FR2524477A1 - BONDING PROCESS - Google Patents

Abstract

THE INVENTION RELATES TO A PROCESS FOR BONDING AN ARTICLE AND A POLYMER FILM (OR SHEET), WHICH CONSISTS OF INTERPOSING A LIQUID SUBSTANCE BETWEEN THE ARTICLE AND THE POLYMER FILM AND GLUING THE ARTICLE AND THE POLYMER FILM THROUGH THE LIQUID SUBSTANCE TO POLYMERIZE THE LIQUID SUBSTANCE BY BONDING SO STRONGLY THE ARTICLE AND THE POLYMER FILM. ACCORDING TO THE INVENTION, THE LIQUID SUBSTANCE INCLUDES AT LEAST ONE PRODUCT CHOSEN FROM VINYL MONOMERS AND OLIGOMERS WHICH DISSOLVE OR SWELL THE SURFACE PORTION OF THE POLYMER FILM, THUS CONFIRMING THE STICKY POWER OF THE POLYMERIC SUBSTANCE OR CONTAINER, THE LIQUID. ONE POLYMERIZATION INDUCER AND THE OTHER CONTAIN A POLYMERIZATION ACCELERATOR.

Description

The present invention relates to a method for firmly bonding a

  single-layer polymer film (or sheet) or composite polymer film comprising the polymer film (or sheet) having on one side a decorative material on the surface of an article at room temperature. Various types of adhesives are known for bonding two articles of different types or of the same type to one another, for example: reaction-curable type adhesives, which are

  liquids at room temperature; glues of the type to be activated

  by water, solvent or heat; glues of the volatile solvent type; etc. U.S. Patent No. 2,331,894 discloses Type A solvent-activated adhesives, and Irving Skeist described in Reinhold Publishing Corporation's Handbook of Adhesives, reaction curable type adhesives.

  (pages 298-343), water-activating type adhesives (pages 574-

  583), glues of the heat-activating type (pages 447-451) and glues of the volatile solvent type (pages 434-446). However, these glues have the disadvantage that the initial adhesion strength is insufficient and complicated gluing operations are necessary. These glues give rise to various problems of

  environmental pollution and safety.

  Reaction-curable adhesives require a heater, and self-cure adhesives which are an improvement to reaction-curable adhesives have a short pot life. Water-activated or solvent-activated adhesives and solvent-type adhesives have a short duration of the sticky state In solvent-based glues, the volatile solvent evaporates in the air, resulting in a pollution of

  the environment and the dangers of poisoning.

  Water-absorbing water absorbs water vapor after solidification, which decreases adhesion strength Heat-activated adhesives can only be applied to heat-resistant gluing articles and their adhesive strength decreases. considerably when exposed to high temperatures,

even after their solidification.

  Other pressure-sensitive glues, which are markedly different from the glues described above and which can establish the bonding of the film to the desired article or the gluing of two articles by a simple pressure bonding, are widely used as described. in U.S. Patent No. 3,738,971 and by LF Martin, Pressure Sensitive Adhesive Formulations and Technology, Noyes Data Corporation These adhesives have excellent initial adhesion strength and excellent bond strength (similar to creep) in comparison with the adhesives described above, but they have

  the disadvantage that the cohesive force does not tend to increase.

  The object of the invention is to propose a new

  gluing process, in which sufficient tackiness is achieved.

  In the initial stage of sticking to retain the article, high adhesion strength is obtained over a large bonding surface and no release of toxic substances during

the bonding operation.

  Still another object of the invention is to provide a method for adhering an article and a polymer film (or sheet) which comprises interposing a liquid substance between the article and the polymer film and adhering the article and the polymer film through the liquid substance to polymerize

  the liquid substance by strongly bonding the article and the film

  wherein the liquid substance comprises at least one product selected from vinyl monomers and oligomers which dissolve or swell the surface portion of the polymer film thereby imparting stickiness;

  polymer or the liquid substance contains a polymerization inducer

  and the other contains a polymerization accelerator.

  According to one embodiment, the method according to the invention is a method for bonding a self-supporting polymer film and an article, which consists in applying a liquid substance at least on the surface of the film or on that of the article. and adhering them to polymerize the liquid substance, said liquid substance comprising at least one product selected from vinyl monomers and oligomers which dissolve or swell the surface portion of the film to make the surface tacky, any of the film of liquid substance containing a

  polymerization inducer, while the second contains an accelerator

polymerization reactor.

