KR19990028271A - Adhesive composition, bonding film prepared therefrom and method for producing the bonding film - Google Patents

Abstract

Photostable adhesive compositions include a) aromatic polyepoxides; b) heat activated curing agents for polyepoxides; c) thermoplastic polymers; d) polyfunctional (meth) acrylates; And e) optionally a direactive compound having at least one (meth) acrylate group and at least one group reactive with an aromatic polyepoxide. An adhesive bond film can be manufactured by the method using electron beam irradiation using an adhesive composition.

Description

Adhesive composition, bonding film prepared therefrom and method for producing the bonding film

Solid continuous adhesive films are frequently used to bond two substrates together when producing structural articles and structural laminates. Such adhesive films are frequently used in the electronics industry, the automotive industry, and the aerospace industry. For example, a laminated circuit board can be fabricated by placing an adhesive bond film between two copper-plated substrates including an etched circuit and thermally curing the adhesive film.

Adhesive bond films useful for the fabrication of structural products and structural laminates should preferably exhibit several properties. For example, they should be easy to manipulate. That is, they must be able to be removed from the temporary carrier (eg, release liner) and placed on the substrate without wrinkling, tearing or permanently stretching.

The adhesive bond film should also exhibit a controlled flow during thermal curing (ie, a slight non-excessive adhesive flow). A slight flow of adhesive is required during thermal curing to wet the substrate surface and form a flat bond line with constant bonding force. However, excessive adhesive flow during thermal curing causes the adhesive to flow out over the edge of the substrate, resulting in uneven bond lines, voids and inconsistent bonding forces. In addition, after thermal curing, the adhesive bonding film should have good adhesion to the substrate. At least for certain applications, in order to increase the heat resistance of the laminate and to reduce thermal expansion, the heat cured adhesive bond film must also have a high glass transition temperature. This is a particularly advantageous property during subsequent high temperature processes such as, for example, soldering circuit boards (ie wave soldering).

In order to be widely accepted commercially, adhesive compositions for producing a bonding film therefrom must also be easily manipulated and processed. For example, the adhesive composition should have a viscosity that can be coated and then mixed at a temperature that is not high enough that any thermally activated curing agent in the adhesive risks premature curing reactions.

Many adhesive compositions include both heat curable materials and materials that polymerize when exposed to actinic light (ie, visible or ultraviolet light). These adhesives require storage under "safe light" conditions. Adhesive compositions that do not need to be stored away from visible or ultraviolet light would be advantageous.

Adhesive bond films comprising both radiation polymerizable resins and thermosetting resins have been disclosed previously. For example, US Pat. No. 4,552,604 (Green) discloses an epoxide resin and photopolymerization essentially by exposing the film to actinic radiation (preferably at a wavelength of 200 to 600 nm) without thermally crosslinking the film. A method for bonding two surfaces together using a liquid composition containing a compound that forms a solid continuous film is described. Epoxide resin: photopolymerizable compounds are generally used in 10: 1 to 1:10 molar ratios to provide satisfactory films and satisfactory cured bonds. Preferably, a photopolymerization catalyst is used. The film can bond the surfaces together by applying heat and, if desired, pressure.

U.S. Patent No. 4,612,209 (Forgo et al.) Describes the use of actinic radiation (preferably in the wavelength range of 200 to 600 nm) for making thermosetting adhesive bond films with varying tackiness. The adhesive may be a photopolymerizable compound comprising at least one CH ₂ = C (R) COO- group where R is hydrogen or methyl, a thermosetting epoxide resin that does not contain a photopolymerizable group, heat for an epoxide resin Mixtures of activated curing agents, accelerators and photopolymerization catalysts for photopolymerizable compounds.

U.S. Patent No. 5,086,088 (Kitano et al.) Describes acrylic ester / epoxy resin compositions that provide a pressure sensitive heat stable adhesive upon exposure to ultraviolet light. The adhesive may comprise about 30 to 80% by weight of a photopolymerizable prepolymeric syrup or monomeric syrup comprising an acrylic ester and a copolymerizable, moderately polar monomer, of an epoxy resin or epoxy resin that does not contain a photopolymerizable group. About 20 to 60% by weight of the mixture, about 0.5 to 10% by weight of the thermally activated curing agent for epoxy resins, about 0.01 to 5% of the photoinitiator, and 0 to about 5% of the photocrosslinker. The adhesive can be used to structurally bond components to metal surfaces or to seal metal seams.

A resin composition comprising a low molecular weight urethane-acrylate, an epoxy resin, an acrylate or methacrylate monomer, and an epoxy curing agent is described in Japanese Patent Laid-Open No. 61/14274 (Ando et al.). The resin composition forms a thermostable adhesive through the use of electrolytic radiation (eg, electron beams, gamma rays or X-rays) reported to polymerize and crosslink urethane acrylate and acrylate monomers.

Japanese Patent Laid-Open No. 1/234417 (Yamamoto et al.) Describes an epoxy resin composition that can be crosslinked using electron beam radiation. The composition comprises a) an epoxy resin, b) an epoxy resin having at least one epoxy group and at least one unsaturated double bond in one molecule, and c) a thermal curing agent for the epoxy resin, containing components (a) of 0.95 / 0.05 to 0.10 / 0.90 and ( It is contained by the weight ratio of b). The composition may first form a surface hardened state by crosslinking via a double bond using electron beam irradiation. The composition can then be further heat cured in a second step. If component (b) is not used sufficiently, it is reported that crosslinking hardly occurs and the surface does not harden sufficiently.

The production method of prepreg is described in Japanese Patent Laid-Open No. 58/19332 (Takita et al.). The reinforcing base material was impregnated using a resin solution containing 100 parts by weight of an epoxy resin, 2 to 150 parts by weight of a curing agent for epoxy resin, and 20 to 150 parts by weight of an acrylate monomer. It irradiated with electron beam radiation to harden only an acrylate monomer, and provided the prepreg which is easy to operate without adhesiveness. It has been reported that when less than the indicated amount of acrylate-containing component is used, curing by electron beam irradiation is insufficient, leaving an adhesive on the surface.

There is still a need for an adhesive composition that can provide a bonding film having some and preferably all of its properties such as ease of operation, controlled resin flow during thermal curing and high glass transition temperature after thermal curing. If the adhesive composition can be stored without protection from visible or ultraviolet light, and if the heat activated catalyst can be processed at a temperature without the risk of causing premature curing reactions, the usefulness of the adhesive composition will be further increased.

FIELD OF THE INVENTION The present invention generally relates to adhesive compositions, bonding films made therefrom, and methods of making the bonding films. More particularly, the present invention relates to an adhesive composition comprising an epoxy resin, a (meth) acrylate-containing resin and a thermoplastic polymer, as well as a method for producing a bonding film therefrom using electron beam irradiation.

<Overview of invention>

In one embodiment, the present invention

a) aromatic polyepoxides;

b) heat activated curing agents for polyepoxides;

c) thermoplastic polymers;

d) polyfunctional (meth) acrylates; And

e) optionally a direactive compound comprising at least one (meth) acrylate group and at least one group reactive with an aromatic polyepoxide (eg hydroxyl, carboxyl, amine or 1,2-epoxide) It relates to an adhesive composition containing a.

The adhesive composition is light stable; They do not need actinic radiation to polymerize. Thus, they do not require photocatalytic or storage under “safety light” conditions (eg, storage in containers that are not transparent to visible and ultraviolet light). Preferred adhesive compositions of the invention also include a temperature (eg, less than about 120 ° C., more preferably less than about 90 ° C., and most preferably from about room temperature to 60 ° C. where the polyepoxide curing agent is not at risk of premature curing reactions). Temperature), and then spread (eg, coated) so that it can be easily manipulated and processed.

Although various aromatic polyepoxides can be used, polyglycidyl ethers of novolac and diglycidyl ethers of 4,4'-dihydroxydiphenyl dimethyl methane are preferred. Similarly, various heat activated curing agents may be used, but aromatic polyamines such as fluorene diamine are preferred.

Thermoplastic polymers useful in the present invention include polysulfones, poly (methyl methacrylate), phenoxy polymers, polycarbonates, and combinations of these materials. Preferably, the thermoplastic polymer has a glass transition temperature of about 90 to 200 ° C. and a number average molecular weight of about 10,000 to 100,000. The thermoplastic polymer is preferably included in about 20 to 40 parts by weight, more preferably about 20 to 30 parts by weight per 100 parts by weight of aromatic polyepoxide.

The multifunctional (meth) acrylate is preferably an aromatic di (meth) acrylate and is typically included in about 5 to 20 parts by weight per 100 parts by weight of aromatic polyepoxide. Optional but highly preferred direactive compounds generally comprise from about 1 to 15 parts by weight per 100 parts by weight of aromatic polyepoxide. The combined amount of the polyfunctional (meth) acrylate and the direactive compound (if the latter component is present) is preferably about 10 to 25 parts by weight (more preferably about 15 to 20) per 100 parts by weight of the aromatic polyepoxide. Parts by weight).

Upon exposure to electron beam irradiation, polyfunctional (meth) acrylates and direactive compounds (if present) polymerize and crosslink to form poly (meth) acrylate networks, but thermally activated curing agents for aromatic polyepoxides and polyepoxides. And preferably the thermoplastic polymer does not polymerize. As a result, the adhesive composition

a) heat curable aromatic polyepoxide;

b) heat activated curing agents for polyepoxides;

c) thermoplastic polymers; And

d) 1) polyfunctional (meth) acrylates and

2) a thermosetting adhesive bond, optionally comprising a (meth) acrylate polymer network comprising an electron beam irradiation polymerization product with a compound comprising at least one (meth) acrylate group and at least one group reactive with an aromatic polyepoxide Films may be provided.

Preferred thermally curable adhesive bonding films of the present invention are easy to handle and exhibit controlled flow during thermal curing. After thermal curing, the preferred adhesive bond films of the present invention have good adhesion to the film-coated substrate and high glass transition temperature.

