JP2010138024A - Polyester film for laminated glass, and laminated glass - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminated polyester film for transparent electroconductive films capable of preventing dust adhesion in a process by imparting antistatic properties by reducing the amount of an oligomer deposited on the surface of the polyester film upon being heat-processed. <P>SOLUTION: There are provided a polyester film for laminated glass having stress at 100% elongation in the range of 100-180 MPa in the longitudinal and lateral directions, and a laminated glass prepared by laminating glasses on both surfaces of the polyester film through a flexible resin layer. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a polyester film for laminated glass and laminated glass having excellent moldability. Specifically, the present invention relates to a polyester film for laminated glass and a laminated glass that can be suitably used without lowering productivity even when laminated with a bent glass.

  Conventionally, window glass for automobiles has been required to have strict optical characteristics, but in addition to that, improvement in performance as heat insulating glass with reduced heat ray transmission into the vehicle has been demanded from the viewpoint of energy saving. As this type of heat insulating glass, various metals are used on the glass inner surface of heat-absorbing glass that is glass rich in Fe, absorbs heat rays, and has a color tone adjusted with trace components, and laminated glass having PVB (polyvinyl butyral) intermediate layer. Laminated heat ray reflective glass coated with a thin film has been applied to some high-grade grades. On the other hand, as a technology to realize a relatively inexpensive laminated heat ray reflective glass, a PET (polyethylene terephthalate) film coated with a metal thin film is sandwiched between PVB sheet layers and adhesive layers having different thicknesses. Etc. have been proposed (for example, Patent Document 1).

  However, when laminating a conventional PET film with glass, it is often difficult to follow the shape of the bent PET film in the laminating process, and the glass shape that can be used for this purpose is extremely Limited.

Japanese National Patent Publication No. 11-509794

  The present invention has been made in view of the above circumstances, and the problem to be solved is a polyester film for laminated glass and a laminated glass that can be suitably used without reducing productivity even when laminated with bent glass. To provide glass.

  As a result of intensive studies in view of the above problems, the present inventors have found that the above problems can be easily solved by a polyester film having a specific configuration, and have completed the present invention.

  That is, the gist of the present invention consists of a polyester film for laminated glass characterized by comprising a polyester film having a stress at 100% elongation of 100 to 180 MPa in the machine and transverse directions of the film, and both sides of the polyester film. The laminated glass is characterized in that glass is laminated through a soft resin layer.

Hereinafter, the present invention will be described in more detail.
The polyester constituting the film of the present invention is preferably terephthalic acid as the dicarboxylic acid component. Besides these, oxalic acid, malonic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, One or more known dicarboxylic acids such as naphthalenedicarboxylic acid, diphenyl ether dicarboxylic acid, and cyclohexanedicarboxylic acid may be included as a copolymerization component. As the diol component, ethylene glycol is preferable. Besides these, propylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, 1,4-cyclohexanedimethanol, diethylene glycol, triethylene glycol, polyalkylene glycol, One or more known diols such as neopentyl glycol may be included as a copolymerization component.

  In addition to the above-mentioned dicarboxylic acid component and diol component, various acid components and alcohol components can be included as a constituent component of the polyester. For example, monofunctional compounds such as oxycarboxylic acid such as p-oxybenzoic acid, benzoic acid, benzoylbenzoic acid, and methoxypolyalkylene glycol are used as modifying components, and polyfunctional such as trimesic acid, trimellitic acid, glycerin, and pentaerythritol. The functional compound can be used as a copolymerization component as long as the product polyester can retain a substantially linear polymer.

  The polyester in the present invention is a conventionally known method, for example, a method of directly obtaining a low-polymerization degree polyester by reaction of a dicarboxylic acid and a diol, or a lower alkyl ester of a dicarboxylic acid and a diol reacted with a conventionally known transesterification catalyst. Then, it can obtain by the method of performing a polymerization reaction in presence of a polymerization catalyst. As the polymerization catalyst, a known catalyst such as an antimony compound, a germanium compound, or a titanium compound can be used.

  In addition, after melt-polymerizing polyester, this may be chipped, and solid-state polymerization may be further performed as necessary under heating under reduced pressure or in an inert gas stream such as nitrogen. The intrinsic viscosity of the obtained polyester is preferably 0.40 dl / g or more, more preferably 0.40 to 0.90 dl / g.