  In accordance with the bonding process, the liquid substance dissolves or swells the surface portion of the film for

  make it sticky and it is polymerized by the action of the induc-

  polymerization accelerator and the polymerization accelerator to form a two-phase microscopic structure consisting of a polymer portion derived from the polymer film and a polymerized product (or cured product) derived from the liquid substance on the

  interfacial portion between the polymer film and the article.

  As a result, a strong bond (bonding) is established between the polymer film and the article.

  according to the invention is interesting for gluing the film of poly-

  mother on items for protection, to prevent corrosion

  and for the decoration of the surface of the articles.

  Another embodiment of the invention is a method for adhering to an article a polymer film carrying a decorative material on one side, so that the face of the film not carrying the decorative material is turned towards the surface. article In the case of this decorative film, the support film constitutes a part of the adhesive material for bonding the material

decorative on an article.

  Examples of decorative materials used according to the invention include papers, nonwovens,

  woven fabrics, films, sheets, ribbons or film

  foils or expanded sheets of rubber or synthetic resin foils or metal plates, etc. The surface of the polymer film on which the decorative material is attached may be subjected to a treatment of

  such as the application of an undercoat with a composition

  primer or corona discharge treatment to increase

  the adhesion between the polymer film and the decorative material.

  Examples of vinyl monomers and oligomers

  The mothers used according to the invention comprise the mono-

  Functional and polyfunctional which can be polymerized by the reactive radicals produced by decomposition of the polymerization inducer. Examples of monofunctional vinyl monomers are the following: (meth) acrylates of alkyl or cycloalkyl such as methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylate

  n-butyl, isobutyl (meth) acrylate, cyclo (meth) acrylate

  hexyl, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate or lauryl (meth) acrylate; vinyl acetate; propionate of

  vinyl; (Mnéth) acrylonitrile; styrene; vinyltoluene, (meth) acid

  acrylic; (meth) acrylic acid hydroxyesters such as

  2-hydroxyethyl or 2-hydroxypropyl (meth) acrylate; the (meth) -

  glycidyl acrylate; diethylaminoethyl (meth) acrylate, etc.

  Examples of polyfunctional vinyl monomers

  These include diesters of ethylene glycol or propylene

  glycol (meth) acrylic acid, such as di (meth) acrylate

  ethylene glycol, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolpropane tetra (meth) acrylate, and the like.

  Examples of monofunctional oligomers include

  Mono (meth) acrylate polyester obtained by reacting a polyester resin and (meth) acrylic acid, etc., are used.

  Examples of polyfunctional oligomers include

  polyethylene glycol di (meth) acrylate; epoxy (meth) acryl

  lates obtained by the reaction of an epoxy resin and (eth) acrylic acid; urethanne- (meth) acrylates obtained by the reaction of a polyisocyanate and a hydroxyalkyl meth) acrylate polyester or polyether-di (meth) acrylatesobtained by the reaction of a Tsinedepolyesteroudepolyether with (meth) acrylic acid, etc. The liquid substance consists of at least one compound

  chosen from the vinyl and oligomeric monomers described above.

  From the point of view of the coating operation, the liquid substance has a viscosity of 0.001 to 10 Pa S (from 0.01 to 100 poise, measured by means of a BL type viscometer manufactured by Tokyo Keiki Co) preferably 0.001 to 5 Pa S (0.01 to 50 poises) The liquid substance is applied to the interface between the polymer film and the article in an amount of 1/100 to 5 times, preferably 1/10 at

  3 times the weight of the polymer film.

  The film (or sheet) of polymer is such that its surface portion is dissolved or swollen by the liquid substance composed of the vinyl monomer and / or the vinyl oligomer described above to activate it and, after the polymerization of the substance liquid, it forms at the interface of the film and

  the article a two-phase microscopic structure made up of a

  of the polymer derived from the polymer film and a product

  polymerized (or hardened product) is derived from the liquid substance.

  Examples of polymer films include

  films (or sheets) of rubbers such as natural rubber

  rel, isoprene rubber, chloroprene rubber, nitrile rubber, butadiene-styrene rubber, acrylic rubber or polyester resin, synthetic resins such as chlorosulfonated polyethylene resin, polybutyral resin, polyacrylic resin, polyether resin, resin polyamides or polyurethane resin Examples of polymer films

  further include foamed films, synthetic papers

  ticks, woven and non-woven fabrics, rubbers and / or

  synthetic resins described above The film has a thick

  5 to 5000 pum Among these materials, dandruff is preferred

  or flakes of polyester resins, chlorinated polyethylene resins

  Sulfone and polyacrylic resins These polymer films may carry the decorative material described above adhering to

  one of their faces The polymer film may contain

  lable at least one product selected from vinyl monomers and oligomers in an amount of 20% by weight or less based on the weight of the film, to accelerate the dissolution or swelling

of the film.

