2-oxazoline), 2,2 '-metaphenylene two (4-methyl-2-oxazoline), 2,2 '-metaphenylene two (4,4-dimethyl-2-oxazoline), 2,2 '-ethylenebis (2-oxazoline), 2,2 '-tetramethylene two (2-oxazoline), 2,2 '-hexa-methylene two (2-oxazoline), 2,2 '-eight di-2-ethylhexylphosphine oxide (2-oxazoline), 2,2 '-decamethylene two (2-oxazoline), 2,2 '-ethylenebis (4-methyl-2-oxazoline), 2,2 '-tetramethylene two (4,4-dimethyl-2-oxazoline), 2,2 '-9,9 '-biphenoxyl ethane two (2-oxazoline), 2,2 '-cyclohexyl two (2-oxazoline) and 2,2 '-diphenylene two (2-oxazoline) etc.In them, from the view point of with the reactivity of polyester is good and the raising effect of weatherability is high, most preferably be 2,2 '-bis-(2-oxazoline).
Only otherwise damage effect of the present invention, then bisoxazoline compounds can be used singly or in combination of two or more.
In the present invention, above-mentioned or described later, 3 officials above polyfunctional monomer, end-capping reagent individually can use one, or both be combinationally used.
As long as the method for the polyester film meeting formula (1) ~ formula (4) can be manufactured, then can make polyester film of the present invention by any means.In the present invention, such as, most preferably can be made by the manufacture method of polyester film of the present invention shown below.
Below, the manufacture method of polyester film of the present invention is specifically described.
The manufacture method > of < polyester film
The manufacture method of polyester film of the present invention comprises:
Film forming process, melt extrudes slabbing by polyester feed stock resin, and cooling on curtain coating drum, makes polyester film be shaped;
Longitudinal stretching operation, by the polyester film longitudinal stretching along its length after shaping;
Cross directional stretch operation, polyester film is transported to following portion successively, by the polyester film after longitudinal stretching along the width cross directional stretch vertical with length direction, wherein said each portion is: the preheating part polyester film after longitudinal stretching being preheated to the temperature that can stretch, polyester film after preheating is applied along the width vertical with length direction the extension section that tension force carries out cross directional stretch, polyester film after longitudinal stretching and cross directional stretch are carried out in heating makes its crystallization to carry out the thermal finalization portion of thermal finalization, polyester film after heat hot sizing, the tension force of lax polyester film is except the hot wire-CVD portion of the residual strain of striping and by the cooling end of the polyester film cooling after hot wire-CVD,
In at least one in thermal finalization portion and hot wire-CVD portion, selective radiation heating is carried out by heater in the end of the polyester film of width, makes the beeline on the surface of heater and the surface of polyester film be more than 10mm and below 300mm.
The manufacture method of polyester film of the present invention also may further include other operations.
The manufacture method of polyester film of the present invention comprises film forming process, longitudinal stretching operation and cross directional stretch operation substantially.Longitudinal stretching is the stretching of the length direction (MD direction) pointing to polyester film, and cross directional stretch is the stretching of the width (TD direction) pointing to polyester film.
Cross directional stretch operation is divided into preheating part, extension section, thermal finalization portion, hot wire-CVD portion and cooling end, is transported by polyester film to each portion.
In addition, in the manufacture method of polyester film of the present invention, thermal finalization portion in cross directional stretch operation or hot wire-CVD portion or thermal finalization portion and hot wire-CVD portion both in, by the end, TD direction of polyester film by carrying out selective radiation heating apart from the heater of the surperficial only specific range of film.
By making the manufacture method of polyester film be above-mentioned formation, easily manufacture the polyester film meeting above-mentioned formula (1) ~ formula (4), even if easily manufacture polyester film film being also difficult to produce fold and damage when heating conveyance.
As mentioned above, also attempt suppressing fold by the manufacture method of polyester film in the past, but the polyester meeting formula (1) ~ (4) cannot be manufactured as in the present invention.
Such as, as in the Japanese Unexamined Patent Publication 2001-191406 publication shown in patent document 2, think for following 1) and 2) shown in reason, the polyester film meeting formula (1) ~ formula (4) and formula (5) ~ formula (7) cannot be manufactured.
1) MD percent thermal shrinkage
The MD percent thermal shrinkage of polyester film is determined by the relax level of the crystallization degree of polyester and the polyester molecule in MD direction that form film usually.The relax level larger then MD percent thermal shrinkage tending to the crystallization degree of polyester and polyester molecule is lower.
Usually, when carrying out the PET of cross directional stretch by stretching devices such as biaxial stretch-formed devices, the crystallization degree of PET and the relax level of PET molecule are determined by the temperature in the thermal finalization portion of stretching device.The heat setting temperature tending to film is higher, and the crystallization degree of polyester is higher, and the MD percent thermal shrinkage of polyester film is lower.
When carrying out cross directional stretch and thermal finalization by stretching device, hold component with clip etc. and hold film, but in most cases this holding component reaches the temperature of about 100 DEG C ~ 150 DEG C by exporting (when polyester film leaves from cooling end) from the entrance (when polyester film enters preheating part) of stretching device.In the case of pet, the heat setting temperature of film reaches about 200 DEG C usually, and the temperature holding component self is lower compared with heat setting temperature, and therefore, heat is scattered and disappeared to holding member side, and the heat setting temperature of inevitable mulch film end side easily reduces.Therefore, the MD percent thermal shrinkage of film also easily forms the distribution that film end increases.
2) film length distribution (circular arc) in MD direction
The distribution of lengths in the MD direction of polyester film easily depends on the type of cooling near the outlet of the stretching device carrying out cross directional stretch.Usually, the position that the length in the MD direction of film is tended to after chilling is longer, and the position of Slow cooling is shorter.This can think due to following reason.Film is shunk (reverse phenomenon of thermal expansion) by cooling, but during chilling, the time of contraction is few, and therefore, film does not fully shrink, result, and the film in MD direction is long elongated.On the contrary, film is when Slow cooling, and owing to shrinking fully, therefore, the film in MD direction is long to shorten.
As mentioned above, the temperature of the holding component of stretching device is 100 DEG C ~ about 150 DEG C, is higher temperature when the chilling temperature of itself and stretching device (usually, normal temperature ~ 100 DEG C about) is compared.Therefore, at the cooling end of stretching device, because the temperature holding component is high, the temperature of film end raises on the contrary, compares with the cooling condition of film central portion, and Slow cooling is tended in film end.Thus, compared with film central portion, the film in the MD direction of film end is long easily to shorten.
In polyester film in the past, owing to occurring above-mentioned 1) and 2), therefore, tend to form the longer film of film central portion MD percent thermal shrinkage compared with film end film that is less, MD direction.
Like this, the film in the original MD direction before film central portion does not only heat is long, and is difficult to shrink by during heating conveyance, therefore, becomes longer, produces lax, easily occur damage and fold.
Therefore, in polyester film in the past, " [(the S in formula (1) s1-S s2)/C s1/ 100] " [{ the S " and in formula (5) cT-(S s1+ S s2)/2}/C cT/ 100] " be negative value, do not meet formula (1) and formula (5).
It should be noted that, the method according to Japanese Unexamined Patent Publication 2001-191406 publication, after carrying out cross directional stretch to polyester film, further off-line carries out hot wire-CVD process.In this situation, easily on film, produce damage and fold by hot wire-CVD process, the state that TD direction central portion MD percent thermal shrinkage compared with end, TD direction film that is little, MD direction that the film after hot wire-CVD process also easily reaches film is grown.Therefore, the polyester film obtained by the method shown in Japanese Unexamined Patent Publication 2001-191406 publication does not meet the key element of formula (1) ~ (7) in the present invention.
Relative to this, according to the manufacture method of polyester film of the present invention, in at least one in thermal finalization portion and hot wire-CVD portion, selective radiation heating is carried out by heater in the end of the polyester film of width (TD direction), now, the beeline on the surface of heater and the surface of polyester film is made to be more than 10mm and below 300mm.Thus, the MD percent thermal shrinkage of film end declines, close to the value of the MD percent thermal shrinkage of film central portion, balanced in the balance of the MD percent thermal shrinkage in TD direction.Its result, separate Decision 1) MD percent thermal shrinkage and 2) and film length distribution (circular arc) problem, the polyester film obtained meets formula (1) ~ (4).
As mentioned above, during heating conveyance film, film produces fold and damage and think because film local is elongated and occur lax.
The manufacture method of polyester film of the present invention is following method: the MD percent thermal shrinkage increasing the position (position that circular arc is large) of the film length length in the TD direction before heating conveyance, position short on the contrary reduces percent thermal shrinkage, optionally make originally long position shrink, eliminate the inequality of focal length thus.
Below, to the details of the manufacture method of polyester film of the present invention, about each operation of film forming process, longitudinal stretching operation and cross directional stretch operation, be described in detail respectively.
[film forming process]
In film forming process, polyester feed stock resin is melt extruded slabbing, cooling on curtain coating drum, makes polyester film be shaped.
About the method that polyester feed stock resin is melt extruded and polyester feed stock resin, be not particularly limited, inherent viscosity can be made to reach the inherent viscosity of expectation by the catalyst, polymerization etc. for the synthesis of polyester feed stock resin.
First, polyester feed stock resin is described.
(polyester feed stock resin)
Polyester feed stock resin is the raw material of polyester film, as long as comprise the material of polyester, is not particularly limited, and except polyester, can also comprise the slurry of inorganic particulate or organic filler.In addition, polyester feed stock resin can also comprise the titanium elements from catalyst.
The kind of the polyester comprised in polyester feed stock resin is not particularly limited.
Dicarboxylic acid component and diol component can be used to synthesize, also can use commercially available polyester.
When synthesizing polyester, can obtain by making such as (A) dicarboxylic acid component and (B) diol component utilize well-known method to carry out esterification and/or ester exchange reaction.
As (A) dicarboxylic acid component, can list: 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, the aliphatic dicarboxylic acid classes such as ethyl malonic acid, adamantane dicarboxylic acids, norbornene dicarboxylic acids, isobide, cyclohexane dicarboxylic acid, the alicyclic dicarboxylic acids such as naphthalane dicarboxylic acids, terephthalic acid (TPA), M-phthalic acid, phthalic acid, 1, 4-naphthalenedicarboxylic acid, 1, 5-naphthalenedicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, 1, 8-naphthalenedicarboxylic acid, 4, 4 '-diphenyldicarboxylic acid, 4, 4 '-diphenyl ether dicarboxylic acids, 5-sodium sulfo isophthalate sodium, phenyl indane dicarboxylic acid, anthracene dicarboxylic acids, luxuriant and rich with fragrance dicarboxylic acids, 9, the dicarboxylic acids such as aromatic dicarboxylic acid or its ester derivants such as 9 '-bis-(4-carboxyl phenyl) fluorenic acid.
As (B) diol component, can list: such as, ethylene glycol, 1,2-PD, 1, ammediol, 1, ester ring type glycols, the bisphenol-As, 1 such as the aliphatic diol classes such as 4-butanediol, 1,2-butanediol, 1,3-BDO, cyclohexanedimethanol, spiral shell glycol, isobide, 3-benzene dimethanol, Isosorbide-5-Nitrae-benzene dimethanol, 9, the diol compounds such as aromatic diol class such as 9 '-bis-(4-hydroxy phenyl) fluorenes.
As (A) dicarboxylic acid component, be preferably the situation of at least one used in aromatic dicarboxylic acid.More preferably aromatic dicarboxylic acid is contained in dicarboxylic acid component as main component.Also can containing the dicarboxylic acid component beyond aromatic dicarboxylic acid.As such dicarboxylic acid component, it is the ester derivant etc. of aromatic dicarboxylic acid etc.
It should be noted that, " main component " refers to that the ratio in dicarboxylic acid component shared by aromatic dicarboxylic acid is more than 80 quality %.
In addition, as (B) diol component, be preferably the situation of at least one used in aliphatic diol.As aliphatic diol, can ethylene glycol be contained, preferably contain ethylene glycol as main component.
It should be noted that, main component refers to that the ratio in diol component shared by ethylene glycol is more than 80 quality %.