  You may mix | blend particle | grains in the polyester layer in the film of this invention with the main objective of providing easy slipperiness. The type of particles to be blended is not particularly limited as long as it is a particle capable of imparting slipperiness, and specific examples include, for example, silica, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate, kaolin, Examples of the particles include aluminum oxide and titanium oxide. Further, the heat-resistant organic particles described in JP-B-59-5216, JP-A-59-217755 and the like may be used. Examples of other heat-resistant organic particles include thermosetting urea resins, thermosetting phenol resins, thermosetting epoxy resins, benzoguanamine resins, and the like. Furthermore, precipitated particles obtained by precipitating and finely dispersing a part of a metal compound such as a catalyst during the polyester production process may be used.

  On the other hand, the shape of the particles to be used is not particularly limited, and any of a spherical shape, a block shape, a rod shape, a flat shape, and the like may be used. Moreover, there is no restriction | limiting in particular also about the hardness, specific gravity, a color, etc. These series of particles may be used in combination of two or more as required.

  Further, the average particle size of the particles used is usually preferably 0.01 to 5 μm. If the average particle size is less than 0.01 μm, the particles tend to aggregate and the dispersibility may be insufficient. On the other hand, if the average particle size exceeds 5 μm, the film particles will be the starting point and may be broken during deformation. Problems may occur.

  The method for adding particles to the polyester is not particularly limited, and a conventionally known method can be adopted. For example, it can be added at any stage for producing the polyester, but the polycondensation reaction may proceed preferably after the esterification stage or after the transesterification reaction. Also, a method of blending a slurry of particles dispersed in ethylene glycol or water with a vented kneading extruder and a polyester raw material, or a blending of dried particles and a polyester raw material using a kneading extruder. It is done by methods.

  In addition to the above-mentioned particles, conventionally known antioxidants, heat stabilizers, lubricants, antistatic agents, fluorescent brighteners, dyes, pigments and the like are added to the polyester film of the present invention as necessary. be able to. Depending on the application, an ultraviolet absorber, particularly a benzoxazinone-based ultraviolet absorber, may be contained.

  The film of the present invention can be formed into a laminated structure using a coextrusion method. For example, by forming the polyester constituting the outermost layer with a small amount of oligomers, oligomers are precipitated due to thermal history during processing. Thus, it is possible to prevent deterioration of the surface quality of the molded product due to contamination of the production line or foreign matter on the film surface. In order to obtain such an effect, the thickness of the outermost layer is preferably 3 μm or more. In addition, film particles may be the starting point, and defects such as tearing may occur during molding. In order to prevent this problem, it is necessary to reduce the amount of particles blended in the outermost layer, and the thickness of the outermost layer is preferably set to ¼ or less of the total thickness. On the other hand, when carried out with a single layer, problems such as solvent resistance may occur, and care must be taken in selecting a coating layer in a subsequent step. It is also preferable to prevent particles from being contained in the film as much as possible, and to contain particles in the front and back coating layers.

  The film thickness of this invention is 50-200 micrometers normally, Preferably it is 75-150 micrometers. When the film thickness is less than 50 μm, there is a tendency for wrinkles or the like to easily enter when making a laminated glass. When the film thickness is greater than 200 μm, the film is highly transparent due to light scattering by particles in the film. It may be difficult to obtain a laminated glass.

  From the viewpoint that the film of the present invention can be suitably used for a bent glass shape in the step of laminating the polyester film with glass, the stress at 100% elongation in the vertical and horizontal directions of the polyester film is in the range of 100 to 180 MPa. It is necessary. When the 100% elongation stress is smaller than 100 MPa, the heat shrinkage stress is generated under the autoclave pressurization condition (120 to 150 ° C., pressure 1.0 to 1.5 MPa), which is a process for producing a laminated glass. The film shrinks to a laminated glass in which no polyester film exists up to the edge of the glass. Further, when the 100% elongation stress is larger than 180 MPa, in the process of making the laminated glass, the followability is poor particularly in a severe part of the three-dimensional bending shape, and the laminated glass is not uniform with wrinkles and cracks. It is not preferable.

  Hereinafter, although the manufacturing method of the polyester film of this invention is demonstrated concretely, as long as the summary of this invention is satisfied, this invention is not specifically limited to the following illustrations.

  First, a dried or undried polyester chip by a known method is supplied to a melt extrusion apparatus and heated to a temperature equal to or higher than the melting point of each polymer and melted. Next, the molten polymer is extruded from a die and rapidly cooled and solidified on a rotary cooling drum so that the temperature is equal to or lower than the glass transition temperature to obtain a substantially amorphous unoriented sheet. In this case, in order to improve the flatness of the sheet, it is preferable to improve the adhesion between the sheet and the rotary cooling drum. In the present invention, an electrostatic application adhesion method and / or a liquid application adhesion method is preferably employed.

