CA2124194A1 - A method for reducing the permeability of paper and board and a substance for the method - Google Patents
A method for reducing the permeability of paper and board and a substance for the methodInfo
- Publication number
- CA2124194A1 CA2124194A1 CA002124194A CA2124194A CA2124194A1 CA 2124194 A1 CA2124194 A1 CA 2124194A1 CA 002124194 A CA002124194 A CA 002124194A CA 2124194 A CA2124194 A CA 2124194A CA 2124194 A1 CA2124194 A1 CA 2124194A1
- Authority
- CA
- Canada
- Prior art keywords
- starch
- coating substance
- dispersion
- ized
- character
- 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.)
- Abandoned
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B29/00—Layered products comprising a layer of paper or cardboard
- B32B29/06—Layered products comprising a layer of paper or cardboard specially treated, e.g. surfaced, parchmentised
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B29/00—Layered products comprising a layer of paper or cardboard
- B32B29/002—Layered products comprising a layer of paper or cardboard as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B29/005—Layered products comprising a layer of paper or cardboard as the main or only constituent of a layer, which is next to another layer of the same or of a different material next to another layer of paper or cardboard layer
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/30—Multi-ply
- D21H27/32—Multi-ply with materials applied between the sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/12—Coating on the layer surface on paper layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/028—Paper layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/726—Permeability to liquids, absorption
- B32B2307/7265—Non-permeable
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2317/00—Animal or vegetable based
- B32B2317/20—Starch
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Paper (AREA)
- Laminated Bodies (AREA)
Abstract
The invention concerns the permeability of paper and board substrate. The permeability of the substrate is reduced by coating it with a modified coating mixture, which is based on a polymer dispersion containing at least one modified starch component. The polymer is prepared preferably by grafting monomers onto the modified starch structure.
Description
WO93/11300 PCT/Fl92/0030 A method for reducing the p2rmeability of paper and board and a substance for the method The object of this invention is a method for reducing the permeability of paper and board in which state the treat-ed product possesses sufficiently good barrier prop-erties against gases and vapours such as water vapour as required in the packaging industry, for example. Despite possessing this property, paper or board treated in ac-cordance with this method is readily disposable as wasteby, for example, composting or recycling the product back as raw material for the fibre-consuming industry (i.e.
the product can be re-pulped; i.e~ disintegrated into fi-brous material without causing problems when used again in papermaking). The invention also involves the substance by means of which the aforementioned properties are achieved.
Increasingly strict regulations pertaining to environ-mental protection have led to a situation in which the manufacturers of packaging materials, for example, are required to organize the post-consumption treatment of the resultant waste in an environment-friendly manner. In other words, packaging waste has to be either recycled to provide industrlàl raw material or it has to be disposed of by composting, for example. If the latter option is resorted to, then the material as a whole must be biode-gradable without releasing any environmentally hazardous chemicals.
The above re~uirements mean that the continued use of conventionai solutions (e.g. papers whose non-permeabi-lity has been achieved by a plastic film lamination) lead - to high costs because of the material's poor degradabili-ty and unsuitability for recycling. This is so in packag-ing situations where the package is required to possess barrier properties against water vapour, for instance.
Certain commonly used polymers that possess good barrier WO93/11300 ~ PCT/Fl92/0030 properties (e.g. products containing polyvinyl chloride) cannot be disposed of by burning because of the hazard caused by hydrogen chloride gas and dioxin.
The purpose of this invention is to eliminate the above shortcomings and to make available a paper product which, while offering adequate barrier properties, can be re-cycled as raw material for the paper industry or disposed of by composting or left to decompose in landfills, for instance.
The method in accordance with the invention is based on spreading onto the surface of paper or board a dispersion product containing a component that includes modified starch. The said dispersion product can also be spread between the layers making up paper or board in which case the polymer layer formed when the dispersion dries pro-vides the required barrier protection. When spread be- ;
tween the layers, the dispersion also forms an adequate adhesion between the layers and thus no actual gluing treatment is needed.
It is known that papers can be treated with products con-taining wax dispersions in order to provide them with protection against moisture. It is also known that the said products usually contain commonly used synthetic polymer dispersions such as styrene butadiene, acrylate or polyvinyl acetate latexes that provide the products with adequate adhesion. The proportion of latexes in the total polymer dispersion's solid matter content is qene-rally high. Examples of the above technology are to be found in patent literature; e.g. GB 1 593 331 (J. Vase, Kemi Oy) and the Finnish patent application 901928 (Neu-siedler AG) contain descriptions of this technology.
The technology in accordance with these inventions pro-vides an adequate barrier against water vapour. However, WO 93/11300 PCI /F192/0030:~
3 '- ~ i r.~ J ~
seeing as the proportion of latex composed entirely of synthetic substances is high, the product's recyclabili-ty is impaired as a result of the latex-based disturban-ce substance accumulation when such material is made into pulp. On the other hand, if the proportion of wax disper-sion is in the vapour barrier substance is raised excess-ively, the dispersion's adhesive and gluing properties are impaired as is also the print~bility of the treated surface due to its ink repelling property.