  The polymerization inducer which is incorporated in either the liquid substance or the polymer film is a

  polymerization inducer which decomposes by a reaction of oxidation

  reduction of the polymerization accelerator to produce

  reactive radicals, which polymerize the liquid substance.

  examples of polymerization inductors

  organic peroxides, such as methyl peroxide,

  ethylcetone or benzoyl peroxide; the hydroxyperoxides

  such as cumene hydroperoxide, etc. The polymerization inducer is incorporated either in the liquid substance or in the polymer film in an amount of from 0.01 to 10% by weight, preferably from 0.1 to 5% by weight. by weight, in relation to the substance

  liquid or polymer film.

  The system containing the polymerization inductor

  may further contain a polymerization inhibitor such as hydrogen

  quinone, hydroquinone monomethyl ether, methylhydroquinone, pbenzoquinone, catechol, phenothiazine picrate, 4-butylcatechol, 2-butyl-4-hydroxyanisole or 2,6-di-tert-butyl-p-cresol, in amounts

  1/10 or less of the weight of the polymerization inducer.

  The liquid substance or polymer film to which the polymerization inducer is not added contains a polymerization accelerator which breaks down the polymerization inducer by an oxidation-reduction reaction to produce

reactive radicals.

  Examples of polymerization accelerators

  include dimethylaniline, dimethyl-p-toluidine, di-

  ethyl-p-toluidine, diisopropanol-p-toluidine, cobalt naphthenate, copper naphthenate, zinc naphtenate, thiourea,

  acetylthiourea, sodium ascorbate and a condensate of n-butyl

  raldehyde and aniline, vanadium pentoxide etc. Accelerating

  can be used alone or as a mixture.

  The amount of the polymerization accelerator is 0.1 to 10% by weight, relative to the liquid substance or

  to the polymer film that does not contain the poly-inducer

  If the amount is less than 0.1% by weight, no addition effect can be obtained and, if the quantity is greater

  at 10% by weight, the adhesion strength decreases.

  The polymer film, the liquid substance or the decorative material may contain a filler, a plasticizer, an anti-aging agent, an anti-mildew agent, an antioxidant, an ultraviolet absorber, an anti-ozone agent, an agent anticorrosion, pigment, dye, etc., in quantity

appropriate according to the desired object.

  The bonding method according to the invention is applied to bonding a film (or sheet) of polymer to structures such as steel structures or building structures of sheet articles, such as metal foils, plastic sheets , rubber sheets or glass plates, or similar materials for purposes of protection, against corrosion, for waterproofing, decoration or display For bonding by the process according to the invention, the liquid substance containing the polymerization inducer at least on the polymer film or the article for dissolving or swelling the

  surface of the polymer film and thus make its surface col-

  the adhesive surface of the polymer film is uniformly applied to the surface of the article and the liquid substance is polymerized at room temperature (for example, about -25 ° C.). To accelerate the polymerization, it is possible to heat the laminate at 40 ° C for 1 to 700 min. This gluing process can also be applied to a film or sheet of polymer having on one side a decorative material to achieve a strong bond between the film of

polymer and the article.

  According to the bonding method of the invention, the

  liquid and the film dissolved or swollen by it

  synergistically enhance the wettability of the article by

  Thus, the bonding surface and the bonding interface have a two-phase microscopic structure composed of a polymer obtained by polymerization of the liquid substance and a polymer portion of the polymer film. high adhesion strength which is not diminished even in

  an environment with high temperature and humidity.

  The following examples illustrate the invention without, however, limiting its scope. In these examples, the percentages, parts, ratios and the like are all by weight.

  measurement of the shear adhesion strength, when the resistance

  the test specimen is less than the adhesion strength,

  the shear adhesion strength is measured after

  the test piece with a reinforcing material.

EXAMPLE 1

  A mixture of 100 parts of a polybuzyr resin is dissolved (degree of polymerization: about 870, butyral content: 72 mole%, modulus of elasticity: 1200 M Pa, elongation at break: 20%, content in acetyl groups: 5 mole%)

  and 3 parts dimethyl-p-toluidine in ethanol solvent mixture.

  toluene 2: 8 to prepare a 50% solution. The solution is applied to a separable paper and dried at 60 ° C. for 10 minutes to obtain a film of resin of polyurethane having a solubilization.

dry thickness of 100 μm.

  A liquid substance is prepared from 50 parts

  methyl acrylate, 50 parts of ethyl methacrylate and

2 parts of benzoyl peroxide.

