White laminated polyester film for metallic plate lamination work

DETAILED DESCRIPTION OF THE INVENTION

1. Technical Field

This invention relates to a white laminated polyester film for metallic plate lamination work, more particularly, relates to a white laminated polyester film for metallic plate lamination work having excellent workability and hiding effect in the case of laminating to a metallic plate and forming the laminate to a metallic can having the film at the outer surface of the can and causing little abrasion of rolls for the manufacture of the film.

2. Background Arts

Metallic cans are generally coated on the inner and outer surfaces to prevent the corrosion of the metal. Coating with a thermoplastic resin film is recently attempted as a means for imparting the metallic can with rustproofness without using organic solvent for the simplification of process, improvement in hygiene, prevention of environmental pollution, etc.

Namely, the investigation is in progress to laminate a thermoplastic resin film to a metallic plate such as tinned sheet iron, tinfree steel or aluminum and manufacture a can by the drawing, etc., of the laminated plate.

Polyolefin films and polyamide films were attempted as the above thermoplastic resin film, however, these films did not satisfy the required workability, heat-resistance and aromaproofness at the same time.

Polyester films, especially polyethylene terephthalate films are attracting attention owing to the balanced characteristics, and several proposals have been made based on the film.

For example, there are the following proposals.

(1) A method to laminate a biaxially oriented polyethylene terephthalate film to a metallic plate and use the laminate as a can-manufacturing-material (Japanese Patent TOKKAISHO 56-10451 and TOKKAIHEI 1-192546),

(2) A method to laminate an amorphous or an extremely low-crystalline aromatic polyester film to a metallic plate and use the laminate as a can-manufacturing material (Japanese Patent TOKKAIHEI 1-192545 and TOKKAIHEI 2-57339) and

(3) A method to laminate a heat-set biaxially oriented polyethylene terephthalate film having low orientation degree to a metallic plate and use the laminate as a can-manufacturing material (Japanese Patent TOKKAISHO 64-22530).

However, these methods have failed in getting sufficiently satisfiable results and revealed the following problems.

In the method (1), the biaxially oriented polyethylene terephthalate film has excellent heat-resistance and aromaproofness, however, the workability is insufficient to generate microscopic cracks and, in extreme cases, cause the breakage of the film in the case of can-manufacturing work accompanying a large deformation.

The method (2) uses an amorphous or extremely low-crystalline aromatic polyester film having good workability but poor aromaproofness and liable to cause the embrittlement by the post-heat treatment such as printing, retort-sterilization, etc., after the manufacture of a can or by the storage over a long period to form a film easily breakable by the external shock.

The method (3) aims at the development of the effect in a region between the methods (1) and (2), however, it is not yet successful to get a film having sufficiently low orientation applicable to the manufacture of a can.

Metallic cans are generally printed on the outer surface, and the print is applied after undercoating the surface with a white coating for light-shielding. The undercoating with a white coating can be omitted by using a light-shielding white film as the thermoplastic resin film to be laminated to the metallic plate, however, the white film produced by adding white pigment to the films of the methods (1), (2) and (3) cannot solve the demerits of each method.

Further, a white film containing titanium oxide at high concentration for improving the hiding effect is brittle to deteriorate the film-forming property by the frequent film breakage in drawing and causes the problem of the abrasion of rolls used in the film-forming process.

Various methods have been proposed to improve the above-mentioned workability, aromaproofness and heat-resistance of the film.

Followings are example of these methods.

(4) A method to use a copolyester having a melting point falling within a specific range as the can-manufacturing material (Japanese Patent TOKKAIHEI 5-339391) and

(5) A method to use a laminated film composed of two layers having different contents of white pigment (Japanese Patent TOKKAIHEI 6-39981).

Although the use of the method (4) or (5) is effective for improving the workability, aromaproofness and heat-resistance, the problem of the roll abrasion remains unsolved and a film having satisfactory characteristics in the film-forming process and the working of a metallic can is not yet attainable.

Problems to be Solved by the Invention

The object of the present invention is to provide a white laminated polyester film for metallic plate lamination work having excellent workability, aromaproofness and heat-resistance and causing little abrasion of rolls.

Means for Solving the Problems

According to the present invention, the above object and advantages of the present invention can be achieved first by a white laminated polyester film for metallic plate lamination work consisting of a laminated film comprising a layer (layer A) composed of a copolyester A and a layer (layer B) composed of a copolyester B, wherein

(I) (i) the copolyester A contains 0 to 15% by weight of rutile titanium oxide having an average particle diameter of from 0.1 to 0.5 μm and has a melting point of from 210 to 245° C., (ii) the copolyester B contains 10 to 50% by weight of rutile titanium oxide having an average particle diameter of from 0.1 to 0.5 μm and has a melting point of from 210 to 245° C. and an intrinsic viscosity of the polymer part of from 0.46 to 0.66,

(II) the intrinsic viscosity (η

A

) of the polymer part of copolyester A and the intrinsic viscosity (η

B

) of the polymer part of the copolyester B satisfy the following relationship:

|η

A

−η

B

|<0.15, and

(III) the ratio of the apparent density (ρ). to the calculated density (ρ

0

) of the whole laminated film (ρ/ρ

0

) satisfies the following formula:

0.65≦ρ/ρ

0

≦1.00

wherein

ρ_{0} = 100 ρ_{t} \frac{\sum_{i = 1}^{n} (\frac{Xi ρ_{i}}{W_{i} (ρ_{i} - ρ_{t}) + 100 ρ_{t}})}{\sum_{i = 1}^{n} X_{i}}

in the above formula,

ρ: apparent density (g/cm

3

) of the whole laminated film:

ρ

0

: calculated density (g/cm

3

) of the whole laminated film:

ρ

i

: density (g/cm

3

) of the polymer part of each copolyester:

ρ

t

: density (g/cm

3

) of rutile titanium oxide:

X

i

: thickness (μm) of each layer:

W

i

: concentration (wt. %) of rutile titanium oxide in each copolyester:

n: number of copolyester layers.

Secondly, the object and advantages of the present invention can be achieved by a white laminated polyester film for metallic plate lamination work consisting of a laminated film (which may be abbreviated hereinafter as a second laminated film) produced by laminating a layer (layer A) composed of a copolyester A and a layer (layer C) composed of a copolyester C to both surfaces of a layer (layer B) composed of a copolyester B, provided that

(i) the copolyester A contains 0 to 10% by weight of rutile titanium oxide having an average particle diameter of from 0.1 to 0.5 μm and 0.01 to 0.1% by weight of silicon dioxide particles having an average particle diameter of from 0.6 to 2.0 9 μm and has a melting point of from 210 to 245° C. and an intrinsic viscosity of the polymer part of from 0.46 to 0.66,

(ii) the copolyester B contains 120 to 50% by weight of rutile titanium oxide having an average particle diameter of from 0.1 to 0.5 μm and has a melting point of from 210 to 245° C. and an intrinsic viscosity of the polymer part of from 0.46 to 0.66 and

(iii) the copolyester C contains 0 to 10% by weight of rutile titanium oxide having an average particle diameter of from 0.1 to 0.54 μm and 0.01 to 0.1% by weight of silicon dioxide particles having an average particle diameter of from 0.6 to 2.0 μm and has a melting point of from 210 to 245° C. and an intrinsic viscosity of the polymer part of from 0.46 to 0.66.

The following descriptions are common to the above two kinds of laminated films unless particularly mentioned to be restricted to the second laminated film.

The copolyester A, copolyester B and copolyester C of the present invention are, for example, a polyethylene terephthalate copolymer, a polyethylene isophthalate copolymer, a polyethylene-2,6-naphthalate copolymer and a polybutylene terephthalate copolymer. Polyethylene terephthalate copolymer is preferable among the above copolymers.

The copolymerizing component of the above copolyester may be an acid component or an |alcohol component. Examples of the acid component are aromatic dicarboxylic acids such as isophthalic acid, phthalic acid and 2,6-naphthalenedicarboxylic acid, aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid and 1,10-decanedicarboxylic acid, and alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, and examples of the alcohol component are aliphatic diols such as 1,4-butanediol and 1,6-hexanediol and alicyclic diols such as 1,4-cyclohexanedimethanol. These compounds may be used singly or as a combination of two or more compounds. Among the above examples, isophthalic acid or sebacic acid is preferable and, above all, isophthalic acid is especially preferable.

The kinds and ratios of the copolymerizing components of the copolyester A, copolyester B and copolyester C may be the same or different from each other.

The ratio of the copolymerizing component depends upon the kind of the component and is selected to give a polymer having a melting point of from 210 to 245° C., preferably from 215 to 235° C. A polymer having a melting point of lower than 210° C. has poor heat-resistance unable to endure the heating in the printing process after the manufacture of a can. When the melting point of the polymer exceeds 245° C., the crystallinity of the polymer is increased to deteriorate the workability to an undesirable level.

The melting point of the copolyester was measured by using DuPont Instruments 910 DSC and determining a melt peak at a heating rate of 20° C./min. The amount of specimen was about 20 mg.

The copolyester of the present invention can be produced by conventional method. For example, a polyethylene terephthalate copolymer can be produced preferably by esterifying terephthalic acid, ethylene glycol and a copolymerizing component and subjecting the obtained reaction product to polycondensation reaction to form a polyethylene terephthalate copolymer or by performing transesterification reaction of dimethyl terephthalate, ethylene glycol and a copolymerizing component and subjecting the resultant reaction product to polycondensation reaction to obtain the objective polyethylene terephthalate copolymer. The copolyester may be incorporated, as necessary, with other additives such as fluorescent brightener, antioxidant, thermal stabilizer, ultraviolet absorber and antistatic agent in the production of the copolyester. The addition of a fluorescent brightener is especially preferable in the case of improving the whiteness of the product.

