The novel polyester (first polyester [A]) of the invention comprises dicarboxylic acid constituent units derived from at least one dicarboxylic acid selected from terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid and diol constituent units derived from diols comprising ethylene glycol and a polyalkylene glycol having a C2-C10 alkylene chain, wherein the proportion of constituent units derived from the polyalkylene glycol is 0.001 to 10% by weight based on the diol constituent units. The polyester [A] has an excellent crystallization rate, is suitably used, singly or as compositions together with another polyester [B] and/or other polymers, for production of molded products such as films, sheets, laminates, preforms and bottles, which have excellent thermal, gas barrier and transparency properties.

The present invention relates to novel polyesters, polyester compositions, polyester laminates and processes for producing biaxially oriented polyester bottles. More particularly, the invention relates to polyesters and polyester compositions, which have excellent high crystallization rate, gas barrier properties, transparency and heat resistance, and also relates to preforms, biaxially oriented bottles and laminates, which are produced from the polyesters, and to processes for producing biaxially oriented polyester bottles having excellent gas barrier properties, transparency and heat resistance.
Because of their excellent gas barrier properties, transparency and mechanical strength, saturated polyesters such as polyethylene terephthalate are widely used for containers such as bottles. Particularly, the bottles obtained by biaxial orientation blow molding of polyethylene terephthalate are excellent in transparency, mechanical strength, heat resistance and gas barrier properties, so that they have been extensively used for containers (PET bottles) to be filled with drinks such as juice, soft drinks and carbonated beverages. These bottles are generally produced by a process comprising the steps of molding saturated polyester to give a preform having a neck and a body, then inserting the preform in a mold of given shape, and subjecting the body of the preform to stretch blow molding, thereby producing bottles each having a neck and a stretched body.
The polyester bottles, particularly polyester bottles for drinks such as juice, are required to have heat resistance high enough for heat sterilization of the contents. Therefore, the bottles are generally further subjected to heat treatment (heat setting) after the blow molding to improve the heat resistance.
However, the necks of the above-obtained polyester bottles are not stretched and are inferior to the bodies in the heat resistance. In general, therefore, the necks of the preforms are heat crystallized before blow molding, or the necks of the bottles obtained by blow molding are heat crystallized, whereby the mechanical resistance and the heat resistance of the necks are improved.
In recent years, the sizes of bottles produced from the polyester resins (particularly polyethylene terephthalate) tend to be made smaller. In case of the small-sized bottles, the content has an increased area in contact with the bottle body per unit volume of content, and hence remarkable loss of gas in the content or transmission of oxygen from the outside takes place to affect the content, resulting in decrease of shelf life of the content. Accordingly, development of polyester bottles having better gas barrier properties than the conventional ones is desired.
Recently, further, the time for producing bottles of polyester resins is desired to be shortened to improve the productivity. In order to shorten the time for producing bottles, it is effective to shorten the crystallization time of the necks or the heat-setting time of the bottle bodies.
However, shortening of the crystallization time of the necks or the heat-setting time of the bottle bodies generally causes decrease of mechanical strength or heat resistance of the resulting bottles. Therefore, in order to carry out crystallization of necks or heat-setting of bottle bodies for a short period of time, it is necessary to use polyesters having a high crystallization rate. As one example of the polyester having a high crystallization rate, a polyester resin composition composed of a virgin polyester and a repro-polyester is known. The term xe2x80x9cvirgin polyesterxe2x80x9d used herein means a polyester prepared from a dicarboxylic acid and a diol and has no history of being passed through a molding machine in a molten state to give any bottle or preform. The term xe2x80x9crepro-polyesterxe2x80x9d used herein means a polyester obtained by passing the virgin polyester in a molten state through a molding machine at least once and pulverizing the resulting polyester molded product.
Although some polyester resin compositions have a high crystallization rate and are able to be heat crystallized for a short period of time, the resulting bottles have a problem of decrease in transparency.
Accordingly, it has been desired to develop polyesters capable of producing molded articles, such as bottles having excellent transparency and gas barrier properties. Also is desired development of preforms and biaxially stretched bottles and processes for producing biaxially stretched polyester bottles made of such polyesters.
The present invention has been made under such circumstances as mentioned above, and it is an object of the invention to provide a polyester and a polyester composition both having a high crystallization rate and having excellent gas barrier properties, transparency and heat resistance.
It is another object of the invention to provide a preform made of the above-mentioned polyester and a biaxially stretched bottle and a polyester laminate both having excellent gas barrier properties, transparency and heat resistance.
It is a further object of the invention to provide a process for producing biaxially stretched polyester bottles, by which bottles of excellent gas barrier properties, transparency and heat resistance can be produced, and to provide a process for producing biaxially stetched polyester bottles, by which bottles of excellent gas barrier properties, transparency and heat resistance can be produced with high productivity.
The novel polyester according to the invention (first polyester [A]) is a polyester comprising:
dicarboxylic acid constituent units derived from at least one dicarboxylic acid selected from the group consisting of terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid, and
diol constituent units derived from diols comprising ethylene. glycol and a polyalkylene glycol having an alkylene chain of 2 to 10 carbon atoms,
wherein the proportion of constituent units derived from the polyalkylene glycol is in the range of 0.001 to 10% by weight based on the diol constituent units.
The polyester composition according to the invention comprises:
1 to 99% by weight of the first polyester [A]; and
1 to 99% by weight of a second polyester [B] comprising dicarboxylic acid constituent units derived from at least one dicarboxylic acid selected from the group consisting of terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid and diol constituent units derived from diols comprising ethylene glycol, wherein the proportion of constituent units derived from a polyalkylene glycol is less than 0.001% by weight based on the diol constituent units.
Each of the preform and the biaxially stretched bottle according to the invention comprises the first polyester [A].
The polyester laminate according to the invention has a multi-layer structure comprising:
[I] a first resin layer formed from the first polyester [A] or the polyester composition of the invention, and
[II] a second resin layer formed from at least one resin selected from the group consisting of (a) the second polyester [B], (b) a polyamide and (c) a polyolefin.
The process for producing biaxially stretched bottle according to the invention comprises the steps of producing a preform from the first polyester [A], the polyester composition or the polyester laminate, heating the preform, subjecting the preform to biaxial stretch blow molding to give a stretched bottle and holding the stretched bottle in a mold at a temperature of not lower than 100xc2x0 C.
In the above process, the neck of the preform may be heat crystallized before the biaxial stretch blow molding, or the neck of the bottle may be heat crystallized after the biaxial stretch blow molding.
The polyester (first polyester [A]), the preform and the biaxially stretched bottle made of the polyester, the polyester composition, the polyester laminate and the process for producing biaxially stretched polyester bottle according to the invention are described in detail hereinafter.
The novel first polyester [A] according to the invention is a polyester comprising:
dicarboxylic acid constituent units derived from at least one dicarboxylic acid selected from the group consisting of terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid, and
diol constituent units derived from diols comprising ethylene glycol and polyalkylene glycol having an alkylene chain of 2 to 10 carbon atoms,
wherein the proportion of constituent units derived from the polyalkylene glycol is in the range of 0.001 to 10% by weight based on the diol constituent units.
The dicarboxylic acid constituent units and the diol constituent units are described below.
The dicarboxylic acid constituent units mainly contain constituent units derived from at least one dicarboxylic acid selected from the group consisting of terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid or its ester derivative (e.g., lower alkyl ester, phenyl ester).
(1) In the first preferred embodiment of the invention, the dicarboxylic acid constituent units mainly contain constituent units derived from terephthalic acid or its ester derivative.
In the dicarboxylic acid constituent units, constituent units derived from dicarboxylic acids other than the terephthalic acid or its ester derivative may be contained in amounts of not more than 15% by mol.
Examples of the dicarboxylic acids other than the terephthalic acid include:
aromatic dicarboxylic acids, such as naphthalenedicarboxylic acid, diphenyldicarboxylic acid and diphenoxyethanedicarboxylic acid;
aliphatic dicarboxylic acids, such as succinic acid, glutaric acid, adipic acid, sebacic acid, azelaic acid and decanedicarboxylic acid; and
alicyclic dicarboxylic acids, such as cyclohexanedicarboxylic acid.
Also employable are ester derivatives of the other dicarboxylic acids than the terephthalic acid. These dicarboxylic acids and their ester derivatives may be used singly or in combination.
(2) In the second preferred embodiment of the invention, the dicarboxylic acid constituent units mainly contain constituent units derived from terephthalic acid or its ester derivative, and contain constituent units derived from isophthalic acid or its ester derivative in the specific proportion.
It is desired that the constituent units derived from the isophthalic acid or its ester derivative are contained in amounts of 1 to 15% by weight, preferably 2 to 12% by weight, more preferably 4 to 10% by weight, based on the dicarboxylic acid constituent units. The first polyester containing the constituent units derived from the isophthalic acid in the amount of this range has excellent heat stability in the molding process and excellent gas barrier properties.
In the dicarboxylic acid constituent units, constituent units derived from dicarboxylic acids other than the terephthalic acid, the isophthalic acid or their ester derivatives may be contained in amounts of not more than 15% by mol.
