CA1257037A - Resin composition containing a saponified ethylene- vinyl acetate copolymer - Google Patents
Resin composition containing a saponified ethylene- vinyl acetate copolymerInfo
- Publication number
- CA1257037A CA1257037A CA000468224A CA468224A CA1257037A CA 1257037 A CA1257037 A CA 1257037A CA 000468224 A CA000468224 A CA 000468224A CA 468224 A CA468224 A CA 468224A CA 1257037 A CA1257037 A CA 1257037A
- Authority
- CA
- Canada
- Prior art keywords
- resin composition
- vinyl acetate
- fiber
- saponified
- copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
Abstract of the disclosure:
A resin composition which comprises 50 to 95%
by weight of a saponified ethylene-vinyl acetate copolymer and 5 to 50 % by weight of potassium titanate fiber, the saponified copolymer being 10 to 55mole% in ethylene content and at least 90Mole% in saponification degree of vinyl acetate portion.
A resin composition which comprises 50 to 95%
by weight of a saponified ethylene-vinyl acetate copolymer and 5 to 50 % by weight of potassium titanate fiber, the saponified copolymer being 10 to 55mole% in ethylene content and at least 90Mole% in saponification degree of vinyl acetate portion.
Description
2 5 7 0 3 7 Tlle inventioll relates to a resin coml-osition containing a saponified ethylene - vinyl acetale copolyMer wbicll gives a molded product haYillg an excellellt property.
The saponified ethylene - vinyl acetate col-oiylner (hereinafter referred to as " E V A cPpolYmer") is excellent in Inechallical strengtll, non - cllar~ing property, resistances to oil and solvent, resistance to abrasion, etc, and is gradually used for preparing mechallical parts, structural parts and the like. P articularly, a molded product obtaind froM the saponified E V A copolylner incorporated glass fiber therein exhibits an improvement in tensile strength, tensile modulus, bending strength, bending modulus, compression strength and like mechallical properties.
T hus, the above saponified copolymer contail~ 25 to 55 % ( % by weigllt, same in hereinafter) of ~lass fiber is sold and used as a material for moldill~
H owever, a molded product of the sapollified E V A copolymer containin~ glass fiber has a drawback that glass fiber comes to the surface to deteriorate the surface - smootllness of the molded product. F urtller, the molded product is poor in appearance due to a slight yellow of the resin.
~2570~
In addition, though the above resin composition is excellent in mechanical strength and modulus, glass fiber is large in an average fiber diameter of 3 to 13~m and an average fiber length of at least 3 mm. Thus, it is very difficult to mold the resin composition into small, thin-wall or fine parts such as those in precision machines, ~usiness machines, electric products for use at home, etc.
The present invention provides a resin composition which can be molded into parts having a very good appearance due to an excellent surface-smoothness and whiteness.
The present invention also provides a resin composition which can be molded into small, thin-wall or fine parts.
The present invention further provides a resin composi-tion which gives a molded product having an excellent mechanical property.
The present invention provides a resin composition which comprises 50 to 95% by weight of a saponified ethylene-vinyl acetate copolymer and 5 to 50% by weight of potassium titanate fiber, the saponified copolymer being 10 to 55 mole% in ethylene content and at X
125703~
least 90mole~ in saponification degree of vinyl acetate portion.
T he resin coMposition of the invention can be molded into parts having a very good appearance due to an excellent surface - smoothness and whiteness. T he molded product of the invention is high in mechanical strength and particularly excellent in modulus despite of shorter fiber length of potassium titanate fiber. F urther, the resin composition of the invention can be molded into sMall, thin - wall or fine parts. I t is easy to design a rnold and to shape the resin composition into minute parts due to a smaller orientation of potassium titanate fiber compared with glass fiber and carbon fiber.
T he saponified E V A copolymer used in the invention has an ethylene content of 10 to 55mole % and a saponification degree of vinyl acetate portion of at least 90mole %. W ith more than 55mole % in ethylene content, heat distortion temperature ( H D T ) of molded product is low. W ith less than 10mole % , it is difficult to mold the composition due to the closeness of melting point and thermal decomposition temperature of the resin. P referable ethylene content is 25 to ~5mole %
from the viewpoint of moldability, mechanical property, H D T and the like. W ith less than 90mole % in saponification de~ree, the molded product is low in thermal stability, H D T and mechanical property.
