CA1158010A - Polypropylene article with improved adhesion - Google Patents
Polypropylene article with improved adhesionInfo
- Publication number
- CA1158010A CA1158010A CA000368762A CA368762A CA1158010A CA 1158010 A CA1158010 A CA 1158010A CA 000368762 A CA000368762 A CA 000368762A CA 368762 A CA368762 A CA 368762A CA 1158010 A CA1158010 A CA 1158010A
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- foil
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- foil according
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Wrappers (AREA)
Abstract
ABSTRACT
A polypropylene article or foil with a content of fine particle cellulose which has greatly improved durable adhesion characteristics brought about by surface activation such as irradiation, flame or chemical treatment. Mineral fillers and modifying agents may be included.
A polypropylene article or foil with a content of fine particle cellulose which has greatly improved durable adhesion characteristics brought about by surface activation such as irradiation, flame or chemical treatment. Mineral fillers and modifying agents may be included.
Description
~ss~ln Polypropyiene ~rticle with Improved Adhesion This invention relates to polypropylene (PP) and particularly foils of polypropylene with improved adhesion characteristlcs, and to a process for its production.
For many areas in whlch they are employed, the wear characteristics of materials have to be enhanced, e.g., by lacquering or by being coated wlth or laminated to thin Einishing foils sheets or veneers. At the present time, predominantly PVC and special papers are used for such improvements especially for metal, wood, and cellulose materials.
When foils are used for surface improvement one proceeds from the assumption that coating on carrier materials or on other films is to be carried out at temperatures which are Erequently in excess of 100C and that it is uneconomic to cool the laminate Ln the roller-coating installation or press. A high level of thermal forming stability is also necessary for coating which makes use of chemically active type adhesives and which, because of the required level of storage stability, are best selected so that the reaction proceeds at a temperature above 80C. This is also necessary for coating with polymer films when no delamination should take place at the temperature involved.
The physical characteristics, especially of thermal forming stability and the good environmental characteristics, of polypropylene and its co-polymerisates are particularly well suited to surface improvement.
However, a decisive disadvantage of polypropylene, results from its surface engergy characteristics which prevent sufficiently good and permanent adhesion of suitable lacquers, adhesives, and polymer films.
1 1 5801 ~
i i~n object o~ the present invention is to improve the adhesion characteristics of polypropylene foils by modifying the surface energy properties so as to ensure that suitable and permanent printing, lacquering, and adhesion will be made possible.
Processes used to improve the adhesion characteristics of films, especially polypropylene films, are already known. ~n example is corona treatment (see Adhaesion, 1979, Volume 12, pp.381 - 389). Although this treatment increases tlle surface tension temporarily, the effect diminishes during storage and/or under the effects of high temperatures. An alternative process involves flame treatment of such foils. The same disadvantages arise as with the corona treatment. Chemical treatment with ozone, fluorine, chlorine, etc., is also known. However a particular disadvantage witll these and which may cause problems is their chemical aggressiveness. ~ further known process is the irradiation with high energy beams such as electron beams, ultra-violet rays, lasers, and the like. Such processes are relatively costly and in most instances require the additional use of seniti~ers and the durability of the effect varies.
~ permanent improvement in surface adhesion can be achieved by chemical grafting using high energy beams. However, this process is too costly to be suitable for the areas of application considered here.
In accordance with the present disclosure, a permanent increase in surface tension and adhesion is achieved by providing a content of finely divided cellulose in the polypropylene foil, which is then subjected to known surface treatment methods for increasing surface tension, but which to date have resulted in no permanent eEfects. The inventive idea is based on the surprising fact that a content of finely divided cellulose in 1~5~01l) the polypropylene improves the effectiveness and the durability of the surEace treatment. This effect c~ln be further increased if the cellulose is added to a polyethylene batch. F~lrther favourable effects result from the accompanying use of mineral Eillers.
Finely divided cellulose produced by the sulfite or sulfate processes is suitable and preferred. Natural or recycled cellulose is also suitable.
The amount of cellulose may be between 30 and 50 percent by weight of ~ the total weight of polypropylene and cellulose. If a content of 50 ; 10 percent by weight is exceeded, the strength characteristics deteriorate unduly.
l~hen the cellulose content is below 3 ~ by weight the desired improvement of surface activation is insufficiently pronounced. It is preferred that the material contain 3 to 30%-wt of cellulose.
The degree of fineness of the cellulose used in the foil lies between 1 to lQ0 um for a fibre thickness of 10 to 30 ym. If the particles are more finely divided the expense rises unduly; larger particles lead to problems in the production of smooth and thin foils. However, for natural or regenerated cellulose particles of up to 100 ,um thick and with a greatest mean length of 200 ~um can be used without difficulties in the formation of the foil.
Commercial grades of polypropylene are suitable, including copolymers with ~-olefins and graft copolymers with vinyl bonds. Random and block copolymers with 1 to 10 mol-~ ethylene or mixtures with polyethylene (PE), particularly with 5 to 20~ PE, that have a thermal resistance VSP/A above 100C are preferred.
~t ~!
~58~n In addition, the new foils can also contain mineral fillers. Flllers of this kind ~or polymer foils are already known. Mlca, talc, silicates and silicic acld in their clifferent forms are especially suitable and for ~his reason are preferred. E~arnples of other usable mineral fillers are carbonates, particularly calcium carbonate such as limestone and chalk, and magnesium carbonate and the like.
Characteristics such as Shore hardness, vicat point, adhesion and tensile strength can be influenced by the addition of suitable mineral fillers. In the event that suitable mineral fillers of this kind are present, it is desirable that the foil contain 3 to 30%-wt and preferrably 3 to 20~-wt, related to the sum of the weight of polyolefine and cellulose.
The foils can also contain one or several organic modifying agents.
