CN1005700B - High solids content cb coating - Google Patents

High solids content cb coating Download PDF

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Publication number
CN1005700B
CN1005700B CN85107728.5A CN85107728A CN1005700B CN 1005700 B CN1005700 B CN 1005700B CN 85107728 A CN85107728 A CN 85107728A CN 1005700 B CN1005700 B CN 1005700B
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China
Prior art keywords
coating
coated paper
paper
regulation
carboxymethyl cellulose
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Expired
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CN85107728.5A
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Chinese (zh)
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CN85107728A (en
Inventor
乔治·奥利维尔·朗拉斯
帕特·杨·鹤·王
约瑟夫·斯塔利·查普利克
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Nashua Corp
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Nashua Corp
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Publication date
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Publication of CN85107728A publication Critical patent/CN85107728A/en
Publication of CN1005700B publication Critical patent/CN1005700B/en
Expired legal-status Critical Current

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/124Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/124Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
    • B41M5/132Chemical colour-forming components; Additives or binders therefor

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Color Printing (AREA)
  • Paints Or Removers (AREA)
  • Paper (AREA)
  • Duplication Or Marking (AREA)
  • Laminated Bodies (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)

Abstract

Disclosed is a coating composition for producing a high solids content carboxymethylcellulose based ''CB'' coating for use in pressure sensitive carbonless copy systems. The formulation comprises carboxylmethylcellulose, a wall-forming carboxylated acrylic resin, an organic cross-linker, a polyvalent metal salt, and an oil containing color-forming dye. The composition has a solids content of at lesat 30% and a viscosity within the range of 50 to 5000 centiposes. The CB paper exhibits the ability to produce improved imaging on computer and dot matrix printers because of better release efficiency and may be manufactured using less energy.

