EP0276291A4 - Verfahren zur behandlung von glasflächen mit verbindungsmitteln und harzen zur herstellung einer verbesserten fläche zum binden eines endharzes. - Google Patents

Verfahren zur behandlung von glasflächen mit verbindungsmitteln und harzen zur herstellung einer verbesserten fläche zum binden eines endharzes.

Info

Publication number
EP0276291A4
EP0276291A4 EP19870905354 EP87905354A EP0276291A4 EP 0276291 A4 EP0276291 A4 EP 0276291A4 EP 19870905354 EP19870905354 EP 19870905354 EP 87905354 A EP87905354 A EP 87905354A EP 0276291 A4 EP0276291 A4 EP 0276291A4
Authority
EP
European Patent Office
Prior art keywords
resin
coupling agent
product
preg
reinforcement
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.)
Withdrawn
Application number
EP19870905354
Other languages
English (en)
French (fr)
Other versions
EP0276291A1 (de
Inventor
Dennis J Vaughan
Mansfield H Creech Jr
Roy C Peek Jr
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
CLARK-SCHWEBEL FIBERGLASS Corp
SCHWEBEL FIBERGLASS
Original Assignee
CLARK-SCHWEBEL FIBERGLASS Corp
SCHWEBEL FIBERGLASS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by CLARK-SCHWEBEL FIBERGLASS Corp, SCHWEBEL FIBERGLASS filed Critical CLARK-SCHWEBEL FIBERGLASS Corp
Publication of EP0276291A1 publication Critical patent/EP0276291A1/de
Publication of EP0276291A4 publication Critical patent/EP0276291A4/de
Withdrawn legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10018—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising only one glass sheet
    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10688—Adjustment of the adherence to the glass layers
    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10697—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer being cross-linked
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/24—Coatings containing organic materials
    • C03C25/26—Macromolecular compounds or prepolymers
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
    • C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0239—Coupling agent for particles

Definitions

  • the present invention relates to the use of synthetic resins with glass and glass fibers to produce composite glass structures.
  • the present invention provides a method for coating glass surfaces with a combination of a reinforcement resin and a coupling agent to produce composites which resist chemical and mechanical stresses before the incorporation of a final resin.
  • These final coated glass fibers exhibit enhanced stability and resistance to chemical and mechanical stresses and can be layered and pressed into glass laminate products.
  • a large number of useful products ranging from automobile windshields to boats, fishing rods, computers and printed circuit boards depend on the adhesion of polymeric resin to glass surfaces in order to withstand heat, light, mechanical stress, moisture, oxidizing conditions, and other stresses that can affect the use of these products.
  • a number of dispersed polymers have been used with glass for coatings to bind, protect, color, or adhere glass materials.
  • examples of such polymers include: polyvinyl alcohol, polyvinyl acetal or butyral, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate or butyrate, acrylonitrile polymers and copolymers, acrylic ester polymers and copolymers, melamine formaldehyde, phenol-formaldehyde, urea-formaldehyde, silicone polymers and copolymers, both inert and with reactive functional groups.
  • a large number of coupling agents and wetting agents have been used with glass.
  • these have included a number of titanate compounds, chromium complexes, silanes, siloxanes, and polymers thereof, and silicones.
  • these coupling agents are most useful when the processing conditions used are consistent with the formation of hydrolytically stable covalent bonds between the silanol groups of the glass surface and the coupling agent, and between reactive groups at other positions of the coupling agent and reactive groups in the intermediate resin.
  • the preservation of reactivity during processing and storage to provide sufficient reactivity for the final linking step presents a problem. This problem is considered acute because of the instability of the coupling agent to moisture, oxygen, carbon dioxide, high temperatures and external contaminants. This reactivity has been responsible for the deleterious impact that chemical stresses occurring during processing and storage have had on glass laminates of the prior art.
  • this invention provides a method for producing glass surfaces coated with reinforcement resin that are storage- stable.
  • a reinforcement resin coated glass surface which is storage stable is that which can react with a pre-preg resin after being stored for a period of at least about 24 hours under conditions that occur during normal storage and shipping and form a multi-ply laminated glass product exhibiting superior characteristics.
