JP6613522B2 - Adhesive composition, film adhesive and method for producing laminate - Google Patents

Description

  The present invention relates to an adhesive composition, a film-like adhesive obtained using the adhesive composition, and a method for producing a laminate using the film-like adhesive.

  At the time of manufacturing a semiconductor device, for example, a step of die-bonding a semiconductor chip having a film-like adhesive affixed to a surface opposite to a circuit surface to a lead frame or a substrate using this adhesive is performed. The film adhesive has thermosetting properties, and finally becomes a cured product having impact resistance. As the film-like adhesive used at this time, an adhesive having sufficient adhesive properties that can be used as a part of a dicing sheet in a process of producing a semiconductor chip by dicing a semiconductor wafer is disclosed.

  Such a film-like adhesive may be deformed into a shape different from a target shape before or after curing at the time of manufacturing a semiconductor device. For example, in the case of the above-mentioned film adhesive used also as a part of a dicing sheet, it is known that it can be deformed due to the influence of frictional heat of the dicing blade, etc., and the film shape in which such deformation is suppressed An adhesive is disclosed (see Patent Documents 1 and 2).

  On the other hand, when manufacturing a semiconductor device, a process of sticking and fixing an inelastic substrate such as a semiconductor chip to an elastic substrate such as a flexible substrate with a film adhesive may be performed. In this case, a non-elastic substrate, a film-like adhesive, and an elastic substrate laminated in this order are pressure-bonded while being heated in these lamination directions. As a result, the film adhesive is thermally cured to form an adhesive layer, and the non-elastic substrate, the adhesive layer, and the elastic substrate are pressure-bonded to obtain a laminate.

  In such a laminate, the cured film adhesive (adhesive layer) may spread beyond the adhesive surfaces of the non-elastic substrate and the elastic substrate by pressure bonding, and may protrude from these adhesive surfaces. The adhesive layer that protrudes in this way can cause trouble in the subsequent manufacturing process of the semiconductor device. Therefore, an adhesive composition for forming an adhesive layer capable of suppressing the protrusion from the adhesive surface even after being crimped is desired.

JP 2012-167174 A JP2013-203895A

  However, sufficient studies have not been made so far for the adhesive composition capable of suppressing the protrusion of the adhesive layer from the adhesive surface. The film-like adhesives described in Patent Documents 1 and 2 that can be used as a part of a dicing sheet are not intended to suppress such protrusion after curing.

  The present invention has been made in view of the above circumstances. When a laminate is manufactured by pressing and laminating a non-elastic substrate, an adhesive layer, and an elastic substrate in this order, the bonding surface of the non-elastic substrate and the elastic substrate is provided. An adhesive composition for forming an adhesive layer capable of suppressing protrusion from the film and having sufficient adhesive force, a film adhesive obtained using the adhesive composition, and the film adhesive It is an object of the present invention to provide a method for producing the laminate to be used.

In order to solve the above problems, the present invention provides an adhesive composition for use in forming the adhesive layer of a laminate comprising a non-elastic substrate, an adhesive layer, and an elastic substrate that are pressure-bonded and laminated in this order. The adhesive composition contains an acrylic resin (a), an epoxy resin (b1) , a phenolic thermosetting agent (b2) , an inorganic filler (c), and a coupling agent (e). the content ratio of the acrylic resin (a) to the total solid content of the composition is 15 to 45 wt%, the inorganic filler to the total solid content of the adhesive composition ( The content ratio of c) is 5 to 25% by mass, and the content ratio of the coupling agent (e) in the adhesive composition is the acrylic resin (a), the epoxy resin (b1), and Total content of phenolic thermosetting agent (b2) Per 100 parts by mass of a 0.03 to 20 parts by weight, the Ri der viscosity 600 Pa · s or more at 0.99 ° C. before thermal curing of the adhesive composition, by using the adhesive composition, A silicon film having a size of 12 mm × 12 mm and a thickness of 350 μm is formed on the entire exposed surface of one of the film-like adhesives having a size of 12 mm × 12 mm and a thickness of 20 μm, which is obtained by forming a film. Affixed to the surface of the chip, the entire other exposed surface was affixed to the surface of a copper foil having a size of 15 mm × 50 mm and a thickness of 350 μm, and while heating the obtained laminate at 150 ° C., In the laminating direction of the silicon chip, film adhesive and copper foil, a load of 14 N is applied for 10 seconds to press the silicon chip, film adhesive and copper foil, and then heat treatment is performed at 130 ° C. for 1 hour. Shi Then, the film-like adhesive is thermally cured to form an adhesive layer, thereby producing a test laminate (2). The copper foil of the test laminate (2) is pulled at a speed of 50 mm / The adhesive composition is characterized in that the peel strength is 7 N / 10 mm or more when peeled at a peel angle of 90 ° and measured for peel strength .
Also, the present invention uses the adhesive composition, to provide a film-like adhesive, characterized in that obtained by forming a film.
Moreover, this invention is a manufacturing method of the laminated body by which a non-elastic board | substrate, an adhesive bond layer, and an elastic board | substrate are crimped | bonded and laminated | stacked in this order, Comprising: The said adhesive bond layer was formed from the said film adhesive And applying a force in the laminating direction of the non-elastic substrate, the film adhesive and the elastic substrate while heating the intermediate structure in which the non-elastic substrate, the film adhesive and the elastic substrate are laminated in this order. The non-elastic substrate, the film adhesive and the elastic substrate are pressure-bonded, and the film adhesive is thermally cured to form the adhesive layer, thereby obtaining the laminate. A method for manufacturing a body is provided.

  According to the present invention, when a laminate is manufactured by pressing and laminating a non-elastic substrate, an adhesive layer, and an elastic substrate in this order, it is possible to suppress the protrusion from the bonding surface of the non-elastic substrate and the elastic substrate, and sufficiently Provided are an adhesive composition for forming an adhesive layer having a sufficient adhesive force, a film adhesive obtained using the adhesive composition, and a method for producing the laminate using the film adhesive Is done.

It is a schematic sectional drawing for demonstrating one Embodiment of the manufacturing method of the laminated body which concerns on this invention. It is a figure which expands and shows typically the laminated body shown in FIG. 1, (a) is the top view seen from the inelastic board | substrate side, (b) is sectional drawing in the II line | wire of (a).

<Adhesive composition>
The adhesive composition according to the present invention is an adhesive composition for use in forming the adhesive layer of a laminate in which a non-elastic substrate, an adhesive layer and an elastic substrate are pressure-bonded and laminated in this order. , Acrylic resin (a), epoxy resin (b1) and phenolic thermosetting agent (b2), the ratio of the content of acrylic resin (a) to the total solid content of the adhesive composition Is 15 to 45% by mass, and the viscosity at 150 ° C. before thermosetting is 600 Pa · s or more.
In the adhesive composition according to the present invention, the content of the acrylic resin (a) and the viscosity at 150 ° C. before thermosetting are within a specific range. It is possible to suppress the protrusion of the elastic substrate and the elastic substrate from the bonding surface, and to form an adhesive layer having a sufficient adhesive force.

[Acrylic resin (a)]
The acrylic resin (a) is for forming a film-like adhesive described later, and the adhesive layer can be formed using a film-like adhesive. Acrylic resin (a) is a polymer compound for imparting film-forming properties, flexibility, etc. to a film-like adhesive and improving the adhesiveness (sticking property) of the film-like adhesive to an adherend It is.
Acrylic resin (a) may be used individually by 1 type, and may use 2 or more types together.

A publicly known acrylic polymer can be used as the acrylic resin (a).
The weight average molecular weight (Mw) of the acrylic resin (a) is preferably 10,000 to 2,000,000, and more preferably 100,000 to 1,000,000. When the weight average molecular weight of the acrylic resin (a) is not less than the lower limit value, the adhesive force to the adherend becomes more appropriate, and the weight average molecular weight of the acrylic resin (a) is not more than the upper limit value. Further, the film-like adhesive follows the uneven surface of the adherend, and the generation of voids and the like is suppressed between the adherend and the adherend.
In the present specification, “weight average molecular weight” is a polystyrene equivalent value measured by gel permeation chromatography (GPC) method unless otherwise specified.

