Title of Invention

CELLULOID-FREE TABLE-TENNIS BALL

Abstract The invention relates on one hand to a celluloid-free table-tennis ball, preferably having a diameter of 38.5 to 48 mm. a weight between 2.0 and 4.5 grams, and a shell thickness (approximately) between 0.20 mm and 1.30 mm, where the shell is composed of plastic, whose principal component is an organic non-crosslinked polymer, which in Its main chain has not only carbon atoms but also heteroatoms; and on the other hand also to a process of manufacturing a table-tennis ball of this kind, where mostly in a first step two or more shell parts are manufactured, these shell parts are joined in a subsequent step.
Full Text CELLULOID-FREE TABLE-TENNIS BALL
The invention relates on one hand to a celluloid-free table-tennis ball, preferably having a diameter of 38.5 to 48 mm. a weight between 2.0 and 4.5 grams, and a shell thickness (approximately) between 0.20 mm and 1.30 mm, where the shell is composed of plastics, whose principal component is an organic, non-crosslinked polymer, and on the other hand a manufacturing process of such a table-tennis ball.
Since about 1930, celluloid is worldwide used as material for table-tennis balls. Celluloid features, however, some essential disadvantages. These disadvantages are extensive manufacture using many solvents, difficult manufacturing of secondary products, explosion hazard. Due to these facts, celluloid is manufactured and processed today almost exclusively in East Asian countries. Quite often accidents happen thereby. Relating to the table-tennis ball, this causes to the fact that the world market completely depends on the manufacturing in China. Japan, and Korea. Increasingly, the technical material properties of celluloid become a problem, because die manufacturing tolerances leave the range accepted by the players.
There is a set of rules for the table-tennis ball defined by the International Table Tennis Federation (ITTF). These are specified by ITTF Technical Leaflet T3. At present following characteristics are defined:
1. Diameter: 39.5 mm to 40.5 mm
2. Weight: 2.67 g to 2.77 g
3. Veer: On a rolling course of 1 m in length, the ball having a roll speed of about 0.3 m/sec. should not differ more than 175 mm
4. Hardness at pole: a piston with 20 mm diameter, a compressive force of 50 N. and a speed of 10 mm/min is allowed to impress the ball at pole between 0.71 and 0.84 m
5. Hardness at equator: such as pole meter; values between 0.72 and 0.84 mm

6. Variance of hardness by pole and equator measurement: less than 0.15
mm
7. Standard deviation of hardness: less than 0.06 mm
8. Bounce: jump height between 240 mm and 260 mm at a drop height of 305 mm to a standard steel block.
Diameter and weight are thereby by the international regulations largely defined characteristics, the veer is such a defined and desired quality, while the according 4 to 8 defined, mechanical properties describe the properties of the used celluloid ball.
General mechanical properties, which characterize a marketable ball, are:
Complete and not visible recovery of deformations within a few milliseconds
No stress-whitening and other, irreversible material changes under load
Stability at impact on a rubber coated surface with a relative speed of up to
250 km/h
Stability at impact on a stiff, coaled surface with a relative speed of up to
120 km/h
breaking strength of material and possible seam by 5000-fold repeated
impact at described contact settings
Stability at rotations up to 180 revolutions per second
As well decisive for the acceptance of the table-tennis ball is the opinion of the players, which judge the ball by play feeling, subjective hardness, and bounce. By the use of celluloid for decades a very established standard has been developed, whereby the new materials must be measured. A decisive property is thereby the sound of the table-tennis ball at bounce on a stiff surface, e.g., on a desk.
In the Eighties, the Dunlop Company, UK, tried to replace the material celluloid, as well as in 1990 the Double Fish company, China. All of these attempts failed until now. The reason for the failure is the fact that the specific properties of celluloid cannot achieve by the new materials.