These serve to control the toughness, calendaring properties, e~trudability and similiar characteristics. A group of materials preferred for this purpose are blockpolymers of styrol with butadiene or isobutylene or isoprene. Other suitable modifying agents are polymers that are based on styrol-butadiene, methacrylate-butadiene-styrol.
Polyolefins, containing functional groups, are particularly suitable for affecting the physical characteristics and adhesability. Modifying additives of this kind are desirably present in the amount of 0.5 to 20~-wt, preferrably 2 to 10%-wt, with respect in each case to the sum of the weights of the polyolefin and cellulose.
The use of wood dust in place of cellulose is not generally recommended, because of its inherent color, insufficient cleanliness, deficient resistance to light and that it changes color when affected by temperature. Also the adhesive effect achieved is not as good.
. . .
The relationship to cellulose content, of the increase in surface tension from coroncl treatment and :its permanence, are shown in the test results reproduced in Table I. In the ~nufacture of the foils tested, the cellulose was Qdded by meclns of a tlD-PE~Masterbatch 1:1 (ilD-PE
Hostalen* GC7260).
~Trade ~lark , l~ssoln Table I
Proportion by I . Surface tension (dynes/cm) weight cellulose I untreated I Corona treated after in PP(l) I ll hr. 3 days 3 weeks . 3 mon~hs l) PP Hostalen* PPN 1060 Since a higher surface tension does not always result simultaneously in a higher level of adhesion for polypropylene (see Adhaesion 1979, Volume 12, pages 381-389) the adhesion characteristics were tested by means of a commercial urea-formaldehyde adhesive. The foil samples were produced under identical conditions, corona treated and then pressed at 140C at lO kp/cm2 for 10 seconds. The durability of the adhesion was assessed by storing for one day at 90C. The results are shown in Table
For many areas in whlch they are employed, the wear characteristics of materials have to be enhanced, e.g., by lacquering or by being coated wlth or laminated to thin Einishing foils sheets or veneers. At the present time, predominantly PVC and special papers are used for such improvements especially for metal, wood, and cellulose materials.
When foils are used for surface improvement one proceeds from the assumption that coating on carrier materials or on other films is to be carried out at temperatures which are Erequently in excess of 100C and that it is uneconomic to cool the laminate Ln the roller-coating installation or press. A high level of thermal forming stability is also necessary for coating which makes use of chemically active type adhesives and which, because of the required level of storage stability, are best selected so that the reaction proceeds at a temperature above 80C. This is also necessary for coating with polymer films when no delamination should take place at the temperature involved.
The physical characteristics, especially of thermal forming stability and the good environmental characteristics, of polypropylene and its co-polymerisates are particularly well suited to surface improvement.
However, a decisive disadvantage of polypropylene, results from its surface engergy characteristics which prevent sufficiently good and permanent adhesion of suitable lacquers, adhesives, and polymer films.
1 1 5801 ~
i i~n object o~ the present invention is to improve the adhesion characteristics of polypropylene foils by modifying the surface energy properties so as to ensure that suitable and permanent printing, lacquering, and adhesion will be made possible.
Processes used to improve the adhesion characteristics of films, especially polypropylene films, are already known. ~n example is corona treatment (see Adhaesion, 1979, Volume 12, pp.381 - 389). Although this treatment increases tlle surface tension temporarily, the effect diminishes during storage and/or under the effects of high temperatures. An alternative process involves flame treatment of such foils. The same disadvantages arise as with the corona treatment. Chemical treatment with ozone, fluorine, chlorine, etc., is also known. However a particular disadvantage witll these and which may cause problems is their chemical aggressiveness. ~ further known process is the irradiation with high energy beams such as electron beams, ultra-violet rays, lasers, and the like. Such processes are relatively costly and in most instances require the additional use of seniti~ers and the durability of the effect varies.
~ permanent improvement in surface adhesion can be achieved by chemical grafting using high energy beams. However, this process is too costly to be suitable for the areas of application considered here.
In accordance with the present disclosure, a permanent increase in surface tension and adhesion is achieved by providing a content of finely divided cellulose in the polypropylene foil, which is then subjected to known surface treatment methods for increasing surface tension, but which to date have resulted in no permanent eEfects. The inventive idea is based on the surprising fact that a content of finely divided cellulose in 1~5~01l) the polypropylene improves the effectiveness and the durability of the surEace treatment. This effect c~ln be further increased if the cellulose is added to a polyethylene batch. F~lrther favourable effects result from the accompanying use of mineral Eillers.
Finely divided cellulose produced by the sulfite or sulfate processes is suitable and preferred. Natural or recycled cellulose is also suitable.
The amount of cellulose may be between 30 and 50 percent by weight of ~ the total weight of polypropylene and cellulose. If a content of 50 ; 10 percent by weight is exceeded, the strength characteristics deteriorate unduly.
l~hen the cellulose content is below 3 ~ by weight the desired improvement of surface activation is insufficiently pronounced. It is preferred that the material contain 3 to 30%-wt of cellulose.
The degree of fineness of the cellulose used in the foil lies between 1 to lQ0 um for a fibre thickness of 10 to 30 ym. If the particles are more finely divided the expense rises unduly; larger particles lead to problems in the production of smooth and thin foils. However, for natural or regenerated cellulose particles of up to 100 ,um thick and with a greatest mean length of 200 ~um can be used without difficulties in the formation of the foil.
Commercial grades of polypropylene are suitable, including copolymers with ~-olefins and graft copolymers with vinyl bonds. Random and block copolymers with 1 to 10 mol-~ ethylene or mixtures with polyethylene (PE), particularly with 5 to 20~ PE, that have a thermal resistance VSP/A above 100C are preferred.
~t ~!