  The glass transition temperature (Tg) of the acrylic resin (a) is preferably −60 to 70 ° C., and more preferably −50 to 50 ° C. When the Tg of the acrylic resin (a) is in such a range, the adhesive force to the adherend becomes more appropriate.

As monomers constituting the acrylic resin (a), methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate , N-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate (lauryl (meth) acrylate), tridecyl ( (Meth) acrylate, tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate (palmityl (meth) acrylate), heptade Le (meth) acrylate, octadecyl (meth) acrylates such as (stearyl (meth) acrylate), alkyl carbon atoms the alkyl group having a chain is 1 to 18 (meth) acrylate;
Cycloalkyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, imide (meth) (Meth) acrylate having a cyclic skeleton such as acrylate;
Hydroxyl group-containing (meth) acrylates such as hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate;
Examples include (meth) acrylic acid esters such as glycidyl group-containing (meth) acrylates such as glycidyl (meth) acrylate.
The acrylic resin (a) may be one obtained by copolymerizing monomers such as acrylic acid, methacrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, N-methylol acrylamide.
In this specification, “(meth) acrylate” is a concept including both “acrylate” and “methacrylate”. Similarly, “(meth) acrylic acid” is a concept including both “acrylic acid” and “methacrylic acid”.

  As for the monomer which comprises acrylic resin (a), only 1 type may be sufficient and 2 or more types may be sufficient.

The acrylic resin (a) may have a functional group capable of binding to other compounds such as a vinyl group, a (meth) acryloyl group, an amino group, a hydroxyl group, a carboxyl group, and an isocyanate group. Bonding with another compound may be performed via a crosslinking agent (f) described later, or the functional group may be directly bonded with another compound without passing through the crosslinking agent (f).
However, the ratio of the amount of the repeating unit having the functional group to the total amount of the repeating unit in the acrylic resin (a) is preferably 30 mol% or less, more preferably 20 mol% or less, It is particularly preferably 15 mol% or less.

  The ratio of the content of the acrylic resin (a) to the total content of the solid content of the adhesive composition (content of the acrylic resin of the film adhesive) is 15 to 45% by mass, It is preferable that it is 43 mass%. When the ratio of the content of the acrylic resin (a) is within such a range, the protrusion of the adhesive layer during the production of the laminate described later is sufficiently suppressed. Moreover, the peel strength of the adhesive layer described later (the peel strength between the inelastic substrate and the elastic substrate in the laminate) is sufficiently high.

[Epoxy resin (b1)]
The epoxy resin (b1) functions as an epoxy thermosetting resin (hereinafter referred to as “epoxy thermosetting resin (b)”) together with the phenol thermosetting agent (b2) described later.

  Examples of the epoxy resin (b1) include known ones, specifically, polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and hydrogenated products thereof, orthocresol novolac epoxy resins, dicyclopentadiene type. Bifunctional or higher functional epoxy compounds such as epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, and phenylene skeleton type epoxy resin can be exemplified.

Moreover, as an epoxy resin (b1), you may use the epoxy resin which has an unsaturated hydrocarbon group. As an epoxy resin which has an unsaturated hydrocarbon group, the compound formed by converting a part of epoxy group of a polyfunctional epoxy resin into the group containing an unsaturated hydrocarbon group can be illustrated. Such a compound can be produced, for example, by addition reaction of acrylic acid to an epoxy group. Moreover, as an epoxy resin which has an unsaturated hydrocarbon group, the compound etc. which the group containing an unsaturated hydrocarbon group directly couple | bonded with the aromatic ring etc. which comprise an epoxy resin can be illustrated. An unsaturated hydrocarbon group is a polymerizable unsaturated group, and specifically includes an ethenyl group (vinyl group), 2-propenyl group (allyl group), acryloyl group, methacryloyl group, acrylamide group, and methacrylamide group. Etc., and an acryloyl group is preferable.
The epoxy resin having an unsaturated hydrocarbon group is more compatible with the acrylic resin (a) than the epoxy resin having no unsaturated hydrocarbon group.

Although the number average molecular weight of an epoxy resin (b1) is not specifically limited, It is preferable that it is 300-30000 from the viewpoint of the sclerosis | hardenability of the said film adhesive, the intensity | strength after hardening, and heat resistance, and is 400-10000. It is more preferable, and it is especially preferable that it is 500-3000.
The epoxy equivalent of the epoxy resin (b1) is preferably 100 to 1000 g / eq, and more preferably 150 to 800 g / eq.

  An epoxy resin (b1) may be used individually by 1 type, and may use 2 or more types together.

[Phenolic thermosetting agent (b2)]
The phenol-based thermosetting agent (b2) is a thermosetting agent having a phenolic hydroxyl group and functions as a curing agent for the epoxy resin (b1).
Examples of the phenol-based thermosetting agent (b2) include polyfunctional phenol resins, biphenols, novolac-type phenol resins, dicyclopentadiene-based phenol resins, and aralkyl phenol resins.

The phenol thermosetting agent (b2) may have an unsaturated hydrocarbon group.
As the phenolic thermosetting agent (b2) having an unsaturated hydrocarbon group, a compound in which a part of the hydroxyl group of the phenol resin is substituted with a group containing an unsaturated hydrocarbon group, an aromatic ring of the phenol resin, Examples thereof include compounds in which a group containing a saturated hydrocarbon group is directly bonded. The unsaturated hydrocarbon group in the phenol thermosetting agent (b2) is the same as the unsaturated hydrocarbon group in the epoxy resin having an unsaturated hydrocarbon group described above.

  The number average molecular weight of the phenol-based thermosetting agent (b2) is preferably 300 to 30000, more preferably 400 to 10000, and particularly preferably 500 to 3000.

  A phenol type thermosetting agent (b2) may be used individually by 1 type, and may use 2 or more types together.

  The proportion of the content of the phenolic thermosetting agent (b2) in the adhesive composition (the film adhesive) is 0.1 to 500 parts by mass with respect to 100 parts by mass of the epoxy resin (b1). It is preferable that it is 1-200 mass parts. If the content ratio of the phenol-based thermosetting agent (b2) is too small, the film-like adhesive may not obtain adhesiveness due to insufficient curing, and the content ratio of the thermosetting agent (b2) is excessive. When it exists, the moisture absorption rate of a film adhesive may increase and the reliability of an adhesive bond layer may fall.

  Ratio of total content of epoxy resin (b1) and phenolic thermosetting agent (b2) in the adhesive composition (the film-like adhesive) (content ratio of epoxy thermosetting resin (b)) Is preferably 50 to 1000 parts by mass, more preferably 65 to 700 parts by mass, and 80 to 400 parts by mass with respect to 100 parts by mass of the acrylic resin (a). Particularly preferred. When the ratio of the total content of the epoxy resin (b1) and the phenol-based thermosetting agent (b2) is within such a range, the adhesive composition can exhibit more appropriate adhesiveness after thermosetting.

[Inorganic filler (c)]
The adhesive composition preferably further contains an inorganic filler (c) in addition to the acrylic resin (a), the epoxy resin (b1), and the phenol thermosetting agent (b2). When the adhesive composition contains the inorganic filler (c), it is easier to suppress the protrusion of the adhesive layer during the production of the laminate described later. Moreover, adjustment of the thermal expansion coefficient of a film adhesive and an adhesive layer becomes easy. Furthermore, the moisture absorption rate of the adhesive layer can also be reduced.

Preferable inorganic fillers (c) include silica, alumina, talc, calcium carbonate, titanium white, bengara, silicon carbide, boron nitride, and the like; beads made by spheroidizing these silicas; single crystal fibers such as these silicas; A glass fiber etc. can be illustrated.
Among these, the inorganic filler (c) is preferably spherical silica, silica filler, or alumina filler.
An inorganic filler (c) may be used individually by 1 type, and may use 2 or more types together.