The present invention also relates to a process for producing the adhesive bond film. This method

a) providing an adhesive composition as described above;

b) forming a layer of adhesive composition on the support surface (eg, a temporary carrier such as a permanent backing, or release liner); And

c) exposing the layer of adhesive composition to electron beam irradiation to polymerize the polyfunctional (meth) acrylate and any direactive compound, if present, but without causing a reaction of the thermally activated curing agent or aromatic polyepoxide. .

A thermosetting adhesive bond film is formed. By heating the heat curable adhesive bond film at a temperature sufficient for curing the aromatic polyepoxide for a sufficient time, a heat cured (ie heat curable) adhesive bond film can be obtained.

<Detailed Description of the Preferred Embodiments>

In one aspect, the invention

a) aromatic polyepoxides;

b) thermally activated curing agents for polyepoxides, sometimes referred to herein as " heat activated polyepoxide curing agents " or " polyepoxide curing agents ";

c) thermoplastic polymers;

d) polyfunctional (meth) acrylates; And

e) optionally containing at least one (meth) acrylate group and at least one group reactive with an aromatic polyepoxide, which compound is sometimes referred to herein as " direactive compound " An adhesive composition composed of components.

The present invention also relates to thermally curable adhesive bonding films made from adhesive compositions, as well as to methods of making the films. Briefly, for example, by forming a layer of adhesive composition on a support surface, such as a permanent backing or a temporary carrier (e.g., a release liner), and then exposing the adhesive layer to electron beam irradiation, a heat curable adhesive bonding film is prepared. can do. (The terms "bonding film", "adhesive bonding film" and "thermally curable adhesive bonding film" are used synonymously herein and refer to an adhesive composition after being formed into a film and exposed to electron beam irradiation, but before heat curing the film. .)

The present invention further relates to various products that can be made using the adhesive composition and the adhesive bonding film. For example, in the manufacture of laminates, an adhesive bond film is placed between two substrates and heat cured with a thermoset material (ie, a crosslinked polymer network that does not flow or melt). (The terms "final adhesive bond film" and "heat cured adhesive bond film" are used synonymously herein and refer to an adhesive bond film that is heat cured with a thermoset material.)

Advantageously, the preferred adhesive composition of the present invention is easily manipulated and processed. These compositions have a viscosity that the polyepoxide curing agent can be mixed at a temperature at which there is no risk of causing premature curing reactions and then coated. Since the adhesive composition of the present invention polymerizes when exposed to electron beam irradiation and includes a material that does not depend on photopolymerization, it is advantageously not necessary to store the adhesive composition under "safe light" conditions.

Preferred thermally curable adhesive bonding films of the present invention are also easily manipulated. These bonding films can be removed from the temporary carrier and placed on the substrate without wrinkling, tearing or permanently stretching (ie, without permanent deformation of size or thickness). Adhesive bond films made from preferred adhesive compositions of the invention may also exhibit controlled adhesive flow during thermal curing. In these binding films, the adhesive flows sufficiently to wet the substrate surface to form a flat bond line with a constant binding force. However, the adhesive flow during thermal curing is not excessive. For example, in the manufacture of laminates, the adhesive does not flow beyond the edge of the substrate or cause uneven bond lines, voids or inconsistent bond forces. After thermal curing, the adhesive bond film of the present invention has excellent adhesion to the substrate on which the film is applied. Preferred thermally cured adhesive bond films have a high glass transition temperature (usually at least 120 ° C., preferably at least 140 ° C., more preferably at least 150 ° C., most preferably at least 160 ° C.) and are reduced to this property It can be used to provide heat resistant structural articles and structural laminates with thermal expansion.

The term "polyepoxide" refers to at least two 1,2-epoxide groups, i.e. It means a compound containing a group having a structure of. Aromatic polyepoxides are preferred because they can impart high temperature practicability (eg, high glass transition temperature) to heat cured adhesive bond films and impart structural properties. Combinations of different aromatic polyepoxides can be used.

Aromatic polyepoxides suitable for use in the adhesive compositions and adhesive bonding films of the invention include polyhydric phenols such as those described in US Pat. No. 4,707,534, such as pyrocatechol, resorcinol, hydroquinone, 4,4'-dihydride. Oxydiphenyl methane, 4,4'-dihydroxy-3,3'-dimethyldiphenyl methane, 4,4'-dihydroxydiphenyl methyl methane, 4,4'-dihydroxydiphenyl dimethyl methane, 4,4'-dihydroxydiphenyl cyclohexane, 4,4'-dihydroxy-3,3'-dimethyldiphenyl propane, 4,4'-dihydroxydiphenyl sulfone, tris- (4-hydroxy Halogenated (e.g., chlorinated or brominated) of polyglycidyl ethers of the above-mentioned polyhydric phenols and oxyphenyl) methane, 9,9-bis (4-hydroxyphenyl) fluorene and their ortho-substituted homologues thereof Polyglycidyl ethers of the product.

Other suitable aromatic polyepoxides include polyglycidyl derivatives (ie glycidylamine) of aromatic amines obtained from the reaction between aromatic amines and epihalohydrin. Examples of such glycidylamines include N, N-diglycidyl aniline, N, N'-dimethyl-N, N'-diglycidyl-4,4'-diaminodiphenyl methane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenyl methane, N, N-diglycidylnaphthaleneamine (Chemical Abstracts 9th Coll. 8505F (1982-1979)) N-1-naphthalenyl-N- (oxyranylmethyl) oxyranmethaneamine), N, N, N ', N'-tetraglycidyl-1,4-bis [(α-4-amino Phenyl) -α-methylethyl] benzene and N, N, N ', N'-tetraglycidyl-1,4-bis [(α- (4-amino-3,5-dimethylphenyl)-[α- Methylethyl] benzenes are also suitable polyglycidyl derivatives of aromatic aminophenols, such as glycidylamino-glycidyloxy benzene, as described in US Pat. No. 2,951,825. An example is N, N-diglycidyl-4-glycidyloxybenzeneamine.

Also useful are polyglycidyl esters of aromatic polycarboxylic acids, such as diglycidyl esters of phthalic acid, isophthalic acid or terphthalic acid.

Preferably, the aromatic polyepoxides are polyglycidyl ethers of novolacs (i.e., reaction products of mono or polyhydric phenols with aldehydes, in particular formaldehyde, in the presence of an acid catalyst); Or diglycidyl ether of 4,4'-dihydroxydiphenyl dimethyl methane.

Examples of commercially available aromatic polyepoxides that can be used in the adhesive compositions and adhesive bonding films of the invention include MY ^TM- 720 (Ciba-Geigy, Inc., Hawthorne, NY); ERL-0510 from Ciba-Geigy, Inc .; EPON ^™ based materials (Shell Chemical Co., Houston, TX) (eg EPON HPT-1071, EPON HPT-1072, EPON HPT-1079 and EPON 828); And materials of the DER ^™ , DEN ^™ and QUATREX ^™ groups (Dow Chemical Company, Midland, MI) (eg, DER 332, DER 361, DEN 438 and QUATREX 1010).

While solid aromatic polyepoxide resins can be used, the polyepoxide or polyepoxide mixture is essentially liquid at room temperature (this term means that the viscosity of the polyepoxide (or polyepoxide mixture) is at room temperature, or polyepoxide curing agent). Means that it is allowed to be mixed and then spread (eg, coated) when heated to a temperature (eg, room temperature to about 120 ° C.) that does not risk premature curing reactions. desirable. Liquid aromatic polyepoxides facilitate mixing and spreading of the adhesive composition at low temperatures that do not activate the polyepoxide curing agent.

Preferably, the aromatic polyepoxide (or polyepoxide mixture) has an average epoxide functional group of 2 to 4 and more preferably an average epoxide functional group of 2 to 3. This facilitates providing both an adhesive composition that can be mixed and spread without causing premature curing reaction of the heat activated curing agent, and a fully crosslinked final adhesive bond film. It is also preferred that the aromatic polyepoxide (or polyepoxide mixture) has an epoxy equivalent weight of about 80-200 g / equivalent. This promotes the formation of an adhesive composition having a viscosity that allows efficient mixing and coating, and a final adhesive bond film having an acceptable high glass transition temperature. In electrical devices, it is further preferred that aromatic polyepoxides have low levels of ionic hydrolyzable halides, since these materials can corrode printed circuit board laminates made using them.

The adhesive composition of the present invention also includes a heat activated curing agent for polyepoxide. Heat activated curing agents may be dissolved or dispersed in the adhesive composition. The term "curing agent" is used broadly to include not only materials that are generally considered to be curing agents, but also materials that catalyze epoxy polymerization, and materials that can act as both curing agents and catalysts. Combinations of different heat activated curing agents can also be used. Examples of thermally activated curing agents useful in the adhesive compositions and adhesive bonding films of the invention include polybasic acids and their anhydrides such as di-, tri- and higher carboxylic acids (eg oxalic acid, phthalic acid, terephthalic acid, succinic acid, alkyl). Substituted succinic acid, tartaric acid, phthalic anhydride, succinic anhydride, malic anhydride, nad acid anhydride, pyromellitic anhydride) and, for example, polymerized unsaturated acids having at least 10 carbon atoms (e.g., dodecenedioic acid and 10 , 12-eicosadiendioic acid, and the like).

Other heat activated curing agents that can be used in the present invention are dicyandiamide, melamine, urea and aliphatic amines (e.g. diethylenetriamine, triethylenetetraamine, cyclohexylamine, triethanolamine, piperidine, tetramethylpipepe Lamin, N, N-dibutyl-1,3-propane diamine, N, N-diethyl-1,3-propane diamine, 1,2-diamino-2-methyl-propane, 2,3-diamino- Nitrogen containing compounds such as 2-methyl-butane, 2,3-diamino-2-methyl-pentane, 2,4-diamino-2,6-dimethyl-octane, dibutylamine and dioctylamine) .