~58~n In addition, the new foils can also contain mineral fillers. Flllers of this kind ~or polymer foils are already known. Mlca, talc, silicates and silicic acld in their clifferent forms are especially suitable and for ~his reason are preferred. E~arnples of other usable mineral fillers are carbonates, particularly calcium carbonate such as limestone and chalk, and magnesium carbonate and the like.
Characteristics such as Shore hardness, vicat point, adhesion and tensile strength can be influenced by the addition of suitable mineral fillers. In the event that suitable mineral fillers of this kind are present, it is desirable that the foil contain 3 to 30%-wt and preferrably 3 to 20~-wt, related to the sum of the weight of polyolefine and cellulose.
The foils can also contain one or several organic modifying agents.
These serve to control the toughness, calendaring properties, e~trudability and similiar characteristics. A group of materials preferred for this purpose are blockpolymers of styrol with butadiene or isobutylene or isoprene. Other suitable modifying agents are polymers that are based on styrol-butadiene, methacrylate-butadiene-styrol.
Polyolefins, containing functional groups, are particularly suitable for affecting the physical characteristics and adhesability. Modifying additives of this kind are desirably present in the amount of 0.5 to 20~-wt, preferrably 2 to 10%-wt, with respect in each case to the sum of the weights of the polyolefin and cellulose.
The use of wood dust in place of cellulose is not generally recommended, because of its inherent color, insufficient cleanliness, deficient resistance to light and that it changes color when affected by temperature. Also the adhesive effect achieved is not as good.
. . .
The relationship to cellulose content, of the increase in surface tension from coroncl treatment and :its permanence, are shown in the test results reproduced in Table I. In the ~nufacture of the foils tested, the cellulose was Qdded by meclns of a tlD-PE~Masterbatch 1:1 (ilD-PE
Hostalen* GC7260).
~Trade ~lark , l~ssoln Table I
Proportion by I . Surface tension (dynes/cm) weight cellulose I untreated I Corona treated after in PP(l) I ll hr. 3 days 3 weeks . 3 mon~hs l) PP Hostalen* PPN 1060 Since a higher surface tension does not always result simultaneously in a higher level of adhesion for polypropylene (see Adhaesion 1979, Volume 12, pages 381-389) the adhesion characteristics were tested by means of a commercial urea-formaldehyde adhesive. The foil samples were produced under identical conditions, corona treated and then pressed at 140C at lO kp/cm2 for 10 seconds. The durability of the adhesion was assessed by storing for one day at 90C. The results are shown in Table
2.
* Trade Mark 1158~1~
Table 2 Formulation l~urface tension I Scaling resistance dynes/cm _I kp/2,4 c L
l hr. 20C 11 day 90C I 1 hr 20C 11 day 90C
PP+0 pts cellulose 1) 1 48 1 42 1 0.1 1 0 PP+20 pts cellulose 1~1 58 ¦ 52 1 1.2 ¦ 1.1 PP+20 pts cellulose 2)1 58 1 56 j 2.6 ¦ 1.9 (PE/cellulose batch) 1) PP Eltex* ~1 100 2) Batch: 50 pts/wt HD~PE Eltex* 2008 50 pts/wt Cellulose Arbocel* B 600/30 These results show that with a cellulose content the effect is not only considerably longer lasting, but is also greatly increased, particularly if the cellulose is added as a polyethylene batch.
further object of this disclosure is to provide a process for manufacturing a polypropylene foil with improved adhesion characteristics, making the foil by conventional methods and then giving a surface activation treatment, and characterized in that fine-grained * Trade Mark ~15801n cellulose is added as a ~iller. It is preferred that 3 to 50%-wt, particularly 3 to 30%-wt of cellulose be added, with respect to the sum of the weights of polyolefin and the cellulose. Cellulose fibers are suitable up to a length of 200 ~Im for a mean diameter of up to lOO,um.
The above statements apply for the preferred polypropylenes. Conventional production methods and mlxing technologies known to those skilled in the art are suitable for the production of the foils.
~ lineral fillers and/or modifying agents can be added in the production of the foils. The foregoing data covering the composition of the foils will apply accordingly.
The surface activation may be achieved by irradiation, or by flame treatment or reaction with ozone. Preferred is corona treatment, or other irradiation methods using electron beams, ultra-violet, or laser light.
The surface adhesion of polypropylene foils is considerably improved by means of the new method and the new foils are particularly suitable for coating, printing, enameling or lacquering, and adhesion, particularly in thos~ present systems which use very short process times and the highest possible temperatures, and in some instances such use is now possible for the first time. When the new foils were cemented, for example, using urea-formaldehyde resin there was no change in adhesion even after several months. The resistance of surface activation to the effects of temperature was also greatly improved. As an example, the adhesion of the new foils which had been laminated by means of urea-formaldehyde resin onto chipboard panels displayed no differences over the range of coating temperatures from 80 to 140C. with a 30 second press time.
1 ~ S80 1~
.
~rinting ink~, for exalnl)le those based on terpolymers of vlnyl chloride - vinyl acetate - ~aleic aclds oE 0~l-group containing vinyl polymers, and also conventional polyethlene printing inks show equally good adhesion as ~eaction lacquers, for example, those based on polyurethane~melamine resins and ultra-violet hardened polyester epoxide and polyurethane acrylates. Even after l,000 hrs of xenotest weathering and cropical testing it was not posslble to determine any change in adilesion according to ~ST~I standard ~2142-63T (lattice~cut method).
The characteristics of the foils could be widely varied by the addition of mineral fillers and organic modifying agents and the advantageous adhesion characteristics could be partially improved by the same method. As an example, the surface adhesion achieved by means of corona treatment of a foil consisting of 95 parts of polypropylene and 5 parts of cellulose could be favourably improved by the addition of 20 or 30 parts of talc.
Conventional dyes and pigments are not disadvantageous.