In GB 1 222 901 of the Dunlop Company the use of styrene-acrylnitrile-acrylic elastomers as shell material is described. The ball was experimentally applied to play in the Eighties, but due to irreversible material deformations (buckles) withdrawn. Moreover, the ball did not have the same play characteristics as celluloid.
In the DE 103 15 154 A1 the integration of macroscopic structural elements in the shell of plastic table-tennis balls is described. This patent describes not the basic plastic of the ball, but only possibilities for its modification.
According to this, it is not succeeded so far, to find a material, which approximately describes the play characteristics of celluloid. Bounce, sound at bounce, hardness at various points of the surface, friction on the surface, the feeling during the contact bat-ball, and rotational behavior are part of these play characteristics of the ball.
From these disadvantages of the previous state of the art results the problem initiated the invention, to find a basic material of a table-tennis ball that is not celluloid and allows of the manufacture of balls with play characteristics similarly to those of celluloid by similar mechanical properties. In addition, a large-scale production of the table-tennis balls using this material by today commonly industrial processes should be possible.
The solution of this problem succeeds that the organic polymer exhibits in the main chain not only carbon atoms but also heteroatoms.
It has been shown that by the use of such plastic materials it is possible to replace the disadvantageous material celluloid in the table tennis ball production and to maintain the playing characteristics in the process largely. In addition, thereby the production can be arranged ecological and economic.
It has proved to be favorable that the organic polymer has no nitrogen atoms outside the main chain. Such a nitration changes the material properties rather negatively.

By the invention, it is possible to use a thermoplastic with a homogeneous structure without fillers and/or reinforcement materials, which can be better processed than inhomogeneous material.
It has been shown, that the principal component of the substance according to the invention should have a minimize water absorption, particularly a water absorption at standard climate according to DIN EN ISO 62 of less than 1.0 %. Thereby uncontrolled swelling is excluded.
Otherwise the ball indentation hardness according DIN EN ISO 2039-1 of the substance according to the invention should be at 120 MPa or higher, so that table tennis ball can be made corresponding to common demands.
Furthermore, the invention recommends to use such substances, that principal component has a density according to DIN EN ISO 1183 of 1.22 g/cm^ or more. With these by predetermined cross-section of the shell, the weight of a table-tennis ball can be optimal adjusted.
The principal component of substance according to the invention should feature a long-term service temperature of 80 X or more (engineering thermoplastics, high temperature thermoplastics) in order to be sufficiently resistant to thermal exposure. Substances, whose main component exhibits long-term service temperature of 150 "^C or more (high temperature thermoplastics), are still better suited.
If the principal component is semi-crystalline, by partially parallel adjustment of polymer chains a high stability can be set. which is just important to comparatively thin shell.
Within the invention, the principal component of the shell is one of the following substances: Polyoxymethylene (POM), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polysulphone (PSU), polyether imide (PEI), polyetherether ketone (PEEK), polyethylene naphthalate (PEN), polybutylene

naphthalate (PBN). polytrimethylene terephthalate (PTT), or a copolymer of one or several of these substances.
These plastics are characterized by a good processability with different shaping techniques such as thermoforming or injection molding and could be further modified and adapted by specific modification of the basic components or by appropriate blends. In extensive test series, these different plastic materials were pre-selected based on their mechanical characteristics and aftenA/ards tested by manufacturing and testing table-tennis balls with the appropriate standard size und standard weight. Particularly good results were achieved by partly aromatic polyesters and POM.
If the molding material is a mixture or a blend of one or several of mentioned plastics, substances with particularly favorable properties can be created.
If necessary, selected, mainly mechanical properties of the table-tennis ball can be improved by modifying the molding material by nanofillers. preferably layered silicates, nanotubes, or spherical nanoparticles.
A possibly further development serves to the same in such a way, that the shell has a structured inner surface, and/or a structured outer surface.
Further it is possible, that the shell has a tailored variation of the wall thickness to compensate inhomogeneities or anisotropies by the manufacturing process (e.g. welding of two half shells) where required.
This makes it possible, to join the table-tennis ball from a multipart, preferably two-piece, shell, what is proved particularly economical.
Optimal characteristics has the table-tennis ball, if it achieves by impact of 305 mm height on a standard stone plate a jump height between 220 mm und 280 mm. and shows on its surface at a compressive force of 50 N on an area of 20 mm diameter on the ball's surface a reversible deformation between 0.65 mm und 0.90 mm with a standard deviation of about various points of the surface of less than 0.20 mm.