The intrinsic viscosity of the polymer part of the copolyester B is from 0.46 to 0.66, preferably from 0.48 to 0.64 in the present invention. A polymer having an intrinsic viscosity of smaller than 0.46 causes frequent film breakage in the drawing of film and gives a drawn film liable to be broken in the case of forming a metallic can from a laminate of the film and a metallic plate. Intrinsic viscosity exceeding 0.66 is over-quality and lowers the productivity of the polymer material to raise the production cost.

The intrinsic viscosity (η

A

) of the polymer part of the copolyester A, the intrinsic viscosity (η

B

) of the polymer part of the copolyester B and the intrinsic( viscosity (η

C

) of the polymer part of the copolyester C are required to satisfy the following relationships.

&LeftBracketingBar; η_{A} - η_{B} &RightBracketingBar; < 0.15

&LeftBracketingBar; η_{C} - η_{B} &RightBracketingBar; < 0.15

&LeftBracketingBar; η_{A} - η_{C} &RightBracketingBar; < 0.15

All of the absolute values of the intrinsic viscosity difference of the polymer parts in each layer are preferably smaller than 0.12, more preferably smaller than 0.10.

Even if either one of the intrinsic viscosity difference of the polymer parts of these layers is 0.15 or more, a large orientation difference is caused between the layers of the laminated film to generate the curling and the laminate wrinkle and lower the lamination workability of the film to an undesirable level.

In the case of the second laminated film of the present invention containing silicon dioxide particles in the copolyester (A) and the copolyester (B), the above relationships are not necessarily fulfilled provided that all of the intrinsic viscosity of the polymer parts of the polyesters A, B and C are in the range of from 0.46 to 0.66.

The intrinsic viscosity of the polymer part of the copolyester was measured by dissolving the specimen in o-chlorophenol, removing the filler such as titanium oxide by a centrifugal separator and measuring the viscosity at 35° C.

In the present invention, the copolyesters A, B and C are incorporated with titanium Oxide to impart the film with white hiding power. It is necessary to use rutile titanium oxide having an average particle diameter of from 0.1 to 0.5 μm as the titanium oxide. The average particle diameter is preferably between 0.2 and 0.4 μm. Titanium oxide having an average particle diameter smaller than 0.1 μm is difficult to be uniformly dispersed in a copolyester and gives a film having poor white hiding power. On the other hand, rutile titanium oxide having an average particle diameter exceeding 0.5 μm is undesirable because such titanium dioxide is difficult to produce and the produced particles contain large amount of coarse particles.

The purity of the rutile titanium oxide is preferably 95% or above. Titanium oxide having a purity lower than 95% is undesirable because it has pool dispersibility in the case of adding at a high concentration and remarkably lowers the molecular weight of the copolyester.

In the present invention, the concentration of the rutile titanium oxide of the copolyester B is required to fall within the range of from 10,to 50% by weight, preferably from 20 to 50% by weight, especially from 20 to 40% by weight. The white hiding power of the film is insufficient when the concentration is lower than 10% by weight. On the other hand, the hiding power is saturated and further improvement in the hiding effect is not expectable at a concentration exceeding 50% by weight and, besides, the film becomes brittle to cause frequent breakage of the film in drawing and the produced film is liable to break in the case of forming a metallic can from a laminate of the film and a metallic plate.

The rutile titanium oxide concentration in the copolyesters A and C is 0 to 15% by weight each, preferably 0 to 10% by weight each, more preferably 0 to 6% by weight each. The roll abrasion becomes an undesirable level in the film-forming process when the concentration exceeds 15% by weight.

The rutile titanium oxide concentrations of both copolyesters A and C are preferably lower than the rutile titanium oxide concentration of the copolyester B.

For the second laminated film, the rutile titanium oxide concentration of the copolyester B is from 20 to 50% by weight and the rutile titanium oxide concentration of the copolyesters A and C is 0 to 10% by weight each.

In the present invention, the rutile titanium oxide may be used in combination with other white pigments such as alumina, calcium carbonate, silica, barium sulfate, zinc sulfide or anatase titanium oxide.

The rutile titanium oxide for the present invention is preferably subjected to the control of particle size and the removal of coarse particles by a purifying process before adding the titanium oxide to the copolyester. An example of the industrial means for the purification is dry or wet centrifugal separation. It is especially preferable to use two or more of the above purifying means in combination and purify the titanium oxide in stepwise.

The addition of the rutile titanium oxide to the copolyester can be performed by various means. Representative means are as follows.

(a) addition of titanium oxide after the transesterification reaction or esterification reaction or before the start of polycondensation reaction in the synthesis of the copolyester,

(b) addition of titanium oxide to the copolyester and kneading of the mixture in molten state,

(c) production of master pellets containing a large amount of rutile titanium oxide by the method (a) or (b) and kneading of the master pellet with a copolyester free from rutile titanium oxide to obtain a copolyester containing a desired amount of rutile titanium oxide.

In the case of using the method (a) comprising the addition of rutile titanium oxide in the synthesis of polyester, it is preferable to add the rutile titanium oxide to a reaction system in the form of a slurry dispersed in glycol.

The second laminated film of the present invention contains silicon dioxide particles in the copolyesters A and C.

The average particle diameter of the silicon dioxide particles is preferably between 0.6 and 2.0 μm, more preferably between 0.8 and 1.7 μm and especially preferably between 1.2 and 1.7 μm. The content of the silicon dioxide particles is preferably between 0.01 and 0.1% by weight, more preferably between 0.03 and 0.08% by weight. The copolyesters A and C preferably contain the same amount of silicon dioxide particles. The slipperiness of the film and the form of wound roll become poor and the scratch resistance, chipping resistance and transportability of the film are lowered when the average particle diameter is smaller than 0.6 μm or the content of the particle is less than 0.01% by weight, and troubles such as falling off of particles may occur in the manufacturing process when the average particle diameter is larger than 2.0 μm or the content of the particle is more than 0.1% by Weight. The silicon dioxide particle may have various forms such as block, coagulate or true sphere and the use of silicon dioxide particles having truly spherical form is preferable from the viewpoints of small amount of coarse particle and the resistance to falling off The truly spherical form means particles having a ratio of the major diameter to the minor diameter of smaller than 1.2.

The addition of silicon dioxide particles to a copolyester is preferably carried out by the method used in the addition of rutile titanium oxide.

The average particle diameter was determined by metallizing the surface of the particles, photographing the particles by an electron microscope with magnification of 10,000 to 30,000, measuring the major diameters, minor diameters and diameters of equivalent area circle, and using the average value of the equivalent area circle diameter as the average particle diameter.

The surface of the second laminated film of the present invention preferably has the following characteristics. The surface roughness (Ra) is between 0.103 and 0.08 μm, the 10-point surface roughness (SRz) is between 0.7 and 1.5 μm and the frictional coefficient is smaller than 0.35.

A laminated film having surface characteristics satisfying the above three characteristic requirements has good film transportability, scratch resistance, chipping resistance and windability in the film-forming process and workability of a metallic can.

A film satisfying the above three characteristic requirements can be produced by compounding copolyesters A and C with silicon dioxide particles having the above-mentioned average particle diameter at the above-mentioned ratio.

The surface roughness (Ra) is a value defined by JIS B0601. In the present invention, it was measured by a tracer-type surface roughness tester manufactured by Kosaka Kenkyusho Co. (SE-3FAT) using a feeler having a tip radius of 2 μm at a feeler pressure of 30 mg, a cut-off of 0.25 mm and a measuring length of 2.5 mm. The 10-point average roughness (SRz) was measured by measuring the three-dimensional roughness profile of the film surface by a three-dimensional roughness tester manufactured by Kosaka Kenkyusho Co. (SE-3CK) using a feeler having a tip radius of 2 μm at a feeler pressure of 30 mg, a measuring length of 1.3 mm, a sampling pitch of 2 μm, a cut-off of 0.25 mm, a vertical magnification of 20,000, a horizontal magnification of 200 and a scanning line number of 100, and using the distance between the mean height of the highest 5 peaks and the mean depth of the deepest 5 valleys in the measured profile as the 10-point average roughness (SRz). The friction coefficient was measured in conformity to ASTM D1894 and the value of kinetic friction coefficient (μk) was used as the friction coefficient.

The ratio (ρ/ρ

0

) of the apparent density (ρ) to the calculated density (ρ

0

) of the film of the present invention is required to fall between 0.65 and 1.00. The ratio (ρ/ρ

0

) is preferably between 0.75 and 1.00, especially preferably, between 0.90 and 1.00.

The density ratio of the second laminated film is not necessarily but preferably satisfy the above requirement.

The calculated density (ρ

0

) is defined by the following formula.

ρ_{0} = 100 ρ_{t} \frac{\sum_{i = 1}^{n} (\frac{Xi ρ_{i}}{W_{i} (ρ_{i} - ρ_{t}) + 100 ρ_{t}})}{\sum_{i = 1}^{n} X_{i}}

For the second laminated film containing silicon dioxide particles, the calculated density (ρ

0

) is calculated by the following formula.