The new foils can also be bonded directly to metals, wood, polymers and copolymers with polymer groups and the like, by fusion without the ~Ise of adhesives.
Coating is also possible at low temperatures, e.g., using epoxy resins and polyurethanes as well as vinyl acetate-copolymers.
The following examples illustrate embodiments of the invention.
Example 1.
Polyethylene ~fI 190/2 = ~ (g/lO min) density 0.958 (Hostalen* GC
7260) and cellulose having a particle size less than 50 ~m (Arbocel* B
600/30) were mixed in a weight ratio of l : l, homogenized for 10 minutes _ g _ ~580~n at 160C in ~ rolling mi LI, cooled ancl then granulated. Ten parts by weight of the bat~h obtained in this manner were mixed with 90 parts by weight of PPI ~Ifl l90/5 ~ 3 (g/10 rnin) clensity 0.905 (g/cm3) Hostalen* PPN
1060 and extrude(l in tlle form o~ an 80 ~Im thick film at a mass temperature of 220C.
The e~truded foil was subjected to corona treatment. The corona treatment was carried out at full power on a Demes-VM pre-treatment device and at a strip speed of 5 m/min. The treated foil displayed the following characteristics:
Surface tension after 1 hour 52 dynes/cm
* Trade Mark 1158~1~
Table 2 Formulation l~urface tension I Scaling resistance dynes/cm _I kp/2,4 c L
l hr. 20C 11 day 90C I 1 hr 20C 11 day 90C
PP+0 pts cellulose 1) 1 48 1 42 1 0.1 1 0 PP+20 pts cellulose 1~1 58 ¦ 52 1 1.2 ¦ 1.1 PP+20 pts cellulose 2)1 58 1 56 j 2.6 ¦ 1.9 (PE/cellulose batch) 1) PP Eltex* ~1 100 2) Batch: 50 pts/wt HD~PE Eltex* 2008 50 pts/wt Cellulose Arbocel* B 600/30 These results show that with a cellulose content the effect is not only considerably longer lasting, but is also greatly increased, particularly if the cellulose is added as a polyethylene batch.
further object of this disclosure is to provide a process for manufacturing a polypropylene foil with improved adhesion characteristics, making the foil by conventional methods and then giving a surface activation treatment, and characterized in that fine-grained * Trade Mark ~15801n cellulose is added as a ~iller. It is preferred that 3 to 50%-wt, particularly 3 to 30%-wt of cellulose be added, with respect to the sum of the weights of polyolefin and the cellulose. Cellulose fibers are suitable up to a length of 200 ~Im for a mean diameter of up to lOO,um.
The above statements apply for the preferred polypropylenes. Conventional production methods and mlxing technologies known to those skilled in the art are suitable for the production of the foils.
~ lineral fillers and/or modifying agents can be added in the production of the foils. The foregoing data covering the composition of the foils will apply accordingly.
The surface activation may be achieved by irradiation, or by flame treatment or reaction with ozone. Preferred is corona treatment, or other irradiation methods using electron beams, ultra-violet, or laser light.
The surface adhesion of polypropylene foils is considerably improved by means of the new method and the new foils are particularly suitable for coating, printing, enameling or lacquering, and adhesion, particularly in thos~ present systems which use very short process times and the highest possible temperatures, and in some instances such use is now possible for the first time. When the new foils were cemented, for example, using urea-formaldehyde resin there was no change in adhesion even after several months. The resistance of surface activation to the effects of temperature was also greatly improved. As an example, the adhesion of the new foils which had been laminated by means of urea-formaldehyde resin onto chipboard panels displayed no differences over the range of coating temperatures from 80 to 140C. with a 30 second press time.
1 ~ S80 1~
.
~rinting ink~, for exalnl)le those based on terpolymers of vlnyl chloride - vinyl acetate - ~aleic aclds oE 0~l-group containing vinyl polymers, and also conventional polyethlene printing inks show equally good adhesion as ~eaction lacquers, for example, those based on polyurethane~melamine resins and ultra-violet hardened polyester epoxide and polyurethane acrylates. Even after l,000 hrs of xenotest weathering and cropical testing it was not posslble to determine any change in adilesion according to ~ST~I standard ~2142-63T (lattice~cut method).
The characteristics of the foils could be widely varied by the addition of mineral fillers and organic modifying agents and the advantageous adhesion characteristics could be partially improved by the same method. As an example, the surface adhesion achieved by means of corona treatment of a foil consisting of 95 parts of polypropylene and 5 parts of cellulose could be favourably improved by the addition of 20 or 30 parts of talc.
Conventional dyes and pigments are not disadvantageous.
The new foils can also be bonded directly to metals, wood, polymers and copolymers with polymer groups and the like, by fusion without the ~Ise of adhesives.
Coating is also possible at low temperatures, e.g., using epoxy resins and polyurethanes as well as vinyl acetate-copolymers.
The following examples illustrate embodiments of the invention.
Example 1.
Polyethylene ~fI 190/2 = ~ (g/lO min) density 0.958 (Hostalen* GC
7260) and cellulose having a particle size less than 50 ~m (Arbocel* B
600/30) were mixed in a weight ratio of l : l, homogenized for 10 minutes _ g _ ~580~n at 160C in ~ rolling mi LI, cooled ancl then granulated. Ten parts by weight of the bat~h obtained in this manner were mixed with 90 parts by weight of PPI ~Ifl l90/5 ~ 3 (g/10 rnin) clensity 0.905 (g/cm3) Hostalen* PPN
1060 and extrude(l in tlle form o~ an 80 ~Im thick film at a mass temperature of 220C.