Chloro-, bromo- and fluoro-containing Lewis acids of aluminum, boron, antimony and titanium, such as aluminum trichloride, aluminum tribromide, boron trifluoride, antimony fluoride and titanium tetrafluoride and the like are also useful as curing agents. Do. It is also sometimes desirable for these Lewis acids to be blocked to increase the latency of the adhesive composition containing them. Representative examples of blocked Lewis acids are BF ₃ -monoethylamine, as described in US Pat. No. 4,503,211, and HSbF ₅ X {where X is halogen, -OH or -OR ¹ , where R ¹ is Aliphatic or aromatic alcohol, aniline or a derivative thereof)}. Pyridine, benzyldimethylamine, benzylamine and diethylaniline are also useful as heat activated curing agents. Some of the curing agents described herein are more typically used in combination with other curing agents than alone.

Preferably, the heat activated curing agent is o-, m- and p-phenylene diamine, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodi Phenyl sulfide, 4,4'-diaminodiphenyl ketone, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl methane, 1,3-propanediol-bis- (4-amino Benzoate), 1,4-bis [α- (4-aminophenyl) -α-methylethyl] benzene and 1,4-bis [α- (4-amino-3,5-dimethylphenyl) -α-methyl Ethyl] benzene, bisα- (4-amino-3-methylphenyl) sulfone, 1,1'-biphenyl-3,3'-diphenyl-4,4'-diamine, 1,1'-biphenyl-3 Aromatic polyamines such as, 3'-dimethoxy-4,4'-diamine and diaminonaphthalene.

9,9'-bis (4-aminophenyl) fluorene, 9,9'-bis (3-methyl-4-aminophenyl) fluorene and 9,9'-bis (3-chloro-4-aminophenyl) Fluorene diamines such as fluorene are most preferred as heat activated curing agents.

Examples of commercially available heat activated curing agents useful in the present invention include EPON ^™ HPT-1061 and EPON ^™ HPT-1062 (Shell Chemical Co., respectively), HT-9664 (Ciba Geigy, Inc.) and AMICURE ^™ CG-1400 ( Air Products, Pacific Chemical, Allentown, PA).

The heat activated polyepoxide curing agent used in the adhesive composition and adhesive bonding film of the present invention does not react with the polyepoxide when exposed to electron beam irradiation, and preferably does not inhibit polymerization by electron beam irradiation. Preferred thermally activated curing agents for use in the present invention exhibit potential thermal reactivity; That is, they react mainly at higher temperatures (preferably at least 120 ° C, more preferably at least 130 ° C, most preferably at least 140 ° C). Because of this the adhesive composition is easily mixed and coated at room temperature (about 20-22 ° C.) or under slight warming (ie, below the reaction temperature of the polyepoxide curing agent) without activating the curing agent.

In electrical appliances, it is more preferred that the polyepoxide curing agents have little or no ionic or hydrolyzable halides since they can corrode printed circuit board laminates made using them.

Adhesive compositions and adhesive bond films of the present invention also include thermoplastic polymers. The term "thermoplastic" means an uncrosslinked polymer that can be softened and reshaped at least repeatedly under the application of heat and pressure.

Preferably, the thermoplastic polymer is soluble in aromatic polyepoxides prior to exposure to electron beam irradiation. The glass transition temperature of the thermoplastic polymer is preferably from about 90 ° C. to 200 ° C. in order to promote good high temperature performance when the adhesive composition is heat cured, such that the adhesive has increased utility in, for example, electrical use only. It is also preferred that the number average molecular weight of the thermoplastic polymer is about 10,000 to 100,000. If the number average molecular weight is much lower than about 10,000, the adhesive composition is difficult to form easily manipulated bonding films. If the number average molecular weight far exceeds about 100,000, the viscosity of the adhesive composition increases, making it difficult to coat the adhesive on the film, and the solubility of the thermoplastic polymer in the aromatic polyepoxide is reduced. Preferably, the thermoplastic polymer is aromatic to provide a more heat resistant adhesive bond film. It is also preferred that the thermoplastic polymer does not react when exposed to electron beam irradiation.

Thermoplastic polymers suitable for use in the adhesive compositions and adhesive bonding films of the present invention may be prepared by copolymerizing polysulfones such as 4,4'-dichlorodiphenyl sulfone and 2,2'-bis (4-hydroxyphenyl) propane. Polysulfone formed; Poly (methyl methacrylate); Phenoxy polymers such as phenoxy polymers formed by copolymerizing 2,2-bis (4-hydroxyphenyl) propane and diglycidyl ethers thereof; And combinations of these materials.

Commercially available thermoplastic polymers that can be used in the present invention include PKHP ^™ 200 (Phenoxy Associates, Rock Hill, SC), PKHJ ^™ (Phenoxy Associates), UDEL ^™ 1700 and UDEL ^™ 3500 (Amoco Performance Products, Inc., Ridgefield, respectively). , CT), PLEXIGLASS ^™ (Rohm & Haas, Philadelphia, Pa.) And LEXAN 141 (General Electric Co.).

The adhesive composition and adhesive bonding film of the present invention also include a multifunctional (meth) acrylate. The term "(meth) acrylate" refers to compounds comprising acrylate or methacrylate residues; That is, the chemical formula Meaning a compound of which R is hydrogen or methyl and R 'is an organic radical. The term "polyfunctional" means a compound having at least two (meth) acrylate groups.

The polyfunctional (meth) acrylates useful in the present invention are preferably difunctional to provide di (meth) acrylates. When using mixtures of different polyfunctional (meth) acrylates, small amounts of monofunctional (meth) acrylates can be used, for example, to adjust the viscosity of the adhesive. However, too much monofunctional (meth) acrylate can cause excessive adhesive flow and / or reduced adhesion during thermal curing.

Both aromatic and aliphatic (meth) acrylates can be used. Preferably, the (meth) acrylate is aromatic in order to increase the solubility in the aromatic polyepoxide and the heat resistance of the heat cured adhesive bond film before exposure to electron beam irradiation. Preferred polyfunctional (meth) acrylates are soluble in aromatic polyepoxides prior to electron beam irradiation. It is also preferred that the polyfunctional (meth) acrylates are essentially liquid at room temperature, as they facilitate mixing and coating of the adhesive composition. If the adhesive composition can be mixed and coated at room temperature or under slight warming, solid polyfunctional (meth) acrylates can be used.

Examples of suitable multifunctional (meth) acrylates useful in the present invention include bisphenol A epoxy di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, pentaerythritol tetra (meth) acrylate, diethylene glycol Di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, epoxy novolac poly (meth) acrylate, and the like. Preferred multifunctional (meth) acrylates include bisphenol A based di (meth) acrylates such as bisphenol A epoxy di (meth) acrylate and ethoxylated bisphenol A di (meth) acrylate.

Examples of commercially available polyfunctional (meth) acrylates suitable for use in the present invention include SARTOMER ^™ family of materials such as SARTOMER205, SARTOMER231, SARTOMER238, SARTOMER239, SARTOMER348, and SARTOMER349 (Sartomer Co., Exton, PA), and EBECRYL600 And substances of the EBECRYL ^™ family such as EBECRYL616 and EBECRYL639 (UCB Radcure, Inc., Smyrna, GA).

The adhesive composition and adhesive bonding film of the present invention are optional but very preferably direactive compounds; That is, it may contain a compound comprising at least one (meth) acrylate group and at least one group reactive with an aromatic polyepoxide. The direactive compound can enhance the adhesion of the final adhesive binding film. The direactive compound must be soluble in the aromatic polyepoxide prior to electron beam irradiation. Both aromatic and aliphatic direactive compounds can be used. Preferably, however, the direactive compound is aromatic in order to increase both the solubility in the aromatic polyepoxide and the heat resistance of the final adhesive bond film prior to electron beam irradiation. It is also preferred that the direactive compound is essentially liquid at room temperature to facilitate mixing and coating of the adhesive composition. However, if the adhesive composition can be mixed and coated at room temperature or under slight warming, a solid direactive compound can be used.

Examples of groups reactive with polyepoxides for use in direactive compounds include hydroxyl, carboxyl, amines (preferably aromatic amines) and 1,2-epoxides. Specific examples of direactive compounds that can be used in the present invention include carboxylic acid functional acrylates such as (meth) acrylic acid, and 2-hydroxy-3-phenoxypropyl (meth) acrylate and 2-hydroxy-3 Phenyl-containing hydroxy-functional (meth) acrylates, such as -phenylphenoxy (meth) acrylate. As suitable polyfunctional (meth) acrylates, di (meth) acrylates described above are also useful, but here one of the (meth) acrylate groups is substituted with a group reactive with a polyepoxide, an example of such a material being glycy Dill (meth) acrylate, epoxy novolac (meth) acrylate, triethylene glycol (meth) acrylate, and the like. Mono (meth) acrylates of various polyepoxide resins such as bisphenol A epoxy mono (meth) acrylate and the like are particularly preferred as direactive compounds. Commercially available suitable direactive compounds for use in the present invention include EBECRYL ^™ 3605 (UCB Radcure Inc.) and SARTOMER ^™ 379 (Sartomer Co.).

Thermally activated curatives are used in a cure effective amount to provide the final adhesive bond film with the desired high temperature performance that depends on the intended use of the adhesive bond film. The actual amount of curing agent used will also be influenced by the type and amount of other components in the mixture. The use of small amounts of curing agent can produce thermally cured adhesive bond films having low glass transition temperatures, high coefficients of thermal expansion and reduced solvent content. The use of large amounts of curing agents results in very rapid curing with potentially uncontrolled heat build-up, in addition to the final adhesive bonds that absorb too much moisture, are brittle or have low glass transition temperatures. The film can be produced.

Within these parameters, the curing agent is typically used in an amount of about 2 to 100 parts by weight per 100 parts by weight of aromatic polyepoxide. When the curing agent is based on a Lewis acid, it is typically used at a level of about 0.1 to 5 parts by weight per 100 parts by weight of aromatic polyepoxide. If the curing agent is a carboxylic acid, anhydride, or primary or secondary amine, the curing agent typically comprises about 0.5 to 1.7 equivalents of acid, anhydride or amine per equivalent of epoxy group. In the anhydride curing agent, any promoter in the range of about 0.1 to 5 parts by weight per 100 parts by weight of the aromatic polyepoxide, for example, an aromatic tertiary amine such as benzyldimethyl amine or 2-ethyl-4-methylimidazole Imidazole may be present.