The inorganic filler (c) is preferably in the form of a sphere or the like, and the average particle diameter is preferably 0.01 to 1 μm, and more preferably 0.04 to 0.8 μm. In the present specification, “average particle diameter” means a value of particle diameter (D ₅₀ ) at an integrated value of 50% in a particle size distribution curve obtained by a laser diffraction scattering method, unless otherwise specified. .

  When using the inorganic filler (c), the ratio of the content of the inorganic filler (c) to the total solid content of the adhesive composition (the content of the inorganic filler (c) of the film adhesive) ) Is preferably 5 to 25% by mass, more preferably 5 to 20% by mass, and particularly preferably 6 to 17% by mass. When the ratio of the content of the inorganic filler (c) is within such a range, it becomes easier to obtain the above-described effect when the inorganic filler (c) is used.

[Other ingredients]
The adhesive composition is other than acrylic resin (a), epoxy resin (b1), phenolic thermosetting agent (b2), and inorganic filler (c) in order to improve various physical properties of the film adhesive. Furthermore, you may contain the other component which does not correspond to these as needed.
The other components contained in the adhesive composition include: a curing accelerator (d); a coupling agent (e); a crosslinking agent (f); the acrylic resin (a), an epoxy resin (b1), and a phenol type. Other resins (g) not corresponding to any of the thermosetting agents (b2); photopolymerization initiators (h); thermosetting agents other than phenolic thermosetting agents (b2) (i); general-purpose additives (j) Etc. can be illustrated.
The other components may be used alone or in combination of two or more.

(Curing accelerator (d))
The curing accelerator (d) is used for adjusting the curing rate of the adhesive composition.
Preferred curing accelerators (d) include tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole, 2 -Imidazoles such as phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole (groups in which one or more hydrogen atoms are other than hydrogen atoms) Substituted imidazole); organic phosphines such as tributylphosphine, diphenylphosphine, triphenylphosphine (phosphine in which one or more hydrogen atoms are substituted with organic groups); tetraphenylphosphonium tetraphenylborate, trif Tetraphenyl boron salts such as sulfonyl phosphine tetraphenyl borate can be mentioned.
A hardening accelerator (d) may be used individually by 1 type, and may use 2 or more types together.

  When the curing accelerator (d) is used, the ratio of the content of the curing accelerator (d) in the adhesive composition (the film adhesive) is that of the epoxy resin (b1) and the phenol-based thermosetting agent (b2). It is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the total content (content of the epoxy thermosetting resin (b)). . When the content of the curing accelerator (d) is within such a range, the film adhesive exhibits excellent adhesive properties even under high temperature and high humidity conditions. When there is too little content of a hardening accelerator (d), the effect by using a hardening accelerator (d) will not fully be acquired, but when the content of a hardening accelerator (d) is excessive, it will be highly polar. The curing accelerator (d) moves toward the interface with the adherend in the film adhesive under high temperature and high humidity conditions, and segregates, thereby reducing the adhesive force.

(Coupling agent (e))
Improving the adhesion and adhesion of the film adhesive to the adherend by using a coupling agent (e) having a functional group that reacts with an inorganic compound and a functional group that reacts with an organic functional group. Can do. In addition, by using the coupling agent (e), the water resistance of the cured product (adhesive layer) obtained by curing the film adhesive can be improved without impairing its heat resistance.

The coupling agent (e) is preferably a compound having a functional group that reacts with a functional group of the acrylic resin (a), the epoxy resin (b1), the phenol thermosetting agent (b2), or the like. A ring agent is preferred.
Preferred examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 2- (3,4-epoxycyclohexyl). Ethyltrimethoxysilane, 3- (methacryloyloxypropyl) trimethoxysilane, 3-aminopropyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, N-6- (aminoethyl) -3-aminopropyltrimethoxysilane, N-6- (aminoethyl) -3-aminopropylmethyldiethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyl Me Dimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, imidazole silane and the like.
A coupling agent (e) may be used individually by 1 type, and may use 2 or more types together.

  When the coupling agent (e) is used, the proportion of the content of the coupling agent (e) in the adhesive composition (the film adhesive) is acrylic resin (a), epoxy resin (b1) and phenolic. It is preferable that it is 0.03-20 mass parts with respect to 100 mass parts of total content of a thermosetting agent (b2), It is more preferable that it is 0.05-10 mass parts, 0.1-5 mass Part is particularly preferred. If the content of the coupling agent (e) is too small, the above-mentioned effect due to the use of the coupling agent (e) may not be obtained. If the content of the coupling agent (e) is too large, Outgas may occur.

(Crosslinking agent (f))
In the case of using a polymer component such as an acrylic resin (a) having a functional group that can be bonded to another compound such as an isocyanate group, a crosslinking agent for bonding the functional group to the other compound to crosslink (F) can be used. By crosslinking using the crosslinking agent (f), the initial adhesive force and cohesive force of the film adhesive can be adjusted.
Examples of the crosslinking agent (f) include organic polyvalent isocyanate compounds and organic polyvalent imine compounds.

  Examples of the organic polyvalent isocyanate compound include aromatic polyvalent isocyanate compounds, aliphatic polyvalent isocyanate compounds, alicyclic polyvalent isocyanate compounds, trimers of these compounds, isocyanurates, and adducts (ethylene glycol, propylene glycol). A reaction product with a low molecular active hydrogen-containing compound such as neopentyl glycol, trimethylolpropane or castor oil, such as trimethylolpropane adduct xylylene diisocyanate), or an organic polyvalent isocyanate compound and a polyol compound. The terminal isocyanate urethane prepolymer obtained can be exemplified.

  More specifically, as the organic polyvalent isocyanate compound, 2,4-tolylene diisocyanate; 2,6-tolylene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylene diisocyanate; diphenylmethane-4,4 Diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; trimethylolpropane, etc. A compound obtained by adding one or both of tolylene diisocyanate and hexamethylene diisocyanate to all or part of the hydroxyl groups of Isocyanate, etc. can be exemplified.

  Examples of the organic polyvalent imine compound include N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxamide), trimethylolpropane-tri-β-aziridinylpropionate, tetramethylolmethane-tri Examples include -β-aziridinyl propionate, N, N′-toluene-2,4-bis (1-aziridinecarboxyamide) triethylenemelamine, and the like.

  When an isocyanate crosslinking agent is used as the crosslinking agent (f), it is preferable to use a hydroxyl group-containing polymer as the polymer component such as the acrylic resin (a). When the crosslinking agent (f) has an isocyanate group and the polymer component has a hydroxyl group, a crosslinked structure can be easily introduced into the film adhesive by a reaction between the crosslinking agent (f) and the polymer component. .

  The content ratio of the crosslinking agent (f) in the adhesive composition (the film adhesive) is preferably 1 part by mass or less with respect to 100 parts by mass of the polymer component. More preferably, it is 1 part by mass or less. When the content of the crosslinking agent (f) in the adhesive composition (the film adhesive) increases, the peel strength of the adhesive layer described later (peel strength between the non-elastic substrate and the elastic substrate in the laminate) Will fall. Therefore, in terms of improving the peel strength, it is preferable that the adhesive composition (the film adhesive) does not contain a crosslinking agent (f).

(Other resins (g))
As the other resin (g), any of thermosetting resin and ultraviolet curable resin can be used. Polyester, urethane resin, acrylic urethane resin, silicone resin, rubber polymer, phenoxy resin, polybutene, polybutadiene, polystyrene Etc. can be illustrated.
Other resin (g) may be used individually by 1 type, and may use 2 or more types together.