  • the method comprises applying a coupling agent to a glass surface concurrently with, or followed closely by, a compatible reinforcement resin dispersion which can wet and cover, react with, and protect the coupling agent while the surface is in an intermediate stage during processing, transit or storage. Further, the reinforcement resin and coupling agent should also be able to aid in wetting the pre-preg resin for reaction and curing into a finished composite structure.
  • This invention further provides a superior multi-ply laminated glass product produced by this method. This multi-ply laminated glass product finds particular use in the manufacture of printed circuits, as printed circuit substrates, or as structural or decorative panels.
  • a glass surface is first coated with a coupling agent that covalently links to the glass surface and either concurrently or shortly thereafter, a first or reinforcement resin is applied to the glass surface and bonded thereto, at least in part, through covalent linkages with the coupling agent to produce a storage-stable intermediate product.
  • a second or pre-preg resin is applied to the intermediate product and covalently linked at least partially to the reinforcement resin, and preferably, also to the coupling agent to produce a final resin product.
  • This final pre-preg resin product may then be stacked and cured to produce a multi-ply laminated glass product.
  • the pre-preg resin can be strongly bonded to the coupling agent and the reinforcement resin even after long periods of storage of the intermediate product. It is especially surprising that the pre-preg resin can be bonded to the coupling agent and to the reinforcement resin in a manner which provides laminated products of superior strength and quality.
  • the glass substrate may be comprised of glass fabric, filamentous glass or nonwoven fiberglass.
  • a particularly suitable substrate is Fiberglass OCFTM.
  • the surface of the glass substrate may be any dimension that enables coupling agent and polymeric resin to bind to it.
  • the coupling agent in embodiments of the present invention comprises a silane compound containing one or more hydrolyzable groups, or a basic or hydrous derivative of a polyvalent metallic element.
  • the coupling agent can be deposited on the glass surfaces directly when feasible, and can be deposited by exposing the glass surfaces to solutions or suspensions of coupling agent in water or water and organic solvents. It has been found that when the coupling agents of this invention are used in appropriate proportions in the method of the present invention, the resulting product obtained is considerably more stable and resilient to chemical and mechanical stresses than products which do not contain the appropriate quantities of coupling agents.
  • a water or water/organic solvent dispersable reinforcement resin which functions to provide enhanced stability and resilience to the final product may be deposited concurrently with or shortly after the coupling agent onto the glass surface.
  • This reinforcement resin is selected to aid in preserving the coupling agent for subsequent reactions with the pre- preg resin, and for its ability to bind to the pre-preg resin during final processing steps.
  • the storage-stable intermediate glass products can be processed immediately or stored before final processing.
  • the intermediate glass products should be storable under normal conditions of storage and shipping for a least about 24 hours and most preferably, such products should be storable for at least about one week.
  • the coupling agents and reinforcement resins are chosen to provide stability during storage and processing and maximum reactivity of the coupling agent with the pre-preg resins in the final processing stages.
  • the coupling agents and reinforcement resin are subject to the harmful effects of moisture, light, and atmospheric gases (oxygen and carbon dioxide), oftentimes resulting in a decreased reactivity of the coupling agent with the pre-preg resin and weaker linkages with the reinforcement resin already deposited on the glass surfaces.
  • the reinforcement resin is therefore chosen for its ability to be readily dispersible in water or a combination of water and an organic solvent to protect the coupling agent from the deleterious effects of moisture, heat, atmospheric gases, and external contaminants during storage, and processing, and for its potential to covalently bind with the pre-preg resin during final processing.
  • the pre-preg resin can be any resin that can form covalent bonds with the reactive groups of the reinforcement resin and/or coupling agent.
  • the resin can be chosen to elicit the desired physical and aesthetic characteristics of the laminated product, so long as these characteristics are consistent with covalent bonding to the reinforcement resin and/or the coupling agent.
  • a glass surface is treated with a coupling agent and a first or reinforcement resin to produce a storage stable intermediate product in which the cc-upling agent is covalently coupled to the glass surface and the reinforcement resin.