ρ_{0} = 100 ρ_{t} ρ_{s} \frac{\sum_{i = 1}^{n} (\frac{Xi ρ_{i}}{W_{i} ρ_{s} (ρ_{i} - ρ_{t}) + Z_{i} ρ_{t} (ρ_{i} - ρ_{s}) + 100 ρ_{t} ρ_{s}})}{\sum_{i = 1}^{n} X_{i}}

in the above formulas,

ρ

0

: calculated density (g/cm

3

) of the whole laminated film:

ρ

i

: density (g/cm

3

) of the polymer part of each copolyester:

ρ

t

: density (g/cm

3

) of rutile titanium oxide:

ρ

s

: density (g/cm

3

) of silicon dioxide particle:

X

i

: thickness (μm) of each layer:

W

i

: concentration (wt. %) of rutile titanium oxide in each copolyester:

Z

i

: concentration (wt. %) of silicon dioxide particles in each copolyester:

n: number of copolyester layers.

The film-forming property of the polymer and the workability of metallic can can be improved by setting the ratio of apparent density to calculated density (ρ/ρ

0

) within the above range.

When the ratio of the apparent density to calculated density (ρ/ρ

0

) is smaller than 0.65, voids are generated in the produced film to cause the embrittlement of the film and, accordingly, the frequency of the breakage of film in drawing is increased to lower the productivity (film-forming property). The produced film is liable to cause the breakage, cracking or small defects in the case of forming a metallic can from the laminate of the film and a metallic can. The apparent density of the film is measured by using a density gradient tube.

The (100) plane and the (1{overscore (1)}0) plane parallel to the film surface of the film of the present invention preferably satisfy the following relationship:

0.15

≦f

(1{overscore (1)}0)/

f

(100)≦0.40

wherein f(1{overscore (1)}0) is X-ray diffraction intensity attributed to the (1{overscore (1)}0) plane and f(100) is X-ray diffraction intensity attributed to the (100) plane.

The intensity ratio (f(1{overscore (1)}0)/f(100)) is preferably between 0.22 and 0.40.

When the intensity ratio is smaller than 0.15, a number of voids are generated by the high orientation of the film to cause easy breakage in film-forming and deterioration of workability of the film. Conversely, uneven thickness is liable to occur in the film-forming when the intensity ratio exceeds 0.4.

The X-ray diffraction intensity was measured by the following method. The intensity of X-ray diffraction by the (100) plane parallel to the film surface and the intensity of X-ray diffraction by the (1{overscore (1)}0) plane were measured by using CuK-α as the X-ray source under the conditions of a divergence slit of ½°, a scattering slit of {fraction (1/20)}°, a reception slit of 0.15 mm and a scan speed of 1.000°/min by the multiple peak separation method using Pseudo Voight peak model and the intensity ratio was calculated from both intensity values.

The X-ray diffraction intensity was defined by the area of the diffraction peak of each crystal plane. Reflection peaks (anatase (101) and rutile (110)) caused by the pigment such as titanium oxide are present near that of the (100) plane, and the area is calculated omitting the area of these peaks.

The film of the present invention has an MOR value of preferably not smaller than 1.0 and not larger than 1.5, more preferably not smaller than 1.0 and smaller than 1.4, especially not smaller than 1.0 and smaller than 1.3.

When the MOR value exceeds 1.5, the anisotropy in the plane of the laminated film becomes large and microcracks and breakage may occur in the manufacture of a metallic can from a laminate of the film and a metallic plate.

The MOR value is a parameter representing the molecular orientation of a film and calculated by the ratio of the maximum value (X

MAX

) and the minimum value (X

MIN

) (X

MAX

/X

MIN

) of the transmission intensity of microwave transmitted through the film. The MOR value closer to 1 corresponds to the better balance of the orientation of the film in all directions. The MOR value close to 1 is preferable for the laminated film of the present invention.

The transmission intensity of microwave was measured by a molecular orientation tester MOA-2001A manufactured by Kanzaki Paper Co.

The following explanation is, an example of the manufacture of a white laminated polyester film of the present invention by biaxial drawing, especially sequential biaxial drawing.

The explained drawing method does not restrict the scope of the present invention.

Copolyesters constituting the individual layers of the white laminated polyester film of the present invention are separately melted, co-extruded through. a die, brought into contact before solidification and immediately quenched to obtain an essentially amorphous copolyester sheet. The sheet is drawn in longitudinal direction by heating with rolls, infrared rays, etc. The longitudinal drawing is preferably carried out at a drawing temperature higher than the glass transition point (Tg) of the copolyester by 20 to 50° C. at a draw ratio of 2.5 to 3.6 especially in two or more divided steps. The drawing in lateral direction is preferably carried out by starting at a temperature higher than the Tg of the copolyester by 20° C. or more and raising the temperature up to a level lower than the melting point (Tm) of the polyester by 100 to 130° C. at a lateral draw ratio of 2.6 to 3.7. The heat-set temperature is preferably selected between 150° C. and 230° C. taking consideration of the melting point of the copolyester polymer to get a desired film quality. The laminated film is also producible e.g. by separately melting and extruding the copolyesters to form separate films and laminating and welding the films in undrawn state or after drawing by the above drawing methods.

The white laminated polyester film of the present invention preferably has a thickness of from 6 to 75 μm, more preferably from 10 to 75 μm, especially from 15 to 50μm. A film thinner than 6 μm is liable to cause the cracking, etc., in the manufacture of a metallic can and a film having a thickness exceeding 75 μm has an unnecessarily excess quality resulting in high cost.

The white laminated polyester film of the present invention has a double-layered or triple-layered structure consisting of a layer B as the core layer, a layer A laminated to one surface of the layer B and optionally a layer C laminated to the other surface of the layer B. A triple-layered laminated film is preferable from the object of the present invention.

The ratio of the thickness (T

A

) of the layer A to the thickness (T

B

) of the layer B (T

A

/T

B

) and the ratio of the thickness (T

C

) of the layer C to the thickness (T

B

) of the layer B (T

C

/T

B

) are preferably between 0.05 and 1 each, more preferably between 0.1 and 0.7 each.

The white laminated polyester film of the present invention preferably shows an electric current of 0.2 mA or less in the ERV test of a metallic can manufactured by the deep drawing of a laminate of the above film and a metallic plate.

The electric current exceeding 0.2 mA in the ERV test corresponds to the generation of micro-cracks such as pinholes in the film by the deep drawing revealing the poor workability of the film.

The ERV test is carried out by filling a manufactured can with 1% aqueous solution of NaCl, inserting an electrode into the solution and measuring the electric current under the application of electric voltage of 6V between the electrode and the can used as the anode.

The metallic plate to be laminated with the white laminated polyester film of the present invention is preferably a plate of tinplate, tin-free steel, aluminum, etc., especially as a metal plate for canning. The lamination of the film to the metallic plate can be carried out e.g. by the following methods (1) and (2).

(1) A film is laminated to a metallic plate heated at or above the melting point of the film and the laminate is cooled to bond the film to the metallic plate through an amorphous layer formed at the surface layer (thin layer) of the film contacting with the metallic plate.

(2) An adhesive layer is applied to the film as a primer and a metallic plate is bonded to the primer-coated surface of the film. A conventional resin adhesive such as epoxy adhesive, epoxy-ester adhesive or alkyd adhesive can be used as the adhesive layer.

The white laminated polyester film for metallic plate lamination work of the present invention is most suitable for the use to be laminated to a metallic plate to form the outer surface of a metallic can in the case of manufacturing a metallic can by deep-drawing and optionally ironing of a metallic plate.

EXAMPLES

The present invention is described in more detail by the following examples. The characteristic values in the examples were measured and evaluated by the following methods.

(1) Melting Point of Copolyester

The melting point of the copolyester was determined by measuring the melt peak with Du Pont Instruments 910 DSC at a temperature increasing rate of 20° C. /min. The amount of the specimen was about 20 mg.

(2) Intrinsic Viscosity of Copolyester

The intrinsic viscosity was measured by dissolving a specimen film in o-chlorophenol, removing fillers such as titanium oxide by a centrifugal separator and measuring at 35° C.

The intrinsic viscosity of each layer is the value of an undrawn film manufactured by singly extruding the copolyester of each layer.

(3) Average Particle Diameter of Particles

Particles were surface-metallized and the major diameter, the minor diameter and the diameter of equivalent area circle were measured from an image magnified 10,000 to 30,000 times by an electron microscope. The average of the diameters of equivalent area circle was used as the average particle diameter.

(4) X-ray Diffraction Intensity Ratio

The intensity of X-ray diffraction (f(100)) by the (100) plane parallel to the film surface and the intensity of X-ray diffraction (f(1{overscore (1)}0)) by the (1{overscore (1)}0) plane were measured by using CuK-α as the X-ray source under the conditions of a divergence slit of ½°, a scattering slit of ½°, a reception slit of 0.15 mm and a scan speed of 1.000°/min by the multiple peak separation method using Pseudo Voight peak model.

The intensity ratio was calculated from the following formula.

X-ray diffraction intensity ratio=

f

(1{overscore (1)}0)/

f

(100)

The area of diffraction peak attributed to each crystal plane was measured and the area was used as the X-ray diffraction intensity. Reflection peaks caused by the pigment such as titanium oxide (anatase (101), rutile (110)) are present close to the (100) plane peak and these peaks caused by the pigment are omitted. in the calculation of the area.

(5) Density Ratio (ρ/ρ

0

)

The apparent density (ρ) of the film was measured by using a density gradient tube. The density ratio was determined by dividing the apparent density by the calculated density (ρ

0

) calculated by the following formula.