Polyester, urethane resin, acrylic urethane resin, silicone resin, rubber polymer, and phenoxy resin, in addition to the acrylic resin (a), impart film-forming properties, flexibility, etc. Adhesiveness (adhesiveness) of the adhesive to the adherend can be improved.
In addition, by using a thermoplastic resin such as polyester, urethane resin, phenoxy resin, polybutene, polybutadiene, or polystyrene, the followability of the film adhesive to the uneven surface of the adherend is improved, and the occurrence of voids is suppressed. Will improve.

  When other resin (g) is used, the ratio of the content of the other resin (g) to the total solid content of the adhesive composition (the content of the other resin (g) of the film adhesive) ) Is preferably 5 to 30% by mass, and more preferably 5 to 25% by mass. When the ratio of the content of the other resin (g) is within such a range, it becomes easier to obtain the above-described effect when the other resin (g) is used.

(Photopolymerization initiator (h))
When using an ultraviolet curable resin, it is preferable that the said adhesive composition contains a photoinitiator (h).
The photopolymerization initiator (h) may be a known one, specifically, 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, α-hydroxy-α, α′-dimethyl. Α-ketol compounds such as acetophenone, 2-methyl-2-hydroxypropiophenone, 1-hydroxycyclohexyl phenyl ketone; methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 2 Acetophenone compounds such as methyl-1- [4- (methylthio) -phenyl] -2-morpholinopropane-1; benzoin ether compounds such as benzoin ethyl ether, benzoin isopropyl ether and anisoin methyl ether; benzyldimethyl ketal and the like Ketal compounds; 2-naphth Aromatic sulfonyl chloride compounds such as lensulfonyl chloride; photoactive oxime compounds such as 1-phenone-1,1-propanedione-2- (o-ethoxycarbonyl) oxime; benzophenone, benzoylbenzoic acid, 3,3 ′ -Benzophenone compounds such as dimethyl-4-methoxybenzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone And thioxanthone compounds such as 2,4-diethylthioxanthone and 2,4-diisopropylthioxanthone; camphorquinone; halogenated ketone; acyl phosphinoxide; acyl phosphonate.

  The ratio of the content of the photopolymerization initiator (h) in the adhesive composition (the film adhesive) is 0.05 to 20 parts by mass with respect to 100 parts by mass of the ultraviolet curable resin. Is preferred.

(Thermosetting agent (i))
The thermosetting agent (i) may be anything other than the phenol thermosetting agent (b2), and examples thereof include compounds having two or more functional groups capable of reacting with an epoxy group in one molecule. Examples of the functional group include alcoholic hydroxyl groups (excluding phenolic hydroxyl groups), amino groups, carboxyl groups, and groups in which acid groups are anhydrideized.
A thermosetting agent (i) may be used individually by 1 type, and may use 2 or more types together.

  The content ratio of the thermosetting agent (i) in the adhesive composition (the film adhesive) is 1 part by mass or less with respect to 100 parts by mass of the phenol thermosetting agent (b2). Is preferable, and it is more preferable that it is 0.1 mass part or less.

(General-purpose additive (j))
Examples of the general-purpose additive (j) include known plasticizers, antistatic agents, antioxidants, pigments, dyes, gettering agents and the like.
General-purpose additive (j) may be used individually by 1 type, and may use 2 or more types together.

(solvent)
When the adhesive composition further contains a solvent, the handleability is improved by dilution.
The solvent contained in the adhesive composition is not particularly limited, but preferred are hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-1-ol), 1 Examples include alcohols such as butanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone.
The solvent contained in the adhesive composition may be only one type or two or more types.
The solvent contained in the adhesive composition is preferably methyl ethyl ketone from the viewpoint of uniformly mixing the components used in the adhesive composition.

The said adhesive composition is obtained by mix | blending each above-mentioned component for comprising the said film adhesives, such as acrylic resin (a), an epoxy resin (b1), and a phenol-type thermosetting agent (b2). It is done.
The order of addition at the time of blending each component is not particularly limited, and two or more components may be added simultaneously.
When a solvent is used, it may be used by mixing the solvent with any compounding component other than the solvent and diluting the compounding component in advance, or by diluting any compounding component other than the solvent in advance. You may use it by mixing a solvent with these compounding ingredients, without leaving.

The method of mixing each component at the time of compounding is not particularly limited, from a known method such as a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves What is necessary is just to select suitably.
The temperature and time at the time of addition and mixing of each component are not particularly limited as long as each compounding component does not deteriorate, and may be adjusted as appropriate, but the temperature is preferably 15 to 30 ° C.

The adhesive composition has a viscosity at 150 ° C. before thermosetting of 600 Pa · s or more, preferably 625 Pa · s or more, more preferably 650 Pa · s or more, and 675 Pa · s or more. It is particularly preferred. When the viscosity of the adhesive composition is equal to or higher than the lower limit value, the adhesive composition has an appropriate wetting and spreading property. During the production of a laminate described later, a non-elastic substrate, a film-like adhesive, and elasticity When the substrate is pressure-bonded, excessive spread of the film adhesive can be suppressed, and as a result, the protrusion of the adhesive layer from the bonding surface of the non-elastic substrate and the elastic substrate can be suppressed. The upper limit of the viscosity of the adhesive composition is not particularly limited, but is preferably 20000 Pa · s from the viewpoint of easier handling of the adhesive composition.
The viscosity of the adhesive composition before thermosetting can be measured using a torsional shear type viscosity measuring device.

  The viscosity before thermosetting of the adhesive composition can be adjusted by the type and content of the components contained in the adhesive composition, and is greatly influenced by the content of the acrylic resin (a). When the inorganic filler (c) is contained, it is easily affected by the content of the inorganic filler (c).

<Film adhesive>
The film adhesive according to the present invention is obtained by forming into a film using the adhesive composition.
The film adhesive which concerns on this invention is for using for manufacture of the said laminated body, and forms an adhesive bond layer in the said laminated body.
For example, an adhesive sheet provided with a film adhesive according to the present invention on a substrate is suitable for use in the production of the laminate.

  The film adhesive has pressure-sensitive adhesiveness and thermosetting. Since the film adhesive has pressure-sensitive adhesiveness, it can be attached to an adherend by lightly pressing in an uncured state. The film adhesive may be one that can be applied to an adherend by heating and softening. And a film-form adhesive becomes a hardened | cured material with high impact resistance, having sufficient adhesive property by heating by having thermosetting property.

  Although the thickness of a film adhesive can be suitably selected according to the objective, it is preferable that it is 1-100 micrometers, it is more preferable that it is 2-75 micrometers, and it is especially preferable that it is 5-50 micrometers. When the thickness of the film adhesive is equal to or more than the lower limit value, the adhesive force to the adherend becomes higher. Moreover, when the thickness of a film adhesive is below the said upper limit, it will be suppressed from becoming excessive thickness.

[Base material]
The material of the base material is preferably various resins, specifically, polyethylene (low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE, etc.)), polypropylene, polybutene. , Polybutadiene, polymethylpentene, styrene / ethylene butylene / styrene block copolymer, polyvinyl chloride, vinyl chloride copolymer, polyethylene terephthalate, polybutylene terephthalate, polyurethane, polyurethane acrylate, polyimide, ethylene vinyl acetate copolymer, ionomer Resin, ethylene / (meth) acrylic acid copolymer, ethylene / (meth) acrylic acid ester copolymer, polystyrene, polycarbonate, fluororesin, water additive, modified product, cross-linked product or Copolymer and the like.

  The substrate may be composed of one layer (single layer), may be composed of two or more layers, and when composed of a plurality of layers, the material of each layer may be the same or all may be different. , Some may be the same.

  Although the thickness of a base material can be suitably selected according to the objective, it is preferable that it is 20-300 micrometers, and it is more preferable that it is 30-150 micrometers. When the substrate is composed of a plurality of layers, the total thickness of all the layers is preferably in such a numerical range.

  The contact surface of the substrate with the film adhesive may be subjected to a peeling treatment such as a silicone treatment.

  The base material may be provided on only one surface of the film adhesive or may be provided on both surfaces.