A method of manufacturing of a table-tennis ball according to the invention is characterized, that in a first step several shell parts are manufactured, which are joined in a following step.
It has been shown that for these purpose the newly found materials are particularly suitable to join, by application of modern technologies the forming of a welding seam could be largely or completely avoided. Where necessary the surface can be smoothed to remove seam residues completely.
The shells respectively shell parts are manufactured by forming a blank, e.g., a flat body, e.g.. by thermoforming. This procedure can be implemented possibly near or below the softening temperature, so that the material behavior is very well controllable.
Furthermore, it is also possible to manufacture shells respectively shell parts by shaping from a liquid or paste-like molding compound by a molding process, e.g. by injection molding. Thus, the cross-section can be accurately affected and thereby a constant shell thickness guaranteed.
The invention recommends that the shell parts be joined by gluing, welding, and/or clips. While the first procedures result in a very stable table-tennis ball, by the last procedure an accurately defined cross-section of the ball can be guaranteed also at join patch. By a strong enough undercut, it is achieved that the two shell parts cannot be separated without destruction of the ball.
The expenditure in manufacturing can be further reduced by joining the shell parts directly in the tool, preferably by assembly injection molding or hollow body injection molding.
By the use of modern, plastics processing techniques it is possible to vary specifically the wall thickness of the shell, especially between equator and pole, preferably during the injection molding process to compensate the anisotropy caused by joining.

Finally, it corresponds to lore of invention that during the manufacture of the ball one or more steps run at a minimum temperature of 110*'C, preferably at more than 140 'C. Here the thermoplastic material is particularly well ductile.
EXAMPLES
Further characteristics, properties, and advantages based on the invention result
from following description of some preferred embodiments of the invention.
Example 1
A table-tennis ball was made from two injection molded PEI half shells, which
were joined after a plasma surface treatment by a polyvinyl butyral hot-melt
adhesive.
Example 2
A table-tennis ball was made from two injection molded PET half shells, which
were joined after plasma surface treatment by reaction adhesive on epoxy basis.
Example 3
A table-tennis ball was made from two thermoformed POM half shells, which were
joined after surface treatment by reaction adhesive on epoxy basis.












1. A celluloid-free table-tennis ball, preferably having a diameter of 38.5 to 48
mm, a weight between 2.0 and 4.5 grams and a shell thickness (approximately)
between 0.20 mm and 1.30 mm. where the shell is composed of plastics whose
principal component is an organic non-cross linked polymer, which in its main
chain has not only carbon atoms but also heteroatoms. characterized in that the
principal component is
a) a thermoplastic material, furthermore,
b) having a density according to ISO 1183 of more than 1.22 g/cm^, and
c) water absorption according to ISO 62 of less than 1.0 %.
2. A celluloid-free table-tennis ball, preferably having a diameter of 38.5 to 48
mm, a weight between 2.0 and 4.5 grams and a shell thickness (approximately)
between 0.20 mm and 1.30 mm, where the shell is composed of plastics whose
principal component is an organic non-crosslinked polymer, which in its main
chain has not only carbon atoms but also heteroatoms, characterized in that the
principal component is
a) a thermoplastic material, that is semi-crystalline and/or has a long-thermo service temperature of 150 °C or more (high temperature thermoplastic), furthermore,
b) has a density according to ISO 1183 of more than 1.22 g/cm^. and
c) water absorption according to ISO 62 of less than 1.0 %.
3. The table-tennis ball according to claim 1 or 2. characterized in that the
organic polymer has no group of nitrate.
4. The table-tennis ball according to one (or more) of the preceding claims,
characterized in that the organic polymer has no nitrogen atoms outside the main
chain.
5. The table-tennis ball according to one (or more) of the preceding claims,