Thermoplastic polymers are used in an effective amount, which can be mixed without causing pre-cure reaction of the polyepoxide curing agent and then spread (eg, by coating), subsequently thermally cured to have a controlled adhesive flow. It is meant an amount sufficient to provide an adhesive composition capable of forming an easily manipulated bonding film.

Very advantageously, only a small amount of thermoplastic polymer is required for the adhesive composition of the present invention. Typical amounts of thermoplastic polymers are preferably about 20 to 40 parts by weight, more preferably about 20 to 30 parts by weight per 100 parts by weight of aromatic polyepoxide, but the actual amount is not only the type and amount of other components of the adhesive composition, The ultimate use of the adhesive will vary depending on the intended use. For thermoplastic polymers greater than about 40 parts by weight, the mixing and spreading temperatures for the adhesive composition can be increased to a temperature at which premature thermal curing can occur, and the adhesive bond film formed therefrom tends to break too easily for easy operation. There may be. At less than about 20 parts by weight thermoplastic polymer, the adhesive bond film is difficult to manipulate and excessive adhesive flow during thermal curing.

An effective amount of multifunctional (meth) acrylate is used, which means an amount sufficient to provide an adhesive composition that can be subsequently heat cured to provide an easily manipulated bond film that can have a controlled adhesive flow. Within these parameters, the multifunctional (meth) acrylate is preferably used at about 5-20 parts by weight, more preferably about 12-20 parts by weight per 100 parts by weight of the aromatic polyepoxide, although the actual amount of the adhesive composition The type and amount of other components, as well as the ultimate purpose of the adhesive, will vary depending on the intended use. If used at less than about 5 parts by weight, the adhesive bond film formed therefrom may be difficult to manipulate, and the adhesive flow may be excessive during thermal curing. When used in excess of about 20 parts by weight, the adhesive bond film may be difficult to manipulate, and thermally cured results in compositions having low stability and reduced stability under elevated temperatures (eg, temperatures encountered during soldering of printed circuit boards). Can produce.

An effective amount of the direactive compound, if present, is used, which means an amount sufficient to provide an adhesive composition that can be subsequently heat cured to provide an easily manipulated bond film that can have a controlled adhesive flow. Within these parameters, the direactive compound is preferably used in an amount of about 1 to 15 parts by weight, more preferably about 4 to 10 parts by weight, although the actual amount is not only the type and amount of other components of the adhesive composition, but also the adhesive Will ultimately change depending on its intended use. At less than about 1 part by weight, the heat cured adhesive bond film formed therefrom may lose adhesion. In amounts exceeding about 15 parts by weight, the adhesive bond film may be difficult to manipulate and excessive adhesive flow may occur during thermal curing.

The effective amounts of the polyfunctional (meth) acrylates and direactive compounds (if any) can also be determined in the amounts used in combination, the combined effective amounts of these two materials being easily manipulated and with heat resistant materials having good adhesion. It is sufficient to provide an adhesive bond film that is heat cured. Generally, about 10 to 25 parts by weight, more preferably about 15 to 20 parts by weight of polyfunctional (meth) acrylate and direactive compound are used per 100 parts by weight of aromatic polyepoxide, but the actual amount is different from that of the adhesive composition. In addition to the type and amount of ingredients, it will vary depending on the ultimate use of the adhesive. When the combined amount of the multifunctional (meth) acrylate and the direactive compound is less than about 10 parts by weight, the adhesive bonding film formed therefrom may be difficult to operate. When the combined amount of the multifunctional (meth) acrylate and the direactive compound exceeds about 25 parts by weight, the adhesive bond film is easy to tear, and the heat cured adhesive bond film may have reduced heat resistance and low adhesion.

The weight ratio of the polyfunctional (meth) acrylate: direactive compound (if present) can range from about 95: 5 to 50:50. More preferably about 80:20 to 50:50, and most preferably about 80:20 to 75:25. At weight ratios greater than about 95: 5, adhesive bond films made using them can be difficult to manipulate, and heat cured adhesive bond films can have low adhesion. At weight ratios less than about 50:50, the adhesive bond film can be difficult to manipulate and excessive adhesive flow during thermal curing.

Various additives may be usefully incorporated to impart certain desired properties to the adhesive compositions and adhesive bond films of the present invention. Suitable additives are knitting, such as flame retardants, electrically conductive particles, thermally conductive particles, pigments, hollow or solid microspheres that may be polymeric or inorganic, inorganic fillers, antioxidants, or made from carbon, glass or polyaramid materials. Fibers or nonwoven fibers.

The adhesive composition and adhesive bonding film of the present invention are easily produced. The various components may be combined by extruder, planetary mixer or heated mogul to form a mixture having a coatable viscosity. The ingredients must be added sequentially. Preferably, the aromatic polyepoxide and thermoplastic polymer are combined in solution, followed by the addition of the multifunctional (meth) acrylate and the direactive compound (if included), followed by the addition of the curing agent. No solvent is required. Thus, the adhesive composition of the present invention can be provided in a 100% solid mixture.

Preferably and very advantageously, the aromatic polyepoxides, thermoplastic polymers, polyfunctional (meth) acrylates and direactive compounds (if present) are chosen to be soluble in one another. Heat activated curing agents can be dissolved or dispersed in these components. The term "soluble" means mixing soluble materials (by heating if necessary), bringing the mixture back to room temperature, and then no evidence of phase separation at room temperature is observed visually. Lack of solubility can result in inconsistent bonding, poor film handling properties, low adhesion and poor adhesive flow control. The components that make up the adhesive composition (except for the polyepoxide curing agent when dispersed) remain soluble after mixing and spreading into the film.

Since the adhesive composition of the present invention does not rely on exposure to actinic radiation to form an adhesive bond film, the composition does not require a photocatalyst. In conclusion, the adhesive composition and adhesive bonding film of the present invention are photostable. That is, because they are sufficiently unreactive when exposed to visible or ultraviolet light, packaging and storage under “stable light” conditions (eg, storage in containers that are not transparent to visible and ultraviolet light) are not considered essential.

Once the various components are mixed, the adhesive composition is delivered by spreading (eg, coating) between one removable release liner or two release liners, which may have the same or different release values, in the form of a film. Products can be provided. Useful release liners include silicone paper and plastic films. Alternatively, the adhesive composition may be coated onto a permanent backing that may be formed of a material such as polyolefin, polyester, polyimide or paper. If desired, for example, priming of a backing using a chemical primer, or corona discharge can be used. The exposed adhesive surface can be protected with a removable release liner as mentioned above. In another embodiment, a layer of adhesive composition is applied to a knitted or nonwoven fibrous support surface (eg, carbon, glass, aramid, polyester or polyimide fibers), for example, by impregnating the support with the adhesive composition. Fiber reinforced composite products can be prepared.

The adhesive composition of the present invention can be spread by various techniques including coating methods such as heated knife-over-bed coating, roll coating and die coating. Advantageously, in order to inhibit premature curing of the thermally activated polyepoxide curing agent, the adhesive composition is relatively low temperature (ie, from about room temperature to about 120 ° C.), preferably from about 30 to 120 ° C., more preferably about 30 To 90 [deg.] C., most preferably about 30 to 60 [deg.] C .. The coating thickness can vary from about 10 to 130 μm or more.

Once the adhesive composition is spread in the form of a film, it causes polymerization and crosslinking of the (meth) acrylate residues of the polyfunctional (meth) acrylate and the direactive compound (if present), but the thermally activated curing agent, aromatic polyepoxy Or electron beam irradiation for a sufficient time, preferably at a sufficient exposure level that does not cause the reaction of the thermoplastic polymer. Typical irradiation conditions are about 2-10 M㎭ (megarad). A dose of 5 M㎭ is useful. The adhesive bond film may or may not be tacky to the touch depending on the particular composition.

Since the (meth) acrylate functional component is soluble in aromatic polyepoxides prior to irradiation, exposure to electron beam irradiation results in the formation of a (meth) acrylate polymer network in the unreacted aromatic polyepoxide. (Meth) acrylate polymer networks and thermoplastic polymers contribute to the preferred easily manipulated adhesive bond films of the present invention. These adhesive bond films can be removed from the temporary carrier (eg, release liner) and placed on the substrate without wrinkling, tearing or permanently stretching (ie, without permanent deformation of size or thickness). Although the adhesive bond film can be removed from the temporary carrier manually or by an automated machine, the previous method may require a film with good operating characteristics due to the inconsistent stress applied to the film during removal. Adhesive-bonded films with acceptable operating characteristics are promoted by having a modulus of about 1 to 300 MPa (megapascals) after exposure to electron beam irradiation, and a glass transition temperature of about 20 ° C. or less.

The adhesive bond films of the present invention can be made into knitted fibers and nonwoven fibers (eg glass, carbon and aramid), metals (eg aluminum, stainless steel and copper), plastics (eg polyimide and polyester) And a wide variety of materials including ceramics. The adhesive compositions and bonding films of the present invention are useful for providing composite products reinforced with fiber webs or tows and for general industrial bonding applications such as making structural (ie high strength) laminates. Adhesive bond films are particularly useful in the electronics industry. One particularly preferred use is the fabrication of laminated printed circuit boards, wherein the adhesive bond film is used to laminate a copper plating polymer (eg polyimide) substrate comprising an etched circuit. Another particularly preferred use includes combining the integrated circuit chip and the flexible circuit to the rigid printed circuit board, as well as joining the printed circuit board together.

When an adhesive is made between two release liners to provide a deliverable adhesive bond film, one release liner is removed, the adhesive liner film is placed on the substrate to be bonded, the second liner is removed, and the second substrate Is placed on the adhesive. If the adhesive comprises a permanent backing (which provides one substrate) and a protective release liner, the latter is removed and the adhesive layer is placed against the second substrate.