The use amount of diol component (such as ethylene glycol), relative to 1 mole of dicarboxylic acid component's (particularly aromatic dicarboxylic acid (such as terephthalic acid (TPA))) and its ester derivant as required, be preferably the scope of 1.015 ~ 1.50 moles.This use amount is more preferably the scope of 1.02 ~ 1.30 moles, more preferably the scope of 1.025 ~ 1.10 moles.Time in the scope of this use amount more than 1.015 moles, esterification is carried out well, during scope below 1.50 moles, the pair of the diethylene glycol suppressing the dimerization of such as ethylene glycol to cause generates, thus can keep the multifrequency natures such as fusing point, glass transition temperature, crystallinity, heat resistance, hydrolytic resistance, weatherability well.
The total (a+b) that polyester feed stock resin in the present invention preferably comprises the number (a) of carboxylic acid group and the number (b) of hydroxyl is that the polyfunctional monomer of more than 3 is as copolymer composition (3 officials can constituent) above." comprise polyfunctional monomer as copolymer composition (3 officials can constituent) above " and refer to the Component units comprised from polyfunctional monomer.
As the Component units from the number (a) of carboxylic acid group and the total (a+b) of the number (b) of hydroxyl being the polyfunctional monomer of more than 3, the Component units from carboxylic acid shown below can be listed.
Number (a) as carboxylic acid group is the example of the carboxylic acid (polyfunctional monomer) of more than 3, as the aromatic carboxylic acid of 3 officials' energy, can list such as: trimesic acid, trimellitic acid, PMA, naphthalene tricarboxylic acids, anthracene tricarboxylic acids etc., as the aliphatic carboxylic acid of 3 officials' energy, can list such as: methane tricarboxylic acids, ethane tricarboxylic acids, tricarballylic acid, butane tricarboxylic acid etc., as the aromatic carboxylic acid of 4 officials' energy, can list such as: benzene tertacarbonic acid, benzophenone tetrabasic carboxylic acid, naphthalene tetracarboxylic acid, anthracene tetrabasic carboxylic acid, perylene tetracarboxylic acids etc., as the aliphatic carboxylic acid of 4 officials' energy, can list such as: ethane tetrabasic carboxylic acid, ethylidene tetrabasic carboxylic acid, BTCA, pentamethylene tetrabasic carboxylic acid, cyclopentanetetracarboxylic, adamantane tetrabasic carboxylic acids etc., can above aromatic carboxylic acid as 5 officials, can list such as: benzene pentacarbonic acid, benzene hexacarboxylic acid, naphthalene pentacarboxylic acid, naphthalene hexacarboxylic acid, naphthalene seven carboxylic acid, naphthalene eight carboxylic acid, anthracene pentacarboxylic acid, anthracene hexacarboxylic acid, anthracene seven carboxylic acid, anthracene eight carboxylic acids etc., can above aliphatic carboxylic acid as 5 officials, can list such as: ethane pentacarboxylic acid, ethane seven carboxylic acid, butane pentacarboxylic acid, butane seven carboxylic acid, pentamethylene pentacarboxylic acid, cyclohexane pentacarboxylic acid, cyclohexane hexacarboxylic acid, adamantane pentacarboxylic acid, adamantane hexacarboxylic acid etc.
In the present invention, their ester derivant or acid anhydrides etc. can be enumerated as an example, but be not limited to these.
In addition, the hydroxyl acids such as carboxyl terminal addition 1-lactide, d-lactide, hydroxybenzoic acid of above-mentioned carboxylic acid and derivative, the multiple compounds linked of this hydroxyl acids etc. are also preferably used in and the compound obtained.
These can be used alone one, also can as required and with multiple.
It is the example of the polyfunctional monomer of more than 3 as hydroxyl value (b), as the aromatic compound of 3 officials' energy, can list such as: trihydroxy benzene, trihydroxynaphthalene, trihydroxy anthracene, trihydroxy chalcone, trihydroxyflavone, trihydroxy cumarin, as the aliphatic alcohol of 3 officials' energy, can list such as: glycerine, trimethylolpropane, propane triol, as the aliphatic alcohol of 4 officials' energy, can list such as: pentaerythrite etc.In addition, the C-terminal addition glycols of above-claimed cpd is also preferably used in and the compound obtained.
These can be used alone one, also can as required and with multiple.
In addition, as other polyfunctional monomers other than the above, also can list: there is in a part both hydroxyl and carboxylic acid group and the total (a+b) of the number (b) of the number (a) of carboxylic acid group and hydroxyl be more than 3 hydroxyl acids.As the example of such hydroxyl acids, can list: Hydroxy M Phthalic Acid, hydroxyterephthalic acid, dihydric para-phthalic acid, trihydroxy terephthalic acid (TPA) etc.
In addition, the hydroxyl acids such as carboxyl terminal addition 1-lactide, d-lactide, hydroxybenzoic acid of these polyfunctional monomers and derivative, the multiple compounds linked of this hydroxyl acids etc. are also preferably used in and the compound obtained.
These can be used alone one, also can as required and with multiple.
In polyester feed stock resin in the present invention, from the Component units of polyfunctional monomer in polyester feed stock resin containing ratio, relative to whole Component units of the polyester in polyester feed stock resin, be preferably more than 0.005 % by mole and less than 2.5 % by mole.The ratio that contains from the Component units of polyfunctional monomer is more preferably more than 0.020 % by mole and less than 1 % by mole, more preferably more than 0.025 % by mole and less than 1 % by mole, more preferably more than 0.035 % by mole and less than 0.5 % by mole, be particularly preferably more than 0.05 % by mole and less than 0.5 % by mole, most preferably be more than 0.1 % by mole and less than 0.25 % by mole.
Can the Component units of above polyfunctional monomer from 3 officials by existing in polyester feed stock resin, as mentioned above, when finally making polyester film be shaped, hydrogen bond, covalent bond is not formed by the composition be coated with in the coating layer of formation in the functional group that uses and polyester film in polycondensation, thus, keep the adhesiveness of coating layer and polyester film more well, thus effectively can prevent the generation of stripping.In addition, the Component units of above polyfunctional monomer can obtain the structure making polyester molecule chain component by from 3 officials, thus the complexing between polyester molecule can be promoted.
Known catalysts all the time can be used in esterification and/or ester exchange reaction.As this catalysts, can list: 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 any stage before the manufacture method of polyester completes, preferably add antimonial, germanium compound, titanium compound as polymerization catalyst.As such method, such as, time for germanium compound, preferably directly add germanium compound powder.
Such as, aromatic dicarboxylic acid is polymerized under the catalyst containing titanium compound exists with aliphatic diol by esterification operation.In this esterification operation, arrange following process to form, that is: as the titanium compound of catalyst, while using organic chelated titanium complex using organic acid as part, in operation, add organic Ti chelator complex compound, magnesium compound at least successively and not there are 5 valency phosphates of aromatic rings alternatively base.
First, at first before interpolation magnesium compound and phosphorus compound, using aromatic dicarboxylic acid and aliphatic diol and the catalyst mix contained as the organic chelated titanium complex of titanium compound.The titanium compounds such as organic chelated titanium complex have high catalyst activity for esterification, therefore, it is possible to make esterification carry out well.Now, titanium compound can be added in mixed dicarboxylic acid composition and diol component, also can mixed dicarboxylic acid composition (or diol component) with mix diol component (or dicarboxylic acid component) after titanium compound.In addition, also dicarboxylic acid component can be mixed with titanium compound with diol component simultaneously.Mixing is not particularly limited its method, can be undertaken by known method.
Preferred polyester is PETG (PET), poly-NDA glycol ester (PEN), more preferably PET.In addition, PET preferably uses one kind or two or more polymerization theing be selected from germanium (Ge) series catalysts, antimony (Sb) series catalysts, aluminium (A1) series catalysts and titanium (Ti) series catalysts, is more preferably Ti series catalysts.
The reactivity of Ti series catalysts is high, can reduce polymerization temperature.Therefore, particularly polyester generation thermal decomposition in the polymerization, can suppress to produce COOH.That is, by using Ti series catalysts, the amount of the terminal carboxylic of the polyester as thermal decomposition reason can be reduced, thus foreign matter can be suppressed to be formed.By reducing the amount of the terminal carboxylic of polyester, after manufacture polyester film, also can suppress polyester film generation thermal decomposition.
As Ti series catalysts, can list: oxide, hydroxide, alkoxide, carboxylate, carbonate, oxalates, organic chelated titanium complex and halide etc.As long as Ti series catalysts is in the scope not damaging effect of the present invention, then can be used together the titanium compound of more than two kinds.
As the example of Ti series catalysts, can list: metatitanic acid four n-propyl, tetraisopropyl titanate, tetra-n-butyl titanate, tetra-n-butyl titanate tetramer, metatitanic acid four tert-butyl ester, metatitanic acid four cyclohexyl, metatitanic acid tetraphenyl ester, the Titanium alkoxides such as metatitanic acid tetrabenzyl ester, the titanium oxide obtained by the hydrolysis of Titanium alkoxides, by the hydrolysis of the mixture of Titanium alkoxides and silicon alkoxide or zirconium alkoxide and the titanium-silicon obtained or zirconium mixed oxide, acetic acid titanium, titanium oxalate, titanium potassium oxalate, titanium oxalate sodium, potassium titanate, sodium titanate, metatitanic acid-alumag, titanium chloride, titanium chloride-aluminum chloride mixture, titanium acetylacetone, using organic acid as the organic chelated titanium complex etc. of part.
When making polyester, preferably counting more than 1ppm with titanium elements scaled value and below 50ppm, being more preferably more than 2ppm and below 30ppm, more preferably more than 3ppm and be used as titanium (Ti) compound of catalyst in the scope of below 15ppm, be polymerized.In this situation, in polyester feed stock resin, contain more than 1ppm and the titanium elements of below 50ppm.
When the amount of the titanium elements comprised in polyester feed stock resin is more than 1ppm, the weight average molecular weight (Mw) of polyester improves, and is difficult to thermal decomposition occurs.Therefore, in extruder, foreign matter reduces.When the titanium of the titanium elements comprised in polyester feed stock resin is below 50ppm, Ti series catalysts is difficult to form foreign matter, and stretch when the stretching of polyester film uneven minimizing.
[titanium compound]
As the titanium compound of catalyst component, preferably use at least one in the organic chelated titanium complex using organic acid as part.As organic acid, can list such as: citric acid, lactic acid, trimellitic acid, malic acid etc.Wherein, be preferably using citric acid or citrate as the organic chelated complex compound of part.
When using Ti chelator complex compound such as using citric acid as part, the generation of the foreign matters such as minuteness particle is few, compared with other titanium compounds, obtains polymerization activity and the good polyester of tone.In addition, when using citric acid Ti chelator complex compound, by the method for adding in the stage of esterification, compared with the situation of adding after esterification, obtain polymerization activity and tone is good, terminal carboxyl group is few polyester.In this, be presumed as follows: titanium catalyst also has the catalyst effect of esterification, by adding in Esterification Stage, oligomer acid number at the end of esterification reduces, the polycondensation reaction after more effectively carrying out, in addition, using citric acid as the complex compound of part compared with Titanium alkoxides etc., hydrolysis patience is high, and not hydrolysis in esterification reaction process, the catalyst as esterification and polycondensation reaction under the state that maintenance is originally active plays a role effectively.
In addition, the more hydrolytic resistances of usual known terminal carboxyl group amount are poorer, and by above-mentioned adding method, terminal carboxyl group quantitative change is few, thus, expect the raising of hydrolytic resistance.
As citric acid Ti chelator complex compound, easily can obtain as commercially available products such as the VERTECAC-420 of such as JohnsonMatthey Inc..
It by preparing the slurry comprising these, can supply to esterification operation and importing by aromatic dicarboxylic acid and aliphatic diol continuously.
In addition, as titanium compound, except organic chelated titanium complex, usually can also list oxide, hydroxide, alkoxide, carboxylate, carbonate, oxalates and halide etc.As long as in the scope not damaging effect of the present invention, then except organic chelated titanium complex can also and use other titanium compounds.