  The polybutyral film is cut into a sample 20 mm wide and 100 mm long. The liquid substance is applied to the end portion 20 mm wide (in the longitudinal direction) of the film sample in an amount of 10 g / m 2 The film is then partially adhered to one end of a "B'akelite" panel having a thickness of 3 mm,

  width of 20 mm and length of 100 mm, then leave

  apply for 24 hours to polymerize the liquid substance to obtain

a test tube.

  The shear adhesion strength is measured

  between the film sample and the "Bakelite" panel in use

  reading a device manufactured by the company Toyo Boldwin Co, under the name "Tensilon Tensile Tester Model TM-III-500" (speed of

  tensile strength 5 mm / min. The resistance is 2.57 M Pa.

EXAMPLE 2

  A copolymer prepared by copolymerization of 80 parts of ethyl methacrylate and 20 parts of

  butyl in a 15% aqueous solution of toluene, in the methyl-

  ethylcetone to prepare a 30% solution 2 parts (solids content) of zinc naphtenate are added The solution is applied

  on a separable paper and dried to obtain a poly-

  acrylic having a dry thickness of 500 μm.

  A liquid substance is prepared from 70 parts of methyl methacrylate, 15 parts of bisphenol F epoxydimethacrylate, 15 parts of 2-hydroxyethyl acrylate, 1.5 parts of methyl ethyl ketone peroxide and 0.01 parts of monomethyl ether of hydroquinone. A specimen is prepared in the same manner as in Example 1, except that the specimen is allowed to stand at 25 ° C. for 36 hours. The measured shear adhesion strength is

of 2.12 M Pa.

EXAMPLE 3

  A copolymer, prepared from parts of methyl methacrylate and 50 parts of ethyl acrylate, is dissolved in toluene to prepare a 30% solution. 4 parts of benzoyl peroxide are added. The solution is applied to a film. polyimide (film obtained by casting an aromatic polyimide resin), tensile strength 120 M Pa (20 C), elongation at break: 8% (20 C), modulus of elasticity 2100 M Pa (20 C)) having a thickness of 80 μm as a decorative material and dried to obtain a layer of polyacrylic resin having

  a dry thickness of 10 μm on the polyimide film.

  A liquid substance is prepared from portions of polyesterpolymethacrylate having a viscosity of 0.12 Pa S at 25 ° C. (reaction product of 152 parts of anhydride).

  tetrahydrophthalic acid, 212 parts of diethylene glycol and 172 parts of

  methacrylic acid) and 4 parts of benzoyl peroxide.

  The test specimen is prepared in the same manner as in Example 1, except that it is left standing at 25 ° C. for 8 hours and that

  the liquid substance is applied to the poly-resin layer

  acrylic The measured shear adhesion strength is

1.94 M Pa.

EXAMPLE 4

  A mixture of 100 parts of a soluble saturated polyester resin (tensile strength: 50 M Pa at 20 C, elongation at break: 640% at 20 C, Shore D hardness: 25 to 25 C) is dissolved and 1 Part of the cobalt naphthenate in a solvent mixture

  Methyl ethyl ketone-toluene 1: 4 to obtain a 30% solution.

  The solution is applied to a biaxially stretched insoluble polyester film (polyethylene terephthalate film:

  breaking strength: 230> Sa at 20 C, elongation at rup-

  150% at 20 ° C., modulus of elasticity in tension: 4000 I Pa at 20 ° C.) having a thickness of 50 μm as decorative material and dried at 800 ° C. for 5 minutes to obtain an unsaturated polyester resin layer. soluble having a dry thickness of 20 μm

on the polyester film.

  A liquid substance is prepared from

  60 parts of butyl methacrylate, 35 parts of styrene, 5 parts of

  bisphenol F epoxyacrylate fractions having a viscosity of

  500 Pa S at 20 C and 1.5 parts of cumene hydroxyperoxide.

  The test specimen is prepared in the same manner as in Example 1 except that it is allowed to stand at 20 ° C. for 24 hours.

  The measured shear adhesion strength is 1.25 M Pa.

EXAMPLE 5

  A copolymer prepared from 50 parts of styrene and 50 parts of ethyl acrylate is dissolved in toluene to prepare a 15% solution. 2 parts (solids content) are added.

  of dimethylaniline The solution is applied to a fluorocarbon resin

  bone whose surface has been treated with sodium (copolymer of tetra-

  fluoroethylene and a fluorinated monomer; breaking strength: 28} Pa at 20 ° C, elongation at break: 10%, pencil hardness: 2 H) having a thickness of 75 μm as a decorative material and dried at 80 ° C. for 3 minutes to obtain a layer of polyacrylic resin

  having a dry thickness of 150 μm on the fluorocarbon resin.