  • the ' reinforcement resin serves to promote the stability of the coupling agent before reaction of the final or pre-preg resin to form a final pre-preg resin product, and to provide structural integrity to the multi-ply laminated glass product to resist the effects of mechanical and chemical stresses.
  • a glass surface reactive with silicon-containing or polyvalent metallic coupling agents can be used in the present invention.
  • a glass surface useful in this invention is any surface containing silicon, silicate, borate, or phosphate or combinations of these units capable of covalently binding to chemical compounds through silanol chemical groups.
  • the glass surface is comprised of glass fabric, filamentous glass or Fiberglass OCFTM, one or more dimensions of which is about .01 microns to about 100 microns in size.
  • the silicon-containing or polyvalent metallic compounds which are capable of functioning as the coupling agents in the method of the present invention should have the following three characteristics:
  • the coupling agent should contain at least one chemical group reactive with the glass surface directly, or preferably, after this group is hydrolyzed, and one group reactive with the reinforcement resin.
  • the coupling agent therefore, preferably contains at least two reactive chemical groups, and may contain at least three reactive chemical groups, each chemical group being reactive at a different stage in the formation of the finished product.
  • the coupling agents are preferably deposited onto the glass surfaces so that the coupling agent comprises about 0.001% to about 2% of the total weight of the final glass laminate product and most preferably comprises about 0.002% to about 0.3% of the total weight of the final product.
  • the coupling agents can be coated onto the glass surfaces directly where feasible (e.g., if the coupling agent is itself a liquid) or by immersing the glass surface in a solution or suspension of the coupling agent in water or a combination of water and a water miscible solvent.
  • this solution or suspension is comprised of about 0.05% to about 5% by weight of coupling agent, and most preferably about 0.05% to about 2.0% by weight.
  • the coupling agent should contain at least one chemical group which is reactive directly with the glass surface or is a precursor which can be easily manipulated by hydrolysis or other chemical techniques to form a group reactive with the glass surface.
  • the coupling agent should also contain at least one group which is reactive with the reinforcement resin in addition to that which is reactive with the glass surface.
  • the second group serves to covalently bond the reinforcement resin to the glass surface through the coupling agent.
  • the coupling agent may contain at least two reactive groups in addition to that which is reactive with the glass surface. These groups covalently link the reinforcement resin and the pre-preg resin to the coupling agent.
  • the first and second chemical groups allow direct reaction of the glass surface and reinforcement resin with the silicon molecule.
  • some of these moieties are hydrolyzed to hydroxyl groups (silanol) which can in turn, react directly with the glass surface or may react with reactive groups on the reinforcement resin.
  • These groups include, but are not limited to halogens, hydroxides, hydrogens (silanes) and alkoxide groups (silyl esters) which are easily displaced by the silanol groups on the surface of the glass forming a Si-O-Si bond, or are easily hydrolyzed with water to form a silanol group which can then react with the glass surface to form a Si-O-Si bond.
  • silanol groups on the coupling agent for coupling to the glass surface because silanol groups form strong bonds between the coupling agent and the glass surface.
  • Hydrogen containing coupling agents are less preferred, at least in certain applications, because of their tendency to form hydrogen gas during reaction with the silanol groups on the glass surface.
  • the first chemical group is a halogen, hydroxide, hydrogen or alkoxide bound directly to the silicon atom
  • the second chemical group is a vinyl, mercapto, halogenated alkyl, hydroxyalkyl, epoxide, or amine among other chemical groups. These groups have been found to be selectively reactive with functional groups of the reinforcement resin.
  • the coupling agent contains a third group which does not react during application of the coupling agent or the first polymeric resin, and which is stable to the adverse chemical stresses that occur during storage and shipment before final processing.
  • this group does react with or couples to the pre-preg resin during final processing.
  • preferred groups include but are not limited to, amine groups, hydroxyl groups, sulfhydryl groups, halogen groups not bonded to silicon, epoxide groups, and groups containing olefinic unsaturation.