Description

Highly filled CB coating
The present invention relates to the CB coating composition of pressure sensitivity recording element (being often referred to NCR), more more specifically, the present invention relates to highly filled sodium carboxymethylcellulose (CMC)-Ji formulation for coating material, this coating has suitable coating viscosity; The present invention has also related to the paper that scribbles this coating simultaneously.
NCR by two pages or multipage quires altogether, the back side of single-sheet stationery has one deck to contain the coating (being commonly referred to CB coating or " CB ") of chromonic materials, coating is made up of continuous film that contains chromonic materials or microcapsules.In use, accept the front of page and the back side of upper paper and be in contact with one another, the front of accepting page scribble can with the interactional developer of chromonic materials.When upper paper was imposed local pressure, the coating that contains colour former will break and make the co-reactant on colour former and the lower floor paper or developer coating contacts and chemically reactive.So just with the corresponding position of compression point on show visible coloured image.Therefore, the pressure that puts on upper paper can produce corresponding image at each other superimposition single page recto of page or leaf.
Prior art has disclosed the coating producing process that contains the chromonic materials (being also referred to as alluring colouration agent or leuco dye) that is dissolved in the solvent.No. the 4397483rd, the patent in the past such as the U.S. and No. 1280769 patent of No. 4082688 patent and Britain (GB) described a kind of be used for the pressure sensitivity recording materials contain the sedimental CB coating of carboxymethyl cellulose, this coating contains a kind of oils solvent and a kind of color development reactant.With this fluid emulsification in sodium carboxymethyl cellulose solution that contains the color development reactant, and add a kind of slaine so that make cellulose reach the dyestuff oil droplet coprecipitation that exists in solution with decentralized photo.Then the emulsion that makes is coated in the carbonless copying system upper paper the back side and carry out drying, usually in emulsion, add crosslinked resin to improve the intensity of coating.
Though these coating are desirable economically, very poor according to the highly filled CB paint stability that these prior arts are produced, and viscosity is too high, is unsuitable for coating apparatus and the technology used at present.And the coating energy consumption of low solid content is too high and prolonged drying time greatly.Thereby we expect to have a kind of coating with high percent solids content of suitable coating viscosity.
To known CMC base coating compound is impossible with the content that the method for the minimizing water yield increases solid only, because this will cause serious rheological characteristic problem.To be its viscosity with the increase of CMC content form exponentially the characteristics of the CMC aqueous solution increases.Thereby, can produce quick-drying coating although increase CMC content simply, its advantage is owing to the practicality of the high viscosity of coating and the extreme difference that causes has therefrom been offset.
An object of the present invention is to provide the highly filled CB coating of a kind of improved low viscosity, so that it is applied on paper or other base material better; Another purpose provides a kind of solids content height, the coating that the water yield is low, thus improve drying efficiency.A further object of the invention is promptly produced the low coating of a kind of water content to save the manpower and the energy.Another purpose is to improve the colour former release efficiency of CB paper, thereby improves the electronic computer of use action paper and the image quality on the dot-matrix printer.Another purpose is to improve the whiteness of CB paper.A further object of the invention promptly reduces the distortion of paper base material by wetting fiber.Another purpose provides a kind of CB coating that can be coated with on paper machine.
We have invented a kind of highly filled CB coating with suitable, stable coating viscosity, and improved CB paper, and this coating can be prepared with certain type CMC and following material, and these materials are acrylic resins.Organic crosslinking agent and the slaine that can bring out the CMC precipitation.Can be made into a kind of highly filled coating with prescription of the present invention, it contains the above anhydrous material of about 30% weight and has suitable coating viscosity, thus the problem of a lot of CB coating that run into before reducing to greatest extent.
This formulation for coating material that can be coated with comprises the emulsus oil that contains one or more colour formers, the continuous phase of emulsion is the aqueous solution of following material, they are the CMC sodium of the best substitution value of CMC(between 0.65-1.8), the film forming acrylic resin, multivalent metal salt, the component that organic crosslinking agent and other are selected for use, they are enough to make solid total content wherein to be at least 30% weight in the quantity of prescription, but are preferably at least 35%.Its viscosity will be controlled at Bu Shi (Brookfield) viscosity about 50 and arrive within about 5000 centipoises (CPS), to be applicable to special-purpose coating apparatus and certain selected speed of a motor vehicle.Here said solid weight percentage comprises all components outside dewatering in the prescription, promptly comprises oil in the coating and one or more dyestuffs of dissolving.In embodiment preferably, the acrylic acid film-forming resin is a kind of copolymer of polyethyl acrylate/methyl methacrylate of carboxylation, and the ratio of ethyl acrylate and methyl methacrylate is preferably 2: 1.Organic crosslinking agent is polyamide-chloropropylene oxide preferably, or other can make CMC and the crosslinked resin of carboxylation acrylic resin.Preferred metal salt is aluminum nitrate.In the present invention thought preferably embodiment at present, used CMC had lower viscosity (being the 60-170 centipoise in 6% the aqueous solution) and high substitution value such as 1.1-1.5.