,, The present invention's point of departure has been to avoid the aforementioned shortcomings by preparing the dispersion so that it contains components that promote the disintegration of the synthetic product in nature and during the various stages of recycling processes. This -has been executed either (A) by joining natural polymer chains (especially starch) to the latex polymer at the manufacturing stage or (B) by replacing a significant part of the latex polymer with a combination polymer ~
starch graft copolymer - consisting of starch and a syn-thetic substance. It has been observed that paper prod-ucts treated with thus manufactured dispersions are more readily made into pulp than papers treated with latexes made according to conventional recipes. Moreover, the dispersion resid~ls formed in conjunction with pulping to be considerabiy less likely to form disturbance resid-uals that cause serious problems in the recycling of pa-per products treated with synthetic adhesives. In extreme cases, the amount of synthetic monomers can be low - even nil. Actually! the properties of a dispersion manufac-tured in this manner are impaired in that the coater sub-stance's adhesion is low but still such a dispersion may find use in less demanding situations.
' 35 As is pointed out in the above, applications for disper-s~ons manufactured in accordance with the invention are -mainly in conjunction with packaging materials and wrap-4 1 ~ L~
WO93/ll300 ' PCT/Fl92/0030 pings that are required to possess certain moisture and vapour barrier properties. In these cases the dispersion can be used in place of conventional plastic/paper la-mination solutions that are non-recyclable as well as being very slowly degradable in nature on the part of their plastic component.
When dispersions manufactured in accordance with the pre-sent invention are used, the resultant paper products degrade relatively quickly in nature. When compared to products made using fully synthetic latexes, the degra-dability of products treated with dispersions manufac--tured in accordance with this invention is also better because the starch components contained by the dispersi-on and polymer structure offer a natural substrate for naturally occurring decomposing hydrolytic enzymes. A
polymer dispersion offering better recycling and degra-ding properties, and manufactured in the manner descri-bed in the above, has reasonable barrier properties to offer as such. When necessary, the vapour barrier pro-- perties can be further modified by means of additives such as a wax dispersion.
The following is a description of ways according to which polymers forming the structure of the dispersion can be manufactured.
-(A) Manufacturing of latex containing starch in a poly-mer structure.
~
The principle hère is that the reaction medium used in the manufacturing of latex by means of the emulsion polymerization method is a water solution containing con-ventio~al additives such as initiators acting as cata-lysts (persulphates, peroxides) and surface-active sub-stances and starch dissolved into the water phase by heating. When this is the case, the initiators cause WO93/11300 PCT/F192/0030~
~ ~i ~ L , 1 . 9 - i radicals to form onto the starch structure and these rad-icals then act as the initial centres of the polymeri-zation reaction. In other words, in addition to the fully synthetic material formed in normal emulsion polymeri-~ation, one obtains starch graft copolymer material inwhich the polymer chains formed of the synthetic monomers used are covalently attached to the starch structure.
Since native starch - regardless of its origin - is a macromolecular compe~nd and water solutions of it have very high viscosities even in very low solid matter con-centrations, one must first reduce the molecular size of the starch or better still use commercially available starch qualities which have usuali~ been split up by means of oxidization. In the event that the user wishes to carry out the oxidization-based splitting up in con-junction with the reaction, this can be done using a known art method advantageously as the first stage in the reaction by using the oxidizing initiators acting as polymerization catalysts.
In order that the viscosity of the polymer dispersion obtained as the end product might fall within the appro-priate range and that it might be a replicable constant, one must take great care to ensure that the degree of splitting of the starch is always precisely that which is required. This can be done by means of viscosity determi-nation, end group analysis or gel permeation chromatogra-phy. The initial starch used in the following examples is either a commercial, hydroqen peroxide oxidized potato starcb Raisamyl 302P with a viscosity of 20-30 mPas when used as a 10% solution at a temperature of 60 ~C or na-; tive potato starch that has been split up enzymatica ly by alpba-amylase possessinq temperature stability with respect to Bacillus licheniformis in the manner described in the example.
WO93/l1300 PCT/Fl92/00 ~. tl~ J 6 Example l:
(Al) 34.30 g of oxidized starch Raisamyl 302P were added to 150 g of water and then transferred into a pressure-proof reactor vessel. The temperature of the mixture was raised to 100 C for a period of 20 minutes in order to dissolve the grains of starch. Following this the mixtu-re was cooled down to 70 C after which a solution con-taining 2~5 g of sodium lauryl sulphate in 50 ml of wa-ter. A monomer mixture containing 116.8 g of styrene, 73.9 g of butadiene washed with a solution of lye and 3.0 g of acrylic acid were then gradually added to the mix-ture over a period of two hours. Initiator solution con-taining 3.o g of ammonium persulphate in 70 g of water was ad~ed from another pressure burette. The polymerizat~
ion reaction was then allowed to proceed for 12 hours.