  • silicon-containing coupling agents useful in this invention include: vinyltrichlorosilane; vinyl- tris (2-methoxyethoxy)silane; gamma- mercaptopropyltrimethoxysilane; gamma- aminopropyltriethoxysilane; Bis-acrylic acid-gamma- aminopropyl triethoxysilane; chloropropyltrimethoxysilane; gamma-methacryloxypropy1- tris-(2-methoxyethoxy)silane; N-beta(aminoethyl)-gamma- aminopropyl trimethoxysilane; Bis-hydroxy-ethyl-gamma- aminopropyl triethoxysilane; beta-(3,4- epoxycyclohexyl)-ethyltrimethoxysilane; vinyltriethoxysilane; methyl [2-(gamma- trimethoxysilypropyl-amino
  • Polyvalent metallic coupling agents preferred for practicing this invention include those compounds containing a trivalent metal ion selected from the group consisting of chromium, cobalt, nickel, copper, titanium and lead, at least one hydroxyl group bonded to the metal ion, and at least one anion of a strong mineral acid attached to the metal.
  • a preferred coupling agent of this type is VolanTM a chromium complex of methacrylic acid.
  • Also preferred in practicing certain aspects of this invention are coupling agents of the Werner type, in which a trivalent atom such as chromium is coordinated with an organic acid containing functional groups which can be used to bind the reinforcement resin or the pre-preg resin to the glass surface.
  • Additional preferred coupling agents include titanium complexes containing functional groups capable of reacting with the reinforcement resin. These agents are described in U.S. Patent Nos. 2,611,718, 2,273,040, and 3,993,835 which are incorporated by reference herein.
  • the reinforcement resins that can be employed in practicing this invention include those resins that can provide protection to the coupling agent in minimizing the harmful effects of chemical stresses that occur during manufacture and storage and can provide structural resiliency to the final product in resisting chemical and mechanical stresses during end use.
  • the reinforcement resins be maximally dispersible in water or water/organic solvent during deposition onto the glass surfaces. This will promote the formation of a thin moisture-proof film. It is preferred that a thin film of reinforcement resin completely coat the coupling agent and glass surface to reduce the effects of moisture, atmospheric gases, and external contaminants as well as insulate the coupling agent from the effects of heat during processing and storage.
  • the coating of reinforcement resin, ⁇ therefore, must be thick enough to prevent the adverse effects of stresses that occur during processing and storage, yet preferably, be thin enough to allow the pre-preg resin to penetrate filament bundles of the intermediate resin coated glass product to form covalent bonds to the reinforcing resin and the coupling agents during final processing.
  • the reinforcement resin preferably comprises from' about 0.001% to about 6.0% by weight of the final glass laminate product and most preferably comprises about 0.1% to about 2.0% by weight of the solids comprising the final glass laminate product. These proportions are based on coupling agent, reinforcement resin, pre-preg resin and glass being the solids comprising the final product. Where desirable, cross-linking agents also comprise part of the solids used to form a final product. In general, below about 0.001% by weight of the final glass product, the amount of reinforcement resin is too small to assure protection of the coupling agents during storage, and above about 6.0% by weight solids the amount of resin may be too great to provide mechanical resiliency to the final product or to allow effective penetration of the pre-preg resin into the filament bundles.
  • the reinforcement resin must be maximally dispersible in a solvent that allows a uniform thin layer to be coated onto the glass surface and coupling agent.
  • the solvent is water or a mixture of water and an organic solvent.
  • the type and amount of solvent mixed with water depends on the dispersibility of the resin in water, and the polarity of the resin.
  • Organic solvents that can be used to aid in dispersing the reinforcement resin include any solvent that does not interfere with the reaction with the coupling agent, for example dimethylacetamide, dimethyl formamide, methyl cellosolve, 1,4 dioxane, acetone, tetrahydrofuran, toluene, methylene chloride, and petroleum ether, among others.
  • Dispersions of reinforcement resin are generally comprised of about 0.01% to about 5% resin by weight and are preferably comprised of about 0.1% to about 2% resin by weight.
  • any polymeric resin that is dispersible in water or a water/organic solvent mixture and contains functional groups which can react with the coupling agent and the second or pre-preg resin can be used as a reinforcement resin in applications of the present invention.