The film adhesive can be formed by applying the adhesive composition on the surface of a support such as the substrate and drying it. Also, by applying the adhesive composition to the surface of the release layer of the release material, and drying the film adhesive formed on the surface of the support, and removing the release material as necessary, A film adhesive can be formed on the support. At this time, you may use the base material to which the above-mentioned peeling process was performed as said peeling material.
The laminate of the support and the film adhesive thus obtained can be used as the adhesive sheet as it is.

  The adhesive composition may be applied by a known method. Air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, knife coater, screen coater, Meyer bar A method using various coaters such as a coater and a kiss coater can be exemplified.

<Method for producing laminate>
The method for producing a laminate according to the present invention is a method for producing a laminate in which a non-elastic substrate, an adhesive layer, and an elastic substrate are pressure-bonded and laminated in this order, and the adhesive layer is the film adhesive. The non-elastic substrate, the film-like adhesive, and the elastic substrate are laminated in this order while heating the intermediate structure formed by laminating the non-elastic substrate, the film-like adhesive, and the elastic substrate in this order. By applying a force in step, the non-elastic substrate, the film adhesive and the elastic substrate are pressure-bonded, and the film adhesive is thermally cured to form the adhesive layer, thereby obtaining the laminate. It is characterized by.
According to the production method of the present invention, by using the film adhesive, the adhesive layer in the laminate is suppressed from protruding from the bonding surface of the non-elastic substrate and the elastic substrate, and the non-elastic substrate and the elastic layer are elastic. Adequate adhesion to the substrate.

[Elastic substrate]
The elastic substrate is, for example, a substrate having elasticity such that a tensile elastic modulus at room temperature (about 25 ° C.) is approximately 1 GPa or more. The “tensile modulus” can be measured by a known method, for example, using a device such as “DMA Q800” manufactured by TA Instruments. A general glass epoxy substrate has a tensile modulus of about 10 GPa at room temperature (about 25 ° C.), and the elastic substrate is less rigid than this. Further, the elastic substrate may be a flexible substrate that can be folded without being broken by a human hand so that the bending angle is 0 ° to 180 ° without applying a particularly large force. it can.

  As an elastic material constituting the elastic substrate (hereinafter sometimes abbreviated as “elastic material”), an elastic resin such as polyimide, polyurethane, epoxy resin, acrylic resin (hereinafter referred to as “elastic resin”). May be abbreviated).

  The elastic substrate may be composed of one layer (single layer), may be composed of two or more layers, and when it is composed of a plurality of layers, the material of each layer may be the same or all may be different. , Some may be the same.

The elastic substrate may be configured only by a flat surface, or may be configured by providing a structure having an arbitrary shape on the flat surface.
Further, the elastic substrate may be configured with a structure of an arbitrary shape inside.
Examples of the structure include a wiring structure such as a circuit.

The elastic substrate is not particularly limited as long as it exhibits elasticity as a whole, and may include a material having no elasticity described below (hereinafter, may be abbreviated as “inelastic material”) in addition to the elastic material described above. .
The elastic substrate including such an inelastic material is composed of a plurality of layers, some of which are made of an inelastic material, or the inside or the upper part of the layer made of the above-mentioned elastic material. What has the structure which becomes can be illustrated.

Although the thickness of an elastic substrate is not specifically limited, It is preferable that it is 10-1000 micrometers, and it is more preferable that it is 20-900 micrometers. When the elastic substrate is composed of a plurality of layers, the total thickness of all the layers is preferably within such a numerical range.
As described above, when the elastic substrate is provided with a structure of an arbitrary shape on the flat surface, the uppermost part of these structures is used as one reference for defining the thickness.

  As the elastic substrate, those used as so-called flexible substrates are preferable.

[Non-elastic substrate]
The inelastic substrate is a substrate that does not correspond to the elastic substrate.
Accordingly, examples of the material constituting the inelastic substrate include materials other than the above-described various elastic resins, and any of inorganic materials and organic materials may be used.
Examples of the inorganic material include silicon.
As said organic material, things other than the said elastic resin can be illustrated among various resin quoted as a base material of the said adhesive sheet.

  The inelastic substrate may be composed of one layer (single layer), or may be composed of two or more layers, and when it is composed of a plurality of layers, the materials of all layers may be the same or different. Well, only a part may be the same.

  The shape of the inelastic substrate is the same as the shape of the elastic substrate.

The non-elastic substrate only needs to exhibit inelasticity as a whole, and may include the elastic material in addition to the above-described non-elastic material.
Examples of the non-elastic substrate containing such an elastic material include those having a structure made of an elastic material inside or on the top of a layer made of the non-elastic material.

Although the thickness of an inelastic board | substrate is not specifically limited, It is preferable that it is 10-1000 micrometers, and it is more preferable that it is 20-900 micrometers. When the inelastic substrate is composed of a plurality of layers, the total thickness of all the layers is preferably within such a numerical range.
When the non-elastic substrate is provided with a structure of an arbitrary shape on a flat surface, the uppermost part of these structures is used as one reference for defining the thickness.

  For example, a silicon chip is suitable as the inelastic substrate.

[Adhesive layer]
The adhesive layer is formed by thermal curing of a film adhesive in the adhesive sheet.
Although the thickness of an adhesive bond layer can be suitably selected according to the objective, it is preferable that it is 0.5-90 micrometers, it is more preferable that it is 1-70 micrometers, and it is especially preferable that it is 3-45 micrometers. When the thickness of the adhesive layer is equal to or more than the lower limit value, higher adhesive force to the adherend can be maintained. Moreover, when the thickness of the adhesive layer is equal to or less than the upper limit value, an excessive thickness is suppressed.

  Hereinafter, the manufacturing method will be described in detail with reference to the drawings. FIG. 1 is a schematic cross-sectional view for explaining an embodiment of a method for producing a laminate according to the present invention, wherein (a) is obtained from the intermediate structure, and (b) is obtained from the intermediate structure. It is a figure which illustrates a laminated body, respectively.

The intermediate structure 10 shown here is formed by laminating a non-elastic substrate 11, a film adhesive 12, and an elastic substrate 13 in this order.
The sizes of the non-elastic substrate 11, the film adhesive 12, and the elastic substrate 13 in the intermediate structure 10 are not particularly limited, and these are in contact with each other (the surface of the non-elastic substrate 11 on the film adhesive 12 side). (Front surface) 11a, surface (back surface) 12b on the non-elastic substrate 11 side and surface (front surface) 12a on the elastic substrate 13 side of the film adhesive 12 and surface (back surface) on the film adhesive 12 side of the elastic substrate 13 The areas of 13b) may all be the same, all may be different, or only a part may be the same. However, as shown here, when the area of the back surface 13b of the elastic substrate 13 is larger than the area of the front surface 12a and the back surface 12b of the film adhesive 12 and the surface 11a of the non-elastic substrate 11, The production method according to the present invention is particularly suitable. The reason will be described later.

  In the intermediate structure 10, it is preferable that the non-elastic substrate 11, the film adhesive 12, and the elastic substrate 13 are arranged so that the areas of the regions in contact with each other are maximized. Here, the “region in contact with each other” refers to a region in contact with the film adhesive 12 in the surface 11 a of the non-elastic substrate 11 and a non-out of the back surface 12 b in the film adhesive 12. Of the region in contact with the elastic substrate 11, the region in contact with the elastic substrate 13 in the surface 12 a of the film adhesive 12, and the film adhesive 12 in the back surface 13 b of the elastic substrate 13. Area.

  The intermediate structure 10 is contacted and held by the fixing portion 91 in the manufacturing apparatus 9 so that the portion on the inelastic substrate 11 side is in contact with the horizontal direction of the intermediate structure 10 (contact with the fixing portion 91 of the inelastic substrate 11). It is being fixed to the manufacturing apparatus 9 so that the movement in the surface (back surface) 11b) is suppressed. The intermediate structure 10 is at least in the direction from the inelastic substrate 11 to the fixing portion 91 in the fixed state (the direction toward the lower side of the paper) in the vertical direction (the direction orthogonal to the horizontal direction). The movement should just be suppressed.