Examples of the dicarboxylic acids other than the terephthalic acid and the isophthalic acid include:
aromatic dicarboxylic acids, such as o-phthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid and diphenoxyethanedicarboxylic acid;
aliphatic dicarboxylic acids, such as succinic acid, glutaric acid, adipic acid, sebacic acid, azelaic acid and decanedicarboxylic acid; and
alicyclic dicarboxylic acids, such as cyclohexanedicarboxylic acid.
Also employable are ester derivatives of the dicarboxylic acids other than the terephthalic acid and the isophthalic acid. These dicarboxylic acids and their ester derivatives may be used singly or in combination.
(3) In the third preferred embodiment of the invention, the dicarboxylic acid constituent units mainly contain constituent units derived from naphthalenedicarboxylic acid or its ester derivative, and optionally contain constituent units derived from terephthalic acid or isophthalic acid or its ester derivative.
It is desired that the constituent units derived from the-naphthalenedicarb6xylic acid or its ester derivative are contained in amounts of 55 to 100% by weight, preferably 75 to 100% by weight, more preferably 85 to 99% by weight, based on the dicarboxylic acid constituent units. The first polyester containing the constituent units derived from the naphthalenedicarboxylic acid in the amount of this range has excellent heat stability in the molding process and excellent gas barrier properties.
In the dicarboxylic acid constituent units, constituent units derived from dicarboxylic acids other than the naphthalenedicarboxylic acid, the terephthalic acid, the isophthalic acid or their ester derivatives may be contained in amounts of not more than 15% by mol.
Examples of the dicarboxylic acids other than the naphthalenedicarboxylic acid, the terephthalic acid and the isophthalic acid include:
aromatic dicarboxylic acids, such as o-phthalic acid, diphenyldicarboxylic acid and diphenoxyethanedicarboxylic acid;
aliphatic dicarboxylic acids, such as succinic acid, glutaric acid, adipic acid, sebacic acid, azelaic acid and decanedicarboxylic acid; and
alicyclic dicarboxylic acids, such as cyclohexanedicarboxylic acid.
Also employable are ester derivatives of the dicarboxylic acids other than the naphthalenedicarboxylic acid, the terephthalic acid and the isophthalic acid. These dicarboxylic acids and their ester derivatives may be used singly or in combination.
The diol constituent units mainly contain constituent units derived from ethylene glycol and contain constituent units derived from polyalkylene glycol having an alkylene chain of 2 to 10 carbon atoms in the specific proportion.
The polyalkylene glycol having an alkylene chain of 2 to 10 carbon atoms, which forms the diol constituent units, is polyalkylene glycol generally known. The polyalkylene glycols can be obtained by condensing an alkylene glycol of 2 to 10 carbon atoms by a known method.
The polyalkylene glycol desirably has a polymerization degree (n) of 5 to 50, preferably 10 to 45, and has a molecular weight of 100 to 10,000, preferably 200 to 5,000, particularly preferably 500 to 3,000.
Examples of the polyalkylene glycols include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyheptamethylene glycol, polyhexamethylene glycol and polyoctamethylene glycol. Of these, particularly preferable is polytetramethylene glycol.
In the present invention, it is desired that the constituent units derived from the polyalkylene glycol in the first polyester are contained in amounts of 0.001 to 10% by weight, preferably 0.01 to 8% by weight, more preferably 0.1 to 6% by weight, particularly preferably 1 to 4% by weight, based on the diol constituent units.
If the amounts of the constituent units derived from the polyalkylene glycol are less than 0.001% by weight, the improvement in the gas barrier properties or the heat-up crystallization rate of the polyester might be insufficient. If the amounts thereof exceeds 10% by weight, the transparency, the heat stability and the gas barrier properties of the polyester might be insufficient.
The diol constituent units may contain constituent units derived from diols other than ethylene glycol and polyalkylene glycol having an alkylene chain of 2 to 10 carbon atoms in amounts of not more than 15% by mol.
Examples of the diols other than ethylene glycol and polyalkylene glycol include:
aliphatic glycols, such as diethylene glycol, triethylene glycol, tetraethylene glycol, trimethylene glycol (propanediol), butanediol, pentanediol, neopentyl glycol, hexamethylene glycol and dodecamethylene glycol;
alicyclic glycols, such as cyclohexanedimethanol; and
aromatic diols, such as bisphenols and hydroquinone.
Also employable are ester derivatives of these diols. These diols and their ester derivatives may be used singly or in combination.
The first polyester [A] of the invention may optionally contain constituent units derived from polyfunctional compounds, such as trimellitic acid, pyromellitic acid, trimethylolethane, trimethylolpropane, trimethylolmethane and pentaerythritol in small amounts, e.g., not more than 2% by mol.
The first polyester [A] of the invention may be prepared from the above-mentioned dicarboxylic acid and diol by a known process. For example, the dicarboxylic acid and the diol are directly subjected to esterification reaction, or when an alkyl ester of the dicarboxylic acid is used, the ester and the diol are subjected to ester interchange reaction, and then the resulting ester is subjected to melt polycondensation reaction by heating the reaction mixture under reduced pressure to remove the excessive diol, thereby preparing the first polyester [A].
These reactions can be carried out in the presence of conventionally known catalysts. Examples of the ester interchange catalysts include compounds of magnesium, manganese, titanium, zinc, calcium and cobalt. Examples of the polycondensation catalysts include compounds of antimony, germanium and titanium.
The ester interchange catalyst or the polycondensation catalyst may be used in any amount, as far as the reactivity and the heat resistance of the polyester are not lowered.
In the polycondensation stage, phosphorus compounds may be added as stabilizers. Examples of the phosphorus compounds include phosphates, such as trimethyl phosphate, triethyl phosphate, tri-n-butyl phosphate, trioctyl phosphate and triphenyl phosphate; phosphites, such as triphenyl phosphite, trisdodecyl phosphite and trisnonyl phosphite; acid phosphates, such as methyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, dibutyl phosphate, monobutyl phosphate and dioctyl phosphate; and other phosphorus compounds, such as phosphoric acid and polyphosphoric acid.
In the polycondensation reaction, the polycondensation catalyst is desirably used in an amount of 0.005 to 0.2% by mol, preferably 0.001 to 0.1% by mol, in terms of the metal atom in the catalyst, based on the dicarboxylic acid.
The first polyester [A] thus obtained has an intrinsic viscosity [IV] of 0.40 to 1.0 dl/g, preferably 0.50 to 0.90 dl/g.
The first polyester [A] obtained by the polycondensation reaction is generally melt-extruded into granules (chips).
The first polyester [A] obtained by the polycondensation reaction can be further subjected to solid phase polycondensation reaction. For example, the polyester chips obtained as above can be polymerized in a solid phase at a temperature of not lower than 160xc2x0 C. and lower than the melting point thereof, preferably 170 to 220xc2x0 C., for 8 to 40 hours, preferably 15 to 30 hours.
The process for preparing the first polyester [A] including the esterification step and the polycondensation step can be carried out batchwise or semi-continuously.
The first polyester [A] is substantially linear, and this can be confirmed by the fact that the first polyester [A] is dissolved in o-chlorophenol.
The first polyester [A] of the invention has an intrinsic viscosity [IV], as measured in o-chlorophenol at 25xc2x0 C., of usually 0.3 to 1.5 dl/g, preferably 0.5 to 1.5 dl/g.
It is desirable that the first polyester [A] of the invention has a heat-up half crystallization time of 10 to 200 seconds, preferably 20 to 120 seconds. The heat-up half crystallization time is measured by the later-described method.
To the first polyester [A], various additives which are generally added to polyesters, such as colorants, antioxidants, ultraviolet light absorbers, antistatic agents, flame retarders and lubricants, may be added, if necessary.
The first polyester [A] of the invention can be used as a molding material for various molded products such as preforms, bottles and (stretched) films.
The first polyester [A] of the invention has a high crystallization rate. In the production of bottles, therefore, it is possible to shorten the time for the heat crystallization of necks of preforms or necks of bottles, and hence bottles having necks of excellent mechanical strength and heat resistance can be efficiently produced.
The preform according to the invention can be obtained by, for example, injection molding or extrusion molding of the first polyester [A].
The bottle according to the invention can be obtained by biaxial stretch blow molding of the preform and then heat setting of the resulting molded product. In the preparation of the bottle, a neck of a preform may be heat crystallized and then the preform may be subjected to biaxial stretch blow molding, or a preform, prior to heat crystallization of its neck, may be subjected to biaxial stretch blow molding and then the neck of the bottle may be heat crystallized.
It is desirable that the bottle of the invention has a carbon dioxide gas transmission rate at its body of generally not more than 17.5 ccxc2x7mm/m2xc2x7dayxc2x7atm, preferably not more than 15 ccxc2x7mm/m2xc2x7dayxc2x7atm, more preferably not more than 4.0xc2x7ccxc2x7mm/m2xc2x7dayxc2x7atm.
In particular, when the bottle is made of the first polyester [A] in which the diarboxylic acid constituent units contain mainly constituent units derived from terephthalic acid or its ester derivative, the carbon dioxide gas transmission rate is preferably not more than 17.5 ccxc2x7mm/m2xc2x7dayxc2x7atm.
When the bottle is made of the first polyester [A] in which the dicarboxylic acid constituent units contain mainly constituent units derived from terephthalic acid or its ester derivative and further contain constituent units derived from isophthalic acid or its ester derivative in the specific amount, the carbon dioxide gas transmission rate is preferably not more than 15 ccxc2x7mm/m2xc2x7dayxc2x7atm.
When the bottle is made of the first polyester [A] in which the dicarboxylic acid constituent units contain mainly constituent units derived from naphthalenedicarboxylic acid or its ester derivative and further contain constituent units derived from terephthalic acid or isophthalic acid or its ester derivative in the specific amount, the carbon dioxide gas transmission rate is preferably not more than 4.0 ccxc2x7mm/m2xc2x7dayxc2x7atm.
Next, the polyester composition according to the invention is described.
The polyester composition of the invention comprises:
1 to 99% by weight of the first polyester [A] comprising dicarboxylic acid constituent units derived from at least one dicarboxylic acid selected from the group consisting of terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid and diol constituent units derived from diols comprising ethylene glycol and polyalkylene glycol having an alkylene chain of 2 to 10 carbon atoms, wherein the proportion of constituent units derived from the polyalkylene glycol is in the range of 0.001 to 10% by weight based on the diol constituent units; and