ρ_{0} = 100 ρ_{t} ρ_{s} \frac{\sum_{i = 1}^{n} (\frac{Xi ρ_{i}}{W_{i} ρ_{s} (ρ_{i} - ρ_{t}) + Z_{i} ρ_{t} (ρ_{i} - ρ_{s}) + 100 ρ_{t} ρ_{s}})}{\sum_{i = 1}^{n} X_{i}}

in the above formula,

ρ

0

: calculated density (g/cm

3

) of the whole laminated film:

ρ

i

: density (g/cm

3

) of the polymer part of each copolyester:

ρ

t

: density (g/cm

3

) of rutile titanium oxide:

ρ

s

: density (g/cm

3

) of silicon dioxide particle (1 in the case free from silicon dioxide particle):

X

i

: thickness (μm) of each layer:

W

i

: concentration (wt. %) of rutile titanium oxide in each copolyester:

Z

i

: concentration (wt. %) of silicon dioxide particle in each copolyester:

n number of copolyester layers.

(6) MOR Value

The MOR value was determined by a molecular orientation tester MOA-2001A manufactured by Kanzaki Paper Co. by measuring the maximum value (X

MAX

) and the minimum value (X

MIN

) of the transmission intensity of microwave and calculating by the following formula:

MOR value=

X

MAX

/X

MIN

(7) Center-line Average Height (Ra)

The center-line average height (Ra) is a value defined by JIS B0601.

In the present invention, it was measured by a tracer-type surface roughness tester manufactured by Kosaka Kenkyusho Co. (SE-3FAT) using a feeler having a tip radius of 2 μm at a feeler pressure of 30 mg, a cut-off of 0.25 mm and a measuring length of 2.5 mm.

(8) Ten-point Average Roughness (SRz)

The 10-point average roughness (SRz) was measured by measuring the three-dimensional roughness profile of the film surface by a three-dimensional roughness tester manufactured by Kosaka Kenkyusho Co. (SE-3CK) using a feeler having a tip radius of 2 μm at a feeler pressure of 30 mg, a measuring length of 1.3 mm, a sampling pitch of 2 μm, a cut-off of 0.25 mm, a vertical magnification of 20,000, a horizontal magnification of 200 and a scanning line number of 100, and using the distance between the mean heights of the highest 5 peaks and the mean depth of the deepest 5 valleys in the measured profile as the 10-point average roughness (SRz).

(9) Friction Coefficient

The friction coefficient was measured in conformity to ASTM D1894 and the value of kinetic friction coefficient (μk) was used as the friction coefficient.

(10) Film-forming Property

The film-forming property in the manufacture of a film was evaluated by the following criterion.

◯: There is little breakage of the film to enable stable film-forming.

X: Breakage of film frequently takes place to exhibit poor film-forming performance.

(11) Windability

The windability of a film was evaluated by winding 10,000 m of a film of 1,000 mm wide at a speed of 500 m/min in the form of a roll and observing the protruding extent of the film from a roll end.

⊚: Protrusion of the film is 3 mm or less and the roll has good appearance.

◯: Protrusion of the film is 5 mm or less.

X: Protrusion of the film exceeds 5 mm.

(12) Abrasion Resistance

A film specimen was cut to ½inch wide at 20° C. and 60% RH, an edge of a blade (blade for industrial razor tester manufactured by GKI Ltd., UK) was applied perpendicularly to the film, pressed into the film to a depth of 1.5 mm and moved at a speed of 60 m/min and an inlet tension of 60 g. The abrasion (W) of the blade was measured by SEM after moving the film over a length of 50 m, and the abrasion resistance was evaluated by the following criterion.

◯: W<4.0×10

4

μcm

3

X: W≧4.0×10

4

μm

3

(13) Lamination suitability

A film was laminated to both surfaces of a tin-free steel plate of 0.25 mm thick heated at 260° C., the laminate was cooled with water, a circular disk of 150 mm diameter was cut off from the laminate and the disk was subjected to deep-drawing with a drawing die and a punch in 3 stages to form a can free from seam at the side face and having a diameter of 55 mm (which may be hereinafter abbreviated as “can”). The worked state was evaluated by the following criterion.

◯: Free from wrinkle showing good lamination suitability

X: Wrinkles are generated in the lamination.

(14) Deep-drawing Suitability-1

The behavior of the film in deep-drawing and the manufactured can were observed and evaluated by the following criterion.

◯: There is no abnormality in the films on the inner and the outer surfaces of the manufactured can and no microcrack and breakage was unobservable on the films.

X: Breakage of film was observable at a part of the films on the inner and the outer surfaces of the manufactured can.

(15) Deep-drawing Suitability-2

The behavior of the film in deep-drawing and the manufactured can were observed and evaluated by the following criterion.

◯: There is no abnormality in the films on the inner and the outer surfaces of the manufactured can and the rust-proofing test (the can was filled with 1% NaCl solution, an electrode was inserted into the can and electric current was measured under a voltage of 6V using the can as the anode. The test may be abbreviated hereunder as ERV test) was 0.2 mA or less.

X: No abnormality was unobservable on both inner and outer face films, however, the electric current was larger than 0.2 mA in the EVR test, and pinhole-like crack was observable on the film starting from a coarse lubricant particle by magnifying the electrified part of the film.

(16) Impact Crack Resistance

A can having good deep-drawing suitability was filled with water and 10 cans for each test were dropped on a PVC tile floor from a height of 30 cm. EVR test was performed on the film of the inner face of the can and the impact crack resistance was evaluated by the following criterion.

◯: The current was 0.2 mA or less for all 10 cans.

Δ: The current was over 0.2 mA for one to five of the cans.

X: The current was over 0.2 mA for six or more cans or crack of the film was observable after the drop test.

(17) Thermal Embrittlement Resistance

A can having good deep-drawing suitability was maintained at 210° C. for 5 minutes and the aforementioned impact crack resistance test was carried out. The result was evaluated by the following criterion.

◯: The current was 0.2 mA or less for all 10 cans.

Δ: The current was over 0.2 mA for one to five of the cans.

X: The current was over 0.2 mA for six or more cans or crack of the film was observable after heating at 210° C. for 5 minutes.

(18) Whiteness of the Outer Surface of the Can

Black lines of 50 mm long and 0.2 mm and 1.4 mm wide were drawn by a drawing pen on the tin-free steel surface forming the outer surface of a can before laminating a film to a tin-free steel. A can was manufactured from a laminate of the tin-free steel and a specimen film and the black lines were observed through the film. The result was evaluated by the following criterion.

◯: Both black lines were invisible.

Δ: One black line was faintly observable and the other one was invisible.

X: One black line was observable and the other one was faintly observable.

Examples 1 to 7 and Comparative Examples 1 to 6

Polyesters for the layer A, layer B and layer C were produced by adding rutile titanium oxides having average particle diameters shown in the Table 1 at concentrations shown in the Table 1 to copolymerized polyethylene terephthalate copolymerized with the components shown in the Table 1. These polyesters were separately melted and then co-extruded through adjacent dies under the film-forming conditions shown in the Table 3 to effect the lamination and welding of the layers. The laminate was solidified by quenching, and the obtained undrawn film was longitudinally drawn in longitudinal direction and then lateral direction and heat-set under conditions shown in the Table 3 to obtain a biaxially oriented white laminated film having a thickness of 20 μm. The properties of the film are shown in the Table 4.

Comparative Example 7 and 8

Polyesters for the layer A, layer B and layer C were produced by adding rutile titanium oxides having average particle diameters shown in the Table 2 at concentrations shown in the Table 2 to a polyethylene terephthalate copolymerized with 12 mol % of isophthalic acid. These polyesters were melted and extruded under the film-forming conditions shown in the Table 3 and solidified by quenching to obtain undrawn films. These undrawn films were drawn in longitudinal direction and lateral direction and subsequently heat-set to obtain biaxially oriented films of 20 μm thick. The properties of the films are shown in the Table 4.

TABLE 1

Layer A

Layer B

Copolymerized

Meltg

Thick-

Aver.

TiO

2

Copolymerized

Meltg

Thick-

Aver.

TiO

2

Component

Point

ness

Diam.

Conc.

Component

Point

ness

Diam.

Conc.

Comp.

Mol %

° C.

μm

μm

Wt. %

Comp

Mol %

° C.

μm

μm

Wt. %

Example 1

IA

12

228

3

0.24

1

IA

12

228

14

0.24

10

Example 2

IA

12

228

3

0.24

10

IA

12

228

14

0.27

15

Example 3

IA

6

244

3

0.24

2

IA

6

244

14

0.24

20

Example 4

SA

12

228

3

—

0

SA

12

228

14

0.24

25

Example 5

SA

14

223

1.5

0.20

5

SA

12

228

17

0.30

30

Example 6

IA

14

223

4

0.20

1

IA

14

223

12

0.30

40

Example 7

IA

12

228

3

0.24

1

IA

12

228

12

0.24

25

Comp-tive

—

260

3

0.24

5

—

260

14

0.24

20

Example 1

Comp-tive

IA

4

250

3

0.24

3

IA

4

250

14

0.24

20

Example 2

Comp-tive

IA

22

208

3

0.24

8

IA

22

208

14

0.24

25

Example 3

Comp-tive

SA

12

228

1.5

0.24

20

IA

12

228

17

0.24

20

Example 4

Comp-tive

IA

12

228

3

0.24

1

IA

12

228

14

0.27

5

Example 5

Comp-tive

IA

12

228

3

0.24

1

IA

12

228

12

0.24

35

Example 6

Layer C

Copolymerized

Meltg

Thick-

Aver.

