US3483048A - Process for preparing blocks of plastics material - Google Patents

Process for preparing blocks of plastics material Download PDF

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Publication number
US3483048A
US3483048A US498105A US3483048DA US3483048A US 3483048 A US3483048 A US 3483048A US 498105 A US498105 A US 498105A US 3483048D A US3483048D A US 3483048DA US 3483048 A US3483048 A US 3483048A
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US
United States
Prior art keywords
etching
polyoxymethylene
paste
acid
silicon dioxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US498105A
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English (en)
Inventor
Hans-Joachim Lenz
Willi Ott
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Hoechst AG
Original Assignee
Hoechst AG
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Filing date
Publication date
Application filed by Hoechst AG filed Critical Hoechst AG
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Publication of US3483048A publication Critical patent/US3483048A/en
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Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12Chemical modification
    • C08J7/14Chemical modification with acids, their salts or anhydrides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/06Solidifying liquids
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41CPROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C1/00Forme preparation
    • B41C1/02Engraving; Heads therefor
    • B41C1/025Engraving; Heads therefor characterised by means for the liquid etching of substrates for the manufacturing of relief or intaglio printing forms, already provided with resist pattern
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41NPRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
    • B41N1/00Printing plates or foils; Materials therefor
    • B41N1/12Printing plates or foils; Materials therefor non-metallic other than stone, e.g. printing plates or foils comprising inorganic materials in an organic matrix
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28HEAT EXCHANGE IN GENERAL
    • F28DHEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D7/00Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall
    • F28D7/04Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall the conduits being spirally coiled
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2359/00Characterised by the use of polyacetals containing polyoxymethylene sequences only
    • C08J2359/02Copolyoxymethylenes

Definitions

  • An etching paste which likewise provides good results consists of aqueous sulfosalicylic acid, a non-ionic wetting agent and pyrogenically produced silicon dioxide.
  • a third paste found to be effective consists of ammonium salts of castor oil sulphuric acid esters containing silicon dioxide in quantities sufiicient to form a paste.
  • the present invention relates to a blocks of plastics material.
  • polyoxymethylenes are understood the known polymers of formaldehyde or trioxane and the copolymers of formaldehyde or trioxane which contain up to by weight of cyclic ethers or formals, for example, diglycol formal, dioxolane, butane diol formal, tetrahydrofurane or ethylene oxide.
  • the desired images to be printed are first covered in known manner with acidproof varnishes. With these varnishes drawings can be made directly on the block material. Other known methods of transmission, for example, photomechanical transmission, may also be applied. According to the desired depth of etching the etching may be carried out in one or several stages.
  • acids may be used inorganic acids such as phosphoric acid, organic acids such as sulfosalicylic acid or compounds that react as acids at the elevated reaction temperatures only, for example, the ammonium salts of castor oil sulfuric acid esters (Turkey-red oil) which at an elevated temperature act as acids while splitting oif ammonia.
  • Solid acids are dissolved in water or mixtures of process for preparing 3,483,048 Patented Dec. 9, 1969 water and solvents that are miscible with water before the thickening fillers are added. They are preferably dissolved in the presence of wetting agents.
  • acidproof non-ionic products for example, reaction products of tributyl phenol and ethylene oxide.
  • Suitable fillers are acidproof inorganic fillers, for example, titanium dioxide, barium sulfate or chromium-III- oxide, pyrogenically prepared silicon dioxide being particularly suitable.
  • the etching pastes according to the invention are thickened with about 5% of pyrogenically produced silicon dioxide and may be applied to the polyoxymethylene plates by means of a brush or spatula.
  • the etchings obtained are very exact since even at an elevated temperature 'the thickened pastes do not spread in an undesired way but penetrate vertically into the parts of plastics material to which they have been applied, thus etching out the images to be printed.
  • the etching pastes are caused to act at a temperature within the range of 40 C. to the melting point of the polymer, preferably of 70 C. to 150 C. Due to the application of heat the etching times are within the range of 5 to minutes, preferably 10 to 30 minutes, depending on the depth of etching.
  • the paste may be brought to the consistency which is most favorable with regard to the kind of its application. Since the etching is carried out at an elevated temperature less aggressive acids which consequently can be handled more easily may be used.
  • etching pastes When etching pastes are used they cover both the bottom and the flanks of the image that has been worked out, the cross-section of the image thus having the form of a U. In the usual metal etching processes this can only be brought about by means of the so-called flank protection.
  • Another advantage of the etching paste is that a previous etching can, if necessary, be corrected by etching certain parts of a block again. In such a case it is not necessary to cover the block additionally as has to be done when liquid acids are used. Particularly suitable for this purpose are the ammonium salts of castor oil sulfuric acid esters which owing to their neutral character can be handled particularly well at' room temperature.
  • a special advantage of the etching pastes based on sulfosalicylic acid is that even at room temperature these pastes attack the known copying layers based on polyvinyl alcohol to such a slight extent only that the covered parts are not etched.
  • the blocks which have thus been prepared have an excellent hardness, a good toughness, a high scratch resistance and a low degree of abrasion. Their dimensional stability is independent of the atmospheric moisture. Owing to their flexibility thin plates may be laid around cylinders as is usually done in flexography. The hardness of the material enables very sharp prints to be obtained.
  • the etching process also enables very fine lines or characters to be transmitted.
  • the resistance to solvents is very good. Blocks of polyoxymethylene or copolymers of trioxane can practically be used for all printing inks.
  • EXAMPLE 1 An etching paste consisting of phosphoric acid of 85% strength and containing 5.5% of pyrogenically prepared silicon dioxide was applied by rolling to an extruded plate of polyoxymethylene which had a thickness of 1.75 millimeters and which at the places which were intended to produce the print was covered with an acidproof varnish.
  • the layer of etching paste applied had a thickness within the range of about 0.005 to 0.01 millimeter. Etching was carried out for minutes at a temperature within the range of 80 C. to 100 C. After washing with water and removal of the coating varnish a block having neat contours was obtained.
  • the etching paste was caused to react at 100 C. for a period of 15 to minutes. After cooling, the remaining portions of the etching paste and the coating were removed with water. An autotypy having sharp contours and a depth of etching of 0.005 to 0.1 millimeter was obtained.
  • EXAMPLE 3 In the manner described in Example 2 a line etching was produced on an injection-molded plate, 1 mm. thick, of polyoxymethylene. In order to increase the depth of relatively large parts of the plate which lay free and which were not intended to produce prints an etching paste prepared from ammonium salts of castor oil sulfuric acid esters (Turkey-red oil) and containing 7% of pyrogenically produced silicon dioxide was applied by means of a brush. The etching paste was caused to react at 150 C. Within 15 minutes an etching depth of about 0.05 millimeter and after minutes an etching depth of 0.1 millimeter was obtained. After cooling, the plate was washed with methyl alcohol.
  • a process for preparing thin printing plates of polyoxymethylene by acid etching comprising the steps of: applying, by screen printing technique, 0.005 to 0.01 millimeter of an etching paste consisting essentially of aqueous phosphoric acid with 5.5 percent by weight pyrogenically prepared silicon dioxide to a surface of said polyoxymethylene; etching said polyoxymethylene therewith at a temperature of 80 C. to C.; and removing said etching paste from etched polyoxymethylene.
  • a process for preparing thin printing plates of polyoxymethylene by acid etching comprising the steps of: applying, by screen printing techniques, an etching paste consisting essentially of 4.5 parts Water, 65 parts sulfosalicylic acid, 21.5 parts of the reaction product of one mole of tributyl phenol and 8 moles of ethylene oxide, and 8.2 parts of pyrogenically produced silicon dioxide to a surface of polyoxymethylene; etching said polyoxymethylene therewith at 100 C. for 15 to 30 minutes; and removing said etching paste from etched polyoxyrnethylene.
  • a process for preparing thin printing plates of polyoxymethylene by acid etching comprising the steps of: applying an etching paste consisting essentially of 93% of at least one ammonium salt of a castor oil sulfuric acid ester and 7% of pyrogenically produced silicon dioxide to a surface of polyoxymethylene; etching said polyoxymethylene therewith at C.; and removing said etching paste from etched polyoxymethylene.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Manufacture Or Reproduction Of Printing Formes (AREA)
  • ing And Chemical Polishing (AREA)
  • Printing Plates And Materials Therefor (AREA)
US498105A 1964-12-12 1965-10-19 Process for preparing blocks of plastics material Expired - Lifetime US3483048A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEF44685A DE1213857B (de) 1964-12-12 1964-12-12 Verfahren zur Herstellung von Kunststoff-Klischees