1 to 99% by weight of a second polyester [B] comprising dicarboxylic acid constituent units derived from at least one dicarboxylic acid selected from the group consisting of terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid and diol constituent units derived from diols comprising ethylene glycol, wherein the proportion of constituent units derived from a polyalkylene glycol is less than 0.001% by weight based on the diol constituent units.
The first polyester [A] as described above can be used herein.
The second polyester [B] is described below.
The second polyester [B] comprises dicarboxylic acid constituent units derived from at least one dicarboxylic acid selected from the group consisting of terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid and diol constituent units derived from diols comprising proportion of constituent units derived from a polyalkylene glycol is less than 0.001% by weight based on the diol constituent units.
Examples of the second polyester [B] are given below.
(i) Polyethylene terephthalate comprising dicarboxylic acid constituent units derived from a terephthalic acid or its ester derivative and diol constituent units derived from ethylene glycol.
In the polyethylene terephthalate (i), constituent units derived from other dicarboxylic acids and/or other diols may be contained in amounts of less than 20% by mol.
Examples of the other dicarboxylic acids include aromatic dicarboxylic acids, such as isophthalic acid, o-phthalic acid, diphenyldicarboxylic acid and diphenoxyethanedicarboxylic acid; aliphatic dicarboxylic acids, such as sebacic acid, azelaic acid and decanedicarboxylic acid; and alicyclic dicarboxylic acids, such as cyclohexanedicarboxylic acid.
Examples of the other diols include aliphatic glycols, such as diethylene glycol, trimethylene glycol, propylene glycol, tetramethylene glycol, hexamethylene glycol, dodecamethylene glycol and polyalkylene glycols; alicyclic glycols, such as cyclohexanedimethanol; bisphenols; and aromatic diols, such as hydroquinone and 2,2-bis(4-xcex2-hydroxyethoxyphenyl)propane.
(ii) Polyethylene naphthalate comprising dicarboxylic acid constituent units derived from naphthalenedicarboxylic acid or its ester derivative and diol constituent units derived from ethylene glycol.
In the polyethylene naphthalate (ii), constituent units derived from other dicarboxylic acids and/or other diols may be contained in amounts of less than 40% by mol.
Examples of the other dicarboxylic acids include aromatic dicarboxylic acids, such as terephthalic acid, isophthalic acid, diphenyldicarboxylic acid, diphenyletherdicarboxylic acid, diphenoxyethanedicarboxylic acid and dibromoterephthalic acid; aliphatic dicarboxylic acids, such as adipic acid, azelaic acid, sebacic acid and decanedicarboxylic acid; alicyclic dicarboxylic acids, such as 1,4-cyclohexanedicarboxylic acid, cyclopropanedicarboxylic acid and hexahydroterephthalic acid; and hydroxycarboxylic acids, such as glycolic acid, p-hydroxybenzoic acid and p-hydroxyethoxybenzoic acid.
Examples of the other diols include propylene glycol, trimethylene glycol, diethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, decamethylene glycol, neopentylene glycol, polyalkylene glycols, p-xylene glycol, 1,4-cyclohexanedimethanol, bisphenol A, p,p-diphenoxysulfone, 1,4-bis(xcex2-hydroxethoxy)benzene, 2,2-bis(p-xcex2-hydroxyethoxyphenol)propane, p-phenylenebis(dimethylsiloxane) and glycerol.
(iii) Copolymerized polyester comprising dicarboxylic acid constituent units and diol constituent units derived from ethylene glycol, wherein the dicarboxylic acid constituent units mainly contain constituent units derived from terephthalic acid or its ester derivative and further contain constituent units derived from isophthalic acid or its ester derivative in the specific proportion.
It is desired that the constituent units derived from the isophthalic acid or its ester derivative are contained in amounts of 0.5 to 15% by mol, preferably 0.5 to 10% by mol, based on the dicarboxylic acid constituent units in the copolymerized polyester (iii).
(iv) Copolymerized polyester comprising dicarboxylic acid constituent units and diol constituent units derived from ethylene glycol, wherein the dicarboxylic acid constituent units mainly contain constituent units derived from terephthalic acid or its ester derivative and further contain constituent units derived from naphthalenedicarboxylic acid or its ester derivative in the specific proportion.
It is desired that the constituent units derived from the naphthalenedicarboxylic acid or its ester derivative are contained in amounts of 0.5 to 20% by mol, preferably 0.5 to 10% by mol, based on the dicarboxylic acid constituent units in the copolymerized polyester (iv).
(v) Copolymerized polyester comprising dicarboxylic acid constituent units and diol constituent units derived from ethylene glycol, wherein the dicarboxylic acid constituent units mainly contain constituent units derived from terephthalic acid or its ester derivative and further contain constituent units derived from adipic acid or its ester derivative in the specific proportion.
It is desired that the constituent units derived from the adipic acid or its ester derivative are contained in amounts of 0.5 to 15% by mol, preferably 0.5 to 10% by mol, based on the dicarboxylic acid constituent units in the copolymer polyester (v).
(vi) Copolymerized polyester comprising dicarboxylic acid constituent units derived from terephthalic acid or its ester derivative and diol constituent units, wherein the diol constituent units mainly contain constituent units derived from ethylene glycol and further contain constituent units derived from diethylene glycol in the specific proportion.
It is desired that the constituent units derived from the diethylene glycol are contained in amounts of 0.5 to 5% by weight, preferably 1.0 to 3.0% by weight, based on the diol constituent units in the copolymer polyester (vi).
(vii) Copolymerized polyester comprising dicarboxylic acid constituent units derived from terephthalic acid or its ester derivative and diol constituent units, wherein the diol constituent units mainly contain constituent units derived from ethylene glycol and further contain constituent units derived from neopentyl glycol in the specific proportion.
It is desired that the constituent units derived from the neopentyl glycol are contained in amounts of 1 to 30% by weight, preferably 5 to 15% by weight, based on the diol constituent units in the copolymerized polyester (vii).
(viii) Copolymerized polyester comprising dicarboxylic acid constituent units derived from terephthalic acid or its ester derivative and diol constituent units, wherein the diol constituent units mainly contain constituent units derived from ethylene glycol and further contain constituent units derived from cyclohexanedimethanol in the specific proportion.
It is desired that the constituent units derived from the cyclohexanedimethanol are contained in amounts of 1 to 30% by weight, preferably 5 to 15% by weight, based on the diol constituent units in the copolymerized polyester (viii).
(ix) Copolymerized polyester comprising:
dicarboxylic acid constituent units mainly containing constituent units derived from isophthalic acid or its ester derivative and optionally containing constituent units derived from terephthalic acid or its ester derivative in the specific proportion, and
diol constituent units containing constituent units derived from dihydroxyethoxyresol and constituent units derived from ethylene glycol.
It is desired that the constituent units derived from the isophthalic acid are contained in amounts of 20 to 100% by weight, preferably 50 to 98% by weight, based on the dicarboxylic acid constituent units in the copolymerized polyester (ix).
It is also desired that the constituent units derived from the dihydroxyethoxyresol are contained in amounts of 5 to 90% by mol, preferably 10 to 85% by mol, based on the diol constituent units in the copolymerized polyester (ix).
In the copolymerized polyester (ix), further, constituent units derived from a polyfunctional hydroxyl compound having at least three hydroxyl groups are desirably present in amounts of 0.05 to 1.0 part by mol, preferably 0.1 to 0.5 part by mol, based on 100 parts by mol of the dicarboxylic acid constituent units.
In the copolymerized polyesters (iii) to (ix), constituent units derived from other dicarboxylic acids and/or other diols than the above-mentioned dicarboxylic acids and diols may be contained in such amounts that the properties of the copolymer polyesters (iii) to (ix) are not marred, for example, in amounts of not more than 1% by mol.
Examples of the other dicarboxylic acids include o-phthalic acid and 2-methylterephthalic acid. Examples of the other diols include 1,3-propanediol, 1,4-butanediol, cyclohexanedimethanol, 1,3-bis(2-hydroxyethoxy)benzene, 1,4-bis(2-hydroxyethoxy)benzene, 2,2-bis(4-xcex2-hydroxyethoxyphenyl)propane and bis(4-xcex2-hydroxyethoxyphenyl)sulfone.
In the second polyester [B] used in the invention, constituent units derived from polyfunctional compounds, such as trimellitic acid, trimethylolethane, trimethylolpropane, trimethylolmethane and pentaerythritol, may be contained in small amounts, e.g., not more than 2% by mol.
In the second polyester [B], further, constituent units derived from monofunctional compounds, such as benzoylbenzoic acid, diphenylsulfonemonocarboxylic acid, stearic acid, methoxypolyethylene glycol and phenoxypolyethylene glycol, may be contained in amounts of not more than 2% by mol.
The heat-up crystallizing temperature (Tc) of the second polyester [B], as measured by means of a differential scanning calorimeter (DSC) in which a sample is heated at a rate of 10xc2x0 C./min, is desired to be not lower than 150xc2x0 C., preferably 160 to 230xc2x0 C., more preferably 170 to 220xc2x0 C.
The heat-up crystallizing temperature (Tc) of the polyesters described herein can be measured in the following manner. About 10 mg of a sample flake is cut from the center part of a saturated polyester resin chip having been dried at about 140xc2x0 C. under a pressure of about 5 mmHg for not less than 5 hours. The sample is sealed in an aluminum pan for liquid in a nitrogen atmosphere. Using a differential scanning calorimeter molded DSC-2 produced by perkin Elmer Co., the measurement is caried out under the conditions such that the sample is rapidly heated from room temperature to 290xc2x0 C., at which the sample is kept in a molten state, for 10 minutes, and then rapidly cooled to room temperature, and thereafter heated again at a rate of 10xc2x0 C./min to detect exothermic peaks. The maximum peak temperature of these exothermic peaks is taken as the heat-up crystallizing temperature (Tc).
The second polyester [B] has an intrinsic viscosity [IV], as measured in o-chlorophenol at 25xc2x0 C., of usually 0.5 to 1.5 dl/g, preferably 0.6 to 1.2 dl/g.
The second polyester [B] can be prepared by a process conventionally known.
The second polyester [B] may be used singly or as a blend of two or more of such polyesters. Examples of blends of polyesters include those of the polyethylene terephthalate (i) and the polyethylene naphthalate (ii), the polyethylene terephthalate (i) and at least one of the copolymerized polyesters (iii) to (ix), and at least two of the copolymerized polyesters (iii) to (ix).
Of the blends, preferably used are a blend of the polyethylene terephthalate (i) and the copolymer polyester (iii) and a blend of the polyethylene terephthalate (i) and the copolymer polyester (ix).
The polyester composition of the invention comprises:
the first polyester [A] in an amount of 1 to 99% by weight, preferably 1 to 50% by weight, more preferably 2 to 25% by weight, and