Once the adhesive binding film is properly positioned relative to the substrate to be bonded, it is heated for a sufficient time at a temperature sufficient to cure the aromatic polyepoxide, and the actual time and temperature depend on the particular component in the adhesive composition and the substrate to be bonded. In general, temperatures of about 50-250 ° C. and curing times of about 20 seconds to 5 hours are available, and higher temperatures generally require less curing time than at lower temperatures. 90 minutes of curing conditions at 180 ° C. are useful.

Prepolymerized and crosslinked meth (acrylate) polymer networks provide preferred adhesive bond films of the present invention with controlled adhesive flow during thermal curing, which together with the thermoplastic polymer form flat bond lines and bond forces. The heat cured adhesive bond film can possess high temperature performance which is not significantly different from the temperature performance of a heat cured epoxy resin that does not include a (meth) acrylate-containing component. Thus, the thermally cured adhesive bond film can withstand exposure to elevated temperatures, such as the temperature experienced during the soldering process of printed circuit boards.

The invention will be more fully understood by reference to the following non-limiting examples. The general techniques used to prepare and test adhesive compositions, adhesive bond films, and laminates made therefrom will now be described. The size is nominal and approximates the conversion from British units to meters.

General Preparation of Adhesive Compositions, Adhesive Bonding Films, and Laminates

General Preparation of Adhesive Compositions

Flowable viscosity for easy weighing and delivery by heating the aromatic polyepoxide for 60 seconds in a 950 W (watt) microwave oven (Model R E53C 002, Hotpoint brand, Hotpoint Company, Louisville, KY) operating at the highest setting It was to have. The resin temperature should not exceed 70 ° C. The thermoplastic polymer was dissolved in aromatic polyepoxide at a resin temperature of 120 ° C. using a 0.2 L metal can, air stirrer and hot plate. The time required for dissolution was typically 20 to 30 minutes. Dissolution was recognized by the formation of a clear homogeneous solution.

Multifunctional (meth) acrylates and direactive compounds (if included) were mixed with the aromatic polyepoxide / thermoplastic polymer blend using either a slow mixing method or a fast mixing method.

In the slow mixing method, the multifunctional (meth) acrylate and the direactive compound were preheated separately in an air convection oven set at 70 ° C. until a flowable viscosity was reached. These ingredients were then weighed into 8 ounce glass jars and manually mixed using a wood depressor. The aromatic polyepoxide / thermoplastic polymer blend is also preheated in an air convection oven set at 70 ° C. until a flowable viscosity is reached, at which 60 g volume is preheated with a cam style mixing blade and preheated to 60 ° C. It was added to a Plasti-corder ^™ PL-2000 mixer (CW Brabender Instrument, Inc., Hackensack, NJ). The mixing speed was 30 rpm (rpm) here and at the addition of all subsequent materials. After 1-2 minutes, the preheated multifunctional (meth) acrylate / direactive compound combination was added with additional mixing at 60 ° C. for 1-2 minutes. The polyepoxide curing agent was then added slowly with stirring each time using a table spoon. Each portion of the curing agent was dispersed completely to remove all visible "clumps" before adding subsequent portions. After all the curing agent was added, the mixing speed was increased to 100 rpm for 5 minutes.

The high speed mixing method allows for faster sample preparation. More specifically, multifunctional (meth) acrylates and direactive compounds were manually formulated at room temperature using wood depressors. The aromatic polyepoxide / thermoplastic polymer blend is heated for 15 seconds in a 720 W microwave oven (model ERS-6831B, Toshiba brand, Toshiba America, Wayne, NJ) operating at the highest setting, removed, and lightly Manual stirring and then heating again for an additional 15 minutes to provide a flowable viscosity for easy weighing and delivery. The blend temperature did not exceed 70 ° C. The flowable aromatic polyepoxide / thermoplastic polymer blend was weighed and placed in a 0.05 L plastic mixing cup, followed by the addition of the multifunctional (meth) acrylate / direactive compound blend. These components were thoroughly mixed at room temperature for about 30 seconds using a Cordless Driver Drill (Model 6211DW, Makita Corporation, Japan) equipped with a metal spatula and operating at 1100 rpm. Subsequently, the entire amount of the polyepoxide curing agent was added to the plastic cup and blended at high speed for about 2 minutes or less using a cordless drill until there was no visible mass and the curing agent was completely dispersed. The contents of the mixing cup were occasionally warmed at 5-10 second intervals using a microwave oven as described for the high speed mixing method.

General Preparation of Adhesive Bonding Films

An adhesive bond film was prepared by coating the adhesive composition and then exposing the coated adhesive to electron beam irradiation.

More specifically, the adhesive composition was coated to a 6 inch wide heated coating station using a knife-over-bed. The knife was fixed in position to maintain a fixed gap. The heating element was included in the bed and the knife respectively, and a radiant heater was installed in the area behind the knife where the adhesive was placed. Place two heating elements (Watlow Firerod cartridge heaters, Model G5A115, 125W; Watlow, St. Louis, MO) in the bed, and use three heating elements (Watlow band heaters, Model STB1E1E2) to Surrounded. One thermocell was mounted on the side of the bed under the knife and the other was in contact with the surface of the radiant heater. The bed and knife heaters were controlled by one Watt Series 965 temperature controller set at 65 ° C. and the radiant heater was controlled by another temperature controller set at 140 ° C. The knife spacing was set to be 0.002 in. (50 μm) larger than the combined thickness of the two release liners used, using a feeler gauge.

The adhesive composition was warmed for 15 seconds in a microwave oven as described above in the high speed mixing method, and left to flow. The adhesive composition was then poured between 0.002 in. (50 μm) thick silicone coated polyester release liner. After placing the radiant heater on the “sandwich” structure, the temperature was equilibrated for 0.5 to 1.0 minutes until the adhesive composition was visually determined to have a coatable viscosity. The release liners containing the adhesive composition were then pulled between the knife and bed by pressing the adhesive under the knife.

Electro Curtain Model CB300 / 30/380 (titanium window: 2.5 in. (6.4 cm) long, 14 in. (36 cm) wide, operating the coated adhesive at 25 feet (7.6 m) / min) Energy Sciences, Inc., Wilmington, Mass.) Device was exposed to electron beam irradiation from one side through a release liner to provide an adhesive bond film according to the present invention. Electron beam treatment was performed at room temperature under a nitrogen purge using an electron accelerator operating at 250 kV (kilovolts) and 5 kPa (milliamperes) (capacity = 5 MPa (megarad)). Total exposure time was about 0.5 seconds.

General recipe of laminate

An adhesive bond film was used to prepare a copper plated polyimide film laminate. Copper, polyimide film, release liner and metal plate surfaces are all tack cloth or Kimwipes ^TM -EX-L Delicate Task Wipers (Kimberly-Clark Corporation) , Atlanta, GA) to remove dust.

More specifically, a pair of about 0.002 in. (50 μm) thick adhesive bond film is cut to 5 in. × 5 in. (13 cm × 13 cm) and one of each bond film is removed by removing one of the release liners. Laminates were made by exposing the surface. Adhesive bonding films were prepared using a Kapton ^™ FPC-ZT polyimide film (EI duPont de Nemours and Company, Wilmington, DE), 6 in. × 6 in. × 0.001 in. Thickness (15 cm x 15 cm x 25 μm thick) was placed on each side of the piece. The second release liner was removed from each adhesive bonding film, and then the adhesive covered polyimide film was placed in a class 1 type of 1 ounce copper foil (Oak-Mitsui) of 6.5 in. × 6.5 in. (16.5 cm × 16.5 cm) size. , TOB finish). The copper foil layer was oriented so that the grain direction was the same on both sides.

Two release liners (Tedlar ^TM MR, EI duPont) each measuring 7 in. × 7 in. (17 cm × 17 cm) layup of copper foil / adhesive bond film / polyimide film / adhesive bond film / copper foil deNemours and Company). A stack comprising two to six such layups, a metal separator plate, a metal base plate and a metal top plate between each layup were assembled. The base plate was 8 inches by 8 inches (20 cm by 20 cm) in size; The top and separator plates were each 6 in. × 6 in. (15 cm × 15 cm) in size. All plates were 0.040 to 0.062 inches (1.02 to 1.57 mm) thick. The adhesive bond film was then thermally cured using one of two different laminate methods. In both cases, a single opening laminate press (Pasadena Hydraulics, Inc. (PHI), City of Industry, CA. model TS-21-HC-8, DT5000 temperature of 8 in. X 8 in. (20 cm x 20 cm)) Regulator / programmer). After thermal curing, the laminate was trimmed to 4.5 inches x 4.5 inches (11.4 cm x 11.4 cm).

In one laminate method (herein referred to as laminate method A), the stack was placed in a press at room temperature. A pressure of 50 pounds / inch ² was applied immediately and heating started to 180 ° C. at 5 ° C./min. The stack was held at 180 ° C. for 90 minutes and then the heated platen was internally cooled back to room temperature over 5 minutes using tap water.

The second laminate method (herein referred to as laminate method B) was identical to laminate method A except that the press was programmed to heat to 190 ° C. and the stack was held at this temperature for 30 minutes. After cooling to room temperature, the laminate was transferred to a preheated air convection oven and postcured at 180 ° C. for 90 minutes.

Test Methods

Glass transition temperature (Tg)

The Tg of the heat-cured adhesive bond film was measured using a single cell deviation scanning calorimeter (DSC) (Model 2920, TA Instruments, New Castle, DE). About 5-15 mg of adhesive binding film was placed in a DSC sample pan, sealed and thermoset at 180 ° C. for 90 minutes in a preheated convection air oven. The sample was then scanned at a rate of 20 ° C./min from 40 to 250 ° C. under a helium purge. The ½ height of the transition on the first scan was taken as Tg. The recorded value was rounded to degrees.

Peel Adhesion

Laminate size to 2.25 in. × 2.75 in. (5.72 cm × 6.99 cm); Three peel pieces were tested; Data (120 data points) was collected over a 2.0 inch (5.1 cm) distance for each peel piece; Discard the first and last 0.17 in (0.43 cm) (20 data points each) for each peeled piece and then analyze by Mitutoyo Digimatic Mini-Processor (Model DP-2 DX) The Institute for Interconnecting and Packaging Electronic Circuits (IPC) Test Method-650 [Number 2.4.9, Revision D (10/88) "Peel Strength, Flexible Printed Wiring Materials, Method A (with Sliding Plate) Test Fixture "] was used to test the peel force of the laminate. The average peel force of each peel piece was used to calculate the total mean value for the three peel pieces, which was best at 0.1 pounds per inch width (piw). Closely recorded.