The e~truded foil was subjected to corona treatment. The corona treatment was carried out at full power on a Demes-VM pre-treatment device and at a strip speed of 5 m/min. The treated foil displayed the following characteristics:
Surface tension after 1 hour 52 dynes/cm
3 weeks 50 dynes/cm 3 months 48 dynes/cm ~ntreated 25 to 28 dynes/cm Thermal forming resistance VSP/A 148C.
Hardness Shore D 69 Tensile Strength (longitudinal) 30 N/mm2 The treated foil was applied to a commercial chipboard panel. A
urea-formaldehyde resin of the following composition was used for adhesion: 100 parts by weight Aerolite* 306 50 parts by weight W 170* hardener 70 parts by weight water Pressing condition: Temperature 140C
Pressure 10 kp/cm2 Time 10 sec 0 ~ () Tearing forces in the peeling test amounted to 1.6 kp/2.4 cm.
Example 2 (Comparison) The polypropylene used in Example I was mixed in a proportion of S5:5 with HD-PE (Hostalen* GC 7260) without any other additives and then under the previously given conditions was extruded, pre-treated and pressed.
Surface tension after 1 hour 48 dynes/cm 3 weeks 28 dynes/cm 3 months 25 dynes/cm Untreated 25 dynes/cm ! 10 Thermal forming resistance VSP/A 145C
Hardness Shore D 68 Tensile Strength, longitudinal 28 N/mm2 Tear Strength in the peeling test 0.1 kg/2.4 cm ;
~ Trade ~lark l~S~Oln E~;amp le .~ mixture consisting of 80 parts by wei~ht of a polypropylene copolymer ~IfI 230/2 = 1.8 g/lO min, dellsity 0.92 g/cm3 (Eltex* Kl lO0) and 20 parts by weight oE ce11ulose Arbocel* (~ 600/S0) and the usual additives was calendared at 200C to a lOO~m thick foil. The pre-treatment and adhesion were carried out according to Rxample I.
Tlle following values were measured:
Surface tension after 1 hour 58 dynes/cm 3 weeks 52 dynes/cm 3 months 52 dynes/cm Untreated 25 dynes/cm Thermal forming resistance VSP/A 150C
Hardness Shore D 72 Tensile Strength, longitudinal 32 M/mm2 Tear force in the peeling test 1.3 kp/2.4 cm Example 4 A mixture consisting of 80 parts by weigh~ of polypropylene according to Example 3 and 40 parts by weight of a batch consisting of 20 parts of cellulose (Arbocel* BO 600/50) 20 parts HD-PE MfI 190/5 =1 (g/lO min) density 0.950 g/cm3 (Eltex* B 2008) was calendared as in Example 3, pre-treated and pressed.
*Trade Mark , i I:ls~oln The following values resulted:
Surface tension aEter 1 hour 58 dynes/cm 3 weeks 58 dynes/cm 3 months 56 dynes/cm IJntreated 25 dynes/cm Thermal forming resistance VSP/A 148C
Hardness Shore D 67 Tensile Strength, longitudial 26 N/mm2 Tear force in the peeling test 2.6 kp/2.4 cm O Example 5 A mixture consisting of 80 parts by weight of polypropylene according to E~ample 3 and 20 parts by weight of cellulose (Arbocel* BO 600/50) and 20 parts by weights oE calcium carbonate (Omya* BSH) were calendared as in Example 3 and pre-treated.
The following results were obtained:
Surface tension after l hour 58 dynes/cm 3 week 56 dynes/cm 3 months 56 dynes/cm Untreated 25 dynes/cm Thermal forming resistance VSP/A 155C
Hardness Shore D 72 Tensile strength, longitudinal 35 N/mm2 Tear force in the peeling test 2.6 kp/2.4 cm * Trade Mark l~ssoln Example 6 95 parts by weigllt of a mLxture according to Example 3 were aclded to j parts by weight of SBS block copoLymer (C~lriflex* 1102) and processed according to Example 3. On calendaring it was shown that a good foil could still be produced at a speed that was 20% higher.
i The measured mechanical and adhesive characteristics were not disadvantageously affected.
The foil obtained was coated with a conventional polyurethane lacquer (Basis Desmophen* 1340 and Desmodur* Hl).
There was no separation of the lacquer layer in an adhesion tèst according to AST~ D.2.1.4.1.-63.
! Example 7 .~ mixture consisting oE 80 parts by weight of a polypropylene copolymer according to Example 3 (K1 100) 20% by weight of cellulose (Arbocel B 600/50), and 20 parts by weight of talc and the usual additives was calendared at 200~C to a 100 ~Im thick foil, activated according to Example I and pressed by means of a 50 ~m thick foil of KR 2683 adhesive agent at 130C, for 10 sec, and 10 kp/cm2. When the foil bond was removed from the chipboard panel, chip tear out resulted.
* Trade ~ark 1~5~1n Example 8 .~ Eoil accord.in~ to Example 7 was pressed by means of an epoxy adhesive (Daubert* Internationa~ 1 TDC 8160 BHV+l ~ DC 8160 AHV) at room temperature and 5 kp/cL~I2 Eor 24 hours. The Eoil tore duriLIg the removal test.
* Trade ~Iark . ,~
Hardness Shore D 69 Tensile Strength (longitudinal) 30 N/mm2 The treated foil was applied to a commercial chipboard panel. A
urea-formaldehyde resin of the following composition was used for adhesion: 100 parts by weight Aerolite* 306 50 parts by weight W 170* hardener 70 parts by weight water Pressing condition: Temperature 140C
Pressure 10 kp/cm2 Time 10 sec 0 ~ () Tearing forces in the peeling test amounted to 1.6 kp/2.4 cm.
Example 2 (Comparison) The polypropylene used in Example I was mixed in a proportion of S5:5 with HD-PE (Hostalen* GC 7260) without any other additives and then under the previously given conditions was extruded, pre-treated and pressed.