the second polyester [B] in an amount of 99 to 1% by weight, preferably 99 to 50% by weight, more preferably 98 to 75% by weight.
When the polyester composition contains the first polyester [A] in the amount of the above range, the composition exhibits sufficiently improved gas barrier properties and heat-up crystallization rate without decreasing the heat stability in the molding process.
The polyester composition of the invention desirably has a heat-up half crystallization time of 10 to 400 seconds, preferably 60 to 300 seconds. The heat-up half crystallization time is measured by the later-described method.
The polyester composition of the invention can be prepared from the first polyester [A] and the second polyester [B] by any process.
For example, the first polyester [A] and the second polyester [B] are directly blended by a blending machine such as a tumbling blender or a Henschel mixer.
Alternatively, the first polyester [A] and the second polyester [B] are previously melt kneaded to prepare a master batch containing the first polyester [A] in a high concentration, then the second polyester [B] is appropriately added to the master batch.
To the polyester composition of the invention, various additives which are generally added to polyesters, such as colorants, antioxidants, ultraviolet light absorbers, antistatic agents, flame retarders and lubricants, may be added, if necessary. These additives may be added to the polyester composition as a master batch previously prepared from the additives and the polyester composition.
The polyester composition of the invention can be used as a molding material for various molded products such as preforms, bottles, (stretched) films and sheets for the good transparency and the superior gas barrier property.
The polyester composition of the invention has a high crystallization rate. In the production of bottles, therefore, it is possible to shorten the time for the heat crystallization of necks of preforms or necks of bottles, and hence bottles having necks of excellent mechanical strength and heat resistance can be efficiently produced.
The polyester laminate according to the invention has a multi-layer structure comprising:
[I] a first resin layer formed from the first polyester [A] or the polyester composition of the invention, and
[II] a second resin layer formed from at least one resin selected from the group consisting of (a) the second polyester [B], (b) a polyamide and (c) a polyolefin.
The second resin layer is formed from at least one resin selected from the group consisting of (a) the second polyester [B], (b) a polyamide and (c) a polyolefin.
Each resin is described below.
The second polyester [B] as described above in the polyester composition can be used herein.
Examples of the polyamide (b) include aliphatic polyamides, such as nylon 6, nylon 66, nylon 10, nylon 12 and nylon 46, and aromatic polyamides prepared from aromatic dicarboxylic acids and aliphatic diamines. Of these, particularly preferable is nylon 6. These polyamides may be used singly or in combination.
These polyamides can be prepared by conventional processes.
Examples of the polyolefin (c) include olefin homopolymers, such as polyethylene, polypropylene, poly-1-butene, polymethylpentene, polymethylbutene, and olefin copolymers, such as propylene/ethylene random copolymer. Of these, particularly preferable are polyethylene and polypropylene. These polyolefins may be used singly or in combination.
These polyolefins can be prepared by conventional processes.
In the present invention, the second resin layer may be formed from a blend of the above resins (a) to (c).
The first resin layer and the second resin layer may contain various additives which are generally added to resin layers, such as colorants, antioxidants, ultraviolet light absorbers, antistatic agents, flame retarders and lubricants, if necessary.
In the polyester laminate of the invention, the first resin layer and the second resin layer are laminated together. It is desirable that the proportion of the thickness of the first resin layer is preferably in the range of 5 to 30%, more preferably 5 to 20%, most preferably 5 to 15%, and that the proportion of the thickness of the second resin layer is preferably in the range of 70 to 95%, more preferably 80 to 95%, most preferably 85 to 95%, both based on the total thickness of the polyester laminate.
The polyester laminate of the invention may have a third layer in addition to the first and second resin layers. For example, third layer may be a layer made of a composition comprising the resin for forming the first resin layer and the resin for forming the second resin layer, or a layer containing additives such as heat stabilizers, weathering stabilizers, lubricants, dyes, pigments, anti-fogging agents and antistatic agents, wherein each of such layers may be provided on at least one surface of the polyester laminate, or may be provided as an intermediate layer between the first and the second resin layers; a layer for adhesive bonding the first resin layer to the second resin layer, such as a modified polyolefin layer; and further a layer made of glass, metal or paper.
The laminate of the invention can be prepared in accordance with conventional processes using the above-described resins.
The polyester which composes laminate of the invention has a high crystallization rate. In the production of bottles, therefore, it is possible to shorten the time for the heat crystallization of necks of preforms or necks of bottles, and hence bottles having necks of excellent mechanical strength and heat resistance can be efficiently produced.
When the polyester laminate of the invention is in the form of a preform or a bottle, its external layer is preferably the first resin layer.
When the polyester laminate of the invention is in the form of a bottle, the body of the bottle has a carbon dioxide gas transmission rate of not more than 17.5 ccxc2x7mm/m2xc2x7dayxc2x7atm, preferably 15.0 ccxc2x7mm/m2xc2x7dayxc2x7atm, more preferably 4.0 ccxc2x7mm/m2xc2x7dayxc2x7atm.
Next, the process for producing biaxially stretched polyester bottle according to the invention is described.
In the process for producing biaxially stretched polyester bottle according to the invention, a preform is produced from either the first polyester [A], the polyester composition or the polyester laminate, the preform is heated, is subjected to biaxial stretch blow molding, and the resulting stretched bottle is held in a mold at a temperature of not lower than 100xc2x0 C.
The preform can be produced by a conventional molding method such as extrusion molding or injection molding.
The preform formed from the polyester laminate can be produced by, for example, subjecting the first polyester [A] or the plyester composition of the invention to form the first resin layer and the resin for forming the second resin layer to co-extrusion molding to form a multi-layer pipe and then providing a bottom at one end of the pipe and a neck at the other end of the pipe. Alternatively, the above-mentioned first layer resin or composition and the second layer resin can be subjected to co-injection molding, to form a multi-layer preform.
The external layer of the preform thus produced is preferably the first resin layer. The proportion of the thickness of the first resin layer is in the range of preferably 5 to 30%, more preferably 5 to 20%, most preferably 5 to 15%, based on the total wall thickness of the preform. The proportion of the thickness of the second resin layer is in the range of preferably 70 to 95%, more preferably 80 to 95%, most preferably 85 to 95%, based on the total wall thickness of the preform. Since such preform can be stretched in a high stretch ratio in the production of bottle, the total length of the preform may be shorter than the conventional one, or the diameter of the preform may be smaller than the conventional one.
In the above process, the temperature for heating the preform is desirably in the range of 70 to 150xc2x0 C., preferably 80 to 140xc2x0 C. The preform can be heated from the outside and the inside (hollow part). As the heat source, infrared rays and the like are employable. The heating from the hollow part is preferably carried out simultaneously with heating from the outside.
In the biaxial stretch blow molding, the stretch ratio is 6 to 15 times, preferably 7 to 12 times, in terms of the area stretch ratio (lengthwise stretch ratioxc3x97crosswise stretch ratio).
In the present invention, the biaxially stretched bottle may be further subjected to heat setting. The heat setting is desirably carried out by holding the oriented bottle in a mold at a mold temperature of 100 to 240xc2x0 C., preferably 110 to 220xc2x0 C., particularly preferably 140 to 210xc2x0 C., for a period of not less than 1 second, preferably not less than 3 seconds. By virtue of heat setting, the heat resistance and the gas barrier properties of the stretched bottle are improved.
In the present invention, the neck of the preform may be heat crystallized before the biaxial stretch blow molding, or the neck of the bottle may be heat crystallized after the biaxial stretch blow molding.
The heat crystallization of the neck of the preform or the neck of the bottle can be carried out at a temperature of 100 to 200xc2x0 C., preferably 120 to 180xc2x0 C. It is desired that the heat crystallization is carried out so that the neck of the preform or the neck of the bottle has a crystallinity of 25 to 60%, preferably 25 to 50%.
The body of the biaxially stretched polyester bottle has a carbon dioxide gas transmission rate of usually not more than 17.5 ccxc2x7mm/m2xc2x7dayxc2x7atm, preferably 15.0 ccxc2x7mm/m2xc2x7dayxc2x7atm, more preferably 4.0 ccxc2x7mm/m2xc2x7dayxc2x7atm. The biaxially stretched polyester bottle has a haze of usually 1.0 to 20%, preferably 5 to 15%.
According to the process of the invention, the transparency of the bottle body is hardly harmed, and hence a biaxially stretched polyester bottle having excellent transparency, gas barrier properties and heat resistance can be produced.
According to the process of the invention, further, heat crystallization of a neck of the preform or a neck of the bottle can be carried out at a high speed, so that a bottle molding cycle including heat crystallization of neck can be shortened, and a biaxially stretched polyester bottle having excellent transparency, gas barrier properties and heat resistance can be produced with high productivity.
The novel polyester and the polyester composition according to the invention show a high crystallization rate and have excellent gas barrier properties, transparency and heat resistance.
The preform and the bottle according to the invention have excellent gas barrier properties, transparency and heat resistance.
The polyester laminate according to the invention has excellent gas barrier properties, transparency and heat resistance. The polyester laminate is suitable for bottles and preforms.
Bottles, sheets and films formed from the novel polyester, the polyester composition and the polyester laminate according to the invention are suitable for bottles for soft drinks such as water, juice, cola and carbonated beverages, bottles for flavoring materials such as soy sauce, Worcester sauce and catsup, bottles for liquors such as wine, sake and whisky, packaging or keeping sheets for dairy products such as butter and cheese, meat and fish, tanks for agricultural chemicals or gasoline, and packaging films for medicines.
According to the process of the invention, biaxially stretched polyester bottles showing excellent gas barrier properties, transparency and heat resistance and having high mechanical strength and heat resistance at their necks can be produced with high productivity.