Publications (1)

Publication Number Publication Date
US3483048A true US3483048A (en) 1969-12-09

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US498105A Expired - Lifetime US3483048A (en) 1964-12-12 1965-10-19 Process for preparing blocks of plastics material

Country Status (9)

Country Link
US (1) US3483048A (de)
AT (1) AT266877B (de)
BE (1) BE673653A (de)
CH (1) CH456644A (de)
DE (1) DE1213857B (de)
DK (1) DK120642B (de)
FR (1) FR1460225A (de)
GB (1) GB1123418A (de)
NL (1) NL6515762A (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3837882A (en) * 1971-09-02 1974-09-24 Kewanee Oil Co Optical bodies with non-epitaxially grown crystals on surface

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3235426A (en) * 1961-08-01 1966-02-15 Du Pont Method of rendering thermoplastic resins receptive to coatings
US3248271A (en) * 1961-05-08 1966-04-26 Celanese Corp Shaped oxymethylene thermoplastic polymer and method of surface treating same
US3255060A (en) * 1963-10-25 1966-06-07 Hoechst Ag Process of treating surfaces of shaped articles of polyacetals with camphorsulfonic acid

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3248271A (en) * 1961-05-08 1966-04-26 Celanese Corp Shaped oxymethylene thermoplastic polymer and method of surface treating same
US3235426A (en) * 1961-08-01 1966-02-15 Du Pont Method of rendering thermoplastic resins receptive to coatings
US3255060A (en) * 1963-10-25 1966-06-07 Hoechst Ag Process of treating surfaces of shaped articles of polyacetals with camphorsulfonic acid

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3837882A (en) * 1971-09-02 1974-09-24 Kewanee Oil Co Optical bodies with non-epitaxially grown crystals on surface

Also Published As

Publication number Publication date
DE1213857B (de) 1966-04-07
CH456644A (de) 1968-07-31
BE673653A (de) 1966-06-13
GB1123418A (en) 1968-08-14
AT266877B (de) 1968-12-10
DK120642B (da) 1971-06-28
NL6515762A (de) 1966-06-13
FR1460225A (fr) 1966-11-25

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