US3615556A - Hydrophobic film coated with acid-modified butadiene copolymer - Google Patents
Hydrophobic film coated with acid-modified butadiene copolymer Download PDFInfo
- Publication number
- US3615556A US3615556A US829807A US3615556DA US3615556A US 3615556 A US3615556 A US 3615556A US 829807 A US829807 A US 829807A US 3615556D A US3615556D A US 3615556DA US 3615556 A US3615556 A US 3615556A
- Authority
- US
- United States
- Prior art keywords
- film
- acid
- copolymer
- coated
- percent
- 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
Links
Classifications
-
- 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
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L13/00—Compositions of rubbers containing carboxyl groups
- C08L13/02—Latex
-
- 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
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
-
- 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
- C08J7/04—Coating
- C08J7/056—Forming hydrophilic coatings
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
- G03C1/795—Photosensitive materials characterised by the base or auxiliary layers the base being of macromolecular substances
- G03C1/7954—Polyesters
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
- G03C1/91—Photosensitive materials characterised by the base or auxiliary layers characterised by subbing layers or subbing means
- G03C1/93—Macromolecular substances therefor
-
- 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
- C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2427/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
-
- 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
- C08J2455/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2423/00 - C08J2453/00
- C08J2455/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/27—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]
- Y10T428/273—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.] of coating
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31725—Of polyamide
- Y10T428/3175—Next to addition polymer from unsaturated monomer[s]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31725—Of polyamide
- Y10T428/3175—Next to addition polymer from unsaturated monomer[s]
- Y10T428/31754—Natural source-type polyamide
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31786—Of polyester [e.g., alkyd, etc.]
- Y10T428/31797—Next to addition polymer from unsaturated monomers
Definitions
- a hydrophobic film is coated with an ethylenically unsaturated carboxylic acid-modified butadiene copolymer.
- the coated film is coated with gelatin and/or light-sensitive gelatine silver halide emulsion layer.
- This invention relates to film base materials suitable for use, inter alia, as base materials for photographic films carrying a coating of a gelatino silver halide photographic emulsion.
- the anchorage may be improved by the introduction, between the film support and the hydrophilic layer applied thereto, of one or more interlayers of suitable filmforming polymeric materials.
- Many such proposals have been made in the past and have met with varying degrees of success. It is an object of the present invention to provide a film base which comprises a hydrophobic film support having a layer coated thereon and which is adapted to receive a hydrophilic coating and thereby to establish an assembly of which the layers are very strongly anchored together.
- a coated film base material which comprises a support film of synthetic film-forming material of hydrophobic character and superimposed thereon a layer of a composition comprising a copolymer of (1) butadiene, (2) an ethylenically unsaturated carboxylic acid, and (3) at least one other ethylenically unsaturated monomer copolymerisable therewith, the said copolymer containing from 18 to 70 percent by weight of butadiene units and from 0.5 to 20 percent by weight of units of the ethylenically unsaturated carboxylic acid.
- the support film may be of any plastics material, especially such materials as are highly hydrophobic, examples being films consisting essentially of polyolefines such as polyethylene, polypropylene, poly-4-methyl pentene-l, and copolymers of such olefines with each other or with other ethylenically unsaturated monomers, polyesters such as polyethylene terephthalate and synthetic linear polycarbonates, and cellulose derivatives such as cellulose diacetate or triacetate or acetobutyrate.
- the support film may be molecularly oriented in one or two directions in its plane before and/or after the application of the anchoring layer thereon. It may also be heat set.
- the invention is of particular value where the film material is biaxially oriented and heat set polyethylene terephthalate both because that material has physical and chemical properties rendering it particularly suitable for the production of photographic materials and because, being highly hydrophobic, the advantages achieved by the present invention are achieved to excellent effect.
- the surface of the film may be subjected to a treatment designed to render it somewhat more capable of readily accepting the copolymer coating.
- a treatment designed to render it somewhat more capable of readily accepting the copolymer coating will vary, of course, with the film material in use but in the case of materials such as the polyolefines the film may be usefully subjected to a high-voltage stress accompanied by corona discharge (commonly referred to as C-treatment) or subjected to treatment with strong oxidizing agents such as fuming sulfuric acid, nitric acid, potassium dichromate or the like.
- C-treatment corona discharge
- strong oxidizing agents such as fuming sulfuric acid, nitric acid, potassium dichromate or the like.
- the film material is polyethylene terephthalate a useful effect is obtained by pretreatment with trichloracetic acid or a halogenated phenol.
- treatment with the organic materials just mentioned may be effected simultaneously with the application of the copolymer layer by including such
- the base film material is oriented.
- the copolymer anchor coat may be applied before the orientation is completed and in this case, pretreatment of the base film surface is not normally necessary.
- This method also has the advantage that very thin coatings may be applied uniformly to the base film.