P referable saponification degree in vinyl acetate portion is at least 95mole %.
T he E V A copoiymer rnay contain a small amount of a copolymerizable monomer other than ethylene, vinyl acetate (or vinyl alcohol derived from saponification of vinyl acetate). E xamples of useful monomers are propylene, isobutylene and like olefins, acrylic acid, methacrylic acid, maleic acid, crotonic acid and like unsaturated acid or esters thereof, etc.
P otassium titanate fiber used in the invention is a single crystal represented by the formula K 2 0 l( T i O 2~ or K 2 0 l( T i O 2) 1/2 H 20 wherein l is an integer of 2 to 8. E xamples thereof are potassium tetratitanate fiber, potassium hexatitanate fiber, potassium octatitanate fiber, etc., and these are used singly or in mixture. T he titanate fiber has an average fiber diameter of preferably up to 2 ~ m, average fiber length of preferably 5 to 100~ m and a ratio of avera~e fiber length to average fiber diameter (aspect ratio) of preferably 10 to 200.
I n the invention, average fiber diameter and average fiber length of potassium titanate fiber are each auerage of values which were rneasured in at least 5 sights and at least 10 fibers in each sight, with use iL 2 5 7 0 3 7 of a scanning - type electron microscope. A n aspect ratio is a divisor of average fiber length by average fiber diameter.
W ith outside of the above ranges of average fiber diameter, average fiber length and aspect ratio, for example, more than 1 ~ m in average fiber diaMeter, less than 5 ~ m in average fiber length, namely when aspect ratio is less than 10, reinforcing effect of molded product is small, hence undesirable.
F urther, fibers having an extremely small length of below 0.1~ m or having a~ long length of more than 100 ~ m are difficult to prepare industrially and have little practical use.
I n general, potassium titanate fiber is added in an amount of 5 to 50 %. W ith less than 5 % , reinforcing effect is low. W hile, with more than 50 % , molding is difficult due to high melt viscosity, hence undesirable.
A lthough potassium titanate fiber can be used as it is but is preferably surface - treated with silane coupling agent, titanate coupling agent, epoxy resin, epoxy - urethane resin and the like to improve an adhesiveness with the saponified E V A copolymer. F urther, it is effective to add silane coupling agent and the like to a mixture of the saponified E V A copolymer and ~2s~ro37 potassiuM titanate fiber in the process of preparing pellets.
T he resin COMpOS i tion of the invention can be prepared by various methods, for exarnple, O a method in which potassiurn titanate fiber is added to a system of polymerization of ethylene, vinyl acetate or like monomer, a rnethod in which potassium titanate fiber is added to the system in the middle of the polymerization, or to 0 the system in the middle of the saponification, a method in which potassium titanate fiber is added to the saponified E V A copolymer, the rnixture was extruded by use of an extruder, cooled and then cut to prepare pellets, etc.
T he third method is most practically eMployed.
T o the resin composition of the invention may be added an additive such as a fire retardant, heat -stabilizer, ultraviolet ray absorbing agent, lubricant in a range without affecting the effects of the present invention.
T he resin composition of the invention can be shaped by injection moldin8, extrusion, transfer Molding and like methods having excellent productivity.
S ince the resin composition of the invention has incorporated therein, as a reinforcing agent, potassium 2 5~0 3 7 titanate fiber which is about 1 /10 to 1 /100 in size compared with conventionai glass fiber or carbon fiber, the resin composition can be molded into a thin - wall parts by a simple method. T he composition provides a molded product having a very good appearance due to the excellent surface - smoothness.
T he molded product of the invention has the same mechanical strength as those reinforced with glass fiber, and has much excellent modulus because potassium titanate fiber is a single crystal and has a very high elasticity compared with glass fiber. T hus, the resin composition can be molded into small, thin - wall or fine parts and has an extremely wide use.