  • the resin is synthetic.
  • the reinforcing resin can be applied to the glass surface after the coupling agent has been coated onto the glass, or can be applied concurrently with the application of the coupling agent.
  • the agents may be coated directly onto the glass surfaces where practical, or may be diluted by solvent and coated onto the glass surface.
  • Any solvent that can solubilize the coupling agent and does not interfere with the glass surface - coupling agent reaction can be used.
  • water is used, but other preferred solvents include dimethylformamide, dimethylacetamide, and ether containing solvents ' such as diethylether, cellosolve solvents, 1,4 dioxane, tetrahydrofuran, and ketones such as acetone, and methyl ethyl ketone, and miscellaneous solvents such as toluene, ethylene chloride, and petroleum ether, among others.
  • the final glass laminates of this invention are produced in three steps. First, the glass surface is reacted with the coupling agent. Second, the glass surface with covalently bonded coupling agent is reacted with the reinforcement resin to form an intermediate product which can be processed immediately or stored. Third, the intermediate product is reacted with the pre-preg resin to produce a final pre-preg resin product comprised of a coupling agent which binds the reinforcement resin to the glass surface, and a pre-preg resin which binds to the reinforcement resin and preferably, also to the coupling agent. The final pre- preg glass product of this invention can then be stacked and pressed into multi-ply laminated glass products.
  • the silane-containing coupling agent be treated with water or water/organic solvent prior to and during application of the coupling agent to the glass surface. It is found that the water will hydrolyze silicon-halogen and silicon-alkoxide groups to reactive silicon-hydroxyl (silanol) groups rather readily. It is quite favorable during application of the coupling agent onto the glass surface to have hydroxyl groups bonded to silicon because the hydroxyl groups aid coating of the coupling agent and promote formation of Si-O-Si bonds between the glass surface and the coupling agent. It is apparent that the coupling between a Si-OH containing coupling agent and the Si-OH containing glass surfaces occurs more readily than the reaction between the glass surface and other functional groups on coupling agents. For example, laminates formed from Si-OH containing coupling agents exhibit superior characteristics over laminates formed from coupling agents containing silicon-halogen, silicon- hydrogen or silicon-alkoxide groups which directly react with glass.
  • Reinforcement resin can be added to the solution containing the coupling agent and reacted concurrently with the reaction of coupling agent.
  • a dispersion of reinforcement resin in water or a combination of water and an organic solvent can be added to the glass surface to which is already bound coupling agent, and then reacted under the appropriate conditions.
  • the coupling agent contains an amino group
  • the reinforcement resin contains an epoxide group. It is believed that reaction occurs by the amino group opening the epoxide, generally at room temperature or slightly elevated temperature. Conditions depend on the chemistry of the coupling agent and the reinforcement resin, but these conditions are well-known in the art.
  • coupling agent and reinforcement resin can be achieved using water or water/organic solvent dispersions, depending on the nature of the reinforcement resin.
  • Wetting agents are sometimes incorporated onto the glass surface along with the coupling agent and reinforcement resin. These agents are useful for wetting during introduction of the pre-preg resin and for softening the products. Examples of such wetting agents that may be employed include, but are not limited to, dioctyl sodium sulfosuccinate (Tradename GR5M from Rohm and Haas), octylphenoxypolyethoxyethanol (Tradename Triton X100 from Rohm and Haas), and alkylarylpolyether alcohol (Tradename Triton X155 from Rohm and Haas).
  • the type of reinforcement resin used in the method of the present invention depends on the nature of the coupling agent used, but is preferably a synthetic resin. It is preferred that the reinforcement resin contain at least two functional groups; one capable of reacting with the coupling agent and the other capable of reacting with the pre-preg resin.
  • the reinforcement resin used in the present invention is a water dispersed/polyepoxy resin containing at least two epoxide functionalities or other reactive functional groups, for example hydroxyl groups.