The end product was a white dispersion with a solid mat-ter concentration of 45.8% and a viscosity of 890 mPas as measured by a Brookfield LVT viscometer using measuring head no. 2 at 2100 r/min. The measurements were conducted after the product had been neutralized with NaOH to a pH
of 6.8. The product's calculatory starch concentration was 13%.
Example 2:
(A2) 34.5 g of oxidized starch were added to 150 g of water and boiled for 20 minutes in order to dissolve the grains of starch. Following this 2.5 g of sodium lauryl sulphate in 50 ml of water were added to the solution as was the catalyst solution and the monomer solution as mentioned in connection with Example l. The composition of the monomer solution in this case was 146 g of vinyl acetate and 22 g of butyl acrylate. The reaction was allowed to proceed for 14 hours. The dry matter concent-ration of the neutralized product was 40.8% and its vis-cosity was 600 mPas at a temperature of 25 C.
W093/ll3~0 , .~.~ ;'i PCr/FI92/~
~xample 3: 49.4 g of oxid_~ed starch were added to 370 g .f water and boiled for 20 minutes in order to dissolve the grains of starch. The reaction mixture was provided with an inert atmosphere by means of a flow of nitrogen.
Next, 0.1 g of CUSO4 was added followed by the addition during a period of 1.5 hours of a monomer mixture com-posed of 75 g of acrylic acid and 53 g of acrylic nitri-te in drops. This was accompanied by the concurrent ad-dition to the reaction mixture of 6 g of 30% hydrogenperoxide given over a period of 2 hours. The reaction was allowed to proceed for 11 hours at a temper.ature of 70 C. The product thus obtained was a white dispersion with a dry matter concentration of 26.3%.
1~ :
Example 4:
(B1) Starch copolymer production. 250 g of native potato starch with a moisture content of 16~ were mixed into 220 g of water~ This was followed by adding 0.05 U/g of starch of alpha-amylase possessing a temperature stabi-lity with rec.pect to B. lichenif~rmis and with an acti-vity value of 984 U/ml. While mixing the suspension vi-gorously, its temperature was raised to 90 C and kept 2 there for 30 minutes. As a mean of stopping enzymatic activity 0.5 ml of 30~ hydrogen peroxide was added and the temperature was brought down to 60 ~C. A flow of ni-trogen was led into the reaction mixture, 0.2. g of CuS04 were added, and 38 g of styrene and 6 g of 30% hydrogen peroxide were administered in drops at the same time for a period of 1.5 hours. The re~ction was allowed to pro-ceed ~ ~ another 2 hours at tne end of which the result-ant whlte dispersion was cooled down to room temperature.
The dispersion's viscosity at 25 C was 670 mPas and its solid matter concentration was 51.8%.
Example 5:
W093/11300 l~CT/Fl92/0~)3~h (B2) Starch graft polymer was produced in the manner described in Example 3 above using butyl acrylate (75 g) as the monomer to be grafted. The amount of starch was 209 g and it was added to 217 g of water. The resultant product was a yellowish dispersion with a room tempera-ture viscosity of 610 mPas and a solid matter concentra-tion of 50.5~.
Example 6:
This example describes the compositions of the formula-tions finally spread onto paper surface, containing dis-persions according to examples 1-4 and control formula-tions and the properties of papers treated with them.
LD460 is a styrene butadiene latex, manufactured by Rai-sion Lateksi Oy, RN11~5 is a vinyl acetate acrylate la-tex, manufactured by Rasional Oy, vahad is a wax disper-sion containing paraffin with a melting range of c. 50-70 C.
Using a laboratory coater machine (Endupapp), the dis-persion was spread onto board (grammage 190 g/m2). The board was then measured for its water vapour permeability (WWP) in accordance with the IS0 258~1974 method (unit:
g/m2/24h). PM= amount of dispersion spread (g/m2)O
The value PA in the table depicts the pulpability pro-perties of treated board. The value is obtained as fol-lows: the treated board was broken down in accordance with the method SCAN-C 18:65. The pulped material was made into laboratory sheets (grammaqe: c. 100 g/m2). The sheet quality was assessed using a scale of 0 - 5 in which 0 indicates good pulpability ~no accumulations of surface treatment material observed) and 5 indicates poor pulpability (numerous accumulations of surface treatment substance or unevenness due to incomplete breaking down WO93/11300 ~ I Z i~ 4 PCT/F192/0030~
g .
of materi ).
Table 1.
RlR2 R3 R4 R5 R6 R7 R8 R9R10 R11 LD460 100~ 70 70 60 90 - -Al - -- 100 90 - - - - - - -Bl - - - - - - 30 - 30 vahad - - - 10 - - - - 10 10 PM 17.8- 20.219.918.721.020.319.4 20.320.118.0 0 WWP 29 98 32 7 36 4 27 38 ~ 5 151 PA 5 3 2 2 0 O 1 1 i 4 0 Example 7: -In this example two pieces of board are made into a lami-nated pro~ct by means of a dispersion manufactured in accordance wi~h *he invention. Dispersions R3, R6 and R8 were spread onto boards using amounts that correspon~ed to c. 20 g/m2 of solid matter. Immediately aft~- th - ;
step anot~er sheet of the same board was press~. aga~nst the treated surface and the thus formed laminated product was then allowed to dry. The outcome of the gluing oper-ation wa-~ assessed on the basis of the fibre tear pro-duced when the two layers were separated from one another (total fibre tear = ex~ellent adhesion). The laminates :~.
were also measured for their vapour barrier values.