T he invention will be described in more detail with reference to E xamples but it is not intended that the invention be restricted by or to the examples.
E xamples 1 to 4 and C omparison E xamples 1 to 2 T o a saponified E V A copolymer (ethylene content 27mole % ; saponificatioD degree in vinyl acetate portion 99.Omole~) was added potassium titanate fiber treated with epoxy - silane (average fiber diameter 0.3~ m, average fiber length 15 ~ m) in amounts as listed in T able 1. T he mixture was weighed, mixed uniformly and then melted in an extruder (45mm, single axis) at a temperature of 240 C. T he molten mixture was cooled with ~L Z 5 7 O 3~7 water and rnade into pel]ets. T he pellets were in;ection molded at an injection temperature of 240~C, mold temperature of 80C and injection pressure of 1000kg/cm~
to prepare a test specirnens. A test specimens for COMpariSOn was prepared in the sarne manner as above except that glass fiher containing no alkali havin~ an average fiber diaMeter of 13~ m and length of 3 mm (chopped strand treated with vinyl silane, filament number : 400) was used in place of potassium titanate fiber. T he following properties were measured with use of the specimens and the results were given in T able 1 .
( B ending strength and bending modulus) M easured according to JIS K 7203 with use of a T est specimens 185 + 1 mm long by 10 + 0.5mm wide by 4 + 0.2mm height. T ests were repeated with 5 specimens.
S upport span: 60mm, crosshead rate: 5 mm/min.
( M olding shrinkage, H unter whiteness and surface smoothness) S hrinkage in longitudinal and latitudinal directions was measured with a micrometer by use of three sidegate speeimens 60mm long by 50mm wide by 3 mm height.
H unter whiteness was measured with use of color and color - difference meter.
S urface smoothness was observed with the unaided eye.
T a b l e E x a m p I e G om. E x.
l 2 ~ 4 _ _ 2 S aponified 93 80 70 5~ 100 70 5E V A copolymer ( % ) P otassium titanate 7 20 30 45 _ fiber ( % ) . _ G lass fiber ( % ) _ _ _ _ _ 30 B ending strength (kgf/cM2) 1710 2280 2690 3340 1370 2570 B ending rnodulus (kgf/cm2) 66000 06000 139000 85000 42000 12000 S~ ~
longitudinal 0.52 0.25 0,17 O.l5 0.95 0.15 latitudinal 0.53 0.27 0.20 0.18 0.98 0.2 H unter whiteness 88 91 92 93 42 47 15S urface sMoothness G ood G ood G ood G ood G ood ~ood A s apparent from T able 1 , potassium titanate fiber extremely improves bending strength and bending modulusl though small in si2e compared with glass fiber, and exhibits a very excellent modulus. T he composition of the invention is low in anisotropy of shrinkage in molding and gives a molded product having a very smooth and good appearance due to 8 large H unter whiteness number.
2~ E xamples 5 to 7 and C omparison E xamples 3 to 4 F ive kinds of resin compositions were prepared 2 5 7 0 3~7 in the same rnanner as in E xamples 1 to 4 with the exception of using saponified E V A copolymer as listed in T able 2 and potassium titanate fiber (30 % , sarne as in E xamples 1 to 4 ). T est specimens were also prepared in the same Manner as in E xamples 1 to 4 with use of the ahove compositions and properties thereof were measured, T he results were shown in T a~le 2.
T a b I e 2 E x a M p I e C om. E x, S aponified ¦ethylene 25,8 6 43,7 ;7 E V A content (mole % ) copolymer S aponification 95.3 97.8 98.5 93.2 87.1 de~ree ( mo ! e~) B ending strength (kgf/cm2) Z770 231C 1900 1380 167( B ending modulus (kgf/cm2) l42000 10900C 88000 8800C 6400C
H unter whiteness 91 91 92 90 84 A s apparent from T able 2 , mechanical properties lower with increase in ethylene content. E thylene content is preferably 10 to 55mole % , more preferably 25 to 45 %.
S sponification degree in vinyl acetate portion is preferably at least 90mole % , more preferably at least 95 nole % from the viewpoint of mechanical property and thermal stability ( H unter whiteness).