  • polyepoxide dispersions include dispersions of epoxidized phenolic ethers such as the dispersion of the Diglycidyl Ether of Bisphenol A (Tradename CMD 35201 from Celanese Corporation), a dispersion of a urethane epoxide (Tradename W60-5520 from Celanese Corporation) , an epoxy dispersion of a polyfunctional, polyaromatic epoxide (Tradename CMD W55-5003 from Celanese Corporation), and water dispersions of difunctional diepoxides for example the diglycidyl ethers of 1,4 butanediol and neopentylglycol (Tradenames WC-67 and WC-68, respectively, from Wilmington Chemical Corporation, Wilmington, Delaware).
  • epoxidized phenolic ethers such as the dispersion of the Diglycidyl Ether of Bisphenol A (Tradename CMD 35201 from Celanese Corporation), a dispersion of a urethan
  • the epoxides are preferred because they are generally dispersible and stable to the solvents employed to provide the most preferred reinforcement layers.
  • the epoxides can also function to bind to the pre-preg resin in subsequent processing steps and are preferred because they are stable to moisture, atmospheric gases, and heat for long periods of time in the absence of catalysts. At a later stage, these epoxide groups can be reacted directly or cross-linked with functional groups on the pre-preg resins.
  • reinforcement resins that can be employed in embodiments of this invention include polyimide resins, polyester resins (saturated or unsaturated) and aldehydic condensation resins, for example, the • condensation product of melamine and formaldehyde, urea and formaldehyde and similar polymers, among others.
  • the reinforcement resin is applied to the glass surface, it is dried at elevated temperatures, between about room temperature and about 500°F, preferably between about 250° and 400°F and most preferably about 280-320°F.
  • the intermediate product can then be stored or further processed by treating this intermediate product with a pre-preg or coating resin emulsion.
  • Pre-preg resins useful in embodiments of this invention include any resin that can covalently bind with the coupling agent, the reinforcement resin, or a cross- linking agent.
  • the pre-peg resins may be solubilzed or emulsified with a solvent, preferably a water soluble solvent.
  • Preferred pre-preg resins may include epoxy containing resins, polyesters, polyimides, phenolic resins, vinyl esters, and melamine resins.
  • Such preferred resins include the polyglycidyl ethers especially those of Bisphenol A, for example, the difunctional epoxide FR4TM of Dow Chemical Company (Commercial name DER -521), tetrafunctional epoxides, for example N,N,N' ,N* ,-tetraglycidyl-4,4'-methylene bis-benzenamine (Commercial name AralditeTM MY 720 of
  • Ciba-Geigy polyimide resins, for example the polyimide amide resin l,l'-(methylene-di-4,l-phenylene) bismaleimide (Commercial name Keramid 601 of Rhone- Poulenc) , polyesters, for example ortho phthalic polyester (Commercial name PolyiteTM 31-006 of Reichhold Chemicals, Inc., Jacksonville, Florida), phenolic resins for example 105B4 Resin of Ironsides Company, Columbus, Ohio and vinylesters, for example DerakaneTM Resin of Dow Chemical.
  • polyimide resins for example the polyimide amide resin l,l'-(methylene-di-4,l-phenylene) bismaleimide (Commercial name Keramid 601 of Rhone- Poulenc)
  • polyesters for example ortho phthalic polyester (Commercial name PolyiteTM 31-006 of Reichhold Chemicals, Inc., Jacksonville, Florida), phenolic resins for example 105B4 Resin of Iron
  • the amount of pre-preg resin incorporated into the final product depends on the desired properties of the final product. Generally, the pre-preg resin comprises about 20% to about 95% by weight of the final product, and preferably about 22% to about 80% of the final product.
  • solutions of pre-preg resins are generally used, but emulsions may also be employed.
  • the preferred solutions of the pre- preg resins generally contain water soluble solvents, preferably with boiling points higher than water.
  • Solvents for solution and deposition of the pre-preg resin are chosen based on the solubility characteristics of the pre-preg resin, the coupling.agent, and the reinforcement resin. " ' It is most preferred that the pre-preg resin bind with both the coupling agent and reinforcement resin. To accomplish this, the pre-preg resin must penetrate the protective reinforcement resin layer and react with functional groups on the coupling agent. Thus, a solvent which maximally solubilizes the pre-preg resin, the coupling agent, and the reinforcement resin without affecting the covalent binding between these components will enable this preferred binding to occur.