Surface tension after 1 hour 48 dynes/cm 3 weeks 28 dynes/cm 3 months 25 dynes/cm Untreated 25 dynes/cm ! 10 Thermal forming resistance VSP/A 145C
Hardness Shore D 68 Tensile Strength, longitudinal 28 N/mm2 Tear Strength in the peeling test 0.1 kg/2.4 cm ;
~ Trade ~lark l~S~Oln E~;amp le .~ mixture consisting of 80 parts by wei~ht of a polypropylene copolymer ~IfI 230/2 = 1.8 g/lO min, dellsity 0.92 g/cm3 (Eltex* Kl lO0) and 20 parts by weight oE ce11ulose Arbocel* (~ 600/S0) and the usual additives was calendared at 200C to a lOO~m thick foil. The pre-treatment and adhesion were carried out according to Rxample I.
Tlle following values were measured:
Surface tension after 1 hour 58 dynes/cm 3 weeks 52 dynes/cm 3 months 52 dynes/cm Untreated 25 dynes/cm Thermal forming resistance VSP/A 150C
Hardness Shore D 72 Tensile Strength, longitudinal 32 M/mm2 Tear force in the peeling test 1.3 kp/2.4 cm Example 4 A mixture consisting of 80 parts by weigh~ of polypropylene according to Example 3 and 40 parts by weight of a batch consisting of 20 parts of cellulose (Arbocel* BO 600/50) 20 parts HD-PE MfI 190/5 =1 (g/lO min) density 0.950 g/cm3 (Eltex* B 2008) was calendared as in Example 3, pre-treated and pressed.
*Trade Mark , i I:ls~oln The following values resulted:
Surface tension aEter 1 hour 58 dynes/cm 3 weeks 58 dynes/cm 3 months 56 dynes/cm IJntreated 25 dynes/cm Thermal forming resistance VSP/A 148C
Hardness Shore D 67 Tensile Strength, longitudial 26 N/mm2 Tear force in the peeling test 2.6 kp/2.4 cm O Example 5 A mixture consisting of 80 parts by weight of polypropylene according to E~ample 3 and 20 parts by weight of cellulose (Arbocel* BO 600/50) and 20 parts by weights oE calcium carbonate (Omya* BSH) were calendared as in Example 3 and pre-treated.
The following results were obtained:
Surface tension after l hour 58 dynes/cm 3 week 56 dynes/cm 3 months 56 dynes/cm Untreated 25 dynes/cm Thermal forming resistance VSP/A 155C
Hardness Shore D 72 Tensile strength, longitudinal 35 N/mm2 Tear force in the peeling test 2.6 kp/2.4 cm * Trade Mark l~ssoln Example 6 95 parts by weigllt of a mLxture according to Example 3 were aclded to j parts by weight of SBS block copoLymer (C~lriflex* 1102) and processed according to Example 3. On calendaring it was shown that a good foil could still be produced at a speed that was 20% higher.
i The measured mechanical and adhesive characteristics were not disadvantageously affected.
The foil obtained was coated with a conventional polyurethane lacquer (Basis Desmophen* 1340 and Desmodur* Hl).
There was no separation of the lacquer layer in an adhesion tèst according to AST~ D.2.1.4.1.-63.
! Example 7 .~ mixture consisting oE 80 parts by weight of a polypropylene copolymer according to Example 3 (K1 100) 20% by weight of cellulose (Arbocel B 600/50), and 20 parts by weight of talc and the usual additives was calendared at 200~C to a 100 ~Im thick foil, activated according to Example I and pressed by means of a 50 ~m thick foil of KR 2683 adhesive agent at 130C, for 10 sec, and 10 kp/cm2. When the foil bond was removed from the chipboard panel, chip tear out resulted.
* Trade ~ark 1~5~1n Example 8 .~ Eoil accord.in~ to Example 7 was pressed by means of an epoxy adhesive (Daubert* Internationa~ 1 TDC 8160 BHV+l ~ DC 8160 AHV) at room temperature and 5 kp/cL~I2 Eor 24 hours. The Eoil tore duriLIg the removal test.
* Trade ~Iark . ,~
Claims (36)
IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Polypropylene article with improved adhesion characteristics, character-ized by a content of fine particle cellulose having a mean particle diameter of from 5 to 100 µm and a maximum mean length of 200 µm, the surface of said article being surfaced activated.
2. A polypropylene foil according to Claim 1, characterized in that it contains 3 to 50% by weight cellulose, in relation to the sum of polyolefin and cellulose.
3. A foil according to Claim 2, characterized in that it contains 3 to 30% by weight of cellulose.
4. A polypropylene foil according to Claim 1, characterized in that the mean particle diameter of the cellulose is in the range of 5 - 100 µm and that the greatest length of the cellulose is up to 200 µm.
5. A foil according to Claim 4, characterized in that it contains cellulose produced by the sulphite or sulphate process having a thickness of 10 - 30 µm at a length of 5 to 100 µm.
6. A foil according to Claim 1, characterized in that the polypropylene is a random or block copolymer with 1 - 10 Mol-% ethylene or a mixture with polyethylene with a thermal resistance VSP/A over 100°C.
7. A foil according to Claim 1, characterized in that the surface is activated by irradiation.
8. A foil according to Claim 6, characterized in that the surface is activated by means of corona treatment.
9. A foil according to Claim 7, characterized in that the surface is activated by means of electron irradiation, ultra-violet radiation or laser radiation.
10. A foil according to any one of Claims 1 to 3, characterized in that the surface is activated by means or treatment with a flame or with ozone.
11. A foil according to Claim 1, characterized in that it contains additional mineral fillers.
12. A foil according to Claim 11, characterized in that it contains mica, talc, silicic acid or silicates and TiO2.
13. A foil according to Claim 11 or Claim 12, characterized in that it contains 1 to 50% by weight of mineral fillers, related based on the sum of the weights of polyolefin and cellulose.