The saponified ethylene - vinyl acetate col-oiylner (hereinafter referred to as " E V A cPpolYmer") is excellent in Inechallical strengtll, non - cllar~ing property, resistances to oil and solvent, resistance to abrasion, etc, and is gradually used for preparing mechallical parts, structural parts and the like. P articularly, a molded product obtaind froM the saponified E V A copolylner incorporated glass fiber therein exhibits an improvement in tensile strength, tensile modulus, bending strength, bending modulus, compression strength and like mechallical properties.
T hus, the above saponified copolymer contail~ 25 to 55 % ( % by weigllt, same in hereinafter) of ~lass fiber is sold and used as a material for moldill~
H owever, a molded product of the sapollified E V A copolymer containin~ glass fiber has a drawback that glass fiber comes to the surface to deteriorate the surface - smootllness of the molded product. F urtller, the molded product is poor in appearance due to a slight yellow of the resin.
~2570~
In addition, though the above resin composition is excellent in mechanical strength and modulus, glass fiber is large in an average fiber diameter of 3 to 13~m and an average fiber length of at least 3 mm. Thus, it is very difficult to mold the resin composition into small, thin-wall or fine parts such as those in precision machines, ~usiness machines, electric products for use at home, etc.
The present invention provides a resin composition which can be molded into parts having a very good appearance due to an excellent surface-smoothness and whiteness.
The present invention also provides a resin composition which can be molded into small, thin-wall or fine parts.
The present invention further provides a resin composi-tion which gives a molded product having an excellent mechanical property.
The present invention provides a resin composition which comprises 50 to 95% by weight of a saponified ethylene-vinyl acetate copolymer and 5 to 50% by weight of potassium titanate fiber, the saponified copolymer being 10 to 55 mole% in ethylene content and at X
125703~
least 90mole~ in saponification degree of vinyl acetate portion.
T he resin coMposition of the invention can be molded into parts having a very good appearance due to an excellent surface - smoothness and whiteness. T he molded product of the invention is high in mechanical strength and particularly excellent in modulus despite of shorter fiber length of potassium titanate fiber. F urther, the resin composition of the invention can be molded into sMall, thin - wall or fine parts. I t is easy to design a rnold and to shape the resin composition into minute parts due to a smaller orientation of potassium titanate fiber compared with glass fiber and carbon fiber.
T he saponified E V A copolymer used in the invention has an ethylene content of 10 to 55mole % and a saponification degree of vinyl acetate portion of at least 90mole %. W ith more than 55mole % in ethylene content, heat distortion temperature ( H D T ) of molded product is low. W ith less than 10mole % , it is difficult to mold the composition due to the closeness of melting point and thermal decomposition temperature of the resin. P referable ethylene content is 25 to ~5mole %
from the viewpoint of moldability, mechanical property, H D T and the like. W ith less than 90mole % in saponification de~ree, the molded product is low in thermal stability, H D T and mechanical property.
P referable saponification degree in vinyl acetate portion is at least 95mole %.
T he E V A copoiymer rnay contain a small amount of a copolymerizable monomer other than ethylene, vinyl acetate (or vinyl alcohol derived from saponification of vinyl acetate). E xamples of useful monomers are propylene, isobutylene and like olefins, acrylic acid, methacrylic acid, maleic acid, crotonic acid and like unsaturated acid or esters thereof, etc.
P otassium titanate fiber used in the invention is a single crystal represented by the formula K 2 0 l( T i O 2~ or K 2 0 l( T i O 2) 1/2 H 20 wherein l is an integer of 2 to 8. E xamples thereof are potassium tetratitanate fiber, potassium hexatitanate fiber, potassium octatitanate fiber, etc., and these are used singly or in mixture. T he titanate fiber has an average fiber diameter of preferably up to 2 ~ m, average fiber length of preferably 5 to 100~ m and a ratio of avera~e fiber length to average fiber diameter (aspect ratio) of preferably 10 to 200.
I n the invention, average fiber diameter and average fiber length of potassium titanate fiber are each auerage of values which were rneasured in at least 5 sights and at least 10 fibers in each sight, with use iL 2 5 7 0 3 7 of a scanning - type electron microscope. A n aspect ratio is a divisor of average fiber length by average fiber diameter.