  In the present invention, the sheet thus obtained is stretched biaxially to form a film. Specifically describing the stretching conditions, the unstretched sheet is preferably stretched 2 to 6 times at 70 to 145 ° C. in the MD direction to form a longitudinal uniaxially stretched film, and then at 90 to 160 ° C. in the TD direction. It is preferable to perform 2-6 times stretching and to heat-process at 150-240 degreeC for 1 to 600 seconds. Further, at this time, a method of relaxing 0.1 to 20% in the longitudinal direction and / or the transverse direction in the maximum temperature zone of the heat treatment and / or the cooling zone at the heat treatment outlet is preferable. Further, it is possible to add re-longitudinal stretching and re-lateral stretching as necessary. In particular, in order to reduce 100% elongation stress, it is effective to increase the relaxation rate in the width direction simultaneously with the high-temperature heat treatment of the film after longitudinal and transverse stretching.

  In the present invention, as described above, two or three or more polyester melt extruders can be used to form a laminated film of two layers or three or more layers by a so-called coextrusion method. As a structure of a layer, it can be set as the film of A / B structure using A raw material and B raw material, or A / B / C structure, or another structure. For example, the surface shape of the A layer can be designed using specific particles as the A raw material, and a film containing no particles can be used as the B raw material to form an A / B film. In this case, since the raw material of B layer can be selected freely, a cost advantage etc. are large. Further, even if the recycled material of the film is blended with the B layer, the surface roughness can be designed by the surface A layer, so that the cost advantage is further increased.

  In the stretching step or after, in order to impart adhesion, antistatic property, slipperiness, releasability, etc. to the film, a coating layer is formed on one or both sides of the film, or a discharge treatment such as corona treatment is performed. It can also be applied.

  The film of the present invention can be used even when laminated with a bent glass having a complicated shape, can provide a laminated glass free from defects, and has high technical value.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to a following example, unless the summary is exceeded. The measuring method used in the present invention is as follows.

(1) Intrinsic viscosity A measurement sample was dissolved in a solvent of phenol / tetrachloroethane = 50/50 (parts by weight) to prepare a solution having a concentration c = 0.01 g / cm ³ , and the relative viscosity with the solvent at 30 ° C. η _r was measured to determine the intrinsic viscosity [η].

(2) Thickness Determined with a micrometer.

(3) Melting peak temperature Tm
Using a differential scanning calorimeter “DSC-2920 type” manufactured by TA Instruments, the temperature of the endothermic peak obtained when the sample was heated from 0 ° C. to 300 ° C. at a rate of 20 ° C./min is Tm did. When a plurality of peaks were obtained by the above method, each was described as a melting peak temperature.

(4) 100% elongation stress Using an Intesco tensile tester Intesco Model 2001, a sample film having a length of 50 mm and a width of 15 mm at a temperature of 25 ° C. is subjected to a tensile test at a speed of 200 mm / min. The stress at 100% elongation in the vertical and horizontal directions was determined.

(5) Heat resistance as a film for laminated glass The total sandwiched between both sides of a polyester film with a resin sheet made of polyvinyl butyral of the same size as the polyester film, and further sandwiched with glass of the same size as the polyester film from both sides of the laminate A laminate composed of five layers was prepared. The laminate was held at 130 ° C. and 1.0 MPa for 30 minutes, the temperature was lowered, and the heat resistance was evaluated according to the following criteria.
○: The size of the polyester film is equal to that of the glass. Δ: The polyester film shrinks slightly and is slightly smaller than the glass.

(6) Formability as a film for laminated glass In order to conduct an experiment assuming curved glass, a quartz watch glass having a diameter of 120 mmφ was used as the glass, and a laminate produced under the same conditions as in (5) above was used as the reference below. Was evaluated.
○: The polyester film completely follows the shape of the glass. Δ: The polyester film does not follow the glass at a part where the curvature is large. ×: The polyester does not follow the glass and wrinkles are generated. Cannot be collected

Examples and Comparative Examples are shown below, and the method for producing the polyester used in the Examples and Comparative Examples is as follows.
<Manufacture of polyester>
(Method for producing polyester A)
100 parts by weight of dimethyl terephthalate and 60 parts by weight of ethylene glycol are used as starting materials, 0.09 parts by weight of magnesium acetate tetrahydrate as a catalyst is placed in the reactor, the reaction start temperature is set to 150 ° C., and the methanol is gradually distilled off. The reaction temperature was raised to 230 ° C. after 3 hours. After 4 hours, the transesterification reaction was substantially terminated. After 0.04 part of ethyl acid phosphate was added to this reaction mixture, 0.03 part of antimony trioxide was added and a polycondensation reaction was carried out for 4 hours. That is, the temperature was gradually raised from 230 ° C. to 280 ° C. On the other hand, the pressure was gradually reduced from normal pressure, and finally 0.3 mmHg. After the start of the reaction, the reaction was stopped at a time corresponding to an intrinsic viscosity of 0.680 due to a change in stirring power of the reaction tank, and the polymer was discharged under nitrogen pressure. The intrinsic viscosity of the obtained polyester A was 0.680.