On the other hand, art of the present invention comprises a kind of improved CB paper, and this paper has the paper web that one deck has adhesion, dry above-mentioned coating, and this coating pressurized can discharge colour former.The characteristics of this CB paper are that developing intensity is improved, and critical pressure is lower, and cost is lower.
Accompanying drawing has provided non-bodystock paper, scribble low solid content prior art coating paper and scribble the reflectance of the paper of coating of the present invention, illustrated that the whiteness according to the CB paper of manufacturing of the present invention has had improvement.
According to the present invention, low viscous, the CMC of substitution value between 0.65-1.8 is dissolved in the water, and CMC is the anionic water-soluble polymer that goes out from cellulose-derived.Substitution value is the average number of substituted carboxymethyl in each AGU, and high substituted degree has improved the compatibility of CMC and other water-soluble component; According to CMC used in the present invention, preferably alkali metal CMC such as CMC sodium (substitution value 1.1-1.5) represent that each AGU has 1.1-1.5 carboxymethyl.
Add a kind of acrylic acid film-forming resin in this aqueous solution, better resin is that BF Goodrich (Goodrich) company makes " Carboset-514H ".This is a kind of ethyl acrylate of carboxylation and the copolymer of methyl methacrylate, and its ratio is preferably 2: 1.Also having other operable resin such as Luo Man. " ACRYSOL-WS-24 " of Haas (Rohm Haas) company supply, this is a kind of butyl acrylate and cinnamic carboxylation copolymer.
Then the oil solution of dyestuff is added in acrylic resin-CMC solution.The dyestuff and the oil solvent that are suitable for are well-known in the art, oil-dye solution contains alkaline color development lactones or 2-benzo (C) furanone dyestuff preferably, and they are colourless or light, when running into acidic materials, Show Color, and be dissolved in active solvent such as the alkyl biphenyl.Though applied concrete dyestuff and oil itself are not formed a part of the present invention, employed dyestuff preferably should be dissolved in a kind of active oil in enforcement of the present invention, and its concentration is 3%-12% weight.
In the two-phase mixture that obtains, add the polyamide-epichlorohydrin resins of a kind of crosslinking agent such as cation water-soluble.It is crosslinked with carboxymethyl cellulose and carboxylation acrylic acid water-soluble film-forming resin.Other useful crosslinking agent comprises the formaldehyde donor resin, as formaldehyde resin, or melamine formaldehyde resin." Kymene557H " that Hull Ke Lishi (Hercules) company makes is crosslinking agent preferably, and " Kymene557H " is a kind of efficient, cationic, wet-strength resins, is used for the environment of acid or alkali.CMC, acrylic resin and this cross-linked material synthetic, material can form have better flexibility and intensity be insoluble in filming of water.According to the result of Hull Ke Lishi (Hercules) company research report, Kymene and hydroxyl, carboxyl reaction, but mainly still be and carboxyl reaction.
Thereafter, aluminum nitrate solution (as being lower than 5% weight concentration) is added in the emulsion, aluminum nitrate is used for deposit C MC in this CB prescription, last, will add mixture as the starch of packing material or the suspension of other particle again.
Resulting formulation for coating material have one be at least 30% highly filled.Its spread of viscosity possibility broad, in concrete the application, can be at an easy rate with reducing water content and/or using the CMC of viscosity higher to control viscosity, for airblade coating, dope viscosity is (under 100 rev/mins, use Brookfield viscometer, No. 4 bars are measured) be controlled at the 50-250 centipoise and be preferably between the 60-100 centipoise; Print roll coating, viscosity should be between the 50-120 centipoise; The scraper coating is between the 300-5000 centipoise; The bar type coating, the 50-600 centipoise.Used concrete viscosity depends on used coating apparatus and coating speed.
In embodiment preferably, compare with prior art, oil and dyestuff decentralized photo and CMC, the ratio of organic crosslinking agent continuous phase increases, and as in outstanding CB paper of the present invention, the quality of decentralized photo is compared with the situation of prior art has increased by 35%.
The coating of this prescription is coated in the back side of paper or other base material and drying, when being used for carbon-free copy system, typical coating weight about 3.00 restrain/square metre more than (dry weight).When base material was exerted pressure, chromonic materials was sent on lower floor's paper by oil, and colour development material that this paper scribbles above and leuco dye effect are showed coloured image at the corresponding site of exerting pressure.
The main component of coating of the present invention comprises the CMC of substitution value between 0.65-1.8, a kind of acrylic resin of film forming carboxylation, a kind of organic crosslinking agent and a kind of slaine.Usually, 100 parts of CMC(dry weights of every use), then mixture must contain 50-200 part acrylic resin, 10-150 part crosslinking agent, 300-1000 part oil and dye well 4.4-12.2 part slaine.But preferably per 100 parts of CMC should have 60-100 part film-forming resin, 60-100 part crosslinking agent, 600-800 part oil and dyestuff, 5-6 part slaine.As selecting the graininess filler for use, per 100 parts of CMC should use 100-500 part, are preferably 200-300 part.
Enforcement of the present invention can bring and compare very significant advantage with former prescription.Highly filled, low viscous CB coating can be used for the coating machine of fair speed and is easy to drying, thereby has saved a large amount of energy.Owing to can just can obtain same dry paint weight with less batch, so this prescription can improve the productivity ratio of coating.The whiteness of this coating is higher than former CMC base CB coating.Simultaneously owing to improved release efficiency, thereby can under low duplicating (writing) pressure, obtain image, in coating of the present invention, adopt CMC, the acrylic resin of carboxylation and crosslinking agent can be produced have the water soluble paint that can regulate steady flow in very wide range of viscosities.