As the example of such titanium compound, can list: metatitanic acid four n-propyl, tetraisopropyl titanate, tetra-n-butyl titanate, tetra-n-butyl titanate tetramer, metatitanic acid four tert-butyl ester, metatitanic acid four cyclohexyl, metatitanic acid tetraphenyl ester, the Titanium alkoxides such as metatitanic acid tetrabenzyl ester, the titanium oxide obtained by the hydrolysis of Titanium alkoxides, by the hydrolysis of the mixture of Titanium alkoxides and silicon alkoxide or zirconium alkoxide and the titanium-silicon obtained or zirconium mixed oxide, acetic acid titanium, titanium oxalate, titanium potassium oxalate, titanium oxalate sodium, potassium titanate, sodium titanate, metatitanic acid-alumag, titanium chloride, titanium chloride-aluminum chloride mixture, titanium acetylacetone etc.
In the present invention, the manufacture method of the polyester formed preferably by arranging following operation makes, described operation is: esterification operation, while aromatic dicarboxylic acid and aliphatic diol are carried out being polymerized under the existence of the catalyst containing titanium compound, the at least one of titanium compound is the organic chelated titanium complex using organic acid as part, at least comprises the process of adding organic Ti chelator complex compound, magnesium compound successively and not having aromatic rings alternatively 5 valency phosphates of base; And polycondensation step, make the esterification reaction product generation polycondensation reaction that generated by esterification operation and generate condensation polymer.
In this situation, in the process of esterification, be set as following order of addition: when the organic chelated titanium complex as titanium compound is existed, add magnesium compound, then, add specific 5 valency phosphorus compounds, thus, appropriateness keeps the reactivity of titanium catalyst higher, while giving the electrostatic applying characteristic of magnesium generation, and effectively can suppress the decomposition reaction in polycondensation, therefore, as a result, obtain painted less, there is the polyester that high electrostatic applies to improve while characteristic xanthochromia when being exposed under high temperature.
Thus, when being polymerized painted with and subsequent melting masking time paintedly to tail off, compared with the polyester of antimony (Sb) catalyst system in the past, yellow sense alleviates, in addition, the polyester with tone, the transparency and excellent heat resistance not a halfpenny the worse compared with the polyester of the germanium catalyst system higher with the transparency can be provided.In addition, do not used cobalt compound and pigment isochrome key material-saving material and be there is high transparent, polyester that yellow sense is few.
This polyester can be used in the purposes (such as optical film, industrial lithograph etc.) high to the requirement of the transparency, without the need to using the germanium series catalysts of high price, therefore, realizing significantly cost and reducing.In addition, also avoid being mixed into of the foreign matter of the catalyst cause easily produced by Sb catalyst system, thus, the generation and the quality that reduce fault in film-forming process are bad, also can realize yield and improve the cost degradation caused.
When carrying out esterification, the process of the organic chelated titanium complex as titanium compound, the magnesium compound as additive and 5 valency phosphorus compounds is added in preferred setting successively.Now, esterification can be carried out under the existence of organic chelated titanium complex, thereafter, before the interpolation of phosphorus compound, start the interpolation of magnesium compound.
[phosphorus compound]
As 5 valency phosphorus compounds, use at least one without aromatic rings alternatively 5 valency phosphates of base.Can list such as: the phosphate [(OR) of the alternatively base of the low alkyl group with carbon number less than 2 3-P=O; The alkyl of R=carbon number 1 or 2], specifically, be particularly preferably trimethyl phosphate, triethyl phosphate.
As the addition of phosphorus compound, be preferably P element scaled value and reach more than 50ppm and the amount of the scope of below 90ppm.The amount of phosphorus compound is more preferably and reaches more than 60ppm and the amount of below 80ppm, more preferably reaches more than 60ppm and the amount of below 75ppm.
[magnesium compound]
By comprising magnesium compound in the polyester, the electrostatic imposing of polyester improves.In this situation, easily cause painted, but in the present invention, suppress painted, obtain excellent tone, heat resistance.
As magnesium compound, can list such as: the magnesium salts such as magnesia, magnesium hydroxide, magnane oxide, magnesium acetate, magnesium carbonate.Wherein, from the deliquescent viewpoint in ethylene glycol, magnesium acetate most preferably is.
As the addition of magnesium compound, in order to give high electrostatic imposing, being preferably the amount that Mg element scaled value reaches more than 50ppm, being more preferably and reaching more than 50ppm and the amount of the scope of below 100ppm.The addition of magnesium compound, in imparting electrostatic imposing, preferably reaches more than 60ppm and the amount of the scope of below 90ppm, more preferably reaches more than 70ppm and the amount of the scope of below 80ppm.
In esterification operation, the mode particularly preferably meeting following relational expression (ii) using the value Z calculated by following formula (i) adds the situation that the titanium compound as catalyst component and the magnesium compound as additive and phosphorus compound make its melt polymerization.At this, P content is the phosphorus amount from the phosphorus compound entirety containing the 5 valency phosphates without aromatic rings, and Ti content is the titanium amount from the Ti compound entirety containing organic chelated titanium complex.By select containing such titanium compound catalyst system in magnesium compound and phosphorus compound and use, control it and add moment and adding proportion, appropriate can maintain the catalyst activity of titanium compound higher, and obtain the tone that yellow sense is few, during masking when polymerisation and thereafter (during melting) etc., though can give be exposed to high temperature under be also difficult to produce yellow painted heat resistance.
(i) Z=5 × (P content [ppm]/P atomic weight)-2 × (Mg content [ppm]/Mg atomic weight)-4 × (Ti content [ppm]/Ti atomic weight)
(ii)0≤Z≤+5.0
Phosphorus compound not only acts on titanium but also interacts with magnesium compound, and therefore, it becomes the index representing three's balance quantitatively.
Formula (i) is the phosphorus part that removing acts on magnesium from the whole phosphorus amounts that can react, and shows the amount of the phosphorus that can act on titanium.When value Z is positive, hinder the phosphorus of titanium to be in residual state, on the contrary, when negative, for hindering titanium, necessary phosphorus is in not enough situation.In the reaction, each atom of Ti, Mg, P 1 non-equivalence, therefore, each molal quantity in formula is multiplied by valence mumber and is weighted.
In the present invention, do not need special synthesis etc., use cheapness and titanium compound, phosphorus compound, the magnesium compound that can easily obtain, can obtain while having the reactivity that reaction is necessary, tone and for the excellent polyester feed stock resin of the painted patience of heat.
In formula (ii), under the state keeping polymerisation reactivity, from the view point of improving tone and the painted patience for heat further, preferably meeting the situation of+1.0≤Z≤+ 4.0, more preferably meeting the situation of+1.5≤Z≤+ 3.0.
As the preferred embodiment in the present invention, can list as under type: before esterification terminates, add in aromatic dicarboxylic acid and aliphatic diol count more than 1ppm with Ti element scaled value and below 30ppm using citric acid or citrate after the Ti chelator complex compound of part, under the existence of this Ti chelator complex compound, add and count more than 60ppm and the magnesium salts of the weak acid of below 90ppm (being more preferably more than 70ppm and below 80ppm) with Mg element scaled value, this interpolation is added further afterwards and is counted more than 60ppm with P element scaled value and below 80ppm (being more preferably more than 65ppm and below 75ppm), not there are 5 valency phosphates of aromatic rings alternatively base.
In above-mentioned, about Ti chelator complex compound (organic chelated titanium complex), magnesium salts (magnesium compound) and 5 valency phosphates, preferably add the mode of more than the 70 quality % of whole addition respectively successively.
Esterification can use the multisection type device being connected in series with at least 2 reactors, under the condition of ethylene glycol backflow, implements while the water generated or alcohol being removed outside system by reaction.
In addition, above-mentioned esterification can be undertaken by a stage, also can be divided into multiple stage to carry out.
When carrying out esterification by a stage, esterification reaction temperature is preferably 230 ~ 260 DEG C, is more preferably 240 ~ 250 DEG C.
When dividing multiple stage to carry out esterification, the temperature of the esterification of the first reactive tank is preferably 230 ~ 260 DEG C, and be more preferably 240 ~ 250 DEG C, pressure is preferably 1.0 ~ 5.0kg/cm 2, be more preferably 2.0 ~ 3.0kg/cm 2.The temperature of the esterification of the second reactive tank is preferably 230 ~ 260 DEG C, and be more preferably 245 ~ 255 DEG C, pressure is preferably 0.5 ~ 5.0kg/cm 2, be more preferably 1.0 ~ 3.0kg/cm 2.In addition, when implementing more than point 3 stages, the condition of the esterification in interstage is preferably set to the condition between the first reactive tank and end reaction groove.
-polycondensation-
Polycondensation makes the esterification reaction product generation polycondensation reaction generated by esterification generate condensation polymer.Polycondensation reaction can be undertaken by a stage, also can be divided into multiple stage to carry out.
The esterification reaction products such as the oligomer generated by esterification, then for polycondensation reaction.This polycondensation reaction suitably can be carried out by the polycondensation reaction groove supply to multiple stage.
Such as, polycondensation reaction condition when carrying out in the reactive tank in 3 stages is preferably following method: the reaction temperature of the first reactive tank is 255 ~ 280 DEG C, is more preferably 265 ~ 275 DEG C, and pressure is 100 ~ 10torr (13.3 × 10 -3~ 1.3 × 10 -3mPa), 50 ~ 20torr (6.67 × 10 is more preferably -3~ 2.67 × 10 -3mPa), the reaction temperature of the second reactive tank is 265 ~ 285 DEG C, is more preferably 270 ~ 280 DEG C, and pressure is 20 ~ 1torr (2.67 × 10 -3~ 1.33 × 10 -4mPa), 10 ~ 3torr (1.33 × 10 is more preferably -3~ 4.0 × 10 -4mPa), the reaction temperature of the 3rd reactive tank in end reaction groove is 270 ~ 290 DEG C, and be more preferably 275 ~ 285 DEG C, pressure is 10 ~ 0.1torr (1.33 × 10 -3~ 1.33 × 10 -5mPa), 5 ~ 0.5torr (6.67 × 10 is more preferably -4~ 6.67 × 10 -5mPa).
In the polyester feed stock resin of as mentioned above synthesis can further containing Photostabilised dose, antioxidant, ultra-violet absorber, the additive such as fire retardant, easily lubrication prescription (particulate), nucleator (crystallization agent), crystallization inhibition agent.
In the present invention, from the view point of the hydrolytic resistance of polyester film, the inherent viscosity (IV) of polyester feed stock resin is preferably more than 0.55dL/g and below 0.90dL/g.Wherein, be more preferably more than 0.60dL/g and below 0.80dL/g, more preferably more than 0.62dL/g and below 0.78dL/g, most preferably be more than 0.63dL/g and below 0.78dL/g.
Inherent viscosity (IV) is by solution viscosity (η) and solvent viscosity (η 0) ratio η r(=η/η 0; Relative viscosity) deduct the specific viscosity (η after 1 sp=η r-1) value obtained divided by concentration is extrapolated to the value that concentration is the state of zero.IV uses Ubbelodhe type viscosimeter, polyester is dissolved in 1,1,2,2-tetrachloroethanes/phenol (=2/3 [mass ratio]) mixed solvent, is tried to achieve by the solution viscosity of 25 DEG C.
(melt extruding)
In film forming process in the present invention, the polyester feed stock resin obtained as mentioned above is melt extruded, then cools, polyester film is shaped.
With regard to the melt extruding of polyester feed stock resin, use the extruder such as possessing more than 1 or 2 screw rod, be heated to the temperature of more than the fusing point of polyester feed stock resin, carry out while making screw rod rotate melting mixing.Polyester feed stock resin is by heating and utilizing the mixing of screw rod in extruder, melting occur and form melt.In addition, from the view point of the thermal decomposition suppressed in extruder (poly-ester hydrolysis), preferably by nitrogen displacement in extruder, melt extruding of polyester feed stock resin is carried out.Extruder is preferably double screw extruder from suppressing the viewpoint of melting temperature lower.
Polyester feed stock resin (melt) after melting is extruded from extrusion die by gear pump, filter etc.Extrusion die is also simply called " die head " [with reference to JISB8650:2006, a) extrusion shaper, numbering 134].
Now, melt can be extruded with individual layer, also can with multilayer extrusion.
In polyester feed stock resin, preferably comprise the end-capping reagent of Xuan Zi oxazoline based compound, carbodiimide compound and epoxide.In this situation, in film forming process, the polyester feed stock resin that with the addition of end-capping reagent is carried out melting mixing, by during melting mixing and the polyester feed stock resin that reacts of end-capping reagent melt extrude.