characterized in that the thermoplastic has a homogeneous structure without fillers and/or reinforcement materials.
6. The table-tennis ball according to one (or more) of the preceding claims, characterized in that a principal component has ball indentation hardness according ISO 2039-1 of 120 MPa or more.
7. The table-tennis ball according to one (or more) of the preceding claims, characterized In that the principal component of the shell is one of the following substances: Polyoxymethylene (POM), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polysulphone (PSU), polyether imide (PEI), polyetherether ketone (PEEK), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polytrimethylene terephthalate (PTT). or a copolymer of one or several of these substances.
8. The table-tennis ball according to claim 7, characterized in that the molding material is a mixture or a blend of one or several of mentioned plastics.
9. The table-tennis ball according to one (or more) of the preceding claims, characterized in that the molding material is modified by nanofillers. preferably layered silicates, nanotubes, or spherical nanoparticles.
10. The table-tennis ball according to one (or more) of the preceding claims, characterized in that the shell has a structured inner surface.
11. The table-tennis ball according to one (or more) of the preceding claims, characterized in that the shell has a structured outer surface.
12. The table-tennis ball according to one (or more) of the preceding claims, characterized in that the shell has a tailored variation of wall thickness.
13. The table-tennis ball according to one (or more) of the preceding claims, characterized in that it is made from a one-piece, preferably by rotational molding manufactured shell.

14. The table-tennis ball according to claim 1 to 12. characterized in that it is joined from a multi-part, preferably two-piece shell.
15. The table-tennis ball according to one (or more) of the preceding claims, characterized in that the ball achieves by impact of 305 mm height on a standard stone plate a jump height between 220 mm and 280 mm. and shows on its surface at a pressure of 50 N on an area of 20 mm diameter on the ball's surface a reversible deformation between 0.65 mm and 0.90 mm with a standard deviation of about various points of the surface of less than 0.20 mm.
16. A process for manufacturing of a table-tennis ball according to one (or more) of the preceding claims, characterized in that in a first step several shell parts are manufactured, these are joined in a subsequent step.
17. The process according to claims 16. characterized in that the shells are
manufactured by deformation of a blank, eg. a flat body, for example by
thermoforming.
18. The process according to claims 16, characterized in that the shells are manufactured by molding from a liquid or paste-like molding compound, e.g. by injection molding.
19. The process according to claims 16 to 18, characterized in that the shell parts are joined by gluing, welding, and/or clips.

20. The process according to claims 16 to 19, characterized in that the shell parts are joined by rotational welding, ultrasonic welding, induction welding, or laser welding.
21. The process according to claims 16 to 20. characterized in that the shells directly joined in the mold, preferably by assembly injection molding or hollow body injection molding.

22. The process according to claims 16 to 21, characterized in that shaping
measures are used to tailored variation of wall thickness of the shells, preferably
during the injection molding process.
23. The process according to claims 16 to 22, characterized in that during the
manufacture of the ball one or more steps run at a minimum temperature of 110
X, preferably at more than 140 X.

Documents:

http://ipindiaonline.gov.in/patentsearch/GrantedSearch/viewdoc.aspx?id=09DL4DPPkCHzzw2KYBAUyA==&loc=egcICQiyoj82NGgGrC5ChA==


Patent Number 268568
Indian Patent Application Number 1861/CHENP/2008
PG Journal Number 36/2015
Publication Date 04-Sep-2015
Grant Date 03-Sep-2015
Date of Filing 15-Apr-2008
Name of Patentee IN SOOK YOO INTERNATIONAL PROJECT MANAGEMENT-IPM
Applicant Address FROHLICHSTRASSE 11, 97082 WURZBURG, GERMANY.
Inventors:
# Inventor's Name Inventor's Address
1 YOO, IN, SOOK FROHLICHSTRASSE 11, 97082 WURZBURG, GERMANY.
2 WOLLHEIM, THOMAS NECKARSTRASSE 1, 95445 BAYREUTH, GERMANY.
PCT International Classification Number A63B 39/00
PCT International Application Number PCT/EP2006/008963
PCT International Filing date 2006-09-14
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 102005044178.5 2005-09-15 Germany