- coat weights of from 0.8 mg./dm. to 4.0 mg./dm. of the biaxially oriented film may be applied in this way.
- the copolymer used in the present invention is a copolymer of three monomeric materials. Of these one is butadiene, which must be present in a proportion of 18 to 70 percent by weight of the final copolymer.
- the second monomer is an ethylenically unsaturated acid and examples are acrylic acid, methacrylic acid, fumaric acid, itaconic acid, maleic acid and crotonic acid. It is to be understood that in the production of the copolymer the anhydrides of such acids may be used instead of the acids themselves.
- the third component is another ethylenically unsaturated monomer and may be, for example, styrene, a-methyl styrene, methyl methacrylate or acrylonitrile.
- the proportion of butadiene in the copolymer may vary (within the limits of 18 to 70 percent by weight referred to above) in dependence on the nature of the other monomers present, and in dependence on the properties required in the coated film which in turn may depend on whether it is to be immediately coated with a further coating e.g., based on gelatin or whether it will first be reeled.
- a further coating e.g., based on gelatin or whether it will first be reeled.
- the proportions of butadiene is too great, particularly when the third component of the copolymer is styrene or methyl methacrylate, the composition may become too soft and give rise (when coated on to film material) to a final film base which shows the phenomenon of blocking, e.g., when wound on a reel.
- concentrations of butadiene in the range 18-30 percent.
- concentrations of from 30 percent to 60 percent preferably from 32 percent to 40 percent by weight of butadiene may be used and are indeed preferred because of the better film-forming properties of the resultant composition.
- the third component is acrylonitrile.
- higher proportions of butadiene e.g., 50 to 70 percent generally afford the best results.
- a preferred copolymer contains, in addition to the butadiene and the third component, from I to 7 percent itaconic acid, optionally with up to Spercent of another ethylenically unsaturated carboxylic acid.
- the copolymer may be applied to the film material by any conventional coating technique and is preferably applied in the form of an aqueous latex, the aqueous medium being dried off, e.g. in an oven at a temperature above C.
- the aqueous latex may contain additives for special purposes, e.g.
- Wetting agents and emulsifiers for imparting stability and wettability e.g. sodium lauryl sulfate, nonyl phenol ethylene oxidecondensate, and cetyl trimethyl ammonium bromide.
- Colloid stabilisers e.g. gelatin, polyvinyl pyrolidone and polyvinyl alcohol.
- Adhesion promoters e.g. chlorophenols, resorcinol and trichloracetic acid.
- Cross-linking agents e.g. hexamethoxy methyl melamine.
- the coated film base as defined will accept with good anchorage a more hydrophilic layer such as a thin layer comprising gelatin which has been applied from an organic solvent or aqueous dispersion.
- the organic solvent or aqueous dispersion of gelatin may also contain at least one synthetic polymer or resin, adhesion promotors and cross-linking agents.
- a light- EXAMPLE 1 Biaxially oriented polyethylene terephthalate was coated with a solution of S-methyl -4- chlorophenol in methanol and dried for 2minutes at 80 C.
- EXAMPLE 2 An aequeous latex containing a copolymer of butadiene, styrene and itaconic acid 38:58:4parts by weight, was applied to polyethylene terephthalate film which had been stretched longitudinally. After drying, the coated film was stretched sideways by a factor of 3 at 100 C. and heat set at a temperature of2l0 C. for lminute.
- a gelatin layer was then applied as in example 1.
- the film blocked if reeled prior to the application of the gelatin layer.
- EXAMPLE 3 An aqueous latex containing a copolymer of butadiene, styrene and itaconic acid 20:75:5parts by weight, was applied to polyethylene terephthalate film which had been stretched longitudinally. After drying the coated film was stretched sideways by a factor of 3at 1 10 C. and heat set at a temperature of 210 C. for lminute. The weight of the coating on the biaxially drawn and heat-set film was 1.5 mg;/dm.. The resultant film was capable of being reeled without any blocking occurring at room temperature, and was so reeled. A gelatin layer of the type described in example lwas then applied to the film.
- a photographic gelatino silver halide emulsion coating was applied directly on the top coating of the film products of examples l, 2 and 3.
- the layers were strongly adherent to one another and to the film support so that the final photographic film could be processed without danger of separation of the layers or frilling.
- a coated film material which comprises a support film oi biaxially oriented and heat-set polyethylene terephthalate and superimposed thereon a layer of a composition comprising a copolymer of l) butadiene, (2) an ethylenically unsaturated carboxylic from the group consisting of itaconic acid, methacrylic acid and acrylic acid and (3) at least one other ethylenically unsaturated monomer copolymerisable therewith, the said copolymer containing from l8to per cent by weight of butadiene units and from 0.5 to 20 percent by weight of units of the ethylenically unsaturated c arboxylic acid.
- a coated film material according to claim 1 including a light-sensitive gelatin layer on said copolymer layer.