Polyester compositions and laminates and processes for producing biaxially stretched polyester bottles


Systems, methods, and apparatus for creating a mold of a patient's teeth to which are installed orthodontic appliances with a support assembly bonded to a tooth. The appliances may include a corresponding corrective assembly with a wire engaging portion removably coupled to the support assembly. The systems and methods may include removing a corrective assembly from a support assembly, applying unset molding compound to the patient's teeth and corresponding support assemblies, setting the molding compound into a mold, and nondeformably removing the mold from the patient's mouth. The support assemblies may include a marker portion to indicate the position of the wire engaging portion of a corrective assembly that may be removed prior to making a mold and/or installed after making the mold. Marker assemblies adapted to removably engage a support assembly, and including such a marker portion, may be temporarily coupled to support assemblies prior to making a mold.

During orthodontic treatment, it is often desirable, and in some cases necessary, to create molds or other impressions of an orthodontic patient's teeth. When conventional orthodontic brackets are not mounted on the patient's teeth, a variety of suitable molding compounds and impression methods may be used. However, when conventional orthodontic brackets are installed on the patient's teeth, the range of suitable molding compounds and impression methods is much more limited, especially when it is desirable or necessary to accurately reproduce the position of the archwire-receiving slot, which is defined by the orthodontic brackets, relative to the patent's teeth.
Many conventional molding compounds, or materials, that are suitable for creating molds or impressions of a patient's teeth prior to the installation of orthodontic brackets are unsuitable for creating impressions of the patient's teeth while the brackets are installed. While these compounds, an example of which is polyvinylsiloxane, are suitable for creating very accurate molds of the patient's teeth, including impressions that are suitable for destructive scanning, or imaging, processes, the molding compounds set, or cure, so solidly that they are likely to debond (detach or otherwise remove) orthodontic brackets from the patient's teeth, damage the orthodontic brackets, and/or deform or otherwise damage or distort the mold during the removal process from the patient's teeth (and installed orthodontic brackets). Specifically, the bracket is typically connected to a patient's tooth with an adhesive that is not strong enough to withstand the imparted forces as the set molding material, or mold, which also extends around the brackets, is drawn away from the patient's teeth. As a result, this removal of the mold may debond the bracket from the tooth as the mold is removed from the patient's teeth. Such a rigid impression material is also prone to solidifying around the undercuts, wings, or other projecting portions of an orthodontic bracket and thereby prevent nondeformable removal of the mold without damaging the bracket or the mold.
Other molding compounds are suitable for making impressions of the patient's teeth even after the installation of orthodontic brackets, but these molding compounds are formed from materials that are sufficiently flexible, soft, and/or deformable that they are not suitable to create molds for use in some orthodontic applications, such as applications where very accurate, or detailed, representations of the patient's teeth and attached brackets are needed. One example of such a compound is alginate, a natural polymer. Such materials, once set, are likely to tear, deform, or otherwise distort during removal of the set molding compound, thereby rendering the resulting mold unable to accurately reproduce the position of the brackets and/or archwires relative to the patient's teeth.
A further method of creating very accurate representations of a patient's teeth after orthodontic brackets are installed involves the use of CT scanners or other intra-oral scanners that create images of the patient's teeth, including any attached orthodontic brackets. These images may be used to make electronic or other models or representations of the patient's teeth and the attached orthodontic brackets. However, this scanning process requires expensive scanning equipment and takes considerable time and practitioner attention (especially when compared to using molding compounds).

This patent is subject to a terminal disclaimer.

Orthodontic treatment methods, systems and apparatus for use therewith


A wireless communication system has no limitation in the number of AP antennas and UT antennas, and determines the parallel-communication data units to be a maximum value of MIMO communication, such that it provides a MIMO-SDMA wireless data communication system having superior transmission characteristics. The MIMO-SDMA wireless data communication system includes a single AP (Access Point) and U UTs (User Terminals) communicating with the AP using the same frequency signal at the same time. The UT includes the SDMA reception (Rx) processor, and synthesizes Rx signals of antennas, such that it controls the number of Rx data units. By the control of the number of Rx data units, the communication system controls the number of parallel-communication data units to be equal to a maximum value capable of being implemented by the MIMO-SDMA wireless data communication. The AP informs the UTs of a coefficient matrix required for the SDMA Rx process, prior to transmitting actual data.

A plurality of conventional wireless data communication technologies are as follows.
For example, many developers have conducted intensive research into a MIMO (Multiple-Input Multiple-Output) technique for increasing spectral efficiency (i.e., an amount of communication information for each unit time and each unit frequency) in a wireless communication field.
For example, there is almost no doubt that the IEEE 802.11 standard for WLAN (Wireless LAN) standardization adopts the MIMO technology in a task group (n).
Also, many developers are conducting research into a method for applying the MIMO technology to the fourth-generation mobile communication system to increase a transmission rate (also called a transfer rate).
The above-mentioned MIMO technology begins to extend/apply to the SDMA technology. The SDMA technology allows a single AP (Access Point) to simultaneously communicate with a plurality of UTs (User Terminals) using the same frequency signal.
Representative examples of the above-mentioned MIMO-SDMA technology are United States Patent Publication No. 2004-0252632A1, and a Japanese reference document entitled "Method for calculating MIMO/SDMA downlink weight using Rx antenna selection" published in The Institute of Electronics, Information and Communication Engineers Book B-5-230, filed by Nishimura Tosihiko, Takatori Yasusi, Ogane Takeo, Ogawa Yasutaka, and Osa Keizo.

Wireless data communication system, wireless data communication method and communication apparatus


A computer implemented method transforms an image comprised of pixels into a vectorized image specified by a plurality of polygons that can be subsequently used to aid in image processing and understanding. The pixelated image is processed to extract edge pixels that separate different colors and a constrained Delaunay triangulation of the edge pixels forms a plurality of triangles having edges that cover the pixelated image. A color for each one of the plurality of triangles is determined from the color pixels within each triangle. A filter is formed with a set of grouping rules related to features of the pixelated image and applied to the plurality of triangle edges to merge adjacent triangles consistent with the filter into polygons having a plurality of vertices. The pixelated image may be then reformed into an array of the polygons, that can be represented collectively and efficiently by standard vector image.

