JP2009251228A - Resin sheet for substrate and sheet for substrate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin sheet for substrate, with which a substrate for display where a semiconductor chip, such as a circuit chip for controlling respective pixels for display and a light-emitting diode, are buried is efficiently fabricated with good quality and high productivity; and to provide a sheet for substrate obtained using the same. <P>SOLUTION: Disclosed are the resin sheet for substrate having a resin layer in which the semiconductor chip is buried and a contact layer for a support substrate which is made of an active energy beam-curing type resin material and/or a cured body thereof; and the sheet for substrate obtained by burying the semiconductor chip in the resin sheet for substrate. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a substrate resin sheet and a substrate sheet. More specifically, a substrate for efficiently producing a display substrate having a semiconductor chip embedded therein, such as a circuit chip or a light emitting diode for controlling each pixel for display, with high quality and high productivity. The present invention relates to a resin sheet and a substrate sheet obtained by using them.

  In a conventional display, a microelectronic device such as a thin film transistor (TFT) is formed in the vicinity of each pixel to control each pixel. However, the process of manufacturing these pixel control elements is complicated in many steps, and it is inevitable that the cost is increased. Therefore, a technique for embedding and fixing a minute circuit chip in an organic substrate has been disclosed for the purpose of cost reduction (see, for example, Patent Document 1). In this case, a polymer film is formed in advance on a glass substrate, and a microcrystalline silicon integrated circuit chip is transferred to the glass substrate by means of printing technology or the like, and the chip is raised by a method such as thermoforming or heating press. Embedding in a molecular film is performed. However, such a method is not efficient because defects such as distortion and foaming of the polymer film are likely to occur and heating takes time.

In addition, by using a circuit board sheet made of an energy beam curable polymer material instead of the polymer film, heating is controlled by controlling the respective storage elastic modulus at the time of circuit chip embedding and after embedding to a predetermined range. A circuit board sheet and a circuit board sheet that can be embedded without being performed are disclosed (for example, see Patent Document 2).
By using such a circuit board sheet, it is possible to efficiently produce a display circuit board sheet in which circuit chips are embedded with high productivity. However, the circuit board sheet is not necessarily satisfactory in terms of solvent resistance, and when the wiring is formed on the surface of the board sheet in which the circuit chip is embedded and washed with the solvent, There were problems such as peeling.
JP 2003-248436 A JP 2006-323335 A

  Under such circumstances, the present invention provides a display substrate in which a semiconductor chip such as a circuit chip or a light emitting diode for controlling each pixel for display is embedded, with high quality and high productivity. An object of the present invention is to provide a resin sheet for a substrate for efficiently producing the substrate and a sheet for a substrate obtained by using the resin sheet.

As a result of intensive studies to achieve the above object, the present inventors have made the resin sheet for a substrate into a multi-layered structure of two or more layers, and the adhesive layer for the support substrate is an active energy ray curable resin material and / or its Based on this finding, it is found that by constituting from a cured product, a substrate sheet having good adhesion to a support substrate is obtained without being affected by acid, aqueous alkali solution, and solvent, and that the purpose can be achieved. The present invention has been completed.
That is, the present invention
[1] A resin sheet for a substrate comprising a resin layer in which a semiconductor chip is embedded, and an adhesive layer made of an active energy ray-curable resin material and / or a cured product thereof, and a support substrate,
[2] The resin sheet for a substrate according to the above [1], wherein the resin layer in which the semiconductor chip is embedded is made of an active energy ray-curable resin material,
[3] The resin sheet for substrates according to the above [1] or [2], wherein the adhesive strength to the glass plate after curing by irradiation with active energy rays is 0.3 N / 25 mm or more,
[4] Any of the above items [1] to [3], wherein in the adhesion layer to the support substrate, the swelling ratio with respect to ethanol after curing by irradiation with active energy rays (immersion in ethanol at 23 ° C. for 5 minutes) is 60% or less. A resin sheet for a substrate according to claim 1,
[5] In the adhesive layer to the support substrate, the active energy ray-curable resin material and / or the cured product thereof includes an acrylic copolymer having a (meth) acrylic acid unit and a (meth) acrylic acid ester unit. 1] to [4] The resin sheet for a substrate according to any one of the items, and [6] The substrate obtained by embedding a semiconductor chip in the resin sheet for a substrate according to any one of the above [1] to [5] items For sheet,
Is to provide.

  According to the present invention, a display substrate in which a semiconductor chip such as a circuit chip or a light emitting diode for controlling each pixel for display is embedded is efficiently manufactured with high quality and high productivity. The board | substrate resin sheet and the board | substrate sheet | seat obtained using the same can be provided.