By being arranged in polyester feed stock resin the operation comprising end-capping reagent, not only weatherability improves, and can suppress thermal contraction lower.In addition, when making polyester film be shaped, due to bonding on polyester end, the end section volume of strand increases, and the micro concavo-convex amount on film surface increases, therefore, easily demonstrate anchoring effect, polyester film improves with the adhesion of the coating layer being coated with formation on this film.
As long as interpolation period of end-capping reagent is being fed into the stage of carrying out melting mixing in the process extruded together with polyester feed stock resin from raw material, then be not particularly limited, but preferably end-capping reagent is until add during delivering to blow vent with screw rod after raw material is dropped into rotating cylinder, is used from melting mixing with material resin one.Such as, the supply port supplying end-capping reagent is set between the material pouring inlet of rotating cylinder carrying out melting mixing and blow vent, thus can directly joins in the material resin in rotating cylinder.Now, end-capping reagent can join and starts to add hot milling but do not reach completely in the polyester feed stock resin of molten condition, also can join in the polyester feed stock resin (melt) of molten condition.
As the amount of end-capping reagent relative to polyester feed stock resin, relative to the gross mass of polyester feed stock resin, be preferably more than 0.1 quality % and below 5 quality %.End-capping reagent is more than 0.3 quality % and below 4 quality % relative to the preferred amounts of polyester feed stock resin, more preferably more than 0.5 quality % and below 2 quality %.
Is more than 0.1 quality % by end-capping reagent containing ratio, and the weatherability that can realize being caused by AV reduction effect improves, and can give low thermal shrinkage behavior and adhesiveness.In addition, end-capping reagent containing ratio be below 5 quality % time, except adhesiveness raising, also suppress the glass transition temperature (Tg) adding the polyester that end-capping reagent causes to reduce, thus the weatherability caused thus can be suppressed to reduce and thermal contraction increase.This is because, Tg reduces, relatively suppress to be increased and the water-disintegrable increase of generation by the reactivity of polyester, or the thermal contraction suppressing the motility of the polyester molecule increased by being reduced by Tg easily to increase and produce.
As the end-capping reagent in the present invention, preferably there is the compound of carbodiimide, epoxy radicals, Huo oxazolinyl.As the concrete example of end-capping reagent, carbodiimide compound, epoxide, oxazoline based compound etc. suitably can be listed.
About carbodiimide compound, epoxide Yi Ji the details of illustration and preferred embodiment etc. of oxazoline based compound is as described in the item of " polyester film ".
Extrude by being roused from die head to curtain coating by melt (polyester), can be shaped (casting process) is for membranaceous.
The thickness of the membranaceous polyester formed body obtained by casting process is preferably 0.1mm ~ 5mm, is more preferably 0.2mm ~ 4.7mm, more preferably 0.3mm ~ 4.6mm.
Be below 5mm by making the thickness of membranaceous polyester formed body, the cooling caused by the accumulation of heat of melt is avoided to postpone, in addition, by for more than 0.1mm, from the OH base be extruded between cooling in polyester and COOH basal orientation polyester diffusion inside, OH base and COOH base as producing the main cause be hydrolyzed is suppressed to expose in surface of polyester.
The method of the melt cooling extruded from extrusion die is not particularly limited, can blows a cold wind over to melt, or contact with curtain coating drum (cooling curtain coating drum), spray water.Cooling means only can carry out a kind, also can combine and carry out two or more.
About cooling means, in above-mentioned, from the view point of oligomer when preventing from operating continuously to film surface attachment, preferably utilize the cooling of cold wind and use at least one in the cooling of curtain coating drum.In addition, while the melt cold front heavy rain will extruded from extruder, melt is contacted with curtain coating drum and cools.
In addition, the polyester formed body of the coolings such as curtain coating drum is used to use the peeling members such as stripper roll to wait cooling component to peel off from curtain coating drum.
[longitudinal stretching operation]
In longitudinal stretching operation of the present invention, the polyester film longitudinal stretching along its length after the shaping of film forming process will be passed through.
The longitudinal stretching of film can carry out as follows, such as, make film pass through to clamp 1 pair of niproll of film, along film length direction conveyance film while, between the niproll that 2 couple arranged along the conveyance direction of film is above, apply tension force.Specifically, such as, 1 couple of niproll A is set in the side, conveyance direction upstream of film, when 1 couple of niproll B is set in side, downstream, during conveyance film, by making the rotary speed of the niproll B of side, downstream faster than the rotary speed of the niproll A of upstream side, film stretches along conveyance direction (MD direction).It should be noted that, can in side, upstream, side, downstream separately arranges 2 to above niproll.In addition, the longitudinal stretching of polyester film can use the longitudinal tensile fixture possessing above-mentioned niproll to carry out.
In longitudinal stretching operation, the longitudinal stretching multiplying power of polyester film is preferably 2 ~ 5 times, is more preferably 2.5 ~ 4.5 times, more preferably 2.8 ~ 4 times.
In addition, be preferably 6 times ~ 18 times of the area of the polyester film before stretching by the area stretch multiplying power of stretching ratio product representation in length and breadth, be more preferably 8 times ~ 17.5 times, more preferably 10 times ~ 17 times.
The temperature during longitudinal stretching of polyester film is (following, also referred to as " longitudinal drawing temperature "), when the glass transition temperature of polyester film is set to Tg, be preferably more than Tg-20 DEG C and less than Tg+50 DEG C, be more preferably more than Tg-10 DEG C and less than Tg+40 DEG C, more preferably more than Tg DEG C and less than Tg+30 DEG C.
It should be noted that, as the method for heating polyester film, when using the roller such as niproll to carry out stretching, by arranging the pipe arrangement that heater and hot solvent can flow in roller inside, the polyester film contacted with roller can be heated.In addition, when not using roller, also can by polyester film blowing hot-air or to contact with thermals source such as heaters or by heating polyester film near thermal source.
In the manufacture method of polyester film of the present invention, except longitudinal stretching operation, also comprise cross directional stretch operation described later.Therefore, in the manufacture method of polyester film of the present invention, make polyester film carry out at least biaxial stretch-formed along the length direction (conveyance direction, MD) of polyester film and the direction vertical with the length direction of polyester film (TD direction).Stretching to MD direction and TD direction can be carried out at least 1 time respectively.
It should be noted that, " direction (TD) vertical with the length direction (conveyance direction, MD) of polyester film " refers to the direction forming vertical (90 °) with the length direction of polyester film (conveyance direction, MD), but also comprises the direction (being such as the direction of 90 ° ± 5 ° relative to MD direction) being considered as in fact 90 ° relative to the angle of length direction (i.e. conveyance direction) due to machine error etc.
As carrying out biaxial stretch-formed method, can for longitudinal stretching and cross directional stretch are carried out respectively successively biaxial stretching method, carry out longitudinal stretching and cross directional stretch simultaneously while any one in biaxial stretching method.Longitudinal stretching and cross directional stretch separately can carry out more than 2 times, and the order of longitudinal stretching and cross directional stretch has nothing to do.Can list such as: longitudinal stretching → cross directional stretch, longitudinal stretching → cross directional stretch → longitudinal stretching, longitudinal stretching → stretching mode such as longitudinal stretching → cross directional stretch, cross directional stretch → longitudinal stretching.Wherein, longitudinal stretching → cross directional stretch is preferably.
[cross directional stretch operation]
Then, the cross directional stretch operation in the present invention is described in detail.
Cross directional stretch operation in the present invention be by longitudinal stretching after polyester film along the operation of the width cross directional stretch vertical with length direction, carry out this cross directional stretch as follows,
Polyester film is transported to following portion successively:
(a) polyester film after longitudinal stretching is preheated to the temperature that can stretch preheating part,
(b) by the polyester film after preheating along the width vertical with length direction apply tension force carry out cross directional stretch extension section,
(c) heating carry out longitudinal stretching and cross directional stretch after polyester film make its crystallization to carry out thermal finalization thermal finalization portion,
Polyester film after the sizing of (d) heat hot, the tension force of lax polyester film except the residual strain of striping hot wire-CVD portion and
E cooling end that polyester film after hot wire-CVD cools by (),
In at least one in (c) thermal finalization portion and (d) hot wire-CVD portion, selective radiation heating is carried out by heater in the end, TD direction of polyester film, makes the beeline on the surface of heater and the surface of polyester film be more than 10mm and below 300mm.
In cross directional stretch operation in the present invention, as long as carried out the mode of cross directional stretch by above-mentioned formation polyester film, then its concrete method does not limit, but preferably uses the transversal stretching device that can implement the process of each operation forming above-mentioned formation or biaxial stretcher to carry out.
-biaxial stretcher-
As shown in Figure 3, biaxial stretcher 100 possesses 1 couple of ring-shaped guide rail 60a and 60b and to install on each ring-shaped guide rail and can holding component 2a ~ 21 of movement along guide rail.Ring-shaped guide rail 60a and 60b clamps polyester film 200 and to be mutually symmetrical configuration, by holding component 2a ~ 21 gripping polyester film 200, moves, can stretch thus along film width along guide rail.
Fig. 3 is the top view of the example that biaxial stretcher is shown from upper surface.
Biaxial stretcher 100 is made up of the region comprised as lower part, that is: preheating polyester film 200 preheating part 10, polyester film 200 stretched along the direction vertical with arrow MD direction and arrow TD direction the extension section 20 of tension force is applied to polyester film, the thermal finalization portion 30 that the polyester film after applying tension force is heated under the state applying tension force, heat hot shape after polyester film and the hot wire-CVD portion 40 of the tension force of polyester film after relaxation heat setting and cooling end 50 that the polyester film through hot wire-CVD portion is cooled.
Ring-shaped guide rail 60a installs can holding component 2a, 2b, 2e, 2f, 2i and 2j of movement along ring-shaped guide rail 60a, and in addition, ring-shaped guide rail 60b installs can holding component 2c, 2d, 2g, 2h, 2k and 21 of movement along ring-shaped guide rail 60b.Hold the end that component 2a, 2b, 2e, 2f, 2i and 2j hold the TD direction of polyester film 200, hold another end that component 2c, 2d, 2g, 2h, 2k and 21 holds the TD direction of polyester film 200.Hold component 2a ~ 21 and be commonly referred to fixture, clip etc.
Hold component 2a, 2b, 2e, 2f, 2i and 2j and be rotated counterclockwise movement along ring-shaped guide rail 60a, hold component 2c, 2d, 2g, 2h, 2k and 21 and to turn clockwise movement along ring-shaped guide rail 60b.
Hold the end that component 2a ~ 2d holds polyester film 200 in preheating part 10, move along ring-shaped guide rail 60a or 60b under the state gripped, the hot wire-CVD portion 40 at stretched portion 20 and holding component 2e ~ 2h place, until hold the cooling end 50 at place, component 2i ~ 21.Then, hold component 2a and 2b and hold component 2c and 2d along conveyance direction successively after the end of polyester film 200 is left in the end of the side, downstream, MD direction of cooling end 50, move along ring-shaped guide rail 60a or 60b further, be back to preheating part 10.Now, polyester film 200 moves along arrow MD direction, carries out the thermal finalization in the preheating in preheating part 10, the stretching in extension section 20, thermal finalization portion 30, the hot wire-CVD in hot wire-CVD portion 40, the cooling in cooling end 50 successively, thus carries out cross directional stretch.The translational speed held in each regions such as the preheating part of component 2a ~ 21 is the conveyance speed of polyester film 200.
Holding component 2a ~ 21 can separately make translational speed change.
Biaxial stretcher 100 is the equipment that can carry out the cross directional stretch stretched along TD direction by polyester film 200 in extension section 20, by making the translational speed of holding component 2a ~ 21 change, also polyester film 200 can be stretched along MD direction.That is, biaxial stretch-formed the while of biaxial stretcher 100 also can being used to carry out.
The holding component holding the end in the TD direction of polyester film 200 is only illustrated as 2a ~ 21 in figure 3, but in order to supporting polyester film 200, biaxial stretcher 100 is also provided with not shown holding component except 2a ~ 21.It should be noted that, below, sometimes holding component 2a ~ 21 are generically and collectively referred to as " holding component 2 ".
(a. preheating part)
At preheating part, the polyester film after longitudinal stretching in longitudinal stretching operation is preheated to the temperature that can stretch.