Image segmentation is the first and perhaps the most critical image processing step to automating image understanding by computers. Segmentation consists of decomposing an image into its constituent salient features and objects that define the semantic content of the image. Image segmentation sets the stage for object detection and recognition by providing a high-level representation of an image in terms of regions of uniform color/intensity and geometric regularity.
Objects in images are typically contiguous subsets of such regions. Thus, image segmentation transforms an image from a low-level pixel-based representation to an intermediate-level region-based representation that enables the piecing together of the 'jigsaw puzzle' of regions into individual objects of the image. Image segmentation can be thought of as representing the method of perception in human vision. This representation does not assume a priori knowledge of the objects in an image; rather it uses local regularities and structure in an image to parse the image into distinct parts.
There has been no universally applicable method to date that can segment all images equally well. Although there are several segmentation methods developed over the decades, almost all can be classified, broadly speaking, into one of two categories: 1) methods that seek structure by decomposing an image into regions of uniform color or intensity, generally assuming that, to a large extent, parts of an object are dominated by one color; 2) methods that seek structure by identifying parts of an image that exhibit rapid change in color/intensity, generally assuming that boundaries of objects are sites of such rapid change in intensity.
Digital images are made up of pixels of subtly varying intensities that are dithered in such a way as to produce the effects of shade and gradation of color. Since methods of the first kind rely on binning pixels into fewer classes, this in general results in speckle noise due to neighboring pixel differences being enhanced. It also has the effect of marring edges that have more gradual variation in intensity across them, or creating false edges due to gradual variation in intensity across a region. While methods of the second kind do produce edges that belong to object boundaries, these edges are typically fragmented and as such do not bear any relationship to one another. Thus, additional work is required to group and interrelate edges belonging to the same object.
Various objects, advantages and novel features of the invention will be set forth in part in the description which follows, and in part will become apparent to those skilled in the art upon examination of the following or may be learned by practice of the invention. The objects and advantages of the invention may be realized and attained by means of the instrumentalities and combinations particularly pointed out in the appended claims.

Vectorized image segmentation via trixel agglomeration

The Regents of the University of California


A system and method for identifying and authenticating a physical article to a virtual environment. A physical article, such as a decorative pin used in gameplay or some purchased article with anti-counterfeiting tag information, may be scanned by a mobile device and verified by a mobile device application. Such a process may uniquely identify a product as being associated with one particular customer, which may limit counterfeiting and may also allow the article to be incorporated in some form into a game or other virtual environment, such as in the form of an accessory for a game character.

Virtual communities, including online and multiplayer gaming communities, allow users to interact in a virtual environment. Most typically, a user of one of these virtual communities may interact and experience the virtual community through an avatar, which the user may be able to customize in order to enhance their enjoyment of the virtual community and in order to enhance their identification with the character.
As noted by Turkay and Kinzer in "The Effects of Avatar-based Customization on Player Identification," player identification with an avatar or character is central to how players experience the game. According to the so-called "mirror hypothesis," viewers of any visual media, including both non-interactive media like television and movies and interactive media like video games, will tend to relate favorably to on-screen characters who are either as similar as possible to themselves (the mirror), or ones who represent someone the viewer would like to be (the magic mirror). Thus, according to this hypothesis, allowing players greater freedom to make characters like themselves or like their idealized self, through allowing full customization of aspects of a character such as character appearance, adornments, and physical properties, may thus help a player to identify with the character and get into a mindset of the character within the gaming world, increasing the likelihood of players empathizing with the characters immediately and over time, and increasing the likelihood of those players having a memorable gaming experience. (For example, a first previous study had found that users of a virtual environment who perceive a smaller psychological difference between their avatar and themselves are generally more satisfied with their avatars and spend more time online, and a second previous study had found that users interacting with a virtual avatar that they perceived as like themselves could have emotional responses similar to that demonstrated when interacting with a close other.) Turkay and Kinzer's own study noted that this effect was most pronounced when players had a greater opportunity to customize their own characters, and that players who had the opportunity to spend a significant amount of time customizing their characters to suit their own vision were much more apparently invested in the character (based on certain psychological tells like how often they mentioned the characters in the first person in follow-up interviews) than a second set of players who played with characters that had been pre-customized to look like the second set of players.
Players, in turn, may often cultivate some aspects of their external identity based on the virtual environment. Fans and users of the virtual environment often wish to purchase merchandise related to the virtual environment, such as physical collectibles or devices that are associated with the virtual environment. These fans and users of the virtual environment may then want to incorporate these purchases into the virtual environment itself. (Likewise, people who are "brand loyalists" in one area of their purchasing are often "brand loyalists" in other areas of their purchasing as well, and often perceive some aspects of their "brand loyalty" to be part of their identity. This means that "brand loyalists" for a particular virtual environment, such as intense players of a particular massively multiplayer online role-playing game (MMORPG), are also likely to be "brand loyalists" for other brands such as clothing brands and may perceive this to be an important part of their identity, and something they want their avatar to reflect if possible.) Fans and users may also wish to have physical collectibles or devices that can impact or be used in a virtual environment, in order to have their physical purchasing habits become part of their gaming experience.
It may be noted, however, that many brands which command "brand loyalty"—particularly clothing brands—may command such loyalty because of the perception that they are expensive, exclusive "luxury brands." A major reason why many people are willing to spend money on iconic fashions is because of the perceived scarcity of those fashions; those fashions are desirable specifically because they are denied to others, and thus signal the wearer's wealth and status. Authentic customers of luxury brands may perceive that their identity has been devalued if other people are able to reliably procure counterfeit versions of those luxury brands for cheap prices, and this may likewise be the case in any virtual community. As such, it may be desirable to restrict player choices in some manner within the virtual community in order to better ensure that the customization options available to a particular user better reflect the identity of the user outside of the virtual community.
There have been various attempts to make use of various smart identification technologies in order to better protect consumers against counterfeit products, and for various other related uses. Smart identification technologies employed for this purpose have included near-field communication (NFC), radio-frequency identification (RFID), quick response (QR) codes, smartcards, tamper-proof labels, and so forth. These technologies have facilitated the process of identity verification in a variety of other fields, such as in the finance sector, where proof of identity (such as proof of the identity of an individual making a transaction) is essential for viable commercial transactions. These technologies have likewise been applied to logistical supply chains in order to attempt to better address the need for identification and verification of products and goods. One exemplary case, provided in PCT Pub. No. 2017116303A1 (the details of which are hereby incorporated by reference), provides a secure dual-mode anti-counterfeit product authentication methodology and system by which a product may be associated with a manufacturer identification code provided during the manufacturing process and an NFC-enabled tag which may likewise be associated with product data, with an authentication client then being used in order to read and compare the manufacturer identification code and NFC-enabled tag in order to see if they match.
To look at NFC more specifically, NFC technology allows for contactless exchange of data between two NFC-capable devices equipped with loop antennas over short distances of several centimeters. NFC communications require an initiator and a target, whereby the initiator actively generates an RF field that can power a passive target by magnetic induction. This enables NFC targets to take very simple form factors without their own power source, including, for example, unpowered tags, stickers, key fobs, or cards. The passive data stores associated with NFC tags can be used for sharing small files such as contacts, or alternatively may provide linking information for retrieving larger media such as photos, videos, and other files from elsewhere. Active NFC devices, such as smartphones, may also be used in order to emulate passive NFC devices like smartcards, which may, for example, allow a user to provide an emulated payment card signature to a payment card reader using their smartphone.
While NFC is most commonly used in dedicated identification structures such as tags and smart cards, the consumer goods field of smart product identification has, somewhat more recently, also made use of NFC tags directly embedded within the products themselves. One example application of this is the "toys-to-life" concept, a video game feature that makes use of physical figurines, like Nintendo's "AMIIBO" figurines, in order to allow players to interact with video games in a different manner. Recent Nintendo consoles, starting with the WII U, have included an active NFC reader, which may be paired with a passive NFC receiver in the AMIIBO figurine. Figures may be scanned into a game, which may allow characters on the figures to be used within the game, or may provide other beneficial effects. It has likewise been contemplated to embed similar smart product identification structures into trading cards, such as Nintendo's AMIIBO cards, which may include an electronic component for contactless communication, as explained in U.S. Pat. No. 10,279,273 (also published as US Pub. No. 20180078864A1), the details of which are incorporated herein by reference.
Existing attempts to use this technology for anti-counterfeiting purposes, however, have all had certain flaws. For example, if a product—like the AMIIBO—encodes product-specific information within the product and uses digital signatures encoded within the product for verification of authenticity, bypassing the need for online verification, the authentication information can simply be cloned from one single authentic product, meaning that each of a million counterfeit articles may all report that they are the authentic version of that cloned authentic product.
If certification is instead done by having the user contact an online server, however, different problems may arise from this. For example, if the product includes a scannable barcode or RFID tag that the user can scan to take them to an online page that shows that the product is authentic, or the product otherwise contains the linking information for an online verification page, the product could easily contain a link to a fraudulent online page that reports that the product is authentic. Such authentication also requires that verification rely on a centralized certificate authority and a centralized database, which carries with it the normal problems associated with centralization. A centralized authentication service inherently relies on a single point of failure—the authentication server operated by the manufacturing company—and if this fails in any way then authentication cannot be performed in any manner. If the authentication server is attacked via cyberattack, records of legitimate products may be lost or fraudulent products may be added; the latter may be performed through insider fraud as well. If authentication via the server includes significant user data being passed to the server, this creates a much higher lower bound on the server resources required to perform verification, and may make many people uncomfortable that the company has that data in the first place. Finally, many luxury goods such as watches or film cameras (or other expensive durable goods such as tools, or products with a collector value such as baseball cards or limited-run toys) may simply outlive the company, or may outlive the company's interest in manufacturing the product. (For example, Minolta or Topcon cameras, Kenner collectible action figures, and Sennheiser consumer audio products are still used and traded at relatively high prices despite the companies exiting that market or going defunct.) Such issues may need to be addressed with product verification systems generally, as well as for product verification systems that may be particularized to the process of verifying consumer products for use in or with a virtual environment.

System, method, and smart device for authentication of products and interaction with a virtual environment


A pre-shaped protective member has, on one side or both sides thereof, a uniform adhesive layer covered with a release film. This protective member is produced by vacuum-molding or pressure-molding a molding laminate comprising a thermoplastic sheet with or without a foamed sheet laminated thereon as a base sheet, an adhesive layer having a thickness of 0.5 mm or more and laminated on at least one surface of the base sheet, and a release film covering the adhesive layer.