A peel adhesion test sample was prepared by etching the peel pieces on one side of the laminate. One side of the laminate was completely covered using 3 in. (7.6 cm) wide 3M Scotch ^™ 1280 Circuit Plating Tape. The other side of the laminate was washed and roughened using a wet heavy duty 3M Scotch-Brite ^™ Scour Pad (Catalog # 220) and dried with a paper towel. One additional piece of 3M Scotch ^™ 281 circuit plating tape was used to seal the edges of the long sides of the laminate and border along the length of the laminate's roughened surface (a separate piece of tape was placed on each of the two sides). Used). Subsequently, using a 0.125 in. (0.318 cm) wide piece of 3M Scotch ^™ 218 Fine Line Tape, eight spaced 0.125 in. (0.318 cm) spaced below the length of the roughened surface of the sample The parallel test pieces were peeled off. The snow liner was used to gently rub the fine line tape to remove all voids and to completely wet the copper surface with tape adhesive. This was visualized by darkening of the surface under the tape.

The taped laminate was KEPRO Bench-Top Etcher (model BTE-202, KEPRO Circuit Systems, Inc.) containing ferric chloride etchant (catalog # E-4G, KEPRO Circuit Systems, Inc.) at 43 ° C and pH 1. , Fenton, MO) was used to etch for 3 minutes to remove unmasked copper. If copper still remained in the unmasked area of the laminate, the laminate was rotated 180 ° in the sample holder and etched for an additional 1 minute to completely remove the remaining unmasked copper. The etched sample was then removed, first rinsed in a tap water bath for 1 minute, then again under running tap water for 1 minute, and then air dried. All tapes were removed from the sample without bending or damaging the sample.

The etched laminates were tested using a Copper Clad Peel Tester (Model TA-630, CFCO Industries, Anaheim, Calif.) Equipped with a 2 pound force gauge. The sample was mounted on a sliding holding stand with the copper test pieces facing upwards. The laminate was aligned and held in place by a grooved fine cover plate securely fixed to the holding stage. The copper test piece on the laminate was placed directly under a 0.188 in. (0.476 cm) wide slot and attached to the force gauge through the groove. The sliding holder and the force gauge were at 90 ° angles to each other. The sample was peeled off at a rate of 2 inches. (5 cm) / minute. For electronic applications, it is desirable that the peel adhesion be at least 6.0 piw, more preferably at least 8.0 piw. For other applications, lower peel adhesion may be acceptable.

Film operability

Remove the 0.5 in. × 5.0 in. (1.3 cm × 12.7 cm) sample from the release liner, hold it at 1 in. (2.5 cm) between the thumb and forefinger of both hands, and stretch to break The film operation characteristic of the bonding film was evaluated. Resistance to elongation and tear was qualitatively determined and rated relative.

Adhesive-bonded films rated as three plus (+++) showed moderate resistance to stretching and tearing. Removal of or release from the release liner has been readily accomplished without wrinkling, tearing or permanently stretching the film (ie, without permanent deformation of size or thickness). The adhesive bond film could be easily manipulated by automated machines or manual methods.

Adhesive bond films rated as plus two (++) had less resistance to elongation or less tearing than the (+++) sample. Removing the release liner or removing it from the release liner without crimping, tearing or permanently stretching the adhesive bond film will be best accomplished by automated mechanical methods or careful manual operation.

One plus (+) graded adhesive bond film has less resistance to stretching than three or two plus graded films, thus releasing the adhesive bond film without wrinkling, tearing or permanently stretching it. It was considered suitable only for use by automated mechanical operating methods to ensure removal from the liner.

One, two or three plus graded adhesive bond films are useful for use as a transfer film (ie, an adhesive bond film delivered between a pair of release liners or on another temporary carrier) or in combination with a permanent backing. Two or three plus graded adhesive bond films are also useful as free-standing films, ie, adhesive bond films that can be physically removed from a support (eg, a release liner or other temporary carrier) and can be manipulated without the support. Do. Wrinkles, tears, agglomerations, or permanently stretched adhesive bond films on removal of release liners or removal from release liners are rated negatively, which is difficult to remove by automated machines or manual methods. While believed, it may be useful to laminate directly to permanent backing (particularly porous backing) without first removing the film from the release liner.

The operating characteristics for some of the adhesive bond films were also evaluated by measuring their modulus. More specifically, Young's modulus was obtained at room temperature using a Thermomechanical Analyzer (TMA), Model 2940 (TA Instruments, Inc.). Sample size was length = 0.16 to 0.50 in. (4.0 to 12.7 mm) and thickness = about 0.002 in. (50 μm). The width: length ratio was maintained at 1: 6 or greater (eg, 1: 8) to match the test conditions. The sample was placed under an applied force (stress) of 0.001 N (Newtons) and the initial length was measured. The force was then increased to 1.0 N at a rate of 1.0 N / min and the change in length (strain) was recorded. The length of the sample was chosen such that the sample broke at an application force of 1 N or less. Modulus was calculated from the initial slope of the stress / strain curve and recorded closest to 0.1 MPa. Preferably, the modulus of the adhesive bond film of the invention is about 1 to 300 MPa for good film operating characteristics.

Glue flow

The adhesive composition flows during thermal curing. Some adhesive flow is desirable to wet the substrate surface and form a flat bond line with a constant bond force. However, excessive adhesive flow during thermal curing such that the adhesive can flow out of the edge of the substrate, or cause uneven bond lines, voids or inconsistent bond forces, should be avoided in the manufacture of the laminate. However, tolerable amount of adhesive flow depends on the ultimate use of the adhesive composition. For example, when impregnating a fiber reinforced web or tow using an adhesive composition or an adhesive bond film, higher amounts of adhesive flow may be allowed.

The degree of adhesive flow was measured by visually inspecting the laminate after removal from the press and before trimming for a peel adhesion test. The grades described below are relative.

More specifically, the distance between the adhesive bond film (prior to heat curing) at the initial center and the outer edge of the copper foil was 0.75 in. (1.91 cm). If the adhesive flow after thermal curing was 0.50 in. (1.27 cm) or more from the outer edge of the copper foil, a plus two (++) grade was assigned, indicating a low degree of adhesive flow. If the adhesive was between 0.50 in. (1.27 cm) and 0.125 in. (0.32 cm) from the outer edge of the copper foil, one plus (+) rating was specified, indicating moderate adhesive flow. One plus or both plus grades represent the best adhesive flow control properties for use in bonding applications where adhesive flow control properties are important. Negative (-) ratings indicating increased adhesive flow were designated when the adhesive was closer than 0.125 in (0.32 cm) to the outer edge of the copper foil, or when it ran beyond the foil edge.

Term Definition

Many abbreviations are used in the examples below. Abbreviations are defined according to the following table.

CAF: 9,9'-bis (3-chloro-4-aminophenyl) fluorene

CG-1400: Dicyandiamide (available from Air Products)

DEH ^TM 85: Phenolic Curing Agent (available from Dow Chemical Company)

DEN ^TM 438 (available from Dow Chemical Company)

DER ^TM 332: Diglycidyl ether of bisphenol A (available from Dow Chemical Company)

EBECRYL ^™ 3605: Monoacrylate of diglycidyl ether of bisphenol A (commercially available from UCB Radcure, Inc.)

EPON ^TM 828: Diglycidyl ether of bisphenol A (available from Shell Chemical Company)

GMA: glycidyl methacrylate (available from Sartomer Company as SARTOMER ^TM 379)

HDDA: 1,6-hexanediol diacrylate (available from Sartomer Company as SARTOMER ^TM 238)

IBA: Isobornyl acrylate (available from San Esters Corporation, New York, NY)

IBMA: Isobornyl methacrylate (available from Sartomer Company as SARTOMER ^TM 423A)

P3500: Udel ^TM P3500 Poly (ether-sulfone) (available from Amoco Performance Products, Inc.)

PEA: 2-phenoxy ethyl acrylate (available from CPS Chemical Company, Old Bridge, NJ)

PhEMA: 2-phenoxy ethyl methacrylate (available from Sartomer Company as SARTOMER ^TM 340)

PKHJ ^TM : Phenoxy Resin (Available from Phenoxy Associates)

PMMA: Poly (methyl methacrylate) (molecular weight = 33,000; available from Scientific Polymer Products, Inc. Ontario, NY)

PolyEMA: Poly (ethyl methacrylate) (available from Aldrich Chemical Company, Catalog # 18,208-7)

QUATREX ^™ 1010: Diglycidyl ether of bisphenol A (available from Dow Chemical Company)

TEGDMA: triethylene glycol dimethacrylate (available from Sartomer Company as SARTOMER ^TM 205)

THFA: tetrahydrofuran acrylate (available from San Esters Corporation)

ULTEM ^™ 1000: Poly (ether-imide) (commercially available from General Electric Company, and subsequently converted to fine particles having a size of about 5 μm or less by an emulsion precipitation method as described in US Pat. No. 5,276,106). Sikkim)

XU AY 238: Hydantoin Epoxy (available under the trade name ARACAST ^TM from Ciba Geigy, Inc.)

Unless otherwise indicated, all amounts in the following examples are negative; That is, parts by weight per 100 parts by weight of aromatic polyepoxide, rounded to the nearest total number.