As shown in Figure 3, preheating polyester film 200 in preheating part 10.In preheating part 10, heat in advance before oriented polyester film 200, thus easily can carry out the cross directional stretch of polyester film 200.
About the film surface temperature (hereinafter also referred to as " preheat temperature ") in preheating part end point, when the glass transition temperature of polyester film 200 is set to Tg, is preferably Tg-10 DEG C ~ Tg+60 DEG C, is more preferably Tg DEG C ~ Tg+50 DEG C.
It should be noted that, preheating part end point refers to the position that moment, the i.e. polyester film 200 of the preheating terminating polyester film 200 leave from the region of preheating part 10.
(b. extension section)
At extension section, the polyester film after preheating in preheating part is applied tension force to carry out cross directional stretch along the width (TD direction) vertical with length direction (MD direction).
As shown in Figure 3, in extension section 20, the polyester film 200 after preheating is at least carried out cross directional stretch along the TD direction vertical with the length direction of polyester film 200, tension force is applied to polyester film 200.
Stretching (cross directional stretch) to the vertical direction (TD) of the length direction (conveyance direction, MD) with polyester film 200 refers to along stretching with the direction of the angle of the length direction (conveyance direction, MD) vertical (90 °) of polyester film 200, but also can be the direction of the scope of machine error.The scope of machine error is the direction being considered as vertical angle (90 ° ± 5 °) with the length direction of polyester film (conveyance direction, MD).
In addition, the area stretch multiplying power (product of each stretching ratio) of polyester film 200, is preferably 6 times ~ 18 times of the area of the polyester film 200 before stretching, is more preferably 8 times ~ 17.5 times, more preferably 10 times ~ 17 times.
In addition, film surface temperature during cross directional stretch about polyester film 200 is (following, also referred to as " transverse drawing temperature "), when the glass transition temperature of polyester film 200 is set to Tg, be preferably more than Tg-10 DEG C and less than Tg+100 DEG C, be more preferably more than Tg DEG C and less than Tg+90 DEG C, more preferably more than Tg+10 DEG C and less than Tg+80 DEG C.
As mentioned above, holding component 2a ~ 21 can separately make translational speed change.Therefore, by making the translational speed ratio of the holding component 2 of the side, downstream, MD direction at extension sections 20 such as extension section 20, thermal finalization portions 30 as fast in the translational speed of the holding component 2 in preheating part 10, also can carry out the longitudinal stretching being carried out along conveyance direction (MD direction) by polyester film 200 stretching simultaneously.
The longitudinal stretching of the polyester film 200 in cross directional stretch operation can only carry out in extension section 20, also can carry out in thermal finalization portion 30 described later, hot wire-CVD portion 40 or cooling end 50.Also longitudinal stretching can be carried out at multiple position.
(c. thermal finalization portion)
In thermal finalization portion, make its crystallization to carry out thermal finalization the polyester film heating after implementing longitudinal stretching and cross directional stretch.
Thermal finalization is heated under referring to the state applying tension force at extension section 20 pairs of polyester films 200, makes crystallizing polyester.
In the thermal finalization portion 30 shown in Fig. 3, for the polyester film 200 applied after tension force, being up to of surface of preferred polyester film 200 reaches film surface temperature (in this description, also referred to as " heat setting temperature ", " T thermal finalization") control to carry out heating film in the scope of 160 DEG C ~ 240 DEG C.
When heat setting temperature is more than 160 DEG C, the easy crystallization of polyester, can be fixed, thus can improve the hydrolytic resistance of polyester film under the state stretching polyester molecule.In addition, when heat setting temperature is below 240 DEG C, between polyester molecule, the part of complexing is difficult to slide, thus polyester molecule is difficult to shrink, therefore, it is possible to suppress the reduction of the hydrolytic resistance of polyester film.In other words, the mode reaching 160 DEG C ~ 240 DEG C with heat setting temperature heats, and thus, makes the crystallization generation orientation of polyester molecule, thus can improve the hydrolytic resistance of polyester film.
Heat setting temperature, for above-mentioned same reason, is preferably the scope of 170 DEG C ~ 230 DEG C, is more preferably the scope of 175 DEG C ~ 225 DEG C.
It should be noted that, be up to and reach film surface temperature (heat setting temperature) and carry out for making the surface contact thermoelectricity of polyester film 200 value measured occasionally.
In addition, when being controlled to be 160 DEG C ~ 240 DEG C by heat setting temperature, the deviation preferably making being up on film width reach film surface temperature is more than 0.5 DEG C and less than 10.0 DEG C.In film width, be more than 0.5 DEG C by the deviation reaching film surface temperature that is up to of film, when the conveyance of operation afterwards fold in favourable, in addition, suppressing by making deviation is less than 10.0 DEG C, and the deviation of the crystallization degree on width is inhibited.Thus, the lax difference on film width reduces, and prevents the generation that the face in manufacture process damages, thus improves hydrolytic resistance.
In above-mentioned, be up to reach film surface temperature deviation for above-mentioned same reason, be more preferably more than 0.5 DEG C and less than 7.0 DEG C, more preferably more than 0.5 DEG C and less than 5.0 DEG C, be particularly preferably more than 0.5 DEG C and less than 4.0 DEG C.
In addition, to the heating of film during thermal finalization, only can carry out from the side of film, also can carry out from both sides.Such as, when cooling on curtain coating drum after melt extruding in film forming process, the mode that the polyester film after shaping cools on a face with the face of its opposition side is different, and therefore, film easily occurs curling.Therefore, preferably the heating in this heat-setting process is carried out for the face contacted with curtain coating drum in film forming process.By face, i.e. cooling surface that setting makes the heating surface in heat-setting process contact with curtain coating drum, can eliminate curling.
Now, carry out heating and preferably make the surface temperature after the firm heating of the heating surface of heat-setting process increase more than 0.5 DEG C and the scope of less than 5.0 DEG C compared with the surface temperature of the non-heated of the opposition side of heating surface.The temperature of heating surface during thermal finalization is higher than the face of its opposition side, and the temperature difference in its table inner room is 0.5 ~ 5.0 DEG C, thus, more effectively eliminates the curling of film.From the view point of curling eradicating efficacy, the temperature difference between heating surface and the non-heated of its opposition side is more preferably the scope of 0.7 ~ 3.0 DEG C, more preferably more than 0.8 DEG C and less than 2.0 DEG C.
When carrying out thermal finalization as mentioned above, the thickness of polyester film be more than 180 μm and less than 350 μm time, curling eradicating efficacy is large.When thickness is thick, if apply variations in temperature from the one-sided of film to film, then easily formation temperature distribution in the film thickness direction, easily produces curling.Such as, if make the polyester after melt extruding contact with curtain coating drum in film forming process, then from one-sided cooling, on the other hand, although the face of its opposition side contacts with such as environmental gas and there is heat release, but owing to carrying out a face and the cooling different from each other of its opposing face, therefore, easily produce temperature difference.Therefore, when the thickness of polyester film is more than 180 μm, easily produce temperature difference, therefore, expect curling eradicating efficacy, in addition, when being below 350 μm, keep well hydrolytic resistance in favourable.
In addition, in the present invention, at least one in thermal finalization portion 30 and hot wire-CVD portion 40, selective radiation heating is carried out by heater in the end, TD direction of polyester film.If do not carry out this radiation heating, MD percent thermal shrinkage then on the TD direction of made polyester film can not decline, the distribution of MD percent thermal shrinkage and the inequality of flatness can not reduce, and therefore, cannot manufacture the film meeting above-mentioned formula (1) ~ (4).
When radiation heating being carried out in the end, TD direction of film in hot wire-CVD portion 40, the radiation heating in thermal finalization portion 30 can be omitted, also can carry out both of thermal finalization portion 30 and hot wire-CVD portion 40.
The heating of the end, TD direction of polyester film uses the heater that can carry out radiation heating to carry out, and optionally heats at least one end in the TD direction of polyester film.From the view point of the MD thermal contraction suppressing local, preferably two ends in the TD direction of heating polyester film.It should be noted that, " optionally heating " is not the film entirety that heating comprises the end of polyester film, and refers to heating film end partly.
As the heater that can carry out radiation heating, such as infrared heater can be listed, preferably use the heater (ceramic heater) of particularly pottery system.
The heater that can carry out radiation heating only can use one, also can use more than two kinds.
The heating of the end, TD direction of polyester film makes polyester film surface and the beeline of heater be more than 10mm and below 300mm carries out.
When polyester film surface is less than 10mm with the beeline of heater, heater spacing easily produces temperature deviation, during more than 300mm, film is difficult to conduct radiation heat fully.
The beeline on heater surfaces and film surface is preferably more than 50mm and below 250mm, is more preferably more than 80mm and below 200mm.
Preferably except film surface and the distance of heater surfaces, the surface temperature of heater is also regulated to heat film as required.
The surface temperature of at least one of pottery heater processed is preferably more than 300 DEG C and less than 700 DEG C.Be more than 300 DEG C by surface temperature, easy conduct radiation heat fully on film, by being less than 700 DEG C, that can suppress film crosses heating.
The surface temperature of pottery heater processed is more preferably more than 400 DEG C and less than 650 DEG C, more preferably more than 450 DEG C and less than 650 DEG C.
Pottery heater processed preferably covers with cancellate crown cap.Heater, by covering with cancellate crown cap, can prevent damaged film and heater from colliding and making heater damaged.The metal forming lid is not particularly limited, and can list the stainless steels etc. such as such as SUS304.
In addition, when radiation heating, preferably the temperature deviation on film TD direction is contracted to more than 0.7 DEG C and the scope of less than 3.0 DEG C, thus, the deviation of the crystallization degree on film width can be reduced to the scope of less than more than 0.5% ~ 3.0%.Like this, lax difference in the direction of the width reduces, and suppresses the generation of damage, can improve hydrolytic resistance further simultaneously.
When heating in thermal finalization portion, the holdup time in thermal finalization portion is preferably made to be more than 5 seconds and less than 50 seconds.Holdup time is the time that the state of heating film in thermal finalization portion continues.Holdup time, when being more than 5 seconds, reduces relative to the crystallization degree change of heat time, therefore, compare be difficult to produce width crystallization degree inequality in favourable, in addition, when being below 50 seconds, without the need to making the linear velocity of stenter extremely reduce, therefore, favourable in productivity ratio.
Wherein, the holdup time, for above-mentioned same reason, is preferably more than 8 seconds and less than 40 seconds, is more preferably more than 10 seconds and less than 30 seconds.
In the present invention, at least one in thermal finalization portion and hot wire-CVD portion, radiation heating is carried out in polyester film end, in addition, also can carry out the optionally radiation heating of film end in preheating part or extension section or preheating part and extension section.
(d. hot wire-CVD portion)
In hot wire-CVD portion, the polyester film after heat hot sizing, the tension force of lax polyester film removes the residual strain of striping.
As mentioned above, in the manufacture method of polyester film of the present invention, at least one in thermal finalization portion and hot wire-CVD portion, selective radiation heating is carried out by heater in the end, TD direction of polyester film.The selective radiation heating of the end, TD direction of the polyester film in hot wire-CVD portion can be heated same method by the selective radiation of the end, TD direction with the polyester film in thermal finalization portion and be carried out, and the number range of heating-up temperature and preferred embodiment are too.
Hot wire-CVD be by thermal finalization after polyester film heating, the tension force of lax polyester film, is preferably as follows the heating of polyester film and carries out in hot wire-CVD portion.
In hot wire-CVD portion 40 shown in Fig. 3, preferably heating polyester film 200 makes being up to of the surface of polyester film 200 reach being up to of polyester film 200 that film surface temperature reaches in specific heat setting section 30 and reach film surface temperature (T thermal finalization) temperature of low more than 5 DEG C.
Below, being up to of the surface of the polyester film 200 during hot wire-CVD is reached film surface temperature also referred to as " hot wire-CVD temperature (T hot wire-CVD) ".
In hot wire-CVD portion 40, make hot wire-CVD temperature (T hot wire-CVD) be than heat setting temperature (T thermal finalization) temperature (T of low more than 5 DEG C hot wire-CVD≤ T thermal finalization-5 DEG C) carry out heating to remove tension force (tensile stress reduces), thus, the dimensional stability of polyester film can be improved further.