TiO

2

Component

Point

ness

Diam.

Conc.

Comp

Mol %

° C.

μm

μm

Wt. %

Example 1

IA

12

228

3

0.24

1

Example 2

IA

12

228

3

0.24

10

Example 3

IA

6

244

3

0.24

2

Example 4

SA

12

228

3

—

0

Example 5

SA

14

223

1.5

0.20

5

Example 6

IA

14

223

4

0.20

1

Example 7

SA

14

223

5

0.24

8

Comp-tive

—

260

3

0.24

5

Example 1

Comp-tive

IA

4

250

3

0.24

3

Example 2

Comp-tive

IA

22

208

3

0.24

8

Example 3

Comp-tive

SA

12

228

1.5

0.24

20

Example 4

Comp-tive

IA

12

228

3

0.24

1

Example 5

Comp-tive

IA

12

228

5

0.24

20

Example 6

Note: IA: Isophthalic acid, SA: Sebacic acid

TABLE 2

Layer A

Layer B

Layer C

Average

Conc. of

Average

Conc. of

Thick-

Average

Conc. of

Thickness

White

diameter

pigment

Thickness

White

diameter

pigment

ness

White

diameter

pigment

μm

pigment

μm

wt. %

μm

pigment

μm

wt. %

μm

pigment

μm

wt. %

Comparative

3

Rutile

0.24

1

14

Calcium

2.70

10

3

Rutile

0.24

1

Example 7

TiO2

carbonate

TiO2

Comparative

3

Rutile

0.24

1

14

Barium

0.8

10

3

Rutile

0.24

1

Example 8

TiO2

sulfate

TiO2

TABLE 3

Melt-extrusion temperature ° C.

Longit-nal drawing conditions

Lateral drawing conditions

Heat-set

Layer A

Layer B

Layer C

Temp. ° C.

Draw ratio

Temp. ° C.

Draw ratio

temp. ° C.

Example 1

290

290

290

115

2.9

130

3.0

180

Example 2

280

280

280

110

3.2

120

3.3

190

Example 3

280

290

280

115

3.1

130

3.1

175

Example 4

285

285

285

110

3.4

120

3.4

185

Example 5

275

280

275

115

3.0

120

3.1

175

Example 6

275

280

275

95

2.8

110

3.0

165

Example 7

275

280

275

100

2.8

115

3.0

175

Comparative

290

290

290

120

3.4

130

3.4

230

Example 1

Comparative

290

290

290

110

3.0

120

3.1

180

Example 2

Comparative

275

275

275

90

2.9

100

3.0

165

Example 3

Comparative

280

280

280

110

3.0

120

3.1

185

Example 4

Comparative

280

280

280

110

3.0

120

3.1

195

Example 5

Comparative

275

280

275

100

2.8

115

3.0

175

Example 6

Comparative

280

280

280

110

3.0

120

3.1

185

Example 7

Comperative

280

280

280

110

3.0

120

3.1

185

Example 8

TABLE 4

Deep-drawing

Impact

Heat

Whiteness of

Intrinsic viscosity

Laminination

Abrasion Resistance

suitability

crack

embrittlement

outer face

ρ/ρo

Layer A

Layer B

Layer C

suitability

Layer A

Layer C

1

2

resistance

resistance

of can

Example 1

0.99

0.60

0.58

0.60

◯

◯

◯

◯

◯

◯

◯

◯

Example 2

0.98

0.56

0.55

0.56

◯

◯

◯

◯

◯

◯

◯

◯

Example 3

0.96

0.60

0.54

0.60

◯

◯

◯

◯

◯

◯

◯

◯

Example 4

0.95

0.60

0.51

0.60

◯

◯

◯

◯

◯

◯

◯

◯

Example 5

0.87

0.58

0.49

0.58

◯

◯

◯

◯

◯

◯

◯

◯

Example 6

0.68

0.60

0.48

0.60

◯

◯

◯

◯

◯

◯

◯

◯

Example 7

0.95

0.60

0.52

0.55

◯

◯

◯

◯

◯

◯

◯

◯

Comparative

0.99

0.58

0.53

0.58

◯

◯

◯

X

—

—

—

◯

Example 1

Comparative

0.94

0.59

0.53

0.59

◯

◯

◯

◯

◯

Δ

X

◯

Example 2

Comparative

0.94

0.55

0.51

0.55

◯

◯

◯

◯

◯

◯

X

◯

Example 3

Comparative

0.98

0.54

0.54

0.54

◯

X

X

◯

◯

◯

◯

◯

Example 4

Comparative

1.00

0.62

0.58

0.62

◯

◯

◯

◯

◯

◯

◯

X

Example 5

Comparative

0.77

0.65

0.50

0.50

X

◯

X

◯

X

—

—

◯

Example 6

Comparative

0.83

0.61

0.52

0.61

◯

◯

◯

◯

X

—

—

X

Example 7

Comparative

0.85

0.63

0.52

0.63

◯

◯

◯

◯

◯

◯

◯

X

Example 8

Examples 8 to 14 and Comparative Examples 9 to 15

Copolyesters for the layer A, layer B and layer C were produced by adding rutile titanium oxides having average particle diameters shown in the Table 5 at concentrations shown in the Table 5 to copolymerized polyethylene terephthalates copolymerized with the components shown in the Table 5. These copolyesters were separately melted and then coextruded through adjacent dies under the film-forming conditions shown in the Table 7 to effect the lamination and welding of the layers. The laminate was solidified by quenching, and the obtained undrawn film was drawn in longitudinal direction and then lateral direction and heat-set under conditions shown in the Table 7 to obtain a biaxially oriented film having a thickness of 20 μm. The drawing in longitudinal direction was carried out in two stages at a draw ratio of 1.7 each for the Examples 8, 10, 11 and 14. The properties of these films are shown in the Table 8.

The intrinsic viscosity of each layer in the Table 8 are the viscosity of undrawn film produced by singly extruding the copolyester for each layer.

Comparative Examples 16 and 17

A polyethylene terephthalate copolymerized with 12 mol % of isophthalic acid was incorporated with rutile titanium oxide, calcium carbonate and barium sulfate having average particle diameters shown in the Table 6 in amounts shown in the Table 6, melted and extruded under the form-forming condition shown in the Table 7 and solidified by quenching to obtain an undrawn film. The undrawn film was drawn in longitudinal direction and then lateral direction and subsequently heat-set to obtain a biaxially oriented film having a thickness of 20 μm. The properties of these films are shown in the Table 8.

TABLE 5

Layer A

Layer B

Copolymerized

Meltg

Thick-

Aver.

TiO

2

Copolymerized

Meltg

Thick-

Aver.

TiO

2

Component

Point

ness

Diam.

Conc.

Component

Point

ness

Diam.

Conc.

Comp.

Mol %

° C.

μm

μm

Wt. %

Comp

Mol %

° C.

μm

μm

Wt. %

Example 8

IA

12

228

1.5

0.22

3

IA

12

228

17

0.22

30

Example 9

IA

12

228

3

0.22

10

IA

12

228

14

0.27

11

Example 10

IA

12

228

1.5

0.24

2

IA

12

228

17

0.24

40

Example 11

SA

14

223

4

—

0

SA

14

223

12

0.24

45

Example 12

SA

6

244

1.5

0.20

5

SA

6

244

17

0.30

20

Example 13

IA

14

223

4

0.20

1

IA

14

223

12

0.30

40

Example 14

IA

14

223

3

0.24

2

IA

12

228

12

0.24

25

Comp-tive

—

260

3

0.24

4

IA

2

255

14

0.24

18

Example 9

Comp-tive

IA

4

250

3

0.24

4

IA

4

250

14

0.24

18

Example 10

Comp-tive

IA

22

208

3

0.24

5

IA

23

206

14

0.24

25

Example 11

Comp-tive

SA

10

233

1.5

0.24

20

IA

12

228

17

0.24

21

Example 12

Comp-tive

IA

12

228

3

0.24

1

IA

12

228

14

0.27

6

Example 13

Comp-tive

IA

12

228

3

0.24

1

IA

12

228

12

0.24

35

Example 14

Comp-tive

SA

14

223

4

—

0

SA

14

223

12

0.24

45

Example 15

Layer C

Copolymerized

Meltg

Thick-

Aver.

TiO

2

Component

Point

ness

Diam.

Conc.

Comp

Mol %

° C.

μm

μm

Wt. %

Example 8

IA

12

228

1.5

0.22

3

Example 9

IA

12

228

3

0.22

10

Example 10

IA

12

228

3

0.24

2

Example 11

SA

14

223

4

—

0

Example 12

SA

6

244

1.5

0.20

5

Example 13

IA

14

223

4

0.20

1

Example 14

SA

10

233

5

0.24

7

Comp-tive

—

260

3

0.24

4

Example 9

Comp-tive

IA

4

250

3

0.24

4

Example 10

Comp-tive

IA

22

208

3

0.24

5

Example 11

Comp-tive

SA

10

233

1.5

0.24

20

Example 12

Comp-tive

IA

12

228

3

0.24

1

Example 13

Comp-tive

IA

12

228

5

0.24

1

Example 14

Comp-tive

SA

14

223

4

—

0

Example 15

Note: IA: Isophthalic acid, SA: Sebacic acid

TABLE 6

Layer A

Layer B

Layer C

Average

Conc. of

Average

Conc. of

Thick-

Average

Conc. of

Thickness

White

diameter

pigment

Thickness

White

diameter

pigment

ness

White

diameter

pigment

μm

pigment

μm

wt. %

μm

pigment

μm

wt. %

μm

pigment

μm

wt. %

Comparative

3

Rutile

0.24

1

13

Calcium

2.70

11

4

Rutile

0.24

1

Example 16

TiO2

carbonate

TiO2

Comparative

3

Rutile

0.24

1

13

Barium

0.70

11

4

Rutile

0.24

1

Example 17

TiO2

sulfate

TiO2

TABLE 7

Melt-extrusion temperature ° C.