  The fixing method of the intermediate structure 10 in the fixing portion 91 is not particularly limited. For example, a guide (not shown) provided in the fixing portion 91 and suppressing movement of the intermediate structure 10 is provided on the surface of the intermediate structure 10. Although the method of making the part contact | abut and fixing the intermediate structure 10 can be illustrated, it is not limited to this. The guide may be a protrusion provided on a contact surface 91a of the fixing portion 91 with the intermediate structure 10, or may be a recess provided on the contact surface 91a.

The intermediate structure 10 may be formed by laminating the non-elastic substrate 11, the film adhesive 12 and the elastic substrate 13 in this order. For example, the back surface 12b of the film adhesive 12 is attached to the non-elastic substrate 11, It can be produced by sticking the surface 12 a to the elastic substrate 13.
More specifically, for example, when the base material is provided on both surfaces (the front surface 12a and the back surface 12b) of the film adhesive 12 using the adhesive sheet, the base material on one surface is removed, While affixing the exposed surface of the film-like adhesive 12 to one of the non-elastic substrate 11 and the elastic substrate 13, the exposed surface of the film-like adhesive 12 newly generated by removing the base material on the other surface, The intermediate structure 10 can be manufactured by sticking to the other non-elastic substrate 11 and the remaining elastic substrate 13.

  The non-elastic substrate 11 and the elastic substrate 13 are both stronger than a predetermined strength that is clearly stronger than the case where they are applied by normal sticking, such as applying the same force to the film adhesive 12 as in, for example, the pressure bonding described later. By applying force, it may be crimped or may not be crimped.

  The intermediate structure 10 may be manufactured using the above-described manufacturing apparatus 9 for obtaining a laminate that is a target product, or may be manufactured using an apparatus other than the manufacturing apparatus 9. When the intermediate structure 10 is manufactured using the manufacturing apparatus 9, the laminated body may be manufactured using the manufacturing apparatus 9, and the intermediate structure 10 is manufactured using an apparatus other than the manufacturing apparatus 9. In this case, the intermediate structure 10 may be moved to the manufacturing apparatus 9 to manufacture the laminate.

  In the intermediate structure 10, one surface (the back surface 12 b) of the film adhesive 12 is affixed to the inelastic substrate 11, and the other surface (the surface 12 a) of the film adhesive 12 is further applied to the elastic substrate 13. It is preferable to prepare by sticking. In this case, the intermediate structure 10 is preferably produced while heating the inelastic substrate 11.

The heating at this time means that the film-like adhesive 12 does not progress significantly. By doing in this way, the film adhesive 12 can be more stably affixed on the inelastic board | substrate 11. FIG.
The heating temperature at this time is preferably 30 to 80 ° C, and more preferably 40 to 70 ° C. The heating time may be set in consideration of the heating temperature, but is preferably 0.1 to 5 seconds.

  When producing the intermediate structure 10 using the manufacturing apparatus 9, it is preferable to heat the inelastic board | substrate 11 by heating the fixing | fixed part 91 of the manufacturing apparatus 9, for example. For this purpose, for example, a manufacturing device in which heating means (not shown) is provided inside or adjacent to the fixing portion 91 and the fixing portion 91 is heated by heat conduction from the heating means. 9 may be used.

  In the manufacturing method, while the intermediate structure 10 is heated, a force is applied to the intermediate structure 10 in the stacking direction of the non-elastic substrate 11, the film adhesive 12, and the elastic substrate 13, as shown in FIG. By applying (load), the non-elastic substrate 11 and the film-like adhesive 12 are pressure-bonded, and the film-like adhesive 12 and the elastic substrate 13 are pressure-bonded. In FIG. 1A, the force applied to the intermediate structure 10 is indicated by an arrow A.

The heating temperature at this time may be a temperature at which the non-elastic substrate 11, the film adhesive 12 and the elastic substrate 13 are all well bonded, but preferably 110 to 160 ° C., and 115 to 155 ° C. It is more preferable.
Moreover, it is preferable that it is 1-20N, and, as for the force added to the intermediate structure 10, it is more preferable that it is 2-16N.
The time for applying force to the intermediate structure 10 while heating is preferably 0.5 to 30 seconds, and more preferably 1 to 15 seconds.
Depending on conditions such as the heating temperature at this time and the time during which the force is applied while heating, there is a possibility that the film-like adhesive 12 will be thermally cured. It is preferable to adjust the conditions so that the progress of thermosetting is suppressed.

  In the manufacturing method, as described above, when the non-elastic substrate, the film adhesive, and the elastic substrate are pressure-bonded while heating the intermediate structure, it is finally obtained by selecting appropriate conditions. In the laminated body, the protrusion of the adhesive layer from the bonding surface of the non-elastic substrate and the elastic substrate can be more significantly suppressed.

  In the manufacturing method, after the non-elastic substrate 11, the film adhesive 12 and the elastic substrate 13 are pressure-bonded, the film adhesive 12 is further heated and thermally cured, as shown in FIG. Thus, the adhesive layer 14 is formed. Thereby, the laminated body 1 by which the inelastic board | substrate 11, the adhesive bond layer 14, and the elastic board | substrate 13 are crimped | bonded and laminated | stacked in this order is obtained.

The heating temperature at this time may be a temperature at which the thermosetting of the film adhesive 12 proceeds satisfactorily, but is preferably 105 to 165 ° C, and more preferably 110 to 160 ° C.
Moreover, what is necessary is just to adjust a heating time suitably according to heating temperature, However, It is preferable that it is 0.1 to 3 hours, and it is more preferable that it is 0.3 to 1.5 hours.

  In the manufacturing method, as described above, when the film adhesive is heated and thermally cured to form an adhesive layer, a laminate obtained finally by selecting appropriate conditions. The protrusion of the adhesive layer from the bonding surface of the non-elastic substrate and the elastic substrate can be more significantly suppressed.

  In the manufacturing method, as shown in FIG. 1A, the area of the back surface 13 b of the elastic substrate 13 is such that the surface 12 a and the back surface 12 b of the film adhesive 12 and the surface 11 a of the non-elastic substrate 11. Is larger than the area of the elastic substrate 13, the elastic substrate 13 is usually supported at the end portion or a portion in the vicinity of the end portion, and is bonded to the film adhesive 12. In this case, the elastic substrate 13 bends in a convex shape toward the film adhesive 12 as shown here in a region on the end side that is not in contact with the film adhesive 12. As a result, the elastic substrate 13 is oriented in the direction opposite to the arrow A shown as the force applied to the intermediate structure 10 in FIG. 1A (the direction from the non-elastic substrate 11 toward the elastic substrate 13, upward). A repulsive force (stress) is generated. Then, in the laminated body 1 in a state of being held by the production apparatus 9 such as the laminated body 1 immediately after production, the force (force indicated by the arrow A) applied from the stage of the intermediate structure 10 is eliminated. Then, the repulsive force generated in the elastic substrate 13 as indicated by the arrow B in FIG. 1B attempts to peel the elastic substrate 13 and the adhesive layer 14 from the inelastic substrate 11. However, in the laminate 1, since the adhesive layer 14 is formed of the film adhesive according to the present invention, the adhesive force is sufficiently high, and thus such peeling is suppressed. On the other hand, in the laminate 1 provided with a conventional adhesive layer instead of the adhesive layer 14, peeling at the interface between the elastic substrate 13 and the adhesive layer due to the repulsive force, There is a possibility that structural destruction, peeling at the interface between the adhesive layer and the non-elastic substrate 11 or the like occurs, and at least the elastic substrate 13 is peeled off, so that the intended laminate cannot be obtained.