W ith outside of the above ranges of average fiber diameter, average fiber length and aspect ratio, for example, more than 1 ~ m in average fiber diaMeter, less than 5 ~ m in average fiber length, namely when aspect ratio is less than 10, reinforcing effect of molded product is small, hence undesirable.
F urther, fibers having an extremely small length of below 0.1~ m or having a~ long length of more than 100 ~ m are difficult to prepare industrially and have little practical use.
I n general, potassium titanate fiber is added in an amount of 5 to 50 %. W ith less than 5 % , reinforcing effect is low. W hile, with more than 50 % , molding is difficult due to high melt viscosity, hence undesirable.
A lthough potassium titanate fiber can be used as it is but is preferably surface - treated with silane coupling agent, titanate coupling agent, epoxy resin, epoxy - urethane resin and the like to improve an adhesiveness with the saponified E V A copolymer. F urther, it is effective to add silane coupling agent and the like to a mixture of the saponified E V A copolymer and ~2s~ro37 potassiuM titanate fiber in the process of preparing pellets.
T he resin COMpOS i tion of the invention can be prepared by various methods, for exarnple, O a method in which potassiurn titanate fiber is added to a system of polymerization of ethylene, vinyl acetate or like monomer, a rnethod in which potassium titanate fiber is added to the system in the middle of the polymerization, or to 0 the system in the middle of the saponification, a method in which potassium titanate fiber is added to the saponified E V A copolymer, the rnixture was extruded by use of an extruder, cooled and then cut to prepare pellets, etc.
T he third method is most practically eMployed.
T o the resin composition of the invention may be added an additive such as a fire retardant, heat -stabilizer, ultraviolet ray absorbing agent, lubricant in a range without affecting the effects of the present invention.
T he resin composition of the invention can be shaped by injection moldin8, extrusion, transfer Molding and like methods having excellent productivity.
S ince the resin composition of the invention has incorporated therein, as a reinforcing agent, potassium 2 5~0 3 7 titanate fiber which is about 1 /10 to 1 /100 in size compared with conventionai glass fiber or carbon fiber, the resin composition can be molded into a thin - wall parts by a simple method. T he composition provides a molded product having a very good appearance due to the excellent surface - smoothness.
T he molded product of the invention has the same mechanical strength as those reinforced with glass fiber, and has much excellent modulus because potassium titanate fiber is a single crystal and has a very high elasticity compared with glass fiber. T hus, the resin composition can be molded into small, thin - wall or fine parts and has an extremely wide use.
T he invention will be described in more detail with reference to E xamples but it is not intended that the invention be restricted by or to the examples.
E xamples 1 to 4 and C omparison E xamples 1 to 2 T o a saponified E V A copolymer (ethylene content 27mole % ; saponificatioD degree in vinyl acetate portion 99.Omole~) was added potassium titanate fiber treated with epoxy - silane (average fiber diameter 0.3~ m, average fiber length 15 ~ m) in amounts as listed in T able 1. T he mixture was weighed, mixed uniformly and then melted in an extruder (45mm, single axis) at a temperature of 240 C. T he molten mixture was cooled with ~L Z 5 7 O 3~7 water and rnade into pel]ets. T he pellets were in;ection molded at an injection temperature of 240~C, mold temperature of 80C and injection pressure of 1000kg/cm~
to prepare a test specirnens. A test specimens for COMpariSOn was prepared in the sarne manner as above except that glass fiher containing no alkali havin~ an average fiber diaMeter of 13~ m and length of 3 mm (chopped strand treated with vinyl silane, filament number : 400) was used in place of potassium titanate fiber. T he following properties were measured with use of the specimens and the results were given in T able 1 .
( B ending strength and bending modulus) M easured according to JIS K 7203 with use of a T est specimens 185 + 1 mm long by 10 + 0.5mm wide by 4 + 0.2mm height. T ests were repeated with 5 specimens.
S upport span: 60mm, crosshead rate: 5 mm/min.