Examples 1 to 17

A series of laminates was prepared as shown in Table 1 below as described above in "General Preparation of Adhesive Compositions, Adhesive Bond Films and Laminates". Based on the description provided above, Table 1 indicates the lamination method and mixing method, the latter identified as "HS" (high speed) or "LS" (low speed). In each example, the adhesive composition comprises DER ^™ 332 aromatic polyepoxide, CAF thermally activated aromatic polyepoxide curing agent, PKHJ ^™ thermoplastic polymer, diglycidyl ether of bisphenol A and dimethacrylate of TEGDMA 90:10 ( Weight ratio) multifunctional (meth) acrylate and EBECRYL ^™ 3605 direactive compound provided in the formulation. The relative amounts of each component are shown in Table 1 below. The combined amounts of polyfunctional (meth) acrylates and direactive compounds varied, but the weight ratio of these two components remained at 80:20. Examples 1 to 8 included 30 parts by weight of thermoplastic polymer, examples 9 to 12 included 25 parts by weight and examples 13 to 17 included 20 parts by weight of thermoplastic polymer.

Various examples were evaluated for one or more of the following properties using the test methods described above, and the results are shown in Table 1 below: film operability, modulus (megapascal or MPa), adhesive flow control, glass transition temperature (Tg) (° C.)), and peel adhesion (lbs / inch width or piw). In order to provide an adhesive bond film, Example 1 was not coated in the form of a film and was not exposed to electron beam irradiation.

The data in Table 1 shows the combined amounts of these materials in the range of about 5-20 parts multifunctional (meth) acrylate, 1-15 parts direactive compound, and about 10-25 parts, more preferably about 15-20 parts. The advantage of using is demonstrated. Particularly good results were obtained when the combined amounts of polyfunctional (meth) acrylate and direactive compound were about 10-20 parts by weight. Outside these ranges, peel adhesion and / or glass transition temperature was reduced. The Tg of Examples 2 to 17 was compared well with the Tg of Example 1, which did not include the (meth) acrylate-containing component, indicating that the adhesive composition of the present invention had a Tg similar to the adhesives described extensively in aromatic polyepoxides. It can be cured to a material having.

Examples 18-20

In Examples 18-20, laminates were prepared and tested as described above with respect to Examples 1-17 and as shown in Table 2 below. The amount of thermoplastic polymer was varied but the amount of all other reactants remained constant. Examples 4, 11 and 14 were repeated in Table 2.

Table 2 shows that increasing the amount of thermoplastic polymer is beneficial for film operability and adhesive flow control of the adhesive bond film. Preferably, the adhesive bond film of the present invention comprises about 20 to 40 parts, preferably about 20 to 30 parts of thermoplastic polymer.

Examples 21 and 22

In Examples 21 and 22, laminates were prepared and tested as described above with respect to Examples 1-17 and as shown in Table 3 below. The individual and combined amounts of the multifunctional (meth) acrylate and the direactive compound were varied. The amount of aromatic polyepoxide and curing agent was kept constant. The amount of thermoplastic polymer was 0 or 30 parts. In Table 3 Examples 4, 7 and 8 were repeated.

Table 3 shows that the amount of polyfunctional (meth) acrylate is outside the preferred range of 5 to 20 parts, the amount of any direactive compound is outside the preferred range of 1 to 15 parts, and the sum of these two materials is 10 to 25 parts If outside the desired range, the peel adhesion is reduced and / or the adhesive flow is increased during thermal curing.

Examples 23-25

In Examples 23 to 25, (1) the polyfunctional (meth) acrylate is replaced with Example 23 (TEGDMA), Example 24 (HDDA) and Example 25 (PhEMA); (2) These materials are weighed individually at room temperature without premixing with the direactive compound, placed in a plastic cup as described in the high speed mixing method, which previously contains an aromatic polyepoxide / thermoplastic polymer blend, and starts high speed mixing. The laminates were prepared and tested as described above with respect to Examples 1-17 and as shown in Table 4, except that.

Table 4 shows that although different multifunctional (meth) acrylates can be used in the adhesive compositions and adhesive bonding films of the present invention, some multifunctional (meth) acrylates can provide low peel adhesion. In Example 25, multifunctional (meth) acrylates were replaced with monofunctional acrylates, which resulted in low adhesive flow control and reduced film handling properties. Tg was also substantially reduced. No effective laminate test sample was produced in Example 25, so no peel adhesion was evaluated.

Examples 26 and 27

In Examples 26 and 27, (1) DER ^™ 332 was replaced with EPON ^™ 828; (2) A thermoplastic comprising a 75 wt% / 25 wt% blend of EPON ^TM 828 and P3500 prepared by dissolving PKHJ ^TM in EPON ^TM 828 with vigorous stirring at 350 ° F. for at least 8 minutes in a large batch mixer. Except for replacement with polymers, the laminates were prepared and tested as described above with respect to Examples 1-17 and as shown in Table 5 below. In Example 27, the thermoplastic polymer was diluted with additional EPON ^™ 828 to obtain the desired ratio between these two components.

Examples 28-30

In Examples 28 to 30, (1) DER ^™ 332 was replaced with QUATREX ^™ 1010; (2) Laminates were prepared and tested as described above with respect to Examples 1-17 and as shown in Table 5, except that aromatic polyepoxide / thermoplastic polymer blends were prepared differently. In Example 28, the PMMA thermoplastic polymer and aromatic polyepoxide were weighed into 8 ounce glass selves and placed in a preheated air convection oven set at 130 ° C. The blend was occasionally manually agitated using a wood depressor until completely dissolved as evidenced by a clear homogeneous mixture. The blend was cooled to room temperature. The blend was not cloudy after cooling, indicating that PMMA remains soluble in aromatic polyepoxide at room temperature.

In Example 29, the thermoplastic polymer was Ultem ^™ 1000 and the aromatic polyepoxide / thermoplastic polymer blend was opaque after cooling to room temperature, indicating that the Ultem ^™ 1000 is not soluble at room temperature because it is phase separated from the aromatic polyepoxide. Indicates.

In Example 30 (prepared similar to Example 28), the thermoplastic polymer was PolyEMA, and the aromatic polyepoxide / thermoplastic polymer load was not cloudy after cooling, which means that PolyEMA is soluble in aromatic polyepoxide at room temperature. Indicates that

Example 31

Except for producing aromatic polyepoxide / thermoplastic polymer blends differently, the laminates of Example 31 were prepared and tested as described above with respect to Examples 1-17 and as shown in Table 5 below. The thermoplastic polymer was Ultem ^™ 1000, which was not dissolved in aromatic polyepoxide. Multifunctional (meth) acrylate / direactive compound blends were mixed with aromatic polyepoxides using a high speed mixing method. Ultem ^™ 1000 was added to this formulation in portions and mixed using a high speed method until fully dispersed as evidenced by the absence of agglomerated or non-wetting particles. The curing agent was added according to the high speed mixing method.

Examples 26 and 27 show that when the thermoplastic polymer is polysulfone, higher amounts are needed for enhanced performance. Examples 4 and 28 illustrate the utility of soluble high Tg (about 90-200 ° C.) thermoplastic polymers in providing good performance, but the lower Tg (less than about 90 ° C.) thermoplastic polymer of Example 30. Gave a laminate with low peel adhesion.

Example 29 shows that thermoplastic polymers which are dissolved and then phase separated upon cooling to room temperature may have low peel adhesion, poor film handling properties and reduced adhesive flow control. It is desirable for the thermoplastic polymer to remain soluble in the adhesive composition.

Example 31 shows that having thermoplastic polymers present in dispersed undissolved form can reduce the operating properties of the adhesive bond film, but still have good peel adhesion and high Tg.

Examples 32 and 33

In Examples 32 and 33, the laminate was prepared as described above with respect to Examples 1-17 and in Table 6, except that the CAF curing agent was replaced with CG-1400 in Example 32 and DEH ^™ 85 in Example 33. Prepared and tested as shown.

Example 32 shows that curing agents other than aromatic amines can be used in the adhesive compositions and adhesive bond films of the present invention. However, using the phenolic curing agent in Example 33, an adhesive composition was provided that did not polymerize when the polyfunctional (meth) acrylate and the direactive compound were exposed to electron beam radiation. No effective laminate test sample could be prepared in Example 33, so no peel adhesion was evaluated.

Examples 34-38

In Examples 34-38, the laminates were described above with respect to Examples 1-17 and in Table 8, except that the EBECRYL 3605 direactive compound was replaced with the various monofunctional (meth) acrylates shown in Table 7. Prepared and tested as shown.

Example Consistent (meth) acrylate 34 PhEMA 35 IBMA 36 IBA 37 PEA 38 THFA

Table 8 shows that the direactive compound need not be included in the adhesive composition of the present invention. Although optional, the presence of a direactive compound is highly desirable as it has a beneficial effect on the adhesive flow control and / or peel adhesion of the adhesive bond film.

Examples 39 and 40

The adhesive compositions of Examples 39 and 40 were prepared as described above in "General Preparation of Adhesive Compositions" using the compositions shown in Table 9 below. Examples 39 and 40 also contained an ultraviolet (UV) irradiation polymerization initiator, DAROCUR ^™ 1173 (Ciba-Geigy, Inc., Hawthorne, NY) in an amount of 2% by weight (polyfunctional (meth) acrylates and direactive compounds Based on the combined amount). In addition, once the adhesive composition was coated between two release liners, they were polymerized by UV irradiation instead of electron beam irradiation.

More specifically, in Example 39, the coated adhesive was used with an RPG UV processor (model QC 1202AN31R, PPG Industries, Inc., Plainfield, IL) equipped with two high intensity mercury lamps with a maximum emission of 365 nm under anoxic conditions. By exposure to high energy UV radiation. One side was exposed nine times for 4.6 seconds each time at an average intensity of 57.83 mW / cm 2 for a total UV energy exposure of 2394 mJ / cm 2. Intensities were measured using a UVIRAD UV integrated radiometer (Model UR365CH3, Electronic Instrumentation & Technology, Sterling, Virginia), which was converted to the National Institute of Standards and Technology (NIST) unit (recorded herein).

In Example 40, the coated adhesives were exposed to low energy UV radiation using a Sylvania ^™ fluorescent lamp with their 90% emission between 300 and 400 nm and a maximum emission of 351 nm under anoxic conditions. Each side was exposed for 20 minutes at an average intensity of 2.045 μs / cm 2 per side, giving a total UV energy exposure of 2451 mJ / cm 2 per side. Intensity was measured as described above.