14. A foil according to Claim 1 characterized in that in addition it contains a modifying agent.
15. A foil according to Claim 14, characterized in that the modifying agent is based on styrol and elastomers.
16. A foil according to Claim 15, characterized in that the elastomer is a block copolymer of styrol with butadiene or styrol with isobutylene or styrol with isoprene.
17. A foil according to Claim 14, characterized in that the modifying agent is a coplymer or graft-copolymer with ethylene with reactive monomers.
18. A foil according to any one of Claims 14 to 16, characterized in that it contains 0.5 to 20% by weight of modifying agent, based on the sum of the weights of polyolefin and cellulose.
19. The process for manufacturing a polypropylene foil with improved adhesion characteristics by forming the foil according to conventional methods and subjecting the surface to a surface activation treatment, characterized in that fine particle cellulose having a mean particle diameter of from 5 to 100 µm and a maximum mean length of 200 µm is added as a filler.
20. A process according to Claim 19, characterized in that 1 to 50% by weight of cellulose is added, related to the sum of polyolefin and cellulose.
21. A process according to Claim 20, characterized in that 3 to 30% by weight of cellulose is added.
22. A process according to one of the claims 19 to 21, characterized in that cellulose has a mean particle diameter of 5 to 100 µm with a maximum mean length to a maximum of 200 µm respectively is used.
23. A process according to any one of Claims 19 to 21, characterized in that the polypropylene is a random or block copolymer with 1 to 10 Mol-%
ethylene or a mixture with polyethylene with a thermal resistance VSP/A
above 100°C.
ethylene or a mixture with polyethylene with a thermal resistance VSP/A
above 100°C.
24. A process according to Claim 19, characterized in that the surface is activated by means of irradiation.
25. A process according to Claim 24, characterized in that the corona treatment is applied as a means of surface activation.
26. A process according to any one of Claims 19 to 21, characterized in that surface activation is carried out by means of irradiation by electron beam, ultra-violet rays, or laser rays.
27. A process according to any one of Claims 19 to 21, characterized in that the surface is activated by treatment with a flame or with ozone.
28. A process according to Claim 19, characterized in that a mineral filler is also included in the foil.
29. A process according to Claim 28, characterized in that mica, talc, silicic acid, silicates or TiO2 is included in the foil.
30. A process according to Claim 28 or 29, characterized in that 1 to 50%
by weight of mineral fillers based on the sum of the weights of the polyolefin and cellulose is included in the foil.
by weight of mineral fillers based on the sum of the weights of the polyolefin and cellulose is included in the foil.
31. A process according to Claim 19, characterized in that a modifying agent is included in the foil.
32. A process according to Claim 31, characterized in that the modifying agent is based on styrol and elastomers.
33. A process according to Claim 32, characterized in that a block co-polymer of styrol with butadiene or styrol with isobutylene or styrol with isoprene is used as the elastomer.
34. A process according to Claim 31, characterized in that copolymer or graft-copolymer of ethylene and reactive monomers is used for modification.
35. A process according to any one of Claims 31 to 33, characterized in that 0.5 to 20% by weight of modifying agent is added, based on the sum of the weights of the polyolefin and cellulose.
36. The use of a foil according to any one of Claims 2 to 4 for hot or cold coating with or without adhesives, imprinting or lacquering.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3001636.5 | 1980-01-17 | ||
| DE3001636A DE3001636C2 (en) | 1980-01-17 | 1980-01-17 | Polyolefin film with improved adhesion, its production and use |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1158010A true CA1158010A (en) | 1983-12-06 |
Family
ID=6092325
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000368763A Expired CA1158011A (en) | 1980-01-17 | 1981-01-19 | Polyethylene article with improved adhesion |
| CA000368762A Expired CA1158010A (en) | 1980-01-17 | 1981-01-19 | Polypropylene article with improved adhesion |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000368763A Expired CA1158011A (en) | 1980-01-17 | 1981-01-19 | Polyethylene article with improved adhesion |
Country Status (6)
| Country | Link |
|---|---|
| EP (2) | EP0032731B1 (en) |
| JP (2) | JPS56104943A (en) |
| AT (2) | ATE13437T1 (en) |
| AU (2) | AU539702B2 (en) |
| CA (2) | CA1158011A (en) |
| DE (3) | DE3001636C2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1987002619A1 (en) * | 1985-11-01 | 1987-05-07 | Biotechnology Australia Pty. Ltd. | Assay supports |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3101479C2 (en) * | 1981-01-19 | 1990-08-23 | Alkor GmbH Kunststoffverkauf, 8000 München | Process for improving the adhesive properties of plastic films |
| DE3122607A1 (en) * | 1981-06-06 | 1982-12-30 | Renolit-Werke GmbH, 6520 Worms | Process for the production of a thermoplastic film from polyolefins by calendering |