Longit-nal drawing conditions

Lateral drawing conditions

Heat-set

Layer A

Layer B

Layer C

Temp. ° C.

Draw ratio

Temp. ° C.

Draw ratio

temp. ° C.

Example 8

275

275

275

120

1.7 × 1.7

130

3.0

180

Example 9

280

280

280

110

3.2

120

3.3

190

Example 10

280

275

280

120

1.7 × 1.7

130

3.0

175

Example 11

280

270

280

120

1.7 × 1.7

130

3.0

175

Example 12

275

280

275

115

3.0

120

3.1

175

Example 13

280

275

280

120

2.8

110

3.0

165

Example 14

275

280

275

100

1.7 × 1.7

135

3.0

175

Comparative

290

290

290

115

3.0

130

3.0

230

Example 9

Comparative

290

290

290

110

3.0

120

3.1

230

Example 10

Comparative

275

275

275

110

2.9

100

3.0

165

Example 11

Comparative

280

280

280

110

3.0

120

3.1

185

Example 12

Comparative

280

280

280

110

3.4

120

3.4

195

Example 13

Comparative

270

280

295

100

2.8

115

3.0

175

Example 14

Comparative

285

270

285

110

3.0

110

3.1

165

Example 15

Comparative

280

280

280

110

3.0

120

3.1

185

Example 16

Comparative

280

280

280

110

3.0

120

3.1

185

Example 17

TABLE 8

X-ray

Deep-

Impact

Heat

Whiteness

diffraction

Film-

Abrasion

drawing

crack

embrittle-

of outer

intensity

Intrinsic viscosity

forming

Lamina-n

Resistance

suitability

resist-

ment

face

ratio

ρ/ρo

Layer A

Layer B

Layer C

property

suitability

Layer A

Layer C

1

2

ance

resistance

of can

Example 8

0.25

0.85

0.60

0.52

0.60

◯

◯

◯

◯

◯

◯

◯

◯

◯

Example 9

0.27

0.99

0.56

0.55

0.56

◯

◯

◯

◯

◯

◯

◯

◯

◯

Example 10

0.29

0.90

0.60

0.50

0.60

◯

◯

◯

◯

◯

◯

◯

◯

◯

Example 11

0.26

0.76

0.58

0.48

0.58

◯

◯

◯

◯

◯

◯

◯

◯

◯

Example 12

0.24

0.96

0.58

0.49

0.58

◯

◯

◯

◯

◯

◯

◯

◯

◯

Example 13

0.26

0.78

0.60

0.48

0.60

◯

◯

◯

◯

◯

◯

◯

◯

◯

Example 14

0.24

0.94

0.60

0.52

0.55

◯

◯

◯

◯

◯

◯

◯

◯

◯

Comparative

0.18

0.71

0.58

0.53

0.58

X

◯

◯

◯

X

—

—

—

◯

Example 9

Comparative

0.22

0.95

0.59

0.53

0.59

◯

◯

◯

◯

◯

◯

Δ

X

◯

Example 10

Comparative

0.23

0.94

0.55

0.51

0.55

◯

◯

◯

◯

◯

◯

◯

X

◯

Example 11

Comparative

0.25

0.97

0.54

0.54

0.54

◯

◯

X

X

◯

◯

◯

◯

◯

Example 12

Comparative

0.23

1.00

0.62

0.58

0.62

◯

◯

◯

◯

◯

◯

◯

◯

X

Example 13

Comparative

0.24

0.77

0.66

0.51

0.50

◯

X

◯

◯

◯

X

—

—

◯

Example 14

Comparative

0.20

0.64

0.57

0.48

0.57

X

◯

◯

◯

◯

X

—

—

◯

Example 15

Comparative

0.24

0.83

0.63

0.52

0.63

◯

◯

◯

◯

◯

X

—

—

X

Example 16

Comparative

0.24

0.85

0.61

0.52

0.61

◯

◯

◯

◯

◯

◯

◯

◯

X

Example 17

Examples 15 to 21 and Comparative Examples 18 to 24

Copolymerized polyethylene terephthalates copolymerized with the components shown in the Table 9 were incorporated with rutile titanium oxides having average particle diameters shown in the Table 9 in amounts shown in the Table 9 to obtain copolyesters for the layer A, layer B and layer C. These copolyesters were separately melted and then coextruded through adjacent dies, laminated and welded under the film-forming conditions shown in the Table 11 and the products were solidified by quenching to obtain undrawn films. The undrawn films were drawn in longitudinal direction and then lateral direction and subsequently heat-set to obtain biaxially oriented films having a thickness of 20 μm. The properties of these films are shown in the Table 12.

In the Examples 15, 17 and 18, the longitudinal drawing was carried out in two steps at a draw ratio of 1.7 each.

Comparative Example 25

A polyethylene terephthalate copolymer copolymerized with 12 mol % of isophthalic acid was incorporated with rutile titanium oxide and calcium carbonate having average particle diameters shown in the Table 10 in amounts shown in the Table 10, melted and extruded under the film-forming condition shown in the Table 11 and solidified by quenching to obtain an undrawn film. The undrawn film was drawn in longitudinal direction and then lateral direction and subsequently heat-set to obtain a biaxially oriented film having a thickness of 20 μm. The properties of the film are shown in the Table 12.

TABLE 9

Layer A

Layer B

Copolymerized

Meltg

Thick-

Aver.

TiO

2

Copolymerized

Meltg

Thick-

Aver.

TiO

2

Component

Point

ness

Diam.

Conc.

Component

Point

ness

Diam.

Conc.

Comp.

Mol %

° C.

μm

μm

Wt. %

Comp

Mol %

° C.

μm

μm

Wt. %

Example 15

IA

12

228

2

0.22

2

IA

12

228

16

0.24

31

Example 16

IA

12

228

3

0.24

10

IA

12

228

14

0.24

12

Example 17

IA

12

228

2

0.24

2

IA

12

228

16

0.24

40

Example 18

IA

15

221

4

—

0

IA

15

221

12

0.24

45

Example 19

SA

6

244

1.5

0.20

7

SA

6

244

17

0.28

20

Example 20

IA

14

223

4

0.20

1

IA

14

223

12

0.28

28

Example 21

IA

14

223

3

0.22

1

IA

12

228

12

0.22

25

Comp-tive

—

260

2

0.27

5

—

260

16

0.27

30

Example 18

Comp-tive

IA

4

250

3

0.22

4

IA

4

250

14

0.22

17

Example 19

Comp-tive

IA

22

208

3

0.22

5

IA

23

206

14

0.22

25

Example 20

Comp-tive

SA

10

233

2

0.22

20

IA

12

228

14

0.22

22

Example 21

Comp-tive

IA

12

228

3

0.22

1

IA

12

228

14

0.27

7

Example 22

Comp-tive

IA

12

228

3

0.22

2

IA

12

228

12

0.22

35

Example 23

Comp-tive

SA

14

223

4

—

0

SA

14

223

12

0.22

45

Example 24

Layer C

Copolymerized

Meltg

Thick-

Aver.

TiO

2

Component

Point

ness

Diam.

Conc.

Comp

Mol %

° C.

μm

μm

Wt. %

Example 15

IA

12

228

2

0.22

2

Example 16

IA

12

228

3

0.24

10

Example 17

IA

12

228

2

0.24

2

Example 18

IA

15

221

4

—

0

Example 19

SA

6

244

1.5

0.20

7

Example 20

IA

14

223

4

0.20

1

Example 21

SA

10

233

5

0.22

7

Comp-tive

—

260

2

0.27

5

Example 18

Comp-tive

IA

4

250

3

0.22

4

Example 19

Comp-tive

IA

22

208

3

0.22

5

Example 20

Comp-tive

SA

10

233

3

0.22

20

Example 21

Comp-tive

IA

12

228

3

0.22

1

Example 22

Comp-tive

IA

12

228

5

0.22

2

Example 23

Comp-tive

SA

14

223

4

—

0

Example 24

Note: IA: Isophthalic acid, SA: Sebacic acid

TABLE 10

Layer A

Layer B

Layer C

Average

Conc. of

Average

Conc. of

Thick-

Average

Conc. of

Thickness

White

diameter

pigment

Thickness

White

diameter

pigment

ness

White

diameter

pigment

μm

pigment

μm

wt. %

μm

pigment

μm

wt. %

μm

pigment

μm

wt. %

Comparative

3

Rutile

0.22

1

14

Calcium

2.90

11

3

Rutile

0.22

1

Example 25

TiO2

carbonate

TiO2

TABLE 11

Melt-extrusion temperature ° C.

Longit-nal drawing conditions

Lateral drawing conditions

Heat-set

Layer A

Layer B

Layer C

Temp. ° C.

Draw ratio

Temp. ° C.

Draw ratio

temp. ° C.