  • the preferred solvents are acetone, methyl ethyl ketone, dimethyl forma ide, methyl cellosolve, propylene glycol and methyl ether.
  • the preferred solvent is N-methyl pyrollidone.
  • polyester or vinylester resins such as PolyliteTM or Derakane m are used, the preferred solvent is styrene or methyl methacrylate.
  • a radical initiator may be added to the pre-preg solution or may be incorporated within the intermediate resin product by adding the initiator to the reinforcement resin dispersion before depositing the dispersion onto the glass surface.
  • Many of these initiators are not stable for long periods of storage however, and this may limit the length of time an intermediate product can be stored and still provide adequate reactivity for curing the pre-preg resins.
  • Radical initiators useful to promote polymerization of ethylenically unsaturated groups include the peroxides, for example benzoyl peroxide, butyryl peroxide, diacyl peroxides, ketone peroxides, perbenzoates, peracetates, among others, peroxycarbonates, for example di-n-propyl peroxydicarbonate, and azo compounds, among others.
  • Crosslinkers may also be employed to aid the bonding of the pre-preg resins.
  • the cross-linkers are designed to link the pre-preg resin with the reinforcement resin and the coupling agent.
  • Cross-linkers may be employed when the coupling agent or the reinforcement resin contain functional groups which can not form covalent bonds directly with functional groups of the pre-preg resin, for example when the only available functional groups on the reinforcement resin and the pre-preg resin capable of reacting are hydroxyl groups or other nucleophiles.
  • coupling agents can be used when the only functional groups capable of reacting are electrophilic, for example epoxy groups.
  • Cross-linkers used in bridging the functional groups of the reinforcement and pre-preg resins of this invention depend on the type of resins used.
  • cross-linkers When epoxy resins are to be cross-linked, a number of cross-linkers may be employed, for example metaphenylenediamine, methylenedianiline, and dicyandiamide. When epoxy resins are to be cross-linked through hydroxyl groups, other cross-linkers may be employed, for example, NMA (nadicmethylanhydride employed when the laminated products are to be used at high temperatures), pyromelliticdianhydride '(also employed when the laminated product is to be used at high temperatures)and chlorendic anhydride (as a fire retardant), among others.
  • NMA nadicmethylanhydride employed when the laminated products are to be used at high temperatures
  • pyromelliticdianhydride ' also employed when the laminated product is to be used at high temperatures
  • chlorendic anhydride as a fire retardant
  • the amount of cross-linker used in the final product may vary from about 2% to about 120% by weight of the pre- preg resin used.
  • an accelerator such as benzyldimethylamine or other amine is employed to enhance the cross-linking reaction. See, in general, Lee and Neville "Handbook of Epoxy Resins" published by McGraw Hill, 1967, Chapters 5-12 .
  • the final glass product of this invention can be stacked and pressed to produce multi-ply glass laminates. These laminates exhibit superior structural characteristics and are very resistant to electrical, chemical and mechanical stresses that may occur during use.
  • test methods and materials are generally described in American Society for Testing Materials (ASTM) Publications. A list of certain applicable specifications might include the following documents and others referenced within those standards.
  • ASTM-D229 Test Procedures for Rigid Insulation ASTM-D790 Flexural Tests ASTM-D695 Compression Tests ASTM-D257 DC Resistance ASTM-D150 AC Loss Characteristics ASTM-D149 Dielectric Strength
  • PAPT N- phenyl-gamma-amino propyltrimethoxysilane
  • the treated fabric was impregnated with a 60% solution of Kerimid 601 in N-Methylpyrollidone and dried to give a pre-preg. Twelve plies 'of pre-preg were then stacked and pressed between plates in a heated hydraulic press for 30 min. at 250° F. and 1 hr. at 360° F. to give a glass-polyimide composite. The composite was post cured for 48 hrs. at 200°C. to produce a material suitable for use in high temperature structural applications.