- a coated film material according to claim I in which said copolymer contains from l8 30 30percent by weight of butadiene units.
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Laminated Bodies (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB3002968 | 1968-06-24 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3615556A true US3615556A (en) | 1971-10-26 |
Family
ID=10301122
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US829807A Expired - Lifetime US3615556A (en) | 1968-06-24 | 1969-06-02 | Hydrophobic film coated with acid-modified butadiene copolymer |
US00142407A Expired - Lifetime US3775160A (en) | 1968-06-24 | 1971-05-11 | Hydrophobic film coated with acid-modified butadiene copolymer |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US00142407A Expired - Lifetime US3775160A (en) | 1968-06-24 | 1971-05-11 | Hydrophobic film coated with acid-modified butadiene copolymer |
Country Status (10)
Country | Link |
---|---|
US (2) | US3615556A (ru) |
BE (1) | BE734703A (ru) |
CA (1) | CA929430A (ru) |
CH (1) | CH503293A (ru) |
DE (1) | DE1930462B2 (ru) |
GB (1) | GB1264955A (ru) |
LU (1) | LU58899A1 (ru) |
NL (1) | NL161269C (ru) |
SE (1) | SE352966B (ru) |
ZA (1) | ZA693889B (ru) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3775160A (en) * | 1968-06-24 | 1973-11-27 | Ici Ltd | Hydrophobic film coated with acid-modified butadiene copolymer |
US4265946A (en) * | 1978-11-13 | 1981-05-05 | Fuji Photo Film Co., Ltd. | Process for forming a subbing layer on a plastic support |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1278924A (en) * | 1970-02-06 | 1972-06-21 | Ici Ltd | Improvements in synthetic film materials |
GB1540067A (en) * | 1975-09-26 | 1979-02-07 | Bexford Ltd | Coated film bases |
GB2040223B (en) * | 1978-12-27 | 1983-05-25 | Asahi Chemical Ind | Laminate with inerlaminate adhesion |
JPS5849944A (ja) | 1981-09-04 | 1983-03-24 | Konishiroku Photo Ind Co Ltd | カラ−写真感光材料 |
US4542093A (en) * | 1983-07-26 | 1985-09-17 | Fuji Photo Film Co., Ltd. | Photographic silverhalide material containing two subbing layers |
GB8911065D0 (en) * | 1989-05-15 | 1989-06-28 | Ici Plc | Polymeric film |
EP0559244B1 (en) * | 1992-02-29 | 1998-04-22 | Agfa-Gevaert N.V. | Primed resin film |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1088906A (en) * | 1964-12-09 | 1967-10-25 | Bexford Ltd | Synthetic film materials |
GB1264955A (ru) * | 1968-06-24 | 1972-02-23 |
-
1968
- 1968-06-24 GB GB3002968A patent/GB1264955A/en not_active Expired
-
1969
- 1969-05-30 CA CA053145A patent/CA929430A/en not_active Expired
- 1969-05-30 ZA ZA693889*A patent/ZA693889B/xx unknown
- 1969-06-02 US US829807A patent/US3615556A/en not_active Expired - Lifetime
- 1969-06-16 DE DE19691930462 patent/DE1930462B2/de not_active Ceased
- 1969-06-16 NL NL6909131.A patent/NL161269C/xx not_active IP Right Cessation
- 1969-06-17 BE BE734703D patent/BE734703A/xx not_active IP Right Cessation
- 1969-06-18 LU LU58899D patent/LU58899A1/xx unknown
- 1969-06-23 SE SE08877/69A patent/SE352966B/xx unknown
- 1969-06-24 CH CH967569A patent/CH503293A/de not_active IP Right Cessation
-
1971
- 1971-05-11 US US00142407A patent/US3775160A/en not_active Expired - Lifetime
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3775160A (en) * | 1968-06-24 | 1973-11-27 | Ici Ltd | Hydrophobic film coated with acid-modified butadiene copolymer |
US4265946A (en) * | 1978-11-13 | 1981-05-05 | Fuji Photo Film Co., Ltd. | Process for forming a subbing layer on a plastic support |
Also Published As
Publication number | Publication date |
---|---|
CA929430A (en) | 1973-07-03 |
US3775160A (en) | 1973-11-27 |
BE734703A (ru) | 1969-12-17 |
NL161269B (nl) | 1979-08-15 |
CH503293A (de) | 1971-02-15 |
DE1930462A1 (de) | 1970-01-02 |
NL161269C (nl) | 1981-11-16 |
DE1930462B2 (de) | 1978-02-23 |
GB1264955A (ru) | 1972-02-23 |
LU58899A1 (ru) | 1969-11-12 |
ZA693889B (en) | 1971-01-27 |
NL6909131A (ru) | 1969-12-30 |
SE352966B (ru) | 1973-01-15 |
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