The present invention can further be understood from following example, but it only plays illustration, and the present invention is not limited.
Example 1:
A kind of highly filled blue target CB coating is produced according to the following step, and all ratios are all used part (weight) expression.Prepare following solution.
Material part (weight)
Preparation liquid A
H 2O 920.00
Carboxymethyl cellulose 80.0
(substitution value 1.2, low viscosity) 1.
The solution that makes contains solid 8%
Preparation liquid B
Oil and dyestuff 2. 1820.0
The solution that makes contains solid 4.7%
Preparation liquid C
Starch filled suspension 3. 1000.0
The solution that makes contains solid 32.48%
1. " Na-CMC12UL " supplied by Hull Ke Lishi (Hercules) company.
2. preferably 820 parts of kerosene of deodorizing (by the supply of Pei Neiluo (Penreco) company) and 1000 parts of alkyl biphenyls (" Suresol290 " of Cork (Koch) chemical company) and crystal violet lactones, " Cohikem XI V " (supply of Hilton Davis (Hilton Davis) company) used together.
3. preferably moisture; " CMC-7H " (supply of Hull Ke Lishi (Hercules) company); Starch particulate (granularity is approximately the 10-25 micron).
120 parts of carboxylation polyethyl acrylate/methylmethacrylate copolymers (preferably " Carboset 514H ") are added among 1300 parts of preparation liquid A, and then 600 parts of preparation liquid B are added in the above-mentioned mixed liquor, and stir till becoming emulsion fully.Next step, (preferably " Kymene 557H ") joins in the emulsion with 100 parts of polyamide epichlorohydrin crosslinking agents, and then 170 parts of aluminum nitrate aqueous solutions (solids content is 1.4%) are slowly added in 1200.0 parts of above-mentioned emulsion.At this moment, solids coatings is 31%, and brookfield viscosity is 250 centipoises (78, PH is 5.9) in the time of 100 rev/mins.The granularity of emulsified oil droplet is the 2-10 micron.Adding 300 parts of preparation liquid C at last, is 32% thereby obtain a kind of solids content, and brookfield viscosity is the coating of 200 centipoises.
Example 2:
Follow these steps to prepare a kind of highly filled CB coating.
Prepare the method preparation of liquid A-C, 120 parts of polyethyl acrylate/methylmethacrylate copolymers are added among 670 parts of preparation liquid A, and then add 600 parts of preparation liquid B, and stir by example 1.Add 480 parts of polyamide-epichlorohydrin cross-linked agent again, in 1200 parts of emulsion, slowly add 190 parts of solids contents then and be 1.4% aluminum nitrate.This moment, the coating compound temperature was 78 °F, and PH is 5.6, and solid is that content is 35%, and Bu Shi is that viscosity is 100 centipoises, and the oil droplet granularity is the 2-10 micron.At last 340 preparation liquid C being added in the coating compound, is 35.4% thereby obtain solids content, and brookfield viscosity is 90 centipoises, stirs after 5 minutes, and viscosity reaches 120 centipoises.
Example 3
125 parts of carboxylation polyethyl acrylates/methylmethacrylate copolymer is added among 765 parts of preparation liquid A, and then add 900 parts of preparation liquid B, and stir it.Add 400 parts of polyamide-epichlorohydrin cross-linked agent again.Slowly add 160 parts of aluminum nitrate solutions (solids content is 1.4%) then in 1200 parts of emulsions that make, at this moment, the solids content of coating is that 42% viscosity is 160 centipoises, and PH is 78 of 5.8(temperature).The oil droplet granularity is the 2-10 micron.At last 220 parts of preparation liquid C being added in the coating compound, is 41% thereby obtain solids content, and viscosity is the coating of 130 centipoises.
Adopt that prepared coating dialogue chromogen paper on the Kohler coater of laboratory is coated with in the above example, the expection coating weight be the 4.8-5.2 gram/square metre, viscosity is above-mentioned measured value.The same coating of prior art that adopts compares test under identical coating weight.Problem for convenience of explanation, the contrast of the experimental data of coating experimental data in the example 3 and prior art coating is listed:
1, the release efficiency of colour former
Paper slip that scribbles test coating and the paper slip of accepting that scribbles developer are piled up, two overlapping like this paper slips are passed through between the press polish rod of pressure fixing.
Measure the reading of accepting the non-developing of paper district with the densitometer that reflectance meter is arranged.And after press polish 60 seconds, measure and accept the same reading in developing district on the paper.
The developing intensity that every kind of situation records (Image Intensity calculates with following method:
Developing intensity=developing district reading/non-developing district reading * 100%
(the developing intensity level is low more, and then developing is dense more strong more)
Result of the test is as follows: developing intensity
The coating 50.0 of prior art
The coating 45.6 of example 3
n=4
2, coating fades
The reflectance of uncoated body paper and test coating adopts Mai Nate (Minolta) II type chromascope to measure.In each experiment, 6 overlapping paper are placed under the measuring head, the test surfaces of every paper is all towards gauge head
The reading that obtains is as follows
L a b
Uncoated paper+94.000-0.65+4.45
Paper+93.200-1.65+9.9 with the coating of prior art coating
Paper+93.235-1.15+6.325 of use-case 3 coating coating
" a " " b " value that records is retouched in the accompanying drawing of this specification, and wherein, circle is represented uncoated paper, the paper that the square expression is coated with prior art coating, the coated paper of triangle typical example 3 coating.
Data show that coating coating than prior art aspect color of example 3 more approaches white body paper (this is desired).
The present invention can other forms implement under the prerequisite that does not deviate from its invention spirit, thereby has other embodiments in following claim scope.