  • Heat cleaned glass fabric, style 7628 (ASTM Standard), was treated with a dispersion of silane and resin prepared by dissolving 0.5% by weight of A-187 (gamma- glycidoxypropyltrimethoxysilane) in 0.01% acetic acid solution and adding 0.75% resin dispersion in the final bath.
  • a urethane epoxy dispersion (CMD-W-60-5520 from Celanese) , was used as the resin dispersion.
  • the treated fabric was prepregged with Dow Epoxy Resin (DER 521-A-80), dicyandiamide crosslinker and benzyldi ethylamine accelerator, stacked, and pressed, a normal procedure for FR-4 laminate production.
  • Dow Epoxy Resin DER 521-A-80
  • dicyandiamide crosslinker dicyandiamide crosslinker
  • benzyldi ethylamine accelerator stacked, and pressed, a normal procedure for FR-4 laminate production.
  • a second laminate was produced with the same procedure except a polyfunctional aromatic epoxy dispersion (CMD- W55-5003 from Celanese) was substituted for the urethane epoxy of the earlier trial.
  • a third laminate was produced using the same procedure without adding a resin dispersion to the silane solution. The advantage of the resin additions is shown by the enhanced solder dip resistance of the 5 laminates containing resin dispersions in the finish.
  • Laminates were prepared as in Example 2 with the exception of the drying temperature of the oven after 5 padding of the finish on the fabrics . The critical nature of the drying conditions are shown by the results .
  • Bisphenol A epoxy resin obtained from Celanese
  • the concentration of silane obviously affects the characteristics of the laminate.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Laminated Bodies (AREA)
  • Reinforced Plastic Materials (AREA)
EP19870905354 1986-07-24 1987-07-24 Verfahren zur behandlung von glasflächen mit verbindungsmitteln und harzen zur herstellung einer verbesserten fläche zum binden eines endharzes. Withdrawn EP0276291A4 (de)

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US889677 1986-07-24

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DE4025715C1 (de) * 1990-08-14 1992-04-02 Robert Bosch Gmbh, 7000 Stuttgart, De
DE4233021A1 (de) * 1992-10-01 1994-04-07 Huels Chemische Werke Ag Organosilanpolykondensate
JP4232537B2 (ja) * 2003-05-22 2009-03-04 住友ベークライト株式会社 合わせガラスの製造方法
DE102004025767A1 (de) 2004-05-26 2005-12-22 Degussa Ag Stabile Lösungen von N-substituierten Aminopolysiloxanen, deren Herstellung und Verwendung
CN114106369B (zh) * 2018-04-25 2025-04-04 旭化成株式会社 连续纤维增强树脂成型体、及其制造方法
EP3611236B1 (de) 2018-08-17 2020-09-30 Evonik Operations GmbH Eine wässrige, lagerstabile zusammensetzung, die n-benzyl-substituierte n-(2-aminoethyl)-3-aminopropylsiloxan-hydrochloride enthält, verfahren zu deren herstellung und deren verwendung

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CA1067230A (en) * 1974-07-01 1979-11-27 William N. Haggerty Size for glass fibers containing leachable tetravalant ions

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CA473440A (en) * 1945-11-13 1951-05-08 Fiberglass Canada Limited Composite bodies of glass fibres and resins
US2720470A (en) * 1954-09-15 1955-10-11 Porter W Erickson Allylaroxydichlorosilane and method of its preparation and application to glass
US3207623A (en) * 1960-07-25 1965-09-21 Owens Corning Fiberglass Corp Sized glass fiber
US3993835A (en) * 1971-12-15 1976-11-23 Ppg Industries, Inc. Transition metal oxide complex coupling agents coated on siliceous substrates
JPS5517508B2 (de) * 1973-03-05 1980-05-12

Patent Citations (1)

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Publication number Priority date Publication date Assignee Title
CA1067230A (en) * 1974-07-01 1979-11-27 William N. Haggerty Size for glass fibers containing leachable tetravalant ions

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 92, no. 18, 5th May 1980, page 90, abstract no 148458a, Columbus, Ohio, US; & CA-A-1 067 230 (OWENS-CORNING FIBERGLAS CORP.) 27-11-1979 *
See also references of WO8800527A1 *

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