First, the substrate resin sheet of the present invention will be described.
[Resin sheet for substrates]
The resin sheet for a substrate of the present invention is characterized by having a resin layer in which a semiconductor chip is embedded and an adhesion layer made of an active energy ray-curable resin material and / or a cured product thereof to a support substrate.
(Resin layer in which semiconductor chip is embedded)
In the resin sheet for a substrate of the present invention, as the resin constituting the resin layer in which the semiconductor chip is embedded, the semiconductor chip can be embedded and wiring can be formed on the surface of the resin layer after the semiconductor chip is embedded. There is no particular limitation, and various resins such as thermoplastic resins, thermal energy curable resin materials, active energy ray curable resin materials, and the like can be used. Among these, an active energy ray curable resin material (hereinafter referred to as an active energy ray curable resin material A) is preferable from the viewpoint of embedding of a semiconductor chip, fixing of a semiconductor chip, and the like. Here, the active energy rays are those having energy quanta among electromagnetic waves or charged particle beams, that is, ultraviolet rays or electron beams.

<Active energy ray-curable resin material A>
As the active energy ray-curable resin material A used in the present invention, for example, (1) a polymer material containing a tacky acrylic polymer, an active energy ray-curable oligomer and / or a monomer, and a photopolymerization initiator as required ( 2) A polymeric material containing a tacky acrylic polymer having an active energy ray-curable group in the side chain and, if desired, a photopolymerization initiator.
In the polymer material of (1), the adhesive acrylic polymer includes (meth) acrylic acid ester having an alkyl group of 1 to 20 carbon atoms in the ester moiety, and a functional group having active hydrogen as required. Preferred examples thereof include a monomer having a monomer and a copolymer with another monomer, that is, a (meth) acrylic acid ester copolymer. In the present invention, "(meth) acrylic acid ..." means both "acrylic acid ..." and "methacrylic acid ...".

Here, examples of the (meth) acrylic acid ester having 1 to 20 carbon atoms of the alkyl group in the ester portion include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth ) Butyl acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, Examples include dodecyl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate, and the like. These may be used alone or in combination of two or more.
On the other hand, examples of the monomer having a functional group having an active hydrogen used as desired include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxy (meth) acrylate. (Meth) acrylic acid hydroxyalkyl esters such as propyl, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; monomethylaminoethyl (meth) acrylate (Meth) acrylic acid monoethylaminoethyl, (meth) acrylic acid monomethylaminopropyl, (meth) acrylic acid monoethylaminopropyl (meth) acrylic acid monoalkylaminoalkyl; acrylic acid, methacrylic acid, crotonic acid, Ethylenically unsaturated carboxylic acids such as maleic acid, itaconic acid, citraconic acid And the like. These monomers may be used independently and may be used in combination of 2 or more type.
In the (meth) acrylic acid ester copolymer, the (meth) acrylic acid ester unit is contained in an amount of about 5 to 100% by mass, preferably about 50 to 99% by mass, and the monomer unit having a functional group having active hydrogen is It is contained in an amount of 0 to 95% by mass, preferably 1 to 50% by mass.

  Examples of other monomers used as desired include vinyl esters such as vinyl acetate and vinyl propionate; olefins such as ethylene, propylene and isobutylene; halogenated olefins such as vinyl chloride and vinylidene chloride; styrene Styrene monomers such as α-methylstyrene; diene monomers such as butadiene, isoprene and chloroprene; nitrile monomers such as acrylonitrile and methacrylonitrile; acrylamide, N-methylacrylamide, N, N- Examples include acrylamides such as dimethylacrylamide. These may be used alone or in combination of two or more. In the (meth) acrylic acid ester copolymer, these monomer units can be contained in an amount of 0 to 30% by mass.

In the polymer material, the (meth) acrylic acid ester copolymer used as the adhesive acrylic polymer is not particularly limited with respect to the copolymerization form, and may be any of random, block, and graft copolymers. May be. The molecular weight is preferably 50,000 or more in terms of weight average molecular weight, more preferably 80,000 to 2,000,000.
In addition, the said weight average molecular weight is the value of polystyrene conversion measured by the gel permeation chromatography (GPC) method.
In the present invention, this (meth) acrylic acid ester copolymer may be used alone or in combination of two or more.

Examples of the active energy ray-curable oligomer include polyester acrylate, epoxy acrylate, urethane acrylate, polyether acrylate