T hot wire-CVDfor " T thermal finalization-5 DEG C " below time, the hydrolytic resistance of polyester film is more excellent.In addition, at T hot wire-CVDdimensional stability become good aspect, be preferably more than 100 DEG C.
In addition, preferred T hot wire-CVDbe more than 100 DEG C and compare T thermal finalizationthe temperature province of low more than 15 DEG C (100 DEG C≤T hot wire-CVD≤ T thermal finalization-15 DEG C), be more preferably more than 110 DEG C and compare T thermal finalizationthe temperature province of low more than 25 DEG C (110 DEG C≤T hot wire-CVD≤ T thermal finalization-25 DEG C), be particularly preferably more than 120 DEG C and compare T thermal finalizationthe temperature province of low more than 30 DEG C (120 DEG C≤T hot wire-CVD≤ T thermal finalization-30 DEG C).
It should be noted that, T hot wire-CVDit is the value measured by making the surface contact of thermocouple and polyester film 200.
(e. cooling end)
At cooling end, by the polyester film cooling after hot wire-CVD in hot wire-CVD portion.
As shown in Figure 3, at cooling end 50, the polyester film 200 through hot wire-CVD portion 40 is cooled.By the polyester film 200 after thermal finalization portion 30 and hot wire-CVD portion 40 heat is cooled, the shape of fixing polyester film 200.
The temperature (hereinafter also referred to as " chilling temperature ") on the surface (face) of the polyester in the cooling end outlet of the polyester 200 in cooling end 50 is preferably lower than the glass transition temperature Tg+50 DEG C of polyester film 200.Specifically, be preferably 25 DEG C ~ 110 DEG C, be more preferably 25 DEG C ~ 95 DEG C, more preferably 25 DEG C ~ 80 DEG C.By chilling temperature in above-mentioned scope, can prevent unclamp clip hold caudacoria be contracted to uneven.
At this, end when cooling end outlet refers to that polyester 200 leaves from cooling end 50, cooling end 50, refers to the position when holding component 2 (in Fig. 3, holding component 2j and 21) holding polyester film 200 leaves polyester film 200.
In the manufacture method of polyester film of the present invention, polyester film is preferably made to be more than 40 DEG C and less than 140 DEG C from the surface temperature of the polyester film held when component departs from.
It refers in figure 3, and the temperature on the surface (face) of the polyester 200 of when polyester 200 is left from cooling end 50, to be positioned at cooling end 50 end is 40 DEG C ~ 140 DEG C.
In addition, about polyester film from the surface temperature of polyester film held when component departs from, preferably relative to the surface temperature of the central portion in the TD direction of polyester film make on TD direction apart from the surface temperature of polyester film of the position holding component 200mm low 1 DEG C ~ 20 DEG C.
About the film length in the MD direction of polyester film, the film length in the MD direction in the end (in Fig. 1, S1 side) of the side that MD percent thermal shrinkage is large and central portion (in Fig. 1, straight line Y1 side) in the film end preferably on TD direction, is made to compare prolongation.
Therefore, preferably make polyester film from temperature reduction by 1 DEG C ~ 20 DEG C compared with the central portion in TD direction of the end, TD direction of the film held when component departs from.
Even if polyester film in stretching device with under holding state that component holds, also easily shrink in the MD direction, from the state holding the state that departs from of component and reach release from the tensioning of tension force, therefore, tend to further contraction.Thus, the central portion of film temperature when preferably making polyester film depart from from holding component in TD direction is higher than the end in TD direction, thus, the film central portion in TD direction is optionally shunk, thus makes the film length in TD direction be less than the end in TD direction at the central portion in TD direction.
From this viewpoint, the surface temperature control of polyester film when preferably being departed from from holding component by polyester film is in the scope of 40 ~ 140 DEG C.
The surface temperature of polyester film when being departed from from holding component by polyester film is more than 40 DEG C, and the film end in TD direction is difficult to the film central authorities minister than TD direction, the C of the polyester film obtained cTeasily be greater than-0.2.On the other hand, the surface temperature of polyester film when being departed from from holding component by polyester film is less than 140 DEG C, the C of the polyester film obtained ceasily be less than 0.2.That is, the polyester of formula (7) is easily met.
Polyester film is more preferably more than 50 DEG C and less than 120 DEG C from the surface temperature of polyester film held when component departs from, more preferably more than 60 DEG C and less than 100 DEG C.
In addition, about the surface temperature of polyester film from the polyester film held when component departs from, relative to the surface temperature of the central portion of the width of polyester film, make on above-mentioned width apart from the surface temperature of polyester film holding component 200mm position low 1 DEG C ~ 20 DEG C.
In preheating in cross directional stretch operation, stretching, thermal finalization, hot wire-CVD and cooling, as heating or the temperature-controlled process cooling polyester film 200, can list: to polyester film 200 blowing hot-air or cold wind, or make polyester film 200 with can the surface contact of metallic plate of control temperature, or by near metallic plate.
(recovery of film)
The polyester film 200 cooled in refrigerating work procedure cuts the grip portion gripped with clip at two ends, TD direction, is wound into roll.
In cross directional stretch operation, in order to improve hydrolytic resistance and the dimensional stability of manufactured polyester film further, relaxing of the polyester film after stretching preferably by following method.
In the present invention, preferably after longitudinal stretching operation, carry out cross directional stretch operation, then, carry out the lax of MD direction at cooling end 50.That is,
Use at least two to hold component at preheating part 10 for an end to hold the both ends of the width of polyester film 200 (TD).Such as, hold an end of the width (TD) of polyester film 200 with holding component 2a and 2b, hold another end with holding component 2c and 2d.Then, holding component 2a ~ 2d is moved, thus, polyester film 200 is transported to cooling end 50 from preheating part 10.
In this conveyance, compared with holding the interval of component 2b (2d) with the holding component 2a (2c) of an end of the width (TD direction) of the polyester film 200 held in preheating part 10, with adjacent other of holding component 2a (2c), reduce the holding component 2a (2c) of an end of the width of the polyester film 200 held in cooling end 50, hold the interval between component 2b (2d) with adjacent other of holding component 2a (2c), thus, the conveyance speed of polyester film 200 is reduced.By the method, the lax of MD direction can be carried out at cooling end 50.
The MD direction of polyester film 200 lax can thermal finalization portion 30, hot wire-CVD portion 40 and cooling end 50 at least partially in carry out.
As mentioned above, narrow than upstream side by making the interval between holding component 2a-2b and being interposed between side, downstream, MD direction between holding between component 2c-2d, the lax of the MD direction of polyester film 200 can be carried out.Therefore, when thermal finalization portion 30 or hot wire-CVD portion 40 carry out MD direction lax, when holding component 2a ~ 2d reaches thermal finalization portion 30 or hot wire-CVD portion 40, can slow down and hold the translational speed of component 2a ~ 2d, reduce the conveyance speed of polyester film 200, make the interval between holding component 2a-2b and the interval held between component 2c-2d be narrower than interval in preheating part.
The conveyance speed of polyester film and the width (total length in the TD direction of film) of polyester film preferably meet following relation.
Namely, the width W 2 of the polyester film the end of the cooling end that the width W 1 of the polyester film when width of the polyester film in preferred cross directional stretch operation reaches maximum and polyester film leave from cooling end, meet following formula (I), and the conveyance speed Sp2 of the conveyance speed Spl of polyester film in preheating part and the polyester film in the end of cooling end meets following formula (II).
[mathematical expression 1]
2 % &le; W 1 - W 2 W 1 &times; 100 &le; 15 % - - - ( 1 )
2 % &le; S p 1 - S p 2 S p 1 &times; 100 &le; 15 % - - - ( 11 )
At this, " width W 1 of the polyester film when width of the polyester film in cross directional stretch operation reaches maximum " be polyester film after extension section is widened along TD direction, the maximum length in the TD direction of polyester film.
Illustrate in Fig. 3, with regard to the width W 0 of the polyester film 200 before the stretching in preheating part 10, widened along TD direction by extension section 20 polyester film 200 and become width W 1, discharge tension force in hot wire-CVD portion 40, polyester film 200 becomes width W 2 when cooling end 50 leaves.In Fig. 3, large with the order width of W0 < W2 < W1.That is, W1 is the Breadth Maximum of the polyester film 200 in the cross directional stretch operation of preheating part 10 ~ cooling end 50.
As shown in Figure 3, heat with the state applying tension force in thermal finalization portion 30 after the polyester film 200 behind stretched portion 20, therefore, usually, width W 1 is also referred to as the width (length in TD direction) of the polyester film 200 in thermal finalization portion 30.
In addition, " width W 2 of the polyester film of the cooling end end that polyester film leaves " is the width being arranged in cooling end, holding the polyester film when holding component (Fig. 3, hold component 2j and 21) of polyester film unclamps polyester film.
The holding component holding polyester film unclamps polyester film, and thus, polyester film leaves from the region of cooling end.Such as, the holding component 2j shown in Fig. 3 is when P point, other holding component 21 unclamp polyester film 200 respectively at Q point, and the end (end in MD direction) of cooling end 50 is represented by the straight line connecting P point and Q point.
" the conveyance speed Spl of the polyester film in preheating part " is equivalent to hold the translational speed of holding component (in Fig. 3,2a ~ 2d) at edge of polyester film, mobile ring-shaped guide rail.
In addition, " the conveyance speed Sp2 of the polyester film in the above-mentioned end of cooling end " make to be arranged in cooling end, the conveyance speed of (Fig. 3 holds component 2j and 21) polyester film when unclamping polyester film that holds the holding component of polyester film.Use Fig. 3, in other words, such as, hold component 2j P point, in addition hold component 21 unclamp polyester film 200 respectively at Q point time, " the conveyance speed Sp2 of the polyester film 200 in the above-mentioned end of cooling end 50 " is equivalent to conveyance speed when polyester film 200 exceedes the straight line of connection P point and Q point.In addition, in other words, " the conveyance speed Sp2 of the polyester film 200 in the above-mentioned end of cooling end 50 " is equivalent to hold the translational speed that component 2j and 21 souththern pines open the holding component 2j and 21 before polyester film 200.
When relaxing along TD direction after formula (I) refers to oriented polyester film 200, preferably with maximum width (length in the TD direction) W1 of polyester film 200 shrink in cooling end 50 2% ~ 15% mode relax.
When formula (II) refers to and is relaxed along MD direction by polyester film 200, preferably with the conveyance speed Spl in the preheating part 10 of polyester film 200 slow down in cooling end 50 2% ~ 15% mode relax.
[mathematical expression 2]
W 1 - W 2 W 1 &times; 100 = &Delta; W
S p 1 - S p 2 S p 1 &times; 100 = &Delta; S p
Δ W represents the relaxation rate in the TD direction (transverse direction) of polyester film, therefore, by Δ W also referred to as " TD relaxation rate ".In addition, Δ Sp represents the relaxation rate in the MD direction (longitudinal direction) of polyester film, therefore, by Δ Sp also referred to as " MD relaxation rate ".
Shown in (I) and (II), Δ W and Δ Sp is all preferably 2% ~ 15% (2%≤Δ W≤15%, 2%≤Δ Sp≤15%).
Be more than 2% by Δ W and Δ Sp, polyester film easily meets formula (1) ~ (7), thus easily suppresses fold when heating conveyance and damage.Be less than 15% by Δ W and Δ Sp, polyester film easily shrinks in stretching device, thus can suppress lax.
Δ W is more preferably 2% ~ 10% (2%≤Δ W≤10%), more preferably 3% ~ 8% (3%≤Δ W≤8%).In addition, Δ Sp is more preferably 2% ~ 10% (2%≤Δ Sp≤10%), more preferably 3% ~ 8% (3%≤Δ Sp≤8%).
The purposes > of < polyester film
Even if polyester film of the present invention heating conveyance is also difficult to produce fold and damage, even if paste coating fluid or functional component sheet etc. on film, the bubble be also difficult to when producing crawling, sheet laminating such as to be mixed at the fault.Therefore, may be used for carrying out heating to transport and the various uses of processing or being shaped.
Can suitably for such as optical film, electric insulation film.
In addition, polyester film of the present invention can be used as the film of solar battery module.In this situation, solar battery module such as can be formed as follows.