| DE3667807D1 (en) * | 1986-03-26 | 1990-02-01 | Kurt Petersen | PLASTIC MATERIAL COATED WITH LAMINATED FABRIC. |
| JPS62238732A (en) * | 1986-04-10 | 1987-10-19 | Gunze Ltd | Film for printed laminate and its hot press bonding method |
| NZ225556A (en) * | 1987-07-31 | 1992-02-25 | Dow Chemical Co | Reinforced laminates with a base layer of wood products |
| JPH0649787B2 (en) * | 1990-01-23 | 1994-06-29 | 工業技術院長 | Surface treatment and coating method for molded products |
| JP3195617B2 (en) * | 1991-08-12 | 2001-08-06 | 住友化学工業株式会社 | Surface treatment method for polypropylene resin molded article and method for coating the molded article |
| ES2439095T3 (en) * | 2003-09-05 | 2014-01-21 | Borealis Technology Oy | Conduit made of a crosslinkable high pressure polyethylene composition |
| DE102004061268A1 (en) * | 2004-12-10 | 2006-06-14 | Volkswagen Ag | Surface activation of plastic component involves treatment of component surface with gas containing ozone |
| WO2006136436A1 (en) * | 2005-06-24 | 2006-12-28 | Dsm Ip Assets B.V. | Styrene block copolymers as infill material in artificial turf systems |
| AT512273B1 (en) * | 2011-11-16 | 2014-06-15 | Chemiefaser Lenzing Ag | HYDROPHOBIC PLASTICS WITH CELLULOSIC HYDROPHILLATION |
| JP7107768B2 (en) * | 2018-06-28 | 2022-07-27 | ポリプラスチックス株式会社 | Adhesive Resin Composition, Composite Molded Article, Method for Improving Adhesion of Crystalline Resin, and Method for Improving Printability and Paintability of Crystalline Resin |
| CN111944189B (en) * | 2020-08-14 | 2022-05-31 | 河南师范大学 | Lignin-iron-containing PE film material and synthetic method thereof |
| CN116478462A (en) * | 2023-04-04 | 2023-07-25 | 华南理工大学 | Printing film suitable for direct inkjet of weak solvent ink and preparation method thereof |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA634179A (en) * | 1962-01-09 | E.I. Du Pont De Nemours And Company | Reinforced resins | |
| US3018189A (en) * | 1952-08-07 | 1962-01-23 | Traver Investments Inc | Method of conditioning polyethylene surfaces for the adhesion of materials coated thereon and resulting product |
| GB805897A (en) * | 1956-02-14 | 1958-12-17 | Ti Group Services Ltd | Improvements relating to the manufacture of plastics |
| US3124729A (en) * | 1957-06-04 | 1964-03-10 | Method for preparing surfaces com- | |
| US2961389A (en) * | 1957-12-10 | 1960-11-22 | Du Pont | Process for modifying polymers and products obtained thereby |
| NL276258A (en) * | 1961-03-23 | |||
| NL292846A (en) * | 1962-05-18 | |||
| US3296046A (en) * | 1963-04-22 | 1967-01-03 | Union Carbide Corp | Method of tack sealing biaxially oriented polypropylene film |
| DE1247641B (en) * | 1963-12-24 | 1967-08-17 | Union Carbide Corp | Thermoplastic mixtures for the production of films |
| FR1470190A (en) * | 1965-03-02 | 1967-02-17 | Du Pont | Process for treating synthetic polymers intended to receive writing in ink, and products obtained |
| US3666836A (en) * | 1969-09-26 | 1972-05-30 | Hercules Inc | Blends of polypropylene with hydrogenated hydrocarbon resins |
| DE2048311A1 (en) * | 1970-10-01 | 1972-04-06 | Basf Ag | Moulded articles especially sheets - comprising polyolefins and/or olefin copolymers, finely-divided wood and fibrous |
| DK136253B (en) * | 1972-12-28 | 1977-09-12 | Ato Chimie | Method for making clear films with little tendency to block. |
| JPS5188541A (en) * | 1975-01-31 | 1976-08-03 | KYOKAKOBUNSHISOSEIBUTSU OYOBI SONOSEIZOHOHO | |
| LU76197A1 (en) * | 1976-11-12 | 1978-07-10 |
-
1980
- 1980-01-17 DE DE3001636A patent/DE3001636C2/en not_active Expired
-
1981
- 1981-01-15 AU AU66223/81A patent/AU539702B2/en not_active Ceased
- 1981-01-15 AU AU66224/81A patent/AU539720B2/en not_active Expired
- 1981-01-15 EP EP81100280A patent/EP0032731B1/en not_active Expired
- 1981-01-15 AT AT81100278T patent/ATE13437T1/en not_active IP Right Cessation
- 1981-01-15 DE DE8181100280T patent/DE3167357D1/en not_active Expired
- 1981-01-15 EP EP81100278A patent/EP0032729B1/en not_active Expired
- 1981-01-15 DE DE8181100278T patent/DE3170555D1/en not_active Expired
- 1981-01-15 AT AT81100280T patent/ATE10505T1/en not_active IP Right Cessation
- 1981-01-16 JP JP492981A patent/JPS56104943A/en active Granted
- 1981-01-16 JP JP56004930A patent/JPS6029741B2/en not_active Expired
- 1981-01-19 CA CA000368763A patent/CA1158011A/en not_active Expired
- 1981-01-19 CA CA000368762A patent/CA1158010A/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1987002619A1 (en) * | 1985-11-01 | 1987-05-07 | Biotechnology Australia Pty. Ltd. | Assay supports |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS56104944A (en) | 1981-08-21 |
| JPS6029741B2 (en) | 1985-07-12 |
| JPS56104943A (en) | 1981-08-21 |
| EP0032731B1 (en) | 1984-11-28 |
| EP0032729B1 (en) | 1985-05-22 |
| CA1158011A (en) | 1983-12-06 |
| DE3001636A1 (en) | 1981-07-23 |
| EP0032729A1 (en) | 1981-07-29 |
| DE3170555D1 (en) | 1985-06-27 |
| DE3001636C2 (en) | 1983-10-20 |
| ATE10505T1 (en) | 1984-12-15 |
| AU539702B2 (en) | 1984-10-11 |
| JPH0219137B2 (en) | 1990-04-27 |
| ATE13437T1 (en) | 1985-06-15 |
| EP0032731A1 (en) | 1981-07-29 |
| AU6622481A (en) | 1981-07-23 |
| DE3167357D1 (en) | 1985-01-10 |
| AU6622381A (en) | 1981-07-23 |
| AU539720B2 (en) | 1984-10-11 |
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