1. Technical Field
This invention relates to a protective member usable in the technical fields of architecture and civil engineering, which is pre-shaped so that it can surely and easily provide a deformed portion with watertightness, corrosion resistance and a water cut-off function.
2. Background Art
Conventionally, watertightening, corrosion protection and water cut-off for a deformed portion have been conducted by cutting a sheet at the construction site in accordance with the shape of the deformed portion, and then pasting the thus-cut piece to the deformed portion and caulking it, by filling a difference level portion with putty, by applying a non-adhesive shaped body to the deformed portion with use of an adhesive at the site, or by using a partly-adhesive shaped body,
However, the conventional protective member obtained by one of the above methods, wherein a sheet is cut and pasted at the construction site to be followed by caulking, tends to suffer such problems that there is leak of water due to the unevenness of works, and that because of difference level caused by overlapping of two or three sheets, the protective member is so unstable as to take in a layer of air, thereby resulting in insufficient airtightness and liquid-tightness. In the method wherein a difference level portion is filled with putty, it sometimes requires a large quantity of putty, thereby increasing the cost of materials as well as of the working hours. In the case of a non-adhesive shaped body, it is necessary to apply an adhesive at the construction site and some kinds of adhesive may cause unevenness of works which result in insufficient airtightness, liquid-tightness and durability. This means that such conventional members have problems in view of safety and stability.
Even in the case of a partly-adhesive shaped body, there has been such a problem that difference in thickness of adhesive layer allows entering of air, thereby failing to attain sufficient sealing as well as sufficient corrosion resistance.

Method of molding a lamina into a protective member


An examination region (12) is defined within the bore of a superconducting magnet assembly (10). An RF coil (22) and gradient magnetic field coils (14) are disposed within the bore of the superconducting magnet assembly around the examination region. The superconducting magnet includes a hollow, cylindrical vacuum vessel (40). An annular, liquid helium holding low temperature reservoir (60) extends centrally through the vacuum vessel, but is sealed therefrom such that liquid helium is not drawn into the vacuum. A plurality of annular superconducting magnets (56) are received in the low temperature reservoir immersed in the liquid helium. A first cold shield (44) and a second cold shield (50) are mounted in the vacuum vessel surrounding the low temperature reservoir. A main magnetic field shield coil (66) is disposed in the low temperature reservoir outside of the annular superconducting magnets for canceling the magnetic field generated by the annular magnets surrounding the magnet. A gradient shield coil (70) is mounted in low temperature reservoir inside the annular superconducting magnets to cancel magnetic fields generated by the gradient magnetic field coils in the region beyond the gradient shield coil. The gradient shield coil is electromagnetically coupled to the gradient field coils to be driven by magnetic fields emanating therefrom. Optionally, the gradient shield coil can be constructed of a higher temperature superconducting material and disposed in association with one of the cold shields.

The present invention relates to superconducting magnets. It finds particular application in conjunction with superconducting magnets used in magnetic resonance imaging apparatus and will be described with particular reference thereto. It is to be appreciated, however, that the invention will also find application in other low temperature magnets in applications in which eddy magnetic fields are undesirable, such as nuclear magnetic resonance spectrometers and the like.
Magnetic resonance imaging systems superpose three magnetic fields over an imaging volume. A superconducting magnet is commonly used to provide a spatially large as well as a temporally and spatially constant main magnetic field. This main field is referred to as the B.sub.O field and is usually between 0.5 to 2.0 Tesla within an imaging volume of 50 cm diameter. A second magnetic field changes with time and has spatial linear .differential.B.sub.z /.differential.x, .differential.B.sub.z /.differential.y, .differential.B.sub.z /.differential.z gradients for spatial encoding that are aligned with the B.sub.O field. These are typically in the range of +/- 10 mT/m. Transverse to the direction of these two fields is an RF magnetic field used for magnetization reorientation during the NMR experiment.
In a conventional MRI magnet system, a set of B.sub.O field generating coils are configured in such a way that they provide only about a 10 micro Tesla variation within the 50 cm diameter imaging sphere. The coils are typically superconductors operating at a temperature near that of liquid helium, 4.2.degree. K. Typically, between six and eleven superconducting coils are series connected and immersed in a common liquid helium reservoir. In order to minimize the heat gain of the magnet from the room temperature environment, a cryostat is provided. The cryostat is an evacuated container to eliminate convective heat transfer. The magnet is immersed in a liquid helium bath at 4.2.degree. K. and near atmospheric pressure. Between these two containers two cold shields are suspended. One is cooled to about 10.degree.-20.degree. K. by refrigeration and/or the boil off helium gas. The other is typically cooled to about 77.degree. K. Several layers of aluminized mylar minimize the radiative heat transfer. The 77.degree. K. cold shield is either maintained by the boil off of liquid nitrogen or by mechanical refrigeration which can cool it to 60.degree.-70.degree. K. There is also a conductive heat transfer in the suspension members of these internal structures. This is, of course, minimized by design. The cryostat design is thus optimized to provide for a minimum heat gain and thus a minimum helium boil off.
A conventional MRI system surrounds the patient or part of the patient with an RF coil, then the gradient field coil, and finally the room temperature bore of the magnet. Although the cryostat does in general provide an excellent barrier to heat transfer, it also provides electrically conductive materials to support eddy currents from the time changing gradient fields. The magnetic fields resulting from these eddy currents may be substantial and require correction. Conventionally, this is done electrically with pre-emphasis. However, the most effective method is not to create the eddy currents in the first place rather than correcting for them after they are created. This is done with self shielded gradients which consist of a primary set of coils at a first radius as well as a secondary or shield set of coils at a second radius. The design of these coils is such as to minimize the eddy currents at the position of the magnet cold shields as described in U.S. Pat. No. 4,896,129 to Turner, et al. The efficiency of the self shield gradient is strongly influenced by the ratio of the shield coil and primary coil radii, because one partially cancels the field of the other over the imaging volume, in addition to cancelling fields outside of the coils.
There are three general types of superconducting magnets, unshielded, passively shielded, and actively shielded. By design, an unshielded magnet makes no provision to control the field external to the magnet. A passively shielded magnet is designed with iron close to the magnet so as to reduce the spatial extend of the magnet's field. An actively shielded magnet is designed with inner and outer coils (like the self shielded gradient) to minimize the magnetic field outside of the magnet. A hybrid magnet may use some active and some passive shielding. All of these types of magnets require a shimset in order to reach the desired level of homogeneity in the patient volume. A set of Garrett coils can be made to provide the additions to the main field to make the main field more uniform. Some of the coils of this shimset, either superconductive or resistive, can couple to the gradient coil, as does the shield coil of the self shielded gradient. To eliminate these interactions and reduce cost, most MRI systems now have a passive (iron) only shimset. This shimset is located in the room temperature bore of the magnet in the vicinity of the gradient coil.
More specifically, the first or higher temperature cold shields which are traditionally disposed along the patient bore and outside diameters of the vacuum chamber are cooled with liquid nitrogen to about 77.degree. K. For example, a cylindrical liquid nitrogen reservoir is provided inside the vacuum chamber around the outside of the superconducting magnet. The reservoir is thermally connected with a cylinder around the bore and disks at the edges, such that the nitrogen reservoir is cooled by conduction. However, this liquid nitrogen cooling is commonly replaced with mechanical refrigeration. The mechanical refrigeration unit is thermally connected with a copper or aluminum cylinder disposed adjacent the interior diameter of the vacuum chamber and another aluminum or copper cylinder disposed adjacent the outer diameter of the vacuum chamber. The mechanical refrigeration cools these cylinders to a temperature around 60.degree.-70.degree. K., the two cylinders being thermally linked at each end by disks.
To reduce the heat transport, second or inner cold shields are commonly disposed between the first cold shields and the liquid helium vessel. The second cold shields includes one copper or aluminum cylinder disposed between the inner diameter of the superconducting magnets and the inner cylinder of the first cold shield and a second copper or aluminum cylinder disposed between the outer diameter of the superconducting magnets and the outer cylinder of the first cold shield. The cylinder is thermally connected by disks at opposite ends. The second cold shield is thermally connected, such as by thermally conductive metal straps, with a second stage of the refrigeration unit which cools it to about 20.degree. K. Again, the cylinders are surrounded inside and out by layers of the super insulation.
A gradient field coil is disposed in the bore displaced from the inner wall of the cryostat for selectively generating magnetic field gradients across an imaging region in the bore. Typically, the gradient magnetic fields are applied for short durations, sufficiently short that they might more aptly be referenced as magnetic field gradient pulses. The gradient magnetic field pulses, particularly the rising and falling edges of the gradient field pulses, induce voltages in surrounding electrically conductive structures which, in turn, cause eddy currents. That is, eddy currents are generated in the magnet formers, the shimming coils, the liquid helium reservoir, the cold shields, and the like. At the very low resistance found at these temperatures, the eddy currents can persist for periods in excess of the repeat time of the magnetic resonance sequence. The generated eddy currents are very complex, varying with frequency, temperature, thickness of the electrically conductive structure, and the like. These generated eddy currents, in turn, generate eddy magnetic fields in the imaging region in the bore of the magnet. These eddy magnetic fields disrupt the precise magnetic fields that make for good quality, high resolution magnetic resonance imaging.
One technique for compensating for the eddy magnetic fields is through pre-emphasis. During initial pre-emphasis calibration, the contribution from the eddy magnetic fields are determined and the current pulses for generating the gradient magnetic fields adjusted accordingly. More specifically, the currents used to generate the gradient magnetic fields are adjusted such that the generated gradient field and the eddy magnetic field sum to produce the desired magnetic field in the image region. See for example, U.S. Pat. No. 4,761,612 issued Aug. 2, 1988 to Holland and Stauber entitled "Programmable Eddy Current Correction", and U.S. Pat. No. 4,703,275 issued Oct. 27, 1987 to Holland entitled "Method and Apparatus to Compensate Eddy Currents in Magnetic Resonance Imaging". Although pre-emphasis is effective, it does not completely correct for the complex gradient magnetic fields. The generated eddy magnetic field is very complex and cannot always be completely compensated for with a linear gradient.
One technique for reducing the eddy magnetic fields is to install a self-shielded gradient coil within the warm bore of the superconducting magnet. The self-shielded gradient coils include a gradient coil and a surrounding active shielding coil. The shielding coils are designed to cancel the gradient magnetic field at the positions of the cold shields to prevent inducing eddy currents, hence eddy magnetic fields. However, the shield coils generally require a diameter that is about 1.3 times the diameter of the primary gradient coil. This either reduces the size of the usable bore within the gradient coil or requires a larger, more expensive superconducting magnet. For medical diagnostic imaging, the minimum size of the bore is generally dictated by the dimensions of the human torso, hence reducing the useful bore size is undesirable.
The present invention contemplates a new and improved gradient shielding coil which overcomes the above-referenced problems and others.