Solar battery module usually configures and converts the luminous energy of sunshine the solar battery element of electric energy to and form between the substrate of the transparency of sunshine incidence and the polyester film (solar cell backboard) of the invention described above.As concrete embodiment, can be configured to as under type: the sealants such as generating element (solar battery element) ethylene-vinyl acetate c system (EVA system) resin connected by the lead-in wire distribution (not shown) of power taking are sealed, it is clamped between the transparency carriers such as glass and polyester film of the present invention (backboard) and is bonded to each other and forms.
As the example of solar battery element, the various known solar battery elements such as iii-v or II-VI group compound semiconductor system such as the silicon systems such as monocrystalline silicon, polysilicon, non-crystalline silicon, copper-indium-gallium-selenium, copper-indium-selenium, cadmium-tellurium, gallium-arsenic can be adopted.Can carry out sealing forming with resins (so-called encapsulant) such as such as ethylene-vinyl acetate c bodies between substrate and polyester film.
Embodiment
Below, by embodiment, the present invention is more specifically described, but the present invention only otherwise exceed its purport, be then not limited to following embodiment.It should be noted that, as long as no special explanation, then " part " is quality criteria.
The synthesis > of < polyester feed stock resin
(polyester feed stock resin 1)
As follows, make that terephthalic acid (TPA) and ethylene glycol directly react, dephlegmate, under reduced pressure carry out the direct esterification of polycondensation after esterification, obtain polyester (Ti catalyst system PET) by continuous polymerization unit.
(1) esterification
In the first esterification groove, high purity terephthalic acid 4.7 tons and ethylene glycol 1.8 tons of use are mixed for 90 minutes, form slurry, supply in the first esterification groove continuously with the flow of 3800kg/ hour.Supply the ethylene glycol solution of the citric acid Ti chelator complex compound (VERTECAC-420, JohnsonMatthey Inc.) of citric acid coordination on Ti metal more continuously, within about 4.3 hours, react with mean residence time under temperature 250 DEG C, stirring in reactive tank.Now, adding citric acid Ti chelator complex compound continuously makes Ti addition reach 9ppm in element scaled value.Now, the acid number of the oligomer obtained is 600 equivalents/ton.It should be noted that, in this description, " equivalent/t " represents the molar equivalent of every 1 ton.
This reactant is transferred to the second esterification groove, under agitation, in reactive tank at temperature 250 DEG C in mean residence time reaction 1.2 hours, obtain the oligomer that acid number is 200 equivalents/ton.The inner area of the second esterification groove is divided into 3 regions, the ethylene glycol solution supplying magnesium acetate from the 2nd region continuously makes Mg addition reach 75ppm in element scaled value, then, the ethylene glycol solution supplying trimethyl phosphate continuously from the 3rd region makes P addition reach 65ppm in element scaled value.
(2) polycondensation reaction
Esterification reaction product obtained above is supplied continuously in the first polycondensation reaction groove, under agitation, pressure 20torr (2.67 × 10 in reaction temperature 270 DEG C, reactive tank -3mPa) within about 1.8 hours, polycondensation is carried out with mean residence time under.
Be transferred in the second polycondensation reaction groove again, in this reactive tank under agitation, pressure 5torr (6.67 × 10 in temperature 276 DEG C, reactive tank in reactive tank -4mpa) carry out reacting (polycondensation) with the condition of about 1.2 hours holdup times under.
Then, then be transferred in the 3rd polycondensation reaction groove, in this reactive tank, pressure 1.5torr (2.0 × 10 in temperature 278 DEG C, reactive tank in reactive tank -4mPa) carry out reacting (polycondensation) with the condition of 1.5 hours holdup times under, obtain reactant (PETG (PET)).
Then, obtained reactant is emitted into strand shape in cold water, cuts at once, make the particle < cross section of polyester: major diameter is about 4mm, minor axis is about 2mm, length: about 3mm>.
About obtained polyester, use high-resolution type high-frequency inductive coupling plasma body-quality analysis (HR-ICP-MS; SIINanotechnologyInc. AttoM processed), as followsly to measure, result, Ti=9ppm, Mg=75ppm, P=60ppm.P reduces slightly relative to initial addition, and supposition is volatilized in the course of the polymerization process.
The polymer obtained is IV=0.67, amount (the AV)=23 equivalents/ton of terminal carboxyl group, fusing point=257 DEG C, solution mist degree=0.3%.The mensuration of IV and AV is undertaken by method shown below.
The mensuration of ~ IV and AV ~
About the inherent viscosity (IV) of polyester feed stock resin, polyester feed stock resin is dissolved in 1,1,2,2-tetrachloroethanes/phenol (=2/3 [mass ratio]) mixed solvent, obtained by the solution viscosity at 25 in this mixed solvent DEG C.
End COOH about polyester feed stock resin measures (AV), makes non-oriented polyester film 1 at phenmethylol/chloroform (=2/3; Volume ratio) mixed solution in dissolve completely, as indicator use phenol red, carry out titration with titer (0.025NKOH-methyl alcohol mixed solution), calculated by this titer.
By upper, synthesizing polyester material resin 1.
(polyester feed stock resin 2)
Polyester feed stock resin 1 is implemented solid phase by batch process.That is, after the particle of polyester being dropped into container, vacuumize while carrying out stirring, at 150 DEG C, carry out Pre-crystallizing process, then, at 190 DEG C, carry out the solid-phase polymerization of 30 hours.
By upper, synthesizing polyester material resin 2.
(polyester feed stock resin 3)
Using as 2 of binary acid, 6-naphthalene diformic acid dimethyl ester 97.6 parts (100 % by mole) and drop in ester exchange groove as the ethylene glycol 49.6 parts (100 % by mole) of dihydroxylic alcohols, distillation for removing methanol, make it heat up while carrying out ester exchange reaction, when methyl alcohol distillation removing until theoretical amount when, reactant is moved in polycondensation groove, after interpolation is as the germanium oxide 0.016 part of polycondensation catalyst, while being decompressed to high vacuum, be heated to 290 DEG C, distillation removing ethylene glycol.When stirring moment of torsion reaches desired value, terminate reaction, take out after making obtained polymer become the strand shape of diameter 2.5mm in water.The polymer slicer of obtained strand shape is cut into flake.The inherent viscosity (IV) of the polymer obtained is 0.60.
Thus, the polyester feed stock resin 3 of poly-NDA glycol ester (PEN) is obtained.
(polyester feed stock resin 4)
With reference to the numbered paragraphs [0072] (embodiment 1) of Japanese Unexamined Patent Publication 2001-191406 publication, prepare the polyester feed stock resin 4 of the PET of inherent viscosity (o-chlorphenol, 35 DEG C) 0.65.
(embodiment 1)
The making > of the non-oriented polyester film of <
-film forming process-
After making polyester feed stock resin 1 be dried to below moisture content 20ppm, drop in the hopper of the single-screw intermixing extruder of diameter 50mm.Polyester feed stock resin 1 melting at 300 DEG C, according to following extrusion condition, is extruded from die head by gear pump, filter (20 μm, aperture).It should be noted that, the mode reaching 3mm with the thickness of polyester sheet regulates the size of the slit of die head.The thickness of polyester sheet is measured by the automatic thickness meter arranged in the exit of curtain coating drum.
Now, pressure oscillation is 1%, the Temperature Distribution of molten resin carries out extruding of molten resin under being the condition of 2% making.Specifically, make the back pressure in the cylinder of extruder be the pressure of average pressure high 1% in cylinder relative to extruder, make the pipe arrangement temperature of extruder be that in cylinder relative to extruder, the temperature of mean temperature high 2% heats.When extruding from die head, molten resin is expressed on the curtain coating drum of cooling, uses electrostatic to apply method, itself and curtain coating drum are adhered to.The cooling of molten resin is set to while 25 DEG C by the temperature of curtain coating drum, from relative with curtain coating drum and blow the cold wind of 25 DEG C the cold wind generator that arranges, blows to molten resin.By with the stripper roll that configure of curtain coating drum subtend, from the non-oriented polyester film (non-oriented polyester film 1) of the bulging cover thickness 3mm of curtain coating, the wide 0.9m of film.
The non-oriented polyester film 1 obtained is inherent viscosity IV=0.64dL/g, amount (the AV)=25 equivalents/ton of terminal carboxyl group, glass transition temperature (Tg)=72 DEG C.
The mensuration of ~ IV and AV ~
About the inherent viscosity (IV) of non-oriented polyester film, non-oriented polyester film is dissolved in 1,1,2,2-tetrachloroethanes/phenol (=2/3 [mass ratio]) mixed solvent, tried to achieve by the solution viscosity at 25 in this mixed solvent DEG C.
End COOH about non-oriented polyester film measures (AV), makes non-oriented polyester film at phenmethylol/chloroform (=2/3; Volume ratio) mixed solution in dissolve completely, as indicator use phenol red, carry out titration with titer (0.025NKOH-methyl alcohol mixed solution), calculated by this titer.
The making > of < biaxially oriented polyester film
About obtained non-oriented polyester film 1, undertaken successively biaxial stretch-formed by following method, stretch thus, make the biaxially oriented polyester film 1 of thickness 250 μm, film wide (total length in TD direction) 2.5m.
-longitudinal stretching operation-
Passed through between 2 pairs of different niprolls of peripheral speed by non-oriented polyester film 1, under the following conditions longitudinally (conveyance direction) stretches.
Preheat temperature: 80 DEG C
Longitudinal drawing temperature: 90 DEG C
Longitudinal stretching multiplying power: 3.1 times
Longitudinal stretching stress: 12MPa
-cross directional stretch operation-
For the polyester film 1 (longitudinal stretching polyester film 1) after longitudinal stretching, use the stenter (biaxial stretcher) with the structure shown in Fig. 3, stretch under following method, condition.
(preheating part)
Make preheat temperature be 110 DEG C, heat in the mode that can stretch.
(extension section)
Under following condition, the longitudinal stretching polyester film 1 after preheating is applied tension force along the film width (TD direction) vertical with the direction (length direction) after longitudinal stretching, carry out cross directional stretch.
< condition >
Draft temperature (transverse drawing temperature): 125 DEG C
Stretching ratio (cross directional stretch multiplying power): 4.0 times
Tensile stress (lateral tensile stress): 18MPa
(thermal finalization portion)
Then, being up to of polyester film is reached film surface temperature (heat setting temperature) and control, in following ranges, to heat, makes its crystallization.
Be up to and reach film surface temperature (heat setting temperature T thermal finalization): 225 [DEG C]
Heat setting temperature T herein thermal finalizationfor the pre-peak temperature [DEG C] of DSC.
In addition, by the both ends of film width (TD direction) from the casting plane side contacted with curtain coating drum film forming process, radiation heating is carried out with the infrared heater (heater surface temperatures: 650 DEG C) of pottery.Now, the distance of heater and polyester film is 170mm.
(hot wire-CVD portion)
Polyester film after thermal finalization is heated to following temperature, the tension force of m flac.Now, radiation heating is carried out from casting plane side infrared heater (heater surface temperatures: 350 DEG C) in the both ends of film width in the same manner as thermal finalization.
Hot wire-CVD temperature (T hot wire-CVD): 150 DEG C
Hot wire-CVD rate: TD direction (TD hot wire-CVD rate; Δ W)=5%
MD direction (MD hot wire-CVD rate; Δ Sp)=0%
(cooling end)
Then, the polyester film after hot wire-CVD is reached 88 DEG C with the temperature of the TD direction central portion of film, the temperature of the end, TD direction of the film chilling temperature that reaches 80 DEG C cools.
-recovery of film-
After cooling terminates, 20cm is respectively pruned in the two ends of polyester film.Then, after two ends carry out extruding processing (embossing) with width 10mm, batch with tension force 25kg/m.
By upper, make the biaxially oriented polyester film (PET film) of thickness 250 μm.
-A. evaluation of measuring-
Following mensuration, evaluation are carried out to the biaxially oriented polyester film of above-mentioned making.The result measured and evaluate as described in Table 2.
(1) cutting of biaxially oriented polyester film
In the end, MD direction of biaxially oriented polyester film, one end is fixed on the eminence apart from ground 26m, under no-station pole canopy, hangs biaxially oriented polyester film.To reach the mode cutting film of 26m (L=26m in Fig. 1) from end to the distance of the other end in the MD direction being fixed on eminence, prepare film wide (W) for the size (in embodiment 1 W=2.5m) shown in table 1 and the film in MD direction long (L) reaches the film F of 26m.