  A liquid substance is prepared from 95 parts

  of methyl methacrylate, 5 parts of dimethacrylate of

  ethylene glycol and 2 parts benzoyl peroxide.

  The test specimen is prepared in the same manner as in Example 1, except that the application amount of the liquid substance is 13 g / m 2 and the specimen is allowed to stand at 20 ° C. for 24 hours and a plate is used. stainless steel instead of Bakelite panel The measured shear adhesion resistance

is 1.82 M Pa.

EXAMPLE 6

  A mixture of parts of a soluble polyester resin (tensile strength: 6 M Pa at 20 ° C., elongation at break: 150% at 20 ° C., Shore D hardness: 34 ° to 25 ° C.) is dissolved in methyl ethyl ketone. 4 parts of cumene hydroperoxide and 0.1 part of hydroquinone to prepare a 30% solution. The solution is applied to the same biaxially unsaturated polyester film as in Example 4, having a thickness of 50 μm. as a decorative material and dried at 130 ° C. for 3 minutes to form a soluble polyester resin having a dry thickness

of 30 μm.

  A liquid substance is prepared from parts of methyl methacrylate and 0.5 parts of pentoxide

of vanadium.

  The specimen is prepared in the same way as

  Example 3, except that the amount of application of the substance

  This is 50 g / m 2 and allowed to stand at 60 ° C. for 240 minutes.

  The measured shear adhesion strength is 3.24 N Pa.

EXAMPLE 7

  A mixture of parts of a copolymer prepared from 80 parts of methylethylketone is dissolved in methyl ethyl ketone.

  butyl methacrylate, 20 parts of butyl acrylate and 50 parts of

  trimethylolpropane trimethacrylate, 15 parts of

  polyethylene glycol methacrylate and 2 parts of benzoyl peroxide to prepare a 30% solution. The solution was applied to the same polyimide film as used in Example 3, having a thickness of 80 μm as a decorative material and dried at 130 ° C. for 3 min to obtain a layer of polyacrylic resin having

  a dry thickness of 30 μm on the polyimide film.

  The liquid substance is prepared from parts of methyl methacrylate, 50 parts of methacrylate of

  butyl and 1.5 parts of dimethylaniline.

  The test specimen is prepared in the same manner as in Example 3, except that the liquid substance is applied in an amount of 20 g / m 2 and allowed to stand at 30 ° C. for 18 hours.

  The measured shear adhesion strength is 1.96 M Pa.

  It is evident from the previous examples that, according to the method of bonding the invention, the surface of the film

  of polymer is firmly adhered to the article.

  It should be understood that the invention is not limited to the preferred embodiments described above by way of illustration and that one skilled in the art may make various modifications and changes thereto without departing of the frame and

the spirit of the invention.

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Claims (8)

R E V E N D I C A T I 0 N S   l Method for adhering an article and a film (or sheet) of polymer, which consists of interposing a substance   liquid between the article and the polymer film and to bond the article   and the polymer film through the liquid substance to polymerize the liquid substance thereby strongly adhering the article and the polymer film, characterized in that the substance   liquid comprises at least one product selected from vinyl monomers   and oligomers that dissolve or swell the super   of the polymer film, thereby imparting stickiness, the polymer film or the liquid substance contains a polymerization inducer and the other contains an accelerator of polymerization.   Process according to Claim 1, characterized in   what the polymer film carries on one side a decorative material   rative. Process according to Claim 1, characterized in that the liquid substance is applied to the interface between the polymer film and the article in an amount of 1/100 to 5 times   the weight of the polymer film.   Process according to Claim 1, characterized in that the vinyl monomer or the oligomer are products which can be polymerized by the reactive radicals produced by   the decomposition of the polymerization inducer.   5. Process according to claim 1, characterized in that the polymerization inducer is an inductor which decomposes by a redox reaction of the polymerization accelerator.   by producing reactive radicals.   Process according to claim 1, characterized in that the polymerization accelerator is an accelerator which   breaks down the polymerization inducer by oxidation of   reduction by easily producing reactive radicals.   Process according to claim 1, characterized in that the amount of the polymerization initiator is 0.01 to 10% by weight, based on the liquid substance or the polymer film. The process according to claim 1, wherein the amount of the polymerization accelerator is 0.1 to 10% by weight, based on the weight of the liquid substance or the polymer film which contains not the induc: 2 eur polynmerisationl.