Table 9 shows that UV irradiation can be used to produce useful adhesives and adhesive bonding films, but the use of electron beam irradiation according to the present invention is more efficient. Total radiation exposure time was 41 seconds for Example 39 and 40 minutes for Example 40. However, other examples were prepared by exposure to electron beam irradiation for only 0.5 seconds.

Examples 39 and 40 were repeated without the photoinitiator. Grade film handling characteristics and adhesive flow control (-); No other properties were measured. After exposure to UV radiation, the repeated embodiments immediately dissolve in methyl ethyl ketone, and the adhesive composition of the present invention is exposed to UV radiation in order to require special storage and packaging (eg, containers that are not transparent to actinic radiation). When fully polymerized and not crosslinked.

Examples 41 to 46

In Examples 41-46, the laminate was described above with respect to Examples 1-17, except that Example 46 was not premixed with the polyfunctional (meth) acrylate and the direactive compound, since it did not include the direactive compound. As prepared and tested as shown in Table 10 below.

Table 10 shows the effect of varying the ratio of polyfunctional (meth) acrylate: direactive compound. Examples of ratios ranging from 80:20 to 50:50 showed good performance. At a ratio outside this range, the peel adhesion is reduced. The ratio of polyfunctional (meth) acrylate: direactive compound can vary widely from 95: 5 to 50:50. Example 45 with the combined amount of 25 parts by weight of polyfunctional (meth) acrylate and direactive compound showed excellent performance.

Examples 47-49

In Examples 47-49, laminates were prepared and tested as described above with respect to Examples 1-17 and as shown in Table 11, with some exceptions. Each of Examples 47-49 included 9 parts hexa- (4-methoxy-phenoxy) cyclotriphosphazene flame retardant and 6 parts AARACAST ^™ XU AY238 Hydantoin epoxy. The flame retardant was dissolved in the aromatic polyepoxide / thermoplastic polymer blend and then the hydantoin epoxy was dissolved in this blend. In each of these examples, the aromatic polyepoxide was provided in the same weight mixture of DER ^™ 332 and DEN ^™ 438. In each example the direactive compound was SARTOMER 379.

In Examples 48 and 49, the aromatic polyepoxide / thermoplastic polymer blend was preheated in an air convection oven set at 100 ° C. until a flowable viscosity was reached, followed by 65 ° C. and Example 49 for Example 48. Was added to a Plastic-corder ^™ PL-2000 mixer set at 70 ° C.

Table 11 shows that combinations of different aromatic polyepoxides can be used in the adhesive compositions and adhesive bond films of the present invention, as can be used for glycidyl methacrylate direactive compounds and various flame retardants.

Various modifications and variations of the present invention will be apparent to those skilled in the art without departing from the scope and spirit of the invention. It is to be understood that the invention is not limited to the exemplary embodiments described herein.

Claims (37)

a) aromatic polyepoxides; b) heat activated curing agents for polyepoxides; c) thermoplastic polymers; d) polyfunctional (meth) acrylates; And e) optionally a solvent free photo-stable adhesive composition containing a direactive compound comprising at least one (meth) acrylate group and at least one group reactive with an aromatic polyepoxide. The solvent-free photostable adhesive composition of claim 1 wherein the thermoplastic polymer has a glass transition temperature of about 90-200 ° C. 3. The solvent-free photostable adhesive composition of claim 1 wherein the thermoplastic polymer has a number average molecular weight of about 10,000 to 100,000. The solvent-free photo-stable adhesive composition of claim 1 wherein the thermoplastic polymer is selected from the group consisting of polysulfones, poly (methyl methacrylates), phenoxy polymers, polycarbonates, and combinations of these materials. The solvent-free photo-stable adhesive composition of claim 1 wherein the thermoplastic polymer comprises about 20 to 40 parts by weight per 100 parts by weight of aromatic polyepoxide. The solvent-free photo-stable adhesive composition according to claim 1, wherein the polyfunctional (meth) acrylate is di (meth) acrylate. The solvent-free photo-stable adhesive composition according to claim 1, wherein the polyfunctional (meth) acrylate is comprised in about 5 to 20 parts by weight per 100 parts by weight of the aromatic polyepoxide. The solvent-free photo-stable adhesive composition of claim 1, wherein the reactive compound is present and comprises from about 1 to 15 weight percent per 100 weight parts of the aromatic polyepoxide. The solvent-free photo-stable adhesive composition according to claim 1, wherein a direactive compound is present and the combined amount of the polyfunctional (meth) acrylate and the direactive compound is comprised in about 10 to 25 parts by weight per 100 parts by weight of the aromatic polyepoxide. . The thermally active curing agent for aromatic polyepoxides and polyepoxides according to claim 1, wherein the polyfunctional (meth) acrylate and any direactive compound polymerize when exposed to electron beam irradiation, and further, when exposed to electron beam radiation. Solvent-free photo-stable adhesive composition that does not react. The solvent-free photo-stable adhesive composition of claim 1 having a viscosity that allows the adhesive composition to be coated at a temperature below the reaction temperature for the heat activated curing agent for the polyepoxide. 12. The solventless light stable adhesive composition of claim 11 which can be coated at a temperature below about 90 &lt; 0 &gt; C. 12. The solventless light stable adhesive composition of claim 11 wherein the aromatic polyepoxide, thermoplastic polymer, polyfunctional (meth) acrylate, and any direactive compound can be provided in solution form at room temperature. a) 100 parts by weight of aromatic polyepoxide; b) a cure effective amount of a heat activated curing agent for polyepoxide; c) about 20 to 40 parts by weight of a thermoplastic polymer selected from the group consisting of polysulfone, poly (methyl methacrylate), phenoxy polymers, polycarbonates and combinations of these materials; d) about 5 to 20 parts by weight of di (meth) acrylate; And e) a substantially photoreactive material comprising about 1 to 15 parts by weight of a compound comprising at least one (meth) acrylate group and at least one group selected from the group consisting of hydroxyl, carboxyl, amine and 1,2-epoxide Solvent-free adhesive composition that does not contain. The solvent-free adhesive composition of claim 14 which is in a solution state having a coatable viscosity at a temperature of about 90 ° C. or less. 15. The solventless adhesive composition of claim 14 comprising about 20 to 30 parts by weight of thermoplastic polymer. The solventless adhesive composition of claim 14 wherein the combined amount of component (d) and component (e) is about 15-20 parts by weight. a) heat curable aromatic polyepoxide; b) heat activated curing agents for polyepoxides; c) thermoplastic polymers; And d) 1) polyfunctional (meth) acrylates and 2) a thermosetting adhesive, optionally comprising a (meth) acrylate polymer network comprising an electron beam irradiation polymerization product with a compound comprising at least one (meth) acrylate group and at least one group reactive with an aromatic polyepoxide Bonding film. 19. The thermally curable adhesive bonding film of claim 18 disposed on a support surface. The heat curable adhesive bonding film of claim 19, wherein the support surface is a temporary carrier. The heat curable adhesive bonding film of claim 19, wherein the support surface is a permanent backing. 19. The heat curable adhesive bonding film of claim 18, which can be removed from the temporary carrier without being wrinkled, torn or permanently stretched. 19. The thermosetting adhesive bond film of claim 18 having a modulus of about 1 to 300 MPa. 19. The thermosetting adhesive bonding film of claim 18, wherein the thermosetting adhesive bonding film exhibits controlled adhesive flow upon thermal curing. 19. The heat curable adhesive bonding film of claim 18 wherein the heat cured adhesive. The thermosetting adhesive bonding film of claim 25 having a glass transition temperature of about 150 ° C. or greater. 19. The fiber reinforced thermosetting adhesive bond film of claim 18. a) 100 parts by weight of a thermosetting aromatic polyepoxide; b) a cure effective amount of a heat activated curing agent for polyepoxide; c) about 20 to 40 parts by weight of a thermoplastic polymer selected from the group consisting of polysulfone, poly (methyl methacrylate), phenoxy polymers, polycarbonates and combinations of these materials; And d) 1) about 5 to 20 parts by weight of di (meth) acrylate; 2) an electron beam irradiation polymerization product with about 1 to 15 parts by weight of a compound comprising at least one (meth) acrylate group and at least one group selected from the group consisting of hydroxyl, carboxyl, amine and 1,2-epoxide A heat curable adhesive bonding film comprising a (meth) acrylate polymer network. 29. The thermally curable adhesive bonding film of claim 28, which can be removed from the temporary carrier without being wrinkled, torn or permanently stretched. 30. The thermosetting adhesive bond film of claim 29 having a modulus of about 1 to 300 MPa. A printed circuit board comprising the heat curable adhesive bonding film of claim 28 which is heat cured. a) 1) heat curable aromatic polyepoxide; 2) heat activated curing agents for polyepoxides; 3) thermoplastic polymers; 4) polyfunctional (meth) acrylates; And 5) optionally providing an adhesive composition containing at least one (meth) acrylate group and a direactive compound comprising at least one group reactive with an aromatic polyepoxide; b) forming a layer of adhesive composition on the support surface; And c) exposing the layer of adhesive composition to electron beam irradiation to polymerize the polyfunctional (meth) acrylate and any direactive compound, but not the thermally activated curing agent or aromatic polyepoxide to form a thermally curable adhesive bond film. Method for producing an adhesive bond film, comprising the step of. 32. The method of claim 31, wherein the thermally curable aromatic polyepoxide, thermoplastic polymer, polyfunctional (meth) acrylate and any direactive compound form a solution in step (a). 33. The method of claim 32, wherein the adhesive composition is formed on the support surface by coating the adhesive composition at a temperature between about room temperature and 120 ° C. 34. The method of claim 33, wherein the adhesive composition is coated at a temperature between about room temperature and 60 ° C. 33. The method of claim 32, further comprising removing the heat curable adhesive bond film from the support surface without pleating, tearing or permanently stretching the heat curable adhesive bond film. 33. The method of claim 32, further comprising heating the heat curable adhesive bond film for a sufficient time at a temperature sufficient to cure the aromatic polyepoxide to produce a heat cured adhesive bond film.