(2) the MD percent thermal shrinkage in TD direction
The film F that cutting obtains as mentioned above, position (the straight line C of Fig. 1 of the half of film that be produced on film F, that reach MD direction long (L=26m) lon) both ends in TD direction at place and the coupons M of TD direction central portion.It should be noted that, coupons M is the size of 30mm, MD direction, TD direction 120mm.
For coupons M, introduce 2 foundation directrixes in MD direction with the interval reaching 100mm, under no-station pole canopy, to be positioned in the heated oven of 150 DEG C 30 minutes.After this placement, coupons M is cooled to room temperature, measures the interval of 2 foundation directrixes, this value is set as A (unit; Mm).Numerical value formula by the A measured and " 100 × (100-A)/100 " calculated is as MD percent thermal shrinkage.
About measuring the coupons M being positioned at end, TD direction in film F and the MD percent thermal shrinkage obtained, value large for numerical value is set as S s1, value little for numerical value is set as S s2.In addition, the coupons M being positioned at the central portion in TD direction in film F will be measured and the MD percent thermal shrinkage obtained is set as S cT.Show the result in table 2.
(3) the overall with circular arc C of film F s1, film F half cut out film partly cut out circular arc C cTmensuration
By the MD percent thermal shrinkage S measured s1and S s2determine S1 side and the S2 side of film F, thus measure the overall with circular arc C of film F s1.In addition, along the center C on the limit of the end, MD direction of junctional membrane F wuand C wdstraight line (the straight line Y1 in Fig. 1), cutting film F, obtains half sanction film.
Measure the C cutting out the bending size of film as obtained half c1and C c2, calculate the C of half sanction film cT.
Show the result in table 2.
In addition, based on obtained S s1, S s2, S cT, C s1, C cTand W, by key element " Δ the S (=S of constitutional formula (1) ~ (7) s1-S s2) ", " S aV[=(S s1+ S s2+ S cT)/3] ", " { S cT-(S s1+ S s2)/2} ", " { S cT-(S s1+ S s2)/2}/C cT/ 100 ", " W/2000 ", " W/1000 " and " 2W " are shown in table 2.
(4) mensuration of thickness
The thickness of the biaxially oriented polyester film obtained is tried to achieve as follows.
For biaxially oriented polyester film, use contact determining film thickness meter (ANRITSU Inc.), 50 points that carry out at equal intervals in the direction (length direction) of longitudinal stretching with 0.5m sample, further at film width (direction vertical with length direction) after film overall with carries out 50 somes samplings with (in the width direction 50 deciles) at equal intervals, measure the thickness of these 100 points.Obtain the average thickness of these 100 points, as the thickness of polyester film.
(5) the pre-peak temperature deviation of DSC (Δ Tpp)
Film F, as the straight line C of Fig. 1 lon position, for the overall width of end to another end from TD direction, to carry out the sampling of 11 points at equal intervals, obtain coupons M2.About the coupons M2 of each position, measure the pre-peak temperature of DSC (Tpp).Using the difference (Δ Tpp) of the maxima and minima of multiple Tpp values of mensuration as the pre-peak temperature deviation of DSC.
It should be noted that, about the pre-peak temperature of DSC, by the film installation provision amount (2 ~ 10mg) of the coupons M2 after sampling on the DSC-60 that Shimadzu Scisakusho Ltd manufactures, be warming up to 300 DEG C to measure with the programming rate of 10 DEG C/min.The peak temperature of the endothermic peak occurred before the melting peak of polyester (PET) is interpreted as the pre-peak temperature of DSC (Tpp).
(6) fold during heating conveyance biaxially oriented polyester film and the presence or absence judgement of damage
About obtained biaxially oriented polyester film, the presence or absence of fold on film surface when heating conveyance 40 seconds by visualization under the conveyance speed 1.0m/s in temperature 170 DEG C, MD direction and the presence or absence of damage, evaluate based on following metewand.
Metewand > with presence or absence of < fold
AA: the generation almost not observing fold.
A: the generation slightly observing fold, but face is good.
B: the generation observing fold, but practical clog-free degree.
C: the generation significantly observing fold.
Metewand > with presence or absence of < damage
AA: the generation almost not observing damage.
A: the generation slightly observing damage, face is good.
B: the generation observing damage, but practical clog-free degree.
C: the generation significantly observing damage.
(embodiment 2 ~ embodiment 15 and comparative example 1 ~ comparative example 5)
In embodiment 1, except the condition shown in list of modification 1, operate all equally, obtain the biaxially oriented polyester film of embodiment 2 ~ embodiment 15 and comparative example 1 ~ comparative example 5.
In addition, about obtained biaxially oriented polyester film, by the method same with the biaxially oriented polyester film of embodiment 1, carry out evaluating with presence or absence of the evaluation of physical property of biaxially oriented polyester film and fold and damage.Show the result in table 2.
(comparative example 6)
With reference to numbered paragraphs [0072] ~ [0073] of Japanese Unexamined Patent Publication 2001-191406 publication, obtain the biaxially oriented polyester film of the embodiment 1 based on Japanese Unexamined Patent Publication 2001-191406 publication.
About obtained biaxially oriented polyester film, by the method same with the biaxially oriented polyester film of embodiment 1, carry out evaluating with presence or absence of the evaluation of physical property of biaxially oriented polyester film and fold and damage.Show the result in table 2.
[table 1]
[table 2]
As shown in table 2, in embodiment, with the contrast of comparative example, the generation of fold during heating conveyance and damage is suppressed less.
In the disclosure of the Japan patent application 2013-069480 of application on March 28th, 2013, its entirety is by reference to being incorporated in this description.The whole documents recorded in this description, patent application and technical specification, with specifically and describe respectively each document, patent application and technical specification by reference to situation about introducing with degree ground, in this manual by reference to introducing.About the above object being recited as illustration and illustrating of illustrative embodiment of the present invention, instead of collect or limit the mode of open invention itself.Obvious multiple change or change it will be apparent to those skilled in the art that.Above-mentioned embodiment is illustrated best to the principle of invention and the application of practicality, carries out selecting and recording together with various change with the such various embodiment of the special-purpose being applicable to suppose in order to make other those skilled in the art understand to invent.Scope of the present invention attempts to be specified by following claim and its equipollent.
Symbol description
2a ~ 21 hold component
10 preheating parts
20 extension sections
30 thermal finalization portions
40 hot wire-CVD portions
50 cooling ends
60 ring-shaped guide rails
100 biaxial stretcher
200 polyester films

Claims (13)

1. a polyester film, it meets following formula (1) ~ (4),
W/1000＜[(S s1-S s2)/C S1/100]＜2W…(1)
0＜(S s1-S s2)＜0.5…(2)
-1＜(S s1+S s2+S CT)/3＜3…(3)
0＜C s1＜0.2…(4)
In formula (1) ~ (4),
S s1represent: in the end of polyester film width, the percent thermal shrinkage [%] in the end of the side that the percent thermal shrinkage under 150 DEG C, 30 minutes of the direction vertical with described polyester film width is large, vertical with described polyester film width direction,
S s2represent: in the end of polyester film width, the percent thermal shrinkage [%] in the end of the side that the percent thermal shrinkage under 150 DEG C, 30 minutes of the direction vertical with described polyester film width is little, vertical with described polyester film width direction,
S cTrepresent: polyester film width central portion, percent thermal shrinkage [%] under 150 DEG C, 30 minutes of vertical with described polyester film width direction,
C s1represent: in the end of polyester film width, the maximum [m] of the end of the side that the percent thermal shrinkage under 150 DEG C, 30 minutes of the direction vertical with described polyester film width is large, bending size,
W represents the width [m] of polyester film.
2. polyester film according to claim 1, it also meets following formula (5) ~ (7),
W/2000＜[{S CT-(S s1+S s2)/2}/C CT/100]＜W…(5)
-0.5＜{S CT-(S s1+S s2)/2}＜0.5…(6)
-0.2＜C CT＜0.2…(7)
In formula (5) ~ (7),
S s1represent: in the end of polyester film width, the percent thermal shrinkage [%] in the end of the side that the percent thermal shrinkage under 150 DEG C, 30 minutes of the direction vertical with described polyester film width is large, vertical with described polyester film width direction,
S s2represent: in the end of polyester film width, the percent thermal shrinkage [%] in the end of the side that the percent thermal shrinkage under 150 DEG C, 30 minutes of the direction vertical with described polyester film width is little, vertical with described polyester film width direction,
S cTrepresent: polyester film width central portion, percent thermal shrinkage [%] under 150 DEG C, 30 minutes of vertical with described polyester film width direction,
C cTrepresent: along the straight line of the central authorities of the polyester film width at the both ends of connection polyester film length direction, cutting polyester film, the maximum that obtain thus two and half cut out the bending size of the end of the width of polyester film is added the value [m] obtained divided by 2
W represents film wide [m].
3. polyester film according to claim 1 and 2, wherein,
The wide W of described film is more than 0.3m and below 8m.
4. the polyester film according to any one of claims 1 to 3, wherein,
Be more than 0.5 DEG C and less than 10 DEG C in the pre-peak temperature deviation measured by means of differential scanning calorimetry mensuration and DSC of described film width.
5. the polyester film according to any one of Claims 1 to 4, wherein,
The inherent viscosity of polyester film is more than 0.55dL/g and below 0.90dL/g.
6. the polyester film according to any one of Claims 1 to 5, wherein,
The amount of the terminal carboxyl group of polyester film is more than 5eq/ ton and below 35eq/ ton.
7. the polyester film according to any one of claim 1 ~ 6, wherein,
From 3 officials can above polyfunctional monomer Component units be more than 0.005 % by mole and less than 2.5 % by mole containing ratio relative to whole Component units of the polyester in polyester film.
8. a manufacture method for polyester film, it comprises:
Film forming process, melt extrudes slabbing by polyester feed stock resin, and cooling on curtain coating drum, makes polyester film be shaped;
Longitudinal stretching operation, carries out longitudinal stretching along its length by the described polyester film after being shaped; And
Cross directional stretch operation, described polyester film is transported to following portion successively, polyester film after described longitudinal stretching is carried out cross directional stretch along the width vertical with described length direction, wherein, described each portion is: the preheating part polyester film after described longitudinal stretching being preheated to the temperature that can stretch; Described polyester film after preheating is applied along the width vertical with described length direction the extension section that tension force carries out cross directional stretch; Heating the described polyester film after carrying out described longitudinal stretching and described cross directional stretch makes its crystallization to carry out the thermal finalization portion of thermal finalization; Polyester film after described thermal finalization is heated, by the tension recovery of polyester film to the hot wire-CVD portion of residual strain except striping; And by the cooling end of the polyester film cooling after hot wire-CVD,
In at least one in described thermal finalization portion and described hot wire-CVD portion, utilize heater to carry out selective radiation heating the end of the polyester film of described width, make the beeline on the surface of the surface of described heater and described polyester film be more than 10mm and below 300mm.
9. the manufacture method of polyester film according to claim 8, wherein,
Described radiation heating utilizes at least one pottery heater processed to carry out.
10. the manufacture method of polyester film according to claim 9, wherein,
The surface temperature of at least one in described pottery heater processed is more than 300 DEG C and less than 700 DEG C.
The manufacture method of 11. polyester films according to claim 9 or 10, wherein,
At least one in described pottery heater processed covers with cancellate crown cap.
The manufacture method of the polyester film according to any one of 12. according to Claim 8 ~ 11, wherein,
Described cross directional stretch operation uses the biaxial stretch-formed device of the following stated, this biaxial stretch-formed device has described preheating part, described extension section, described thermal finalization portion, described hot wire-CVD portion and described cooling end, at least two holding components are used to hold the both ends of the width of described polyester film at described preheating part for an end, by described polyester film from described preheating part conveyance to described cooling end
The surface temperature of described polyester film when described polyester film is departed from from described holding component is 40 DEG C ~ 140 DEG C.
The manufacture method of 13. polyester films according to claim 12, wherein,
The surface temperature of described polyester film when described polyester film is departed from from described holding component, relative to the surface temperature of the central portion of the width of described polyester film, make described width apart from the surface temperature of the described polyester film of the position of described holding component 200mm low 1 DEG C ~ 20 DEG C.
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