:
Table 2.
. .
Fibre tear WWP (g/m2/24h) .
R3 Total 29 R6 Total g R7 Total 28 R9 Almost total 12
the product can be re-pulped; i.e~ disintegrated into fi-brous material without causing problems when used again in papermaking). The invention also involves the substance by means of which the aforementioned properties are achieved.
Increasingly strict regulations pertaining to environ-mental protection have led to a situation in which the manufacturers of packaging materials, for example, are required to organize the post-consumption treatment of the resultant waste in an environment-friendly manner. In other words, packaging waste has to be either recycled to provide industrlàl raw material or it has to be disposed of by composting, for example. If the latter option is resorted to, then the material as a whole must be biode-gradable without releasing any environmentally hazardous chemicals.
The above re~uirements mean that the continued use of conventionai solutions (e.g. papers whose non-permeabi-lity has been achieved by a plastic film lamination) lead - to high costs because of the material's poor degradabili-ty and unsuitability for recycling. This is so in packag-ing situations where the package is required to possess barrier properties against water vapour, for instance.
Certain commonly used polymers that possess good barrier WO93/11300 ~ PCT/Fl92/0030 properties (e.g. products containing polyvinyl chloride) cannot be disposed of by burning because of the hazard caused by hydrogen chloride gas and dioxin.
The purpose of this invention is to eliminate the above shortcomings and to make available a paper product which, while offering adequate barrier properties, can be re-cycled as raw material for the paper industry or disposed of by composting or left to decompose in landfills, for instance.
The method in accordance with the invention is based on spreading onto the surface of paper or board a dispersion product containing a component that includes modified starch. The said dispersion product can also be spread between the layers making up paper or board in which case the polymer layer formed when the dispersion dries pro-vides the required barrier protection. When spread be- ;
tween the layers, the dispersion also forms an adequate adhesion between the layers and thus no actual gluing treatment is needed.
It is known that papers can be treated with products con-taining wax dispersions in order to provide them with protection against moisture. It is also known that the said products usually contain commonly used synthetic polymer dispersions such as styrene butadiene, acrylate or polyvinyl acetate latexes that provide the products with adequate adhesion. The proportion of latexes in the total polymer dispersion's solid matter content is qene-rally high. Examples of the above technology are to be found in patent literature; e.g. GB 1 593 331 (J. Vase, Kemi Oy) and the Finnish patent application 901928 (Neu-siedler AG) contain descriptions of this technology.
The technology in accordance with these inventions pro-vides an adequate barrier against water vapour. However, WO 93/11300 PCI /F192/0030:~
3 '- ~ i r.~ J ~
seeing as the proportion of latex composed entirely of synthetic substances is high, the product's recyclabili-ty is impaired as a result of the latex-based disturban-ce substance accumulation when such material is made into pulp. On the other hand, if the proportion of wax disper-sion is in the vapour barrier substance is raised excess-ively, the dispersion's adhesive and gluing properties are impaired as is also the print~bility of the treated surface due to its ink repelling property.
,, The present invention's point of departure has been to avoid the aforementioned shortcomings by preparing the dispersion so that it contains components that promote the disintegration of the synthetic product in nature and during the various stages of recycling processes. This -has been executed either (A) by joining natural polymer chains (especially starch) to the latex polymer at the manufacturing stage or (B) by replacing a significant part of the latex polymer with a combination polymer ~
starch graft copolymer - consisting of starch and a syn-thetic substance. It has been observed that paper prod-ucts treated with thus manufactured dispersions are more readily made into pulp than papers treated with latexes made according to conventional recipes. Moreover, the dispersion resid~ls formed in conjunction with pulping to be considerabiy less likely to form disturbance resid-uals that cause serious problems in the recycling of pa-per products treated with synthetic adhesives. In extreme cases, the amount of synthetic monomers can be low - even nil. Actually! the properties of a dispersion manufac-tured in this manner are impaired in that the coater sub-stance's adhesion is low but still such a dispersion may find use in less demanding situations.
' 35 As is pointed out in the above, applications for disper-s~ons manufactured in accordance with the invention are -mainly in conjunction with packaging materials and wrap-4 1 ~ L~
WO93/ll300 ' PCT/Fl92/0030 pings that are required to possess certain moisture and vapour barrier properties. In these cases the dispersion can be used in place of conventional plastic/paper la-mination solutions that are non-recyclable as well as being very slowly degradable in nature on the part of their plastic component.
When dispersions manufactured in accordance with the pre-sent invention are used, the resultant paper products degrade relatively quickly in nature. When compared to products made using fully synthetic latexes, the degra-dability of products treated with dispersions manufac--tured in accordance with this invention is also better because the starch components contained by the dispersi-on and polymer structure offer a natural substrate for naturally occurring decomposing hydrolytic enzymes. A
polymer dispersion offering better recycling and degra-ding properties, and manufactured in the manner descri-bed in the above, has reasonable barrier properties to offer as such. When necessary, the vapour barrier pro-- perties can be further modified by means of additives such as a wax dispersion.
The following is a description of ways according to which polymers forming the structure of the dispersion can be manufactured.
-(A) Manufacturing of latex containing starch in a poly-mer structure.
~
The principle hère is that the reaction medium used in the manufacturing of latex by means of the emulsion polymerization method is a water solution containing con-ventio~al additives such as initiators acting as cata-lysts (persulphates, peroxides) and surface-active sub-stances and starch dissolved into the water phase by heating. When this is the case, the initiators cause WO93/11300 PCT/F192/0030~
~ ~i ~ L , 1 . 9 - i radicals to form onto the starch structure and these rad-icals then act as the initial centres of the polymeri-zation reaction. In other words, in addition to the fully synthetic material formed in normal emulsion polymeri-~ation, one obtains starch graft copolymer material inwhich the polymer chains formed of the synthetic monomers used are covalently attached to the starch structure.
Since native starch - regardless of its origin - is a macromolecular compe~nd and water solutions of it have very high viscosities even in very low solid matter con-centrations, one must first reduce the molecular size of the starch or better still use commercially available starch qualities which have usuali~ been split up by means of oxidization. In the event that the user wishes to carry out the oxidization-based splitting up in con-junction with the reaction, this can be done using a known art method advantageously as the first stage in the reaction by using the oxidizing initiators acting as polymerization catalysts.
In order that the viscosity of the polymer dispersion obtained as the end product might fall within the appro-priate range and that it might be a replicable constant, one must take great care to ensure that the degree of splitting of the starch is always precisely that which is required. This can be done by means of viscosity determi-nation, end group analysis or gel permeation chromatogra-phy. The initial starch used in the following examples is either a commercial, hydroqen peroxide oxidized potato starcb Raisamyl 302P with a viscosity of 20-30 mPas when used as a 10% solution at a temperature of 60 ~C or na-; tive potato starch that has been split up enzymatica ly by alpba-amylase possessinq temperature stability with respect to Bacillus licheniformis in the manner described in the example.
WO93/l1300 PCT/Fl92/00 ~. tl~ J 6 Example l:
(Al) 34.30 g of oxidized starch Raisamyl 302P were added to 150 g of water and then transferred into a pressure-proof reactor vessel. The temperature of the mixture was raised to 100 C for a period of 20 minutes in order to dissolve the grains of starch. Following this the mixtu-re was cooled down to 70 C after which a solution con-taining 2~5 g of sodium lauryl sulphate in 50 ml of wa-ter. A monomer mixture containing 116.8 g of styrene, 73.9 g of butadiene washed with a solution of lye and 3.0 g of acrylic acid were then gradually added to the mix-ture over a period of two hours. Initiator solution con-taining 3.o g of ammonium persulphate in 70 g of water was ad~ed from another pressure burette. The polymerizat~
ion reaction was then allowed to proceed for 12 hours.
The end product was a white dispersion with a solid mat-ter concentration of 45.8% and a viscosity of 890 mPas as measured by a Brookfield LVT viscometer using measuring head no. 2 at 2100 r/min. The measurements were conducted after the product had been neutralized with NaOH to a pH
of 6.8. The product's calculatory starch concentration was 13%.
Example 2:
(A2) 34.5 g of oxidized starch were added to 150 g of water and boiled for 20 minutes in order to dissolve the grains of starch. Following this 2.5 g of sodium lauryl sulphate in 50 ml of water were added to the solution as was the catalyst solution and the monomer solution as mentioned in connection with Example l. The composition of the monomer solution in this case was 146 g of vinyl acetate and 22 g of butyl acrylate. The reaction was allowed to proceed for 14 hours. The dry matter concent-ration of the neutralized product was 40.8% and its vis-cosity was 600 mPas at a temperature of 25 C.
W093/ll3~0 , .~.~ ;'i PCr/FI92/~
~xample 3: 49.4 g of oxid_~ed starch were added to 370 g .f water and boiled for 20 minutes in order to dissolve the grains of starch. The reaction mixture was provided with an inert atmosphere by means of a flow of nitrogen.
Next, 0.1 g of CUSO4 was added followed by the addition during a period of 1.5 hours of a monomer mixture com-posed of 75 g of acrylic acid and 53 g of acrylic nitri-te in drops. This was accompanied by the concurrent ad-dition to the reaction mixture of 6 g of 30% hydrogenperoxide given over a period of 2 hours. The reaction was allowed to proceed for 11 hours at a temper.ature of 70 C. The product thus obtained was a white dispersion with a dry matter concentration of 26.3%.
1~ :
Example 4:
(B1) Starch copolymer production. 250 g of native potato starch with a moisture content of 16~ were mixed into 220 g of water~ This was followed by adding 0.05 U/g of starch of alpha-amylase possessing a temperature stabi-lity with rec.pect to B. lichenif~rmis and with an acti-vity value of 984 U/ml. While mixing the suspension vi-gorously, its temperature was raised to 90 C and kept 2 there for 30 minutes. As a mean of stopping enzymatic activity 0.5 ml of 30~ hydrogen peroxide was added and the temperature was brought down to 60 ~C. A flow of ni-trogen was led into the reaction mixture, 0.2. g of CuS04 were added, and 38 g of styrene and 6 g of 30% hydrogen peroxide were administered in drops at the same time for a period of 1.5 hours. The re~ction was allowed to pro-ceed ~ ~ another 2 hours at tne end of which the result-ant whlte dispersion was cooled down to room temperature.
The dispersion's viscosity at 25 C was 670 mPas and its solid matter concentration was 51.8%.
Example 5:
W093/11300 l~CT/Fl92/0~)3~h (B2) Starch graft polymer was produced in the manner described in Example 3 above using butyl acrylate (75 g) as the monomer to be grafted. The amount of starch was 209 g and it was added to 217 g of water. The resultant product was a yellowish dispersion with a room tempera-ture viscosity of 610 mPas and a solid matter concentra-tion of 50.5~.
Example 6:
This example describes the compositions of the formula-tions finally spread onto paper surface, containing dis-persions according to examples 1-4 and control formula-tions and the properties of papers treated with them.
LD460 is a styrene butadiene latex, manufactured by Rai-sion Lateksi Oy, RN11~5 is a vinyl acetate acrylate la-tex, manufactured by Rasional Oy, vahad is a wax disper-sion containing paraffin with a melting range of c. 50-70 C.
Using a laboratory coater machine (Endupapp), the dis-persion was spread onto board (grammage 190 g/m2). The board was then measured for its water vapour permeability (WWP) in accordance with the IS0 258~1974 method (unit:
g/m2/24h). PM= amount of dispersion spread (g/m2)O
The value PA in the table depicts the pulpability pro-perties of treated board. The value is obtained as fol-lows: the treated board was broken down in accordance with the method SCAN-C 18:65. The pulped material was made into laboratory sheets (grammaqe: c. 100 g/m2). The sheet quality was assessed using a scale of 0 - 5 in which 0 indicates good pulpability ~no accumulations of surface treatment material observed) and 5 indicates poor pulpability (numerous accumulations of surface treatment substance or unevenness due to incomplete breaking down WO93/11300 ~ I Z i~ 4 PCT/F192/0030~
g .
of materi ).
Table 1.
RlR2 R3 R4 R5 R6 R7 R8 R9R10 R11 LD460 100~ 70 70 60 90 - -Al - -- 100 90 - - - - - - -Bl - - - - - - 30 - 30 vahad - - - 10 - - - - 10 10 PM 17.8- 20.219.918.721.020.319.4 20.320.118.0 0 WWP 29 98 32 7 36 4 27 38 ~ 5 151 PA 5 3 2 2 0 O 1 1 i 4 0 Example 7: -In this example two pieces of board are made into a lami-nated pro~ct by means of a dispersion manufactured in accordance wi~h *he invention. Dispersions R3, R6 and R8 were spread onto boards using amounts that correspon~ed to c. 20 g/m2 of solid matter. Immediately aft~- th - ;
step anot~er sheet of the same board was press~. aga~nst the treated surface and the thus formed laminated product was then allowed to dry. The outcome of the gluing oper-ation wa-~ assessed on the basis of the fibre tear pro-duced when the two layers were separated from one another (total fibre tear = ex~ellent adhesion). The laminates :~.
were also measured for their vapour barrier values.
:
Table 2.
. .
Fibre tear WWP (g/m2/24h) .
R3 Total 29 R6 Total g R7 Total 28 R9 Almost total 12
Claims (13)
1. A method for reducing the gas and vapour permeability of paper or board by coating it with a coating substance consisting of one or more polymer dispersions, the polymers containing synthetic components, characterized in that a coating substance is used, in which at least one of the polymers contains starch bound as a part of the polymer construction by radical initiated poly-merization reactions.
2. A coating substance for a method as claimed in claim 1, characterized in that the polymer containing a starch component has been prepared from dissolved, split up starch by grafting said starch in water phase by means of a monomer mixture by feeding the monomer mixture into a water phase containing 2-25% of starch as calculated from the finished dispersion's solid matter.
3. A coating substance as claimed in claim 2, character-ized in that the polymer dispersion's starch-containing component has been prepared using a monomer mixture con-taining styrene and butadiene as its main components.
4. A coating substance as claimed in claim 2, character-ized in that the starch-containing component of the poly-mer dispersion has been prepared using a monomer mixture containing esters of vinyl acetate and acrylic acid and lower alcohols (methyl, ethyl, propyl or butyl) as its main components.
5. A coating substance as claimed in claim 2, character-ized in that the polymer dispersion's starch-containing component has been prepared using a monomer mixture con-taining acrylic acid and acryl nitrile as its main com-ponents.
6. A coating substance as claimed in claim 1, character-ized in that the polymer dispersion's starch-containing component has been prepared by grafting to the split up starch unsaturated monomer in amounts corresponding to o-50% of the amount of starch.
7. A coating substance as claimed in claim 6, character-ized in that the polymer dispersion's starch-containing component has been produced by grafting a styrene monomer onto split up starch.
8. A coating substance as claimed in claim 6, character-ized in that the polymer dispersion's starch-containing component has been prepared by grafting onto the split up starch an ester monomer formed of acrylic acid and lower alcohols.
9. A coating substance for reducing the permeability of paper or board, characterized in that it contains a poly-mer dispersion containing 10-100% of starch-containing polymer component and 0-90% of a starch-free component and 0-30% of a wax dispersion.
10. A coating substance as claimed in claim 9, character-ized in that the starch-free polymer dispersion is styrene butadiene latex.
11. A coating substance as claimed in claim 9, character-ized in that the starch-free polymer dispersion is vinyl acetate - acryl latex.
12. A coating substance as claimed in claim 9, character-ized in that the melting point of the wax used in the dispersion is c. 50-70 °C.
13. A method as claimed in claim 1, characterized in that the coating substance is spread between two or more paper and/or board layers and that the layers are bound to one another using the coating substance.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FI915541A FI90793C (en) | 1991-11-25 | 1991-11-25 | Method for reducing the permeability of paper or board and the substance used in the method |
| FI915541 | 1991-11-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2124194A1 true CA2124194A1 (en) | 1993-06-10 |
Family
ID=8533548
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002124194A Abandoned CA2124194A1 (en) | 1991-11-25 | 1992-11-11 | A method for reducing the permeability of paper and board and a substance for the method |
Country Status (8)
| Country | Link |
|---|---|
| CA (1) | CA2124194A1 (en) |
| DE (1) | DE4294110T1 (en) |
| FI (1) | FI90793C (en) |
| FR (1) | FR2685018B1 (en) |
| GB (1) | GB2287420B (en) |
| NL (1) | NL194977C (en) |
| SE (1) | SE505439C2 (en) |
| WO (1) | WO1993011300A1 (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9411080D0 (en) * | 1994-06-02 | 1994-07-20 | Unilever Plc | Treatment |
| NL9401752A (en) * | 1994-10-21 | 1996-06-03 | Walki Sack Bv | Laminated packaging or covering material, method for the production thereof and packaging or covering formed from this material. |
| FI98943C (en) * | 1996-01-10 | 1997-09-10 | Raisio Chem Oy | A method of improving the properties of paper or board |
| US6569539B2 (en) | 1996-10-30 | 2003-05-27 | Tetra Level Holdings & Finance S.A. | Gas barrier packaging laminate method for production thereof and packaging containers |
| FI105566B (en) * | 1996-12-31 | 2000-09-15 | Valtion Teknillinen | Process and preparation of polymer dispersions |
| US6780903B2 (en) | 1996-12-31 | 2004-08-24 | Valtion Teknillinen Tutkimuskeskus | Process for the preparation of polymer dispersions |
| FI980086A (en) | 1997-05-28 | 1998-11-29 | Enso Oyj | Coated paperboard, its method of manufacture and containers and packaging made from it |
| DE10049665B4 (en) * | 2000-07-03 | 2004-04-29 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Multi-layer packaging for greasy goods and the use of a starch derivative therefor |
| WO2002002412A2 (en) | 2000-07-03 | 2002-01-10 | Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung E.V. | Multilayered packaging for greasy products |
| DE102010028952A1 (en) | 2010-05-12 | 2011-11-17 | Wacker Chemie Ag | Low-profile additives based on renewable raw materials |
| EP2514777A1 (en) | 2011-04-20 | 2012-10-24 | Basf Se | Polysaccharide macromonomer based co-polymer |
| FI127819B (en) * | 2017-06-15 | 2019-03-15 | Kemira Oyj | Coating structure, sheet-like product and its use |
| ES2929862A1 (en) * | 2021-06-02 | 2022-12-02 | Mora Martinez Evaristo | Compact water-repellent paper with intermediate polymer (Machine-translation by Google Translate, not legally binding) |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4109056A (en) * | 1975-05-05 | 1978-08-22 | Champion International Corporation | Starch/latex cast coatings for paper |
| US4301017A (en) * | 1980-04-28 | 1981-11-17 | Standard Brands Incorporated | Stable, liquid starch graft copolymer composition |
| US4585501A (en) * | 1984-04-30 | 1986-04-29 | Champion International Corporation | Method of use of corrugating adhesive composition for adhering normally abherent surfaces |
| US4690996A (en) * | 1985-08-28 | 1987-09-01 | National Starch And Chemical Corporation | Inverse emulsions |
| DE3730833A1 (en) * | 1987-09-14 | 1989-03-23 | Nicolaus Md Papier | CATIONICALLY PIGMENT DISPERSION AND STRIP COLOR |
| SE8704754L (en) * | 1987-11-27 | 1989-05-28 | Lacani Ab | PROCEDURES FOR PREPARING MOISTURE RESISTANT WELL PAPER |
| FI82734C (en) * | 1987-12-07 | 1991-04-10 | Enso Gutzeit Oy | Process for making a paper or board product and a product produced by the process |
| US5003022A (en) * | 1989-02-10 | 1991-03-26 | Penford Products Company | Starch graft polymers |
| US5112445A (en) * | 1989-06-23 | 1992-05-12 | Merck & Co., Inc. | Gellan gum sizing |
| DE3922784A1 (en) * | 1989-07-11 | 1991-01-17 | Synthomer Chemie Gmbh | METHOD FOR PRODUCING AQUEOUS, DEXTRINE-CONTAINING POLYMERISATE DISPERSIONS |
| JPH04185797A (en) * | 1990-11-08 | 1992-07-02 | Sumitomo Seika Chem Co Ltd | Coating composition for paper |
| EP0606431B1 (en) * | 1992-06-19 | 1997-08-20 | Penford Products Company | Cationic starch/vinyl acetate coating board binders |
-
1991
- 1991-11-25 FI FI915541A patent/FI90793C/en not_active IP Right Cessation
-
1992
- 1992-11-11 WO PCT/FI1992/000305 patent/WO1993011300A1/en active Application Filing
- 1992-11-11 DE DE4294110T patent/DE4294110T1/en not_active Ceased
- 1992-11-11 NL NL9220027A patent/NL194977C/en not_active IP Right Cessation
- 1992-11-11 CA CA002124194A patent/CA2124194A1/en not_active Abandoned
- 1992-11-11 GB GB9408432A patent/GB2287420B/en not_active Expired - Fee Related
- 1992-11-24 FR FR9214075A patent/FR2685018B1/en not_active Expired - Fee Related
-
1994
- 1994-05-20 SE SE9401765A patent/SE505439C2/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| FI90793C (en) | 1994-03-25 |
| FI90793B (en) | 1993-12-15 |
| DE4294110T1 (en) | 1995-06-01 |
| FR2685018B1 (en) | 1995-12-08 |
| NL194977C (en) | 2003-03-27 |
| FI915541A (en) | 1993-05-26 |
| WO1993011300A1 (en) | 1993-06-10 |
| FI915541A0 (en) | 1991-11-25 |
| SE505439C2 (en) | 1997-08-25 |
| GB2287420A (en) | 1995-09-20 |
| FR2685018A1 (en) | 1993-06-18 |
| GB9408432D0 (en) | 1994-06-22 |
| GB2287420B (en) | 1996-06-05 |
| SE9401765L (en) | 1994-05-20 |
| NL9220027A (en) | 1994-12-01 |
| SE9401765D0 (en) | 1994-05-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2124194A1 (en) | A method for reducing the permeability of paper and board and a substance for the method | |
| KR0135746B1 (en) | Starch graft polymers | |
| EP2596033B1 (en) | Vinyl ester/ethylene-based binders for paper and paperboard coatings | |
| WO1999045059A1 (en) | Repulpable corrugated board | |
| DE69223349T2 (en) | Paper used as a base paper for gypsum board and process for its manufacture | |
| US8450410B2 (en) | Adhesive composition for the manufacturing of corrugated paper board | |
| KR101392326B1 (en) | Starch-based copolymer particle with core-shell structure and composition for coating paper comprising the same | |
| JP2020523495A (en) | Coating structure, sheet product and its use | |
| EP3810856B1 (en) | Coating structure, sheet-like product and its use | |
| CN112469793A (en) | Adhesive based on materials containing latex and lignin and method for producing same | |
| KR101836308B1 (en) | Paper coating material having environment-friendly, water-proof and oil-proof properties, and method of manufacturing paper coated with the same | |
| US4940741A (en) | Process for the production of hardboard | |
| US20110256362A1 (en) | Modified fibrous product and method of producing the same | |
| KR101737004B1 (en) | Method of manufacturing paper coating material having recyclable, water-proof and oil-proof properties | |
| DE69213674T2 (en) | Moisture resistant sack | |
| EP1948729B1 (en) | Lecithin-containing starch compositions, preparation thereof and paper products having oil and grease resistance, and/or release properties | |
| CN112236557B (en) | Surface sizing agent for papermaking | |
| KR20220117609A (en) | Moisturizing resin eco-friendly paper coating agent using acrylic polymers | |
| CA2093092A1 (en) | Aqueous emulsion and easily macerating moisture-proof paper | |
| DE1546315B2 (en) | Binder mixture for paper coating slips | |
| KR100385816B1 (en) | Manufactur method of dampproof covering material for paper and it's used dampproof paper | |
| WO2023112914A1 (en) | Coating Agent for Paper Base Material | |
| WO2015091379A1 (en) | Method for applying dispersion adhesives | |
| KR20240092633A (en) | Composition for barrier coating using organic nanoclay dispersion and manufacturing method thereof | |
| JPH07189181A (en) | Readily disintegrable moistureproof paper |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued | ||
| FZDE | Discontinued |
Effective date: 20041012 |