  In the laminated body obtained by the manufacturing method, the peeling of the elastic substrate is suppressed as described above, and the peeling strength of the adhesive layer is high. The peel strength of the adhesive layer is, for example, a test laminate (hereinafter referred to as “test laminate (2) wherein the substrate is pressure-bonded to the entire surface of the adhesive layer having a size of 12 mm × 12 mm (thickness 20 μm)”. ) ", Which is sometimes referred to as") ", is obtained as a force (peeling force) when one substrate is peeled off under the conditions of a pulling speed of 50 mm / min and a peeling angle of 90 °. The said test laminated body (2) should just be provided with what is in this invention as an adhesive bond layer, and may be the laminated body which concerns on this invention, for example, elastic substrates or non-elastic substrates as a board | substrate The laminated body according to the present invention may not be used. By using the test laminate (2) that is not the laminate according to the present invention, the peel strength of the adhesive layer in the laminate according to the present invention is obtained without using the laminate according to the present invention. It is done.

In the laminate according to the present invention, the peel strength of the adhesive layer can be 7 N / 10 mm or more. With such a peeling strength, peeling of the elastic substrate as described above is sufficiently suppressed, and trouble can be sufficiently prevented from occurring in the manufacturing process of the semiconductor device using the laminated body. Furthermore, in the laminate according to the present invention, the peel strength of the adhesive layer can be preferably 7.4 N / 10 mm or more, more preferably 7.8 N / 10 mm or more.
On the other hand, the upper limit value of the peel strength of the adhesive layer is not particularly limited, but is usually about 20 N / 10 mm.
The peel strength can be adjusted, for example, by adjusting the content of the adhesive composition (film adhesive), the content thereof, and the like.

2A and 2B are diagrams schematically showing the laminated body 1 in an enlarged manner, in which FIG. 2A is a plan view viewed from the inelastic substrate 11 side, and FIG. 2B is a cross-sectional view taken along the line II of FIG. is there.
In the laminate 1 using the adhesive sheet, the adhesive layer 14 is prevented from protruding from the adhesive surfaces of the non-elastic substrate 11 and the elastic substrate 13. In the laminated body 1, as shown here, the maximum value D ₁₁ of the protruding distance of the adhesive layer 14 from the side surface 11 c of the inelastic substrate 11 (distance to the tip of the adhesive layer 14) is set as the adhesive layer 14. It can be defined as the amount of protrusion. For example, when the adhesive layer 14 does not protrude from the side surface 11c of the inelastic substrate 11 but is recessed inward from the side surface 11c of the inelastic substrate 11 (on the inelastic substrate 11 side of the adhesive layer 14). the area of the surface (back surface) 14b is smaller than the area of the adhesive layer 14 side surface (surface) 11a of the non-elastic substrate _{11), D 11} denote a negative value. Therefore, as in the case of inelastic substrate 11, if the maximum value of the protrusion distance of the adhesive layer 14 from the side face of the elastic substrate 13 has a D _13, in the laminate 1 shown in FIG. 2, D ₁₃ is negative (Not shown).

In the laminate according to the present invention, the amount of protrusion of the adhesive layer can be less than 80 μm in a size that can be used in the manufacturing process of the semiconductor device. With such an amount of protrusion, troubles can be sufficiently prevented in various processes such as wire bonding, for example, when the laminate is used at the time of manufacturing a semiconductor device. Furthermore, in the laminate according to the present invention, the protruding amount of the adhesive layer is preferably 75 μm or less, more preferably 65 μm or less, and further preferably 55 μm or less.
The amount of protrusion of the adhesive layer can be adjusted, for example, by adjusting the viscosity at 150 ° C. before thermosetting of the adhesive composition as described above.

Here, as the “laminated body having a size that can be used in the manufacturing process of the semiconductor device”, for example, the area of the smaller one of the elastic substrate and the non-elastic substrate on the side of the adhesive layer is 225 mm ² or less. The laminated body which is is mentioned.

In FIG. 2, as a representative embodiment of the laminate according to the present invention, the area of the back surface 13 b of the elastic substrate 13 is such that the front surface 12 a and the back surface 12 b of the film adhesive 12 and the non-elastic substrate 11 Although it has shown about the thing larger than the area of the surface 11a, for example, the area of the said surface 12a and the said back surface 12b of the film adhesive 12 is the said back surface 13b of the elastic substrate 13, and the said surface 11a of the non-elastic substrate 11 When larger than the area, the larger one of D ₁₁ and D ₁₃ can be defined as the amount of protrusion of the adhesive layer 14. Thus, even in a laminate in which the relationship between the sizes of the non-elastic substrate, the film adhesive, and the elastic substrate is different from that shown in FIG. 2, the amount of protrusion of the adhesive layer is shown in FIG. It can be reduced as in the case of.

  Whether or not the adhesive layer is prevented from protruding in the laminate as described above is, for example, a test in which the substrate is pressure-bonded to both surfaces of the adhesive layer having a size of 8 mm × 8 mm (thickness 20 μm). For the laminate for use (hereinafter sometimes referred to as “test laminate (1)”), the amount of protrusion of the adhesive layer is measured, and whether or not a predetermined value such as less than 80 μm is obtained as described above. This can be determined by checking. What is necessary is just to produce the test laminated body (1) by applying the conditions in the said manufacturing method as a load at the time of crimping | bonding, heating conditions, and hardening conditions. The laminate for testing (1) may be a laminate according to the present invention, or may not be a laminate according to the present invention, for example, one using elastic substrates or non-elastic substrates as substrates. Good. By using what is not the laminated body which concerns on this invention as a laminated body for a test (1), without using the laminated body which concerns on this invention, the protrusion suppression effect of the adhesive layer in the laminated body which concerns on this invention is demonstrated. You can check the degree.

  Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the following examples.

[Examples 1-5, Comparative Examples 1-2]
<Manufacture of adhesive sheet>
(Manufacture of adhesive composition)
Each component was mix | blended with the quantity (solid content) shown in Table 1, and also methyl ethyl ketone was mix | blended, and the adhesive composition was obtained.
In addition, the symbol of each component in Table 1 has the following meaning, respectively. “-” Means that the component is not blended.

・ Acrylic resin (a)
(A) -1: Weight obtained by copolymerizing n-butyl acrylate (55 parts by mass), methyl acrylate (10 parts by mass), glycidyl methacrylate (20 parts by mass) and 2-hydroxyethyl acrylate (15 parts by mass). A copolymer having an average molecular weight of 900,000.
・ Epoxy resin (b1)
(B1) -1: Bisphenol A type epoxy resin (“BPA328” manufactured by Nippon Shokubai Co., Ltd.)
(B1) -2: Phenylene skeleton type epoxy resin (“EPPN-502H” manufactured by Nippon Kayaku Co., Ltd.)
・ Phenolic thermosetting agent (b2)
(B2) -1: Novolac-type phenol resin (“BRG-556” manufactured by Showa Polymer Co., Ltd.)
・ Filler (c)
(C) -1: Spherical silica (“SC2050MA” manufactured by Admatechs)
・ Curing accelerator (d)
(D) -1: “CURESOL 2PHZ” manufactured by Shikoku Kasei Kogyo Co., Ltd.
・ Coupling agent (e)
(E) -1: Silane coupling agent (“KBE-403” manufactured by Shin-Etsu Silicone)
・ Other resins (g)
(G) -1: Thermoplastic resin, polyester (“Byron 220” manufactured by Toyobo Co., Ltd.)
(G) -2: Contains 0.5% of an ultraviolet curable resin (“KAYARAD R-684” manufactured by Nippon Kayaku Co., Ltd.) and a photoinitiator (“Irgacure 184” manufactured by Ciba Specialty Chemicals).

(Measurement of viscosity at 150 ° C. of adhesive composition)
About each adhesive composition obtained above, using a torsional shear type viscosity measuring device (“ARES series” manufactured by Rheometrics), measuring temperature 150 ° C., strain 25%, sample diameter 8 mmφ, length between chucks 1 The viscosity at a temperature of 150 ° C. before thermosetting was measured under the condition of 0.0 mm. The results are shown in Table 1.