(Method for producing polyester B)
Isophthalic acid and terephthalic acid were used as the dicarboxylic acid component, and ethylene glycol was used as the polyhydric alcohol component, respectively, and those produced by the usual melt polycondensation method were used. The obtained polyester B had an intrinsic viscosity of 0.700, and the content of isophthalic acid in the dicarboxylic acid component was 22 mol%.

(Method for producing polyester C)
In the polyester A production method, after adding 0.04 part of ethyl acid phosphate, 3 parts of silica particles having an average particle diameter of 2.5 μm dispersed in ethylene glycol and 0.03 part of antimony trioxide were added to the limit. Polyester C was obtained using the same method as the production method of polyester A except that the polycondensation reaction was stopped at a time corresponding to a viscosity of 0.650. The obtained polyester C had an intrinsic viscosity of 0.650.

<Manufacture of polyester film>
Example 1:
Two vented twin-screw extrusions using the above-mentioned polyesters A and C mixed in 97 parts by weight and 3 parts by weight, respectively, with the mixed raw material as layer A and polyester A as 100 parts by weight as the raw material for layer B Each was supplied to a machine, melted at 285 ° C., and coextruded in a layer configuration of two types and three layers (A / B / A) with the A layer as the outermost layer (surface layer) and the B layer as the intermediate layer The film was cooled and solidified on a casting drum cooled to 0 ° C. to obtain an unstretched film. Next, the film was stretched 3.5 times in the longitudinal direction at a longitudinal stretching temperature of 80 ° C. using the difference in peripheral speed of the roll. Thereafter, the film was guided to a tenter, stretched 3.8 times in the transverse direction at 120 ° C., and subjected to heat treatment at 245 ° C. for 10 seconds. The thickness of each layer of the obtained film was 5/90/5 μm. The obtained results are shown in Table 1 below. From this result, good results were obtained in both heat resistance and moldability.

Example 2:
A polyester film having a thickness of 100 μm was obtained in the same manner as in Example 1 except that the film was stretched 3.1 times in the longitudinal direction and 4.0 times in the lateral direction. Laminates using this film are slightly smaller in the lateral direction of the film, and the film has poor trackability for parts with large curvatures, but can be used sufficiently depending on the shape of the glass. It was a thing.

Comparative Example 1:
Two vented twin-screw extrusions using the above-mentioned polyesters A and C mixed in 97 parts by weight and 3 parts by weight, respectively, with the mixed raw material as layer A and polyester A as 100 parts by weight as the raw material for layer B Each was supplied to a machine, melted at 285 ° C., and coextruded in a layer configuration of two types and three layers (A / B / A) with the A layer as the outermost layer (surface layer) and the B layer as the intermediate layer. The film was cooled and solidified on a casting drum cooled to 0 ° C. to obtain an unstretched film. Next, the film was stretched 3.5 times in the longitudinal direction at a longitudinal stretching temperature of 80 ° C. using the difference in peripheral speed of the roll. Thereafter, the film was guided to a tenter, stretched 3.8 times in the transverse direction at 120 ° C., subjected to heat treatment at 235 ° C. for 10 seconds, and then relaxed 3% in the width direction at 170 ° C. to obtain a polyester film having a thickness of 100 μm. The laminate using this film had no shrinkage of the film and good heat resistance, but the film did not follow the glass, and the moldability was poor.

Comparative Example 2:
In Comparative Example 1, a polyester film having a thickness of 100 μm was prepared in the same manner as in Comparative Example 1, except that polyester A and B were 20 parts by weight and 80 parts by weight, respectively, and heat treatment was performed at 200 ° C. for 10 seconds. Got. The laminate using this film had a large shrinkage of the film and was inferior. The formability was good.

  The physical properties of the obtained film and suitability as a polyester film for laminated glass are summarized in Table 1. It can be seen that a film satisfying the requirements of the present invention has high suitability for laminated glass.

  The film of the present invention can be suitably used as a film for laminated glass.

Claims (2)

A polyester film for laminated glass, comprising a polyester film having a stress at 100% elongation of 100 to 180 MPa in the vertical and horizontal directions of the film. A laminated glass comprising glass laminated on both sides of the polyester film according to claim 1 through a soft resin layer.