Example 15

275

275

275

110

1.7 × 1.7

130

3.0

180

Example 16

280

280

280

110

3.2

120

3.3

190

Example 17

280

275

280

120

1.7 × 1.7

130

3.0

175

Example 18

280

270

280

115

1.7 × 1.7

130

3.0

175

Example 19

275

280

275

115

3.0

120

3.1

175

Example 20

280

275

280

120

3.0

120

3.0

185

Example 21

275

280

275

100

2.9

135

3.0

175

Comparative

290

295

290

115

3.0

130

3.0

230

Example 18

Comparative

290

290

290

110

3.0

120

3.1

230

Example 19

Comparative

275

275

275

110

2.9

100

3.0

165

Example 20

Comparative

280

280

280

110

3.0

120

3.1

185

Example 21

Comparative

280

280

280

120

3.3

120

3.4

195

Example 22

Comparative

270

280

295

100

2.8

115

3.0

175

Example 23

Comparative

285

270

285

110

3.0

110

3.1

165

Example 24

Comparative

280

280

280

100

3.0

120

3.1

185

Example 25

TABLE 12

X-ray

Abrasion

Deep-

Impact

Heat

Whiteness

diffraction

Intrinsic viscosity

Film-

Resistance

drawing

crack

embrittle-

of outer

intensity

MOR

Layer

Layer

Layer

forming

Lamina-n

Layer

Layer

suitability

resist-

ment

face

ratio

value

ρ/ρo

A

B

C

property

suitability

A

C

1

2

ance

resistance

of can

Example 15

0.26

1.31

0.85

0.60

0.52

0.60

◯

◯

◯

◯

◯

◯

◯

◯

◯

Example 16

0.27

1.06

0.99

0.57

0.55

0.57

◯

◯

◯

◯

◯

◯

◯

◯

◯

Example 17

0.29

1.43

0.90

0.58

0.51

0.58

◯

◯

◯

◯

◯

◯

◯

◯

◯

Example 18

0.26

1.45

0.76

0.60

0.49

0.60

◯

◯

◯

◯

◯

◯

◯

◯

◯

Example 19

0.24

1.12

0.95

0.58

0.49

0.58

◯

◯

◯

◯

◯

◯

◯

◯

◯

Example 20

0.26

1.25

0.92

0.58

0.48

0.58

◯

◯

◯

◯

◯

◯

◯

◯

◯

Example 21

0.24

1.23

0.94

0.58

0.52

0.55

◯

◯

◯

◯

◯

◯

◯

◯

◯

Comparative

0.18

1.30

0.74

0.58

0.51

0.58

X

◯

◯

◯

X

—

—

—

◯

Example 18

Comparative

0.22

1.14

0.95

0.59

0.54

0.59

◯

◯

◯

◯

◯

◯

Δ

X

◯

Example 19

Comparative

0.23

1.20

0.94

0.55

0.52

0.55

◯

◯

◯

◯

◯

◯

◯

X

◯

Example 20

Comparative

0.25

1.20

0.97

0.53

0.53

0.53

◯

◯

X

X

◯

◯

◯

◯

◯

Example 21

Comparative

0.26

1.02

1.00

0.63

0.58

0.63

◯

◯

◯

◯

◯

◯

◯

◯

X

Example 22

Comparative

0.24

1.31

0.76

0.65

0.50

0.50

◯

X

◯

◯

◯

X

—

—

◯

Example 23

Comparative

0.20

1.42

0.64

0.56

0.48

0.56

X

◯

◯

◯

◯

X

—

—

◯

Example 24

Comparative

0.25

1.08

0.83

0.61

0.52

0.61

◯

◯

◯

◯

◯

X

—

—

X

Example 25

Examples 22 to 40 and Comparative Examples 26 to 36

Copolymerized polyethylene terephthalates copolymerized with the components shown in the Table 13 were incorporated with rutile titanium oxide and silicon dioxide particles having average particle diameters shown in the Table 13 in amounts shown in the Table 13, melted with separate extruders, coextruded through dies and solidified by quenching to obtain undrawn films. The undrawn films were drawn in longitudinal direction at 120° C. at a draw ratio of 3.0 and then in lateral direction at a draw ratio of 3.0 and subsequently heat-set at 180C to obtain biaxially oriented films composed of layers having thicknesses shown in the Table 13.

In the Example 39, a biaxially drawn film was manufactured by the same method except for the change of the longitudinal draw temperature to 105° C. and the longitudinal draw ratio to 3.3.

In the Comparative Example 36, a biaxially drawn film was manufactured by the same method except for the change of the longitudinal draw temperature to 118° C., the longitudinal draw ratio to 2.6 and the lateral draw ratio to 3.6. The properties of these films are shown in the Table 14.

TABLE 13-1

Layer A

Layer B

Copolymer

Rutile TiO

2

SiO

2

Copolymer

Rutile TiO

2

component

Thick-

Aver

Con-

Aver

Con-

component

Thick-

Aver

Con-

mol

m. p.

ness

dia

tent

dia

tent

mol

m. p.

ness

dia

tent

Comp

%

° C.

μm

μm

wt %

μm

wt %

Comp

%

° C.

μm

μm

wt %

Ex. 22

IA

12

228

1.5

0.22

3

1.6

0.06

IA

12

228

14

0.22

30

Ex. 23

IA

14

223

1.5

0.22

3

1.6

0.06

IA

14

223

14

0.22

30

Ex. 24

IA

6

244

1.5

0.22

3

1.6

0.06

IA

6

244

14

0.22

30

Ex. 25

IA

6

244

1.6

0.22

3

1.6

0.06

IA

12

228

14

0.22

30

Ex. 26

SA

12

228

1.5

0.22

3

1.6

0.06

SA

12

228

14

0.22

30

Ex. 27

IA

12

228

1.5

0.22

3

1.2

0.06

IA

12

228

14

0.22

30

Ex. 28

IA

12

228

1.5

0.22

3

1.9

0.06

IA

12

228

14

0.22

30

Ex. 29

IA

12

228

1.5

0.22

3

1.2

0.06

IA

12

228

14

0.22

30

Ex. 30

IA

12

228

1.5

0.22

3

1.6

0.03

IA

12

228

14

0.22

30

Ex. 31

IA

12

228

1.5

0.22

3

1.6

0.09

IA

12

228

14

0.22

30

Ex. 32

IA

12

228

1.5

0.22

3

1.6

0.03

IA

12

228

14

0.22

30

Ex. 33

IA

12

228

1.5

0.22

3

1.6

0.06

IA

12

228

14

0.22

20

Ex. 34

IA

12

228

1.5

0.22

3

1.6

0.06

IA

12

228

14

0.22

45

Ex. 35

IA

12

228

1.5

0.22

1

1.6

0.06

IA

12

228

14

0.22

30

Ex. 36

IA

12

228

1.5

0.22

6

1.6

0.06

IA

12

228

14

0.22

30

Ex. 37

IA

12

228

1.5

0.22

1

1.6

0.06

IA

12

228

14

0.22

30

Ex. 38

IA

12

228

1.5

0.22

3

1.6

0.06

IA

12

228

14

0.22

30

Ex. 39

IA

12

228

1.5

0.22

3

1.6

0.06

IA

12

228

14

0.22

30

Ex. 40

IA

12

228

3.0

0.22

3

1.6

0.06

IA

12

228

12

0.22

30

Layer C

Copolymer

Rutile TiO

2

SiO

2

component

Thick-

Aver

Con-

Aver

Con-

mol

m. p.

ness

dia

tent

dia

tent

Comp

%

° C.

μm

μm

wt %

μm

wt %

Ex. 22

IA

12

228

1.6

0.22

3

1.6

0.06

Ex. 23

IA

14

223

1.5

0.22

3

1.6

0.06

Ex. 24

IA

6

228

1.5

0.22

3

1.6

0.06

Ex. 25

IA

14

228

1.5

0.22

3

1.6

0.06

Ex. 26

SA

12

228

1.5

0.22

3

1.6

0.06

Ex. 27

IA

12

228

1.5

0.22

3

1.2

0.06

Ex. 28

IA

12

228

1.5

0.22

3

1.9

0.06

Ex. 29

IA

12

228

1.5

0.22

3

1.9

0.06

Ex. 30

IA

12

228

1.5

0.22

3

1.6

0.03

Ex. 31

IA

12

228

1.5

0.22

3

1.6

0.09

Ex. 32

IA

12

228

1.5

0.22

3

1.6

0.09

Ex. 33

IA

12

228

1.5

0.22

3

1.6

0.06

Ex. 34

IA

12

228

1.5

0.22

3

1.6

0.06

Ex. 35

IA

12

228

1.5

0.22

1

1.6

0.06

Ex. 36

IA

12

228

1.5

0.22

6

1.6

0.06

Ex. 37

IA

12

228

1.5

0.22

6

1.6

0.06

Ex. 38

IA

12

228

1.5

0.22

3

1.6

0.06

Ex. 39

IA

12

228

1.5

0.22

3

1.6

0.06

Ex. 40

IA

12

228

3.0

0.22

3

1.6

0.06

Note: IA: Isophthalic acid, SA: Sebacic acid

TABLE 13-2

Layer A

Layer B

Copolymer

Rutile TiO

2

SiO

2

Copolymer

Rutile TiO

2

component

Thick-

Aver

Con-

Aver

Con-

component

Thick-

Aver

Con-

mol

m. p.

ness

dia

tent

dia

tent

mol

m. p.

ness

dia

tent

Comp

%

° C.

μm

μm

wt %

μm

wt %

Comp

%

° C.

μm

μm

wt %

Comp.

IA

22

208

1.5

0.22

3

1.6

0.06

IA

22

208

14

0.22

30

Ex. 26

Comp.

IA

4

250

1.5

0.22

3

1.6

0.06

IA

4

250

14

0.22

30

Ex. 27

Comp.