( M olding shrinkage, H unter whiteness and surface smoothness) S hrinkage in longitudinal and latitudinal directions was measured with a micrometer by use of three sidegate speeimens 60mm long by 50mm wide by 3 mm height.
H unter whiteness was measured with use of color and color - difference meter.
S urface smoothness was observed with the unaided eye.
T a b l e E x a m p I e G om. E x.
l 2 ~ 4 _ _ 2 S aponified 93 80 70 5~ 100 70 5E V A copolymer ( % ) P otassium titanate 7 20 30 45 _ fiber ( % ) . _ G lass fiber ( % ) _ _ _ _ _ 30 B ending strength (kgf/cM2) 1710 2280 2690 3340 1370 2570 B ending rnodulus (kgf/cm2) 66000 06000 139000 85000 42000 12000 S~ ~
longitudinal 0.52 0.25 0,17 O.l5 0.95 0.15 latitudinal 0.53 0.27 0.20 0.18 0.98 0.2 H unter whiteness 88 91 92 93 42 47 15S urface sMoothness G ood G ood G ood G ood G ood ~ood A s apparent from T able 1 , potassium titanate fiber extremely improves bending strength and bending modulusl though small in si2e compared with glass fiber, and exhibits a very excellent modulus. T he composition of the invention is low in anisotropy of shrinkage in molding and gives a molded product having a very smooth and good appearance due to 8 large H unter whiteness number.
2~ E xamples 5 to 7 and C omparison E xamples 3 to 4 F ive kinds of resin compositions were prepared 2 5 7 0 3~7 in the same rnanner as in E xamples 1 to 4 with the exception of using saponified E V A copolymer as listed in T able 2 and potassium titanate fiber (30 % , sarne as in E xamples 1 to 4 ). T est specimens were also prepared in the same Manner as in E xamples 1 to 4 with use of the ahove compositions and properties thereof were measured, T he results were shown in T a~le 2.
T a b I e 2 E x a M p I e C om. E x, S aponified ¦ethylene 25,8 6 43,7 ;7 E V A content (mole % ) copolymer S aponification 95.3 97.8 98.5 93.2 87.1 de~ree ( mo ! e~) B ending strength (kgf/cm2) Z770 231C 1900 1380 167( B ending modulus (kgf/cm2) l42000 10900C 88000 8800C 6400C
H unter whiteness 91 91 92 90 84 A s apparent from T able 2 , mechanical properties lower with increase in ethylene content. E thylene content is preferably 10 to 55mole % , more preferably 25 to 45 %.
S sponification degree in vinyl acetate portion is preferably at least 90mole % , more preferably at least 95 nole % from the viewpoint of mechanical property and thermal stability ( H unter whiteness).
Claims (4)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1 . A resin composition which comprises 50 to 95 % by weight of a saponified ethylene - vinyl acetate copolymer and 5 to 50 % by weight of potassium titanate fiber, the saponified copolymer being 10 to 55mole% in ethylene content and at least 90mole% in saponification degree of vinyl acetate portion.
2. A resin composition as defined in claim wherein the ethylene content is 25 to 45mole%.
3. A resin composition as defined in claim wherein the saponification degree of vinyl acetate portion is at least 95mole%.
4. A resin composition as defined in claim wherein the potassium titanate fiber has an average fiber diameter of up to 2 µm, average fiber length of 5 to 100µm and a ratio of average fiber length to average fiber diameter (aspect ratio) of 10 to 200.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000468224A CA1257037A (en) | 1984-11-20 | 1984-11-20 | Resin composition containing a saponified ethylene- vinyl acetate copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000468224A CA1257037A (en) | 1984-11-20 | 1984-11-20 | Resin composition containing a saponified ethylene- vinyl acetate copolymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1257037A true CA1257037A (en) | 1989-07-04 |
Family
ID=4129186
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000468224A Expired CA1257037A (en) | 1984-11-20 | 1984-11-20 | Resin composition containing a saponified ethylene- vinyl acetate copolymer |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1257037A (en) |
-
1984
- 1984-11-20 CA CA000468224A patent/CA1257037A/en not_active Expired
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