A ceramic filter membrane module enables a fluid to be filtered, such as raw water, with higher efficiency using multiple ceramic filters in a housing. As the diameter of a through-hole located at the center is considerably larger than the diameter of the surrounding flow path, water pressure pushing the raw water is applied from the through-hole at the center toward the outside of a filter body, such that the raw water passes through the filter body smoothly, thereby improving the purification efficiency and uniformly setting the overall flow direction of the raw water. As packing members are installed and fixed between the housing and the ceramic filters, sealing of the incoming raw water and the filtered water becomes more effective, such that the risk of leakage is reduced. As a plurality of ceramic filters are housed in a single housing, economic benefit can be achieved.

Ceramic filters are excellent in heat resistance, durability, stain resistance, corrosion resistance and the like compared to organic polymer membrane filters, and thus widely used in various fields of business as a filter for various kinds of water treatment and liquid or gas filtration. Accordingly, the ceramic filters are useful in wide and various fields of industry.
The ceramic filters have a shape of flat plate, tube, hollow monolith, etc., and are used in various ways, such as having a filtration type like a pressure-resistant type, an immersion type or the like. However, in order to maximally increase filtration area per unit volume, a ceramic filter, which is a hollow monolith type formed with a countless number of through-holes passing through both sections of a cylindrical porous ceramic supporter, has been commercially used as shown in Patent Document 1 (Japanese Patent No. 2002-143655).
However, most of the ceramic filters presented in the above Patent Document 1 are designed to be equipped with only one monolith filter in one filter module (housing). Thus, in case of facilities requiring a large amount of water treatment, for example, water purification plants, it is required to install a large number of modules with a need for wide space, thereby causing a significant problem in an economic aspect.


A semiconductor device includes a first insulating layer, an optical waveguide formed on the first insulating layer, a fixed charge layer formed on the first insulating layer such that the fixed charge layer covers the optical waveguide, and a second insulating layer formed on the fixed charge layer.

The present disclosure relates to semiconductor device and method of manufacturing the semiconductor device, for example, the present disclosure relates to a semiconductor device including an optical waveguide and method of manufacturing the semiconductor device.
As an optical communication technique, a silicon photonics technique is known. The semiconductor device employing the silicon photonics technique has, for example, an optical modulator for changing the phase of light in an optical waveguide.
Japanese Unexamined Patent Application Publication No. 2017-509022 discloses a pn-type optical modulator including an optical waveguide formed of an n-type semiconductor portion containing an n-type impurity and a p-type semiconductor portion containing a p-type impurity. The optical waveguide constituting the optical modulator is patterned by etching. The n-type semiconductor portion and the p-type semiconductor portion are adjacent to each other in the optical waveguide, and form a pn junction surface. The pn junction surface is formed so as to face both side surfaces of the optical waveguide in the optical waveguide. When a reverse bias voltage is applied to the optical modulator, the depletion region expands from the pn junction surface toward the side surface of the optical waveguide. In the state in which the depletion region is formed and the state in which the depletion region is not formed, the phase of the light traveling in the optical waveguide is different. The optical modulator can electrically control the phase of the light traveling in the optical waveguide by using this characteristic.
When the optical waveguide is formed by patterning the semiconductor layer by dry etching, optical loss due to roughness of the surface of the optical waveguide may occur. In addition, when the optical modulator is driven at a low voltage, the depletion region cannot be sufficiently expanded in the optical waveguide, and as a result, the modulation efficiency of the optical modulator may become insufficient. As described above, in the conventional optical modulator, there is room for improvement from the viewpoint of enhancing the characteristics of the semiconductor device.
It is an object of one embodiment to enhance the properties of a semiconductor device. Other objects and novel features will become apparent from the description of the specification and drawings.

Semiconductor device and method of manufacturing the same


A thinner composition includes propylene glycol ether acetate, methyl 2-hydroxy-2-methyl propionate, and an ester compound such as ethyl lactate, ethyl 3-ethoxy propionate or a mixture thereof.

1. Field of the Invention
The present invention generally relates to a thinner composition and a method of removing a photoresist using the thinner composition. More particularly, the present invention generally relates to a thinner composition having improved solubility properties and a method of efficiently removing an edge bead relative to various photoresist or anti-reflective materials using the thinner composition.
A claim of priority is made to Korean Patent Application No. 2004-8678 filed on Feb. 10, 2004, the contents of which are incorporated by reference in their entirety.
2. Description of the Related Art
Semiconductor devices having a high degree of integration and rapid response speed are desired as information processing apparatuses continue to develop. Hence, the technology for manufacturing semiconductor devices has developed to improve the degree of integration, reliability, and response speeds of the semiconductor devices.
To manufacture a conventional microcircuit, for example, impurities are precisely implanted into regions on a silicon substrate, and then the impurity regions are electrically connected to each other to form a very large scale integration (VLSI) circuit. A photolithography process is used to form patterns, which define the impurity regions. After forming a photoresist film on the substrate, the photoresist film is exposed to light such as an ultra violet ray, an e-beam, or an X-ray. The photoresist film is developed and then exposed portions on the substrate are removed.
Conventionally, a photoresist is coated while a substrate is rotated such as a spin coating process; the photoresist evenly coats on an edge and backside of the substrate. However, the photoresist coated on the edge or the backside of the substrate generates particles known as an edge bead, which may cause process failure in subsequent processes such as an etching process or an ion implanting process. Therefore, an edge bead removal (EBR) process using a thinner composition is generally required to remove the unwanted particles from the substrate.
Sometimes, a failure of a photoresist pattern may occur during a photolithography process. When the failure of the photoresist pattern occurs, a reworking process is performed to remove the failed photoresist pattern from the substrate. The reworking process is used to save the substrate.
As patterns on semiconductor devices become finer, photoresist compositions have been developed by an I-line ray or a G-line ray. A photoresist composition generally includes a novolak resin as the main ingredient. In addition, an amplified photoresist that is sensitive to an excimer laser or an extreme ultraviolet ray has been used to manufacture semiconductor devices. Thus, a thinner composition having good solubility relative to these types of photoresist is required.
U.S. Pat. No. 5,866,305 discloses, for example, a thinner composition containing ethyl lactate and ethyl 3-ethoxy propionate, and also discloses another thinner composition containing ethyl lactate, ethyl 3-ethoxy propionate, and gamma-butyro lactone. Although widely used, the above-mentioned thinner compositions have poor solubility relative to certain photoresists such as amplified photoresist. In addition, the thinner compositions are relatively expensive due to ethyl 3-ethoxy propionate, which is used as the main ingredient. Further, the thinner composition has poor solubility and EBR characteristics relative to photoresist using an argon fluoride (ArF) laser.
U.S. Pat. No. 6,159,646 discloses another conventional thinner composition containing ethyl lactate and gamma-butyro lactone; a thinner composition containing ethyl lactate, ethyl 3-ethoxy propionate, and gamma-butyro lactone; and, a thinner composition containing ethyl lactate and ethyl 3-ethoxy propionate. The cost to prepare thinner compositions containing ethyl 3-ethoxy propionate and gamma-butyro lactone is substantially high. These thinner compositions also have substantially poor solubility relative to photoresists using an ArF laser.
The above-described conventional thinner compositions are employed in reworking processes and in EBR processes; however, the thinner compositions are inappropriate for both processes.
A thinner composition containing an acetic acid ester compound, gamma-butyro lactone, and a non-acetate type ester, as disclosed in Korean Patent Laid Open Publication No. 2003-51129, is effective in removing photoresist using an I-line ray, a G-line ray, and krypton fluoride laser in a reworking process or an EBR process. However, the thinner composition has poor solubility relative to a photoresist using an ArF laser. In addition, the thinner composition has poor EBR characteristics. A thinner composition having good solubility relative to THE photoresist exposed to an ArF laser, which effectively removes unwanted photoresist in an EBR process, and is effective in a reworking process is required.

Thinner composition and method of removing photoresist using the same