IA

12

228

1.5

0.22

3

0.5

0.06

IA

12

228

14

0.22

30

Ex. 28

Comp.

IA

12

228

1.5

0.22

3

2.6

0.06

IA

12

228

14

0.22

30

Ex. 29

Comp.

IA

12

228

1.5

0.22

3

1.6

0.004

IA

12

228

14

0.22

30

Ex. 30

Comp.

IA

12

228

1.5

0.22

3

1.6

0.15

IA

12

228

14

0.22

30

Ex. 31

Comp.

IA

12

228

1.5

0.22

3

1.6

0.06

IA

12

228

14

0.22

10

Ex. 32

Comp.

IA

12

228

1.5

0.22

3

1.6

0.06

IA

12

228

14

0.22

60

Ex. 33

Comp.

IA

12

228

1.5

0.22

20

1.6

0.06

IA

12

228

14

0.22

30

Ex. 34

Comp.

IA

12

228

1.5

0.22

3

1.6

0.06

IA

12

228

14

0.22

30

Ex. 35

Comp.

IA

12

228

1.5

0.22

3

1.6

0.06

IA

12

228

14

0.22

30

Ex. 36

Layer C

Copolymer

Rutile TiO

2

SiO

2

component

Thick-

Aver

Con-

Aver

Con-

mol

m. p.

ness

dia

tent

dia

tent

Comp

%

° C.

μm

μm

wt %

μm

wt %

Comp.

IA

22

208

1.5

0.22

3

1.6

0.06

Ex. 26

Comp.

IA

4

250

1.5

0.22

3

1.6

0.06

Ex. 27

Comp.

IA

12

228

1.5

0.22

3

0.5

0.06

Ex. 28

Comp.

IA

12

228

1.5

0.22

3

2.5

0.06

Ex. 29

Comp.

IA

12

228

1.5

0.22

3

1.6

0.004

Ex. 30

Comp.

IA

12

228

1.5

0.22

3

1.6

0.15

Ex. 31

Comp.

IA

12

228

1.5

0.22

3

1.6

0.06

Ex. 32

Comp.

IA

12

228

1.5

0.22

3

1.6

0.06

Ex. 33

Comp.

IA

12

228

1.5

0.22

20

1.6

0.06

Ex. 34

Comp.

IA

12

228

1.5

0.22

3

1.6

0.06

Ex. 35

Comp.

IA

12

228

1.5

0.22

3

1.6

0.06

Ex. 36

Note: IA: Isophthalic acid, SA: Sebacic acid

TABLE 14-1

Film Properties

Abrasion

Ra μm

SRz μm

resistance

Deep-

Whiteness

Layer

Layer

Layer

Layer

Intrinsic viscosity

Film-

Layer

Layer

drawing

of outer

MOR

A

C

A

C

Fric.

Layer

Layer

Layer

forming

Wind-

Lamination

A

C

worka-

face

value

side

side

side

side

Coeff.

A

B

C

property

ability

suitability

side

side

bility - 1

of can

Ex. 22

1.1

0.05

0.05

0.85

0.87

0.33

0.56

0.56

0.56

◯

⊚

◯

◯

◯

◯

◯

Ex. 23

1.1

0.05

0.05

0.87

0.89

0.33

0.56

0.56

0.56

◯

◯

◯

◯

◯

◯

◯

Ex. 24

1.2

0.05

0.05

0.85

0.84

0.33

0.56

0.56

0.56

◯

⊚

◯

◯

◯

◯

◯

Ex. 25

1.1

0.05

0.05

0.83

0.87

0.33

0.56

0.56

0.56

◯

⊚

◯

◯

◯

◯

◯

Ex. 26

1.1

0.05

0.05

0.89

0.9

0.34

0.56

0.56

0.56

◯

◯

◯

◯

◯

◯

◯

Ex. 27

1.1

0.05

0.05

0.71

0.7

0.34

0.56

0.56

0.56

◯

◯

◯

◯

◯

◯

◯

Ex. 28

1.1

0.05

0.05

1.12

1.09

0.32

0.56

0.56

0.56

◯

⊚

◯

◯

◯

◯

◯

Ex. 29

1.1

0.05

0.05

0.69

1.08

0.32

0.56

0.56

0.56

◯

⊚

◯

◯

◯

◯

◯

Ex. 30

1.1

0.05

0.05

0.81

0.79

0.33

0.56

0.56

0.56

◯

◯

◯

◯

◯

◯

◯

Ex. 31

1.1

0.05

0.05

0.89

0.88

0.32

0.56

0.56

0.56

◯

⊚

◯

◯

◯

◯

◯

Ex. 32

1.1

0.05

0.05

0.81

0.92

0.32

0.56

0.56

0.56

◯

⊚

◯

◯

◯

◯

◯

Ex. 33

1.2

0.05

0.05

0.85

0.84

0.33

0.56

0.56

0.56

◯

⊚

◯

◯

◯

◯

◯

Ex. 34

1.3

0.05

0.05

0.86

0.86

0.33

0.56

0.56

0.56

◯

⊚

◯

◯

◯

◯

◯

Ex. 35

1.1

0.65

0.05

0.88

0.92

0.33

0.56

0.56

0.56

◯

⊚

◯

◯

◯

◯

◯

Ex. 36

1.1

0.05

0.05

0.85

0.83

0.32

0.56

0.56

0.56

◯

⊚

◯

◯

◯

◯

◯

Ex. 37

1.1

0.05

0.05

0.85

0.89

0.33

0.56

0.56

0.56

◯

⊚

◯

◯

◯

◯

◯

Ex. 38

1.2

0.05

0.05

0.9

0.86

0.33

0.60

0.57

0.54

◯

◯

◯

◯

◯

◯

◯

Ex. 39

1.3

0.05

0.05

0.88

0.88

0.32

0.56

0.56

0.56

◯

◯

◯

◯

◯

◯

◯

Ex. 40

1.1

0.05

0.05

0.85

0.83

0.33

0.56

0.56

0.56

◯

⊚

◯

◯

◯

◯

◯

TABLE 14-2

Film Properties

Abrasion

Ra μm

SRz μm

resistance

Deep-

Whiteness

Layer

Layer

Layer

Layer

Intrinsic viscosity

Film-

Layer

Layer

drawing

of outer

MOR

A

C

A

C

Fric.

Layer

Layer

Layer

forming

Wind-

Lamination

A

C

work-

face

value

side

side

side

side

Coeff.

A

B

C

property

ability

suitability

side

side

ability

of can

Comp.

1.3

0.05

0.05

0.93

0.92

0.33

0.56

0.56

0.56

X

⊚

◯

◯

◯

◯

◯

Ex. 26

Comp.

1.2

0.05

0.05

0.8

0.83

0.33

0.56

0.56

0.56

X

⊚

X

◯

◯

X

◯

Ex. 27

Comp.

1.1

0.05

0.05

0.61

0.63

0.37

0.56

0.56

0.56

◯

X

X

◯

◯

◯

◯

Ex. 28

Comp.

1.1

0.08

0.08

1.82

1.8

0.31

0.56

0.56

0.56

◯

⊚

◯

◯

◯

X

◯

Ex. 29

Comp.

1.1

0.05

0.05

0.59

0.58

0.36

0.56

0.56

0.56

◯

X

X

◯

◯

◯

◯

Ex. 30

Comp.

1.1

0.06

0.06

1.77

1.7

0.3

0.56

0.56

0.56

◯

⊚

◯

◯

◯

X

◯

Ex. 31

Comp.

1.2

0.05

0.05

0.8

0.89

0.33

0.56

0.56

0.56

◯

⊚

◯

◯

◯

◯

X

Ex. 32

Comp.

1.5

0.05

0.05

0.85

0.84

0.33

0.56

0.56

0.56

X

⊚

◯

◯

◯

◯

◯

Ex. 33

Comp.

1.1

0.05

0.05

0.79

0.83

0.33

0.56

0.56

0.56

◯

⊚

◯

X

X

◯

◯

Ex. 34

Comp.

1.4

0.05

0.05

0.9

0.91

0.33

0.45

0.44

0.45

X

◯

◯

◯

◯

X

◯

Ex. 35

Comp.

1.5

0.05

0.05

0.85

0.84

0.33

0.56

0.56

0.56

X

◯

◯

◯

◯

X

◯

Ex. 36

Number	Date	Country
8-275895	Oct 1996	JP
8-328567	Dec 1996	JP
9-152362	Jun 1997	JP
9-152363	Jun 1997	JP

Number	Name	Date	Kind
5618621	Hasegawa et al.	Apr 1997	A
5874163	Kosuge et al.	Feb 1999	A
6025056	Machii et al.	Feb 2000	A

Number	Date	Country
56-10451	Feb 1981	JP
64-22530	Jan 1989	JP
1-192545	Aug 1989	JP
1-192546	Aug 1989	JP
2-57339	Feb 1990	JP
5-339391	Dec 1993	JP

White laminated polyester film for metallic plate lamination work

Information

Patent Number

Date Filed

Date Issued

Inventors

Original Assignees

Examiners

Agents

CPC

US Classifications

Field of Search

US

International Classifications

Abstract

Description

Claims

Priority Claims (4)

PCT Information

US Referenced Citations (3)

Foreign Referenced Citations (6)

Non-Patent Literature Citations (2)

Entry
Unitane Titanium Dioxide Pigments, American Cyanamid Company, pp. 23 and 36-39, Oct. 1956.*
International Search Report, Dec. 1997.