(Manufacture of adhesive sheets)
The adhesive composition obtained above was applied to the release-treated surface of a release film (“SP-PET 381031” manufactured by Lintec Corporation, thickness 38 μm) from which one side of a polyethylene terephthalate film was released by silicone treatment, A film adhesive having a thickness of 20 μm was formed by drying at 100 ° C. for 1 minute using an oven.
Next, an adhesive sheet was obtained by laminating a polyolefin substrate having a thickness of 100 μm on the surface (exposed surface) of the film adhesive.

<Manufacture of test laminate (1)>
According to the manufacturing method described above, except that an 8 mm × 8 mm silicon chip (thickness: 100 μm) was used instead of the elastic substrate, the adhesive sheet obtained above and a 20 mm × 20 mm silicon chip ( A test laminate (1) in which a silicon chip, an adhesive layer, and a silicon chip were pressure-bonded and laminated in this order was manufactured using a thickness of 350 μm. More specifically, it is as follows.
After peeling off the release film of the adhesive sheet, the 8 mm × 8 mm exposed surface of the film adhesive was affixed to the surface of an 8 mm × 8 mm silicon chip (thickness 100 μm), and the polyolefin substrate was peeled off, Using a die bonder (“BESTEM D02” manufactured by Canon Machinery Co., Ltd.), a film adhesive was applied to the surface of a 20 mm × 20 mm silicon chip (thickness 350 μm). At this time, bonding using a die bonder (treatment of applying force to a laminate of a silicon chip, a film adhesive and a silicon chip while heating) was performed under conditions of a heating temperature of 150 ° C., a load of 14 N, and a time of 10 seconds. Further, the film adhesive and the two silicon chips were arranged so that their centers coincided. Further, the laminate was heat-treated at 130 ° C. for 1 hour to thermally cure the film adhesive to form an adhesive layer, thereby obtaining the test laminate (1).

<Evaluation of protrusion amount of adhesive layer in test laminate (1)>
Using a digital microscope (“VHX1000” manufactured by Keyence Corporation), the test laminate (1) obtained above was observed from the 8 mm × 8 mm silicon chip side, and an 8 mm × 8 mm silicon chip was observed. The maximum value of the amount of protrusion of the adhesive layer from the four sides was measured, and the average value was calculated as the amount of protrusion of the adhesive layer of the test laminate (1). The results are shown in Table 1. In the test laminate (1), the case where the amount of protrusion of the adhesive layer was less than 80 μm was determined to be acceptable, and the case where it was 80 μm or more was determined to be unacceptable.

<Manufacture of test laminate (2)>
After peeling off the release film of the adhesive sheet, the exposed surface of 12 mm × 12 mm of the film adhesive was applied to the surface of a 12 mm × 12 mm silicon chip (thickness 350 μm), and the polyolefin substrate was peeled off, A film adhesive was applied to the surface of a copper foil (specification: JIS H3100, 15 mm × 50 mm × 0.35 mm) in the same manner as in the case of the test laminate (1). Furthermore, this laminate was heat-treated at 130 ° C. for 1 hour to thermally cure the film adhesive to form an adhesive layer, thereby obtaining a test laminate (2).

<Evaluation of peel strength of adhesive layer in test laminate (2)>
Using a tensile tester (“Autograph AG-IS” manufactured by Shimadzu Corporation), the copper foil of the test laminate (2) obtained above was peeled off under the conditions of a pulling speed of 50 mm / min and a peeling angle of 90 °. The peel strength was measured. The measurement was performed four times, and the average value was calculated as the peel strength of the adhesive layer. The results are shown in Table 1. In the test laminate (2), the case where the peel strength of the adhesive layer was 7 N / 10 mm or more was judged as acceptable, and the case where it was less than 7 N / 10 mm was judged as unacceptable.

<Comprehensive judgment of characteristics of adhesive layer>
About both the amount of protrusion of the adhesive layer and the evaluation result of the peel strength, when both passed, the characteristics of the adhesive layer were comprehensively judged as pass (○), and when at least one was rejected, The characteristics of the agent layer were comprehensively judged as rejected (x). The results are shown in Table 1.

As is clear from the above results, as the adhesive composition, the acrylic resin content is in the range of 15 to 45% by mass, and the viscosity at 150 ° C. before thermosetting is in the range of 600 Pa · s or more. An adhesive layer formed from a certain material was prevented from protruding from the adhesive surface and had sufficient adhesive strength.
On the other hand, as an adhesive composition, the adhesive layer formed from the content of acrylic resin and the viscosity at 150 ° C. before thermosetting are both outside the above range, The protrusion of the film was remarkable and the adhesive strength was insufficient.

  The present invention can be used for manufacturing semiconductor devices.

DESCRIPTION OF SYMBOLS 1 ... Laminated body, 10 ... Intermediate structure, 11 ... Inelastic substrate, 11a ... Front surface of inelastic substrate, 11b ... Back surface of inelastic substrate, 11c ... Inelastic substrate Side surface, 12 ... film adhesive, 12a ... surface of film adhesive, 12b ... back surface of film adhesive, 13 ... elastic substrate, 13b ... back surface of elastic substrate, 14 ... adhesive layer, the back surface of the 14b ... adhesive layer, 9 ... manufacturing apparatus, 91 a fixed part of ... manufacturing _apparatus, the adhesive layer from _{D 11} ... side inelastic substrate Maximum protrusion distance

Claims (3)

An adhesive composition for use in the formation of the adhesive layer of a laminate comprising a non-elastic substrate, an adhesive layer and an elastic substrate in this order.
The adhesive composition contains an acrylic resin (a), an epoxy resin (b1) , a phenolic thermosetting agent (b2) , an inorganic filler (c), and a coupling agent (e) .
The content ratio of the acrylic resin to the total solid content of the adhesive composition (a) is 15 to 45 wt%,
The ratio of the content of the inorganic filler (c) to the total solid content of the adhesive composition is 5 to 25% by mass,
The ratio of the content of the coupling agent (e) in the adhesive composition is 100 parts by mass of the total content of the acrylic resin (a), the epoxy resin (b1), and the phenol thermosetting agent (b2). In contrast, 0.03 to 20 parts by mass,
Ri der viscosity of 600 Pa · s or more at 0.99 ° C. before thermal curing of the adhesive composition,
The entire surface of one exposed surface of the film adhesive having a size of 12 mm × 12 mm and a thickness of 20 μm obtained by forming into a film using the adhesive composition has a size of 12 mm × 12 mm. And affixed to the surface of a silicon chip having a thickness of 350 μm, and the other exposed surface was affixed to the surface of a copper foil having a size of 15 mm × 50 mm and a thickness of 350 μm. The silicon chip, the film adhesive, and the copper foil were pressed by applying a load of 14 N for 10 seconds in the laminating direction of the silicon chip, the film adhesive, and the copper foil while heating at 150 ° C. Thereafter, the test laminate (2) was prepared by heat-treating at 130 ° C. for 1 hour to thermally cure the film adhesive to form an adhesive layer. Before Copper foil, speed 50 mm / min pulling, is peeled at a peeling angle of 90 ° conditions, when the peel strength was measured, the adhesive composition, wherein the peel strength is 7N / 10 mm or more. A film adhesive obtained by forming into a film using the adhesive composition according to claim 1 . A non-elastic substrate, an adhesive layer and an elastic substrate are pressure-bonded and laminated in this order, and a method for producing a laminate,
The adhesive layer is formed from the film adhesive according to claim 2 ,
By applying a force in the stacking direction of the non-elastic substrate, the film-like adhesive and the elastic substrate while heating the intermediate structure in which the non-elastic substrate, the film-like adhesive and the elastic substrate are laminated in this order, Production of a laminate characterized in that the laminate is obtained by press-bonding a non-elastic substrate, a film adhesive and an elastic substrate, and further thermosetting the film adhesive to form the adhesive layer. Method.

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