Claims (25)

1, a kind of coated paper that is used for the pressure sensitivity recording element, it discharges a kind of chromonic materials under pressure, it is characterized in that this paper by layer of surface scribble a kind of adhesion, dry, coating weight greater than 3.00 grams/square metre composition, said composition is composed as follows:
Material umber (weight)
Carboxymethyl cellulose 100
Multivalent metal salt 4.4~12.2
Film forming carboxylated acrylic resin 50~200
Can with carboxymethyl cellulose and acrylic acid
The organic crosslinking agent 10~150 of resin reaction
Mineral material 100~500
Be dissolved in the chromophoric dyestuffs 300~1,000 in the oil solvent
The non-water substance content of said composition before using is for 30%(is heavy at least), and the brookfield viscosity under 78 ℃ is about 50~5000 centipoises.
2, by the coated paper of claim 1 regulation, the substitution value that it is characterized in that carboxymethyl cellulose wherein is 0.65-1.8.
3, by the coated paper of claim 1 regulation, it is characterized in that organic crosslinking agent wherein is polyamide-chloropropylene oxide.
4, by the coated paper of claim 1 regulation, it is characterized in that film forming acrylic resin wherein is the copolymer of the polyethyl acrylate/methymethacrylate of carboxylation.
5, by the coated paper of claim 1 regulation, it is characterized in that the quantity of described mineral matter wherein is enough to make non-water substance content to be at least 35%.
6,, it is characterized in that being dissolved in oily dyestuff percentage composition in the composition is 3%-12% by the coated paper of claim 1 regulation.
7, by the coated paper of claim 1 regulation, the substitution value that it is characterized in that carboxymethyl cellulose wherein is 1.1-1.5, and the viscosity of its 6% weightaqueous solution is less than 170 centipoises.
8, by the coated paper of claim 1 regulation, it is characterized in that containing following material:
Material umber (weight)
Carboxymethyl cellulose 100
Multivalent metal salt 5~6
Film forming carboxylated acrylic resin 60~100
Can with carboxymethyl cellulose and propylene
The organic crosslinking agent 60~100 of acid resin reaction
Particle filled composite 200~300
Be dissolved in the chromophoric dyestuffs 600~800 in the oil
CN85107728.5A 1985-06-12 1985-10-22 High solids content cb coating Expired CN1005700B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US74375685A 1985-06-12 1985-06-12
US743,756 1985-06-12

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CN85107728A CN85107728A (en) 1986-12-10
CN1005700B true CN1005700B (en) 1989-11-08

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CN85107728.5A Expired CN1005700B (en) 1985-06-12 1985-10-22 High solids content cb coating

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JP (1) JPS61284479A (en)
KR (1) KR910001575B1 (en)
CN (1) CN1005700B (en)
AU (1) AU560318B2 (en)
CA (1) CA1249436A (en)
DE (2) DE3534031A1 (en)
FI (1) FI853766L (en)
FR (1) FR2583343B1 (en)
GB (1) GB2176203B (en)
IN (1) IN165018B (en)
IT (1) IT1182632B (en)
NO (1) NO169332C (en)
SE (1) SE463966B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ATE168936T1 (en) * 1992-03-06 1998-08-15 Nashua Corp XEROGRAPHICALLY USABLE CARBON SET

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1280769A (en) * 1969-06-09 1972-07-05 Nashua Corp Pressure-sensitive record element
FR2461594A1 (en) * 1979-07-20 1981-02-06 Nashua Corp Backing layer for pressure sensitive recording material - comprises colour former, aluminium ions, urea-formaldehyde resin and CMC with specific substitution degree and viscosity

Also Published As

Publication number Publication date
SE8504229L (en) 1986-12-13
GB2176203A (en) 1986-12-17
NO169332B (en) 1992-03-02
DE3534031C2 (en) 1989-04-06
IN165018B (en) 1989-07-29
IT8567902A0 (en) 1985-10-24
IT1182632B (en) 1987-10-05
SE463966B (en) 1991-02-18
FI853766L (en) 1986-12-13
CN85107728A (en) 1986-12-10
GB2176203B (en) 1988-10-26
CA1249436A (en) 1989-01-31
NO853648L (en) 1986-12-15
FI853766A0 (en) 1985-09-30
NO169332C (en) 1992-06-10
AU4814485A (en) 1986-12-18
DE3546586C2 (en) 1989-04-20
GB8523276D0 (en) 1985-10-23
AU560318B2 (en) 1987-04-02
JPS61284479A (en) 1986-12-15
DE3534031A1 (en) 1986-12-18
SE8504229D0 (en) 1985-09-12
FR2583343B1 (en) 1988-09-30
KR870000178A (en) 1987-02-16
JPH0349757B2 (en) 1991-07-30
KR910001575B1 (en) 1991-03-16
FR2583343A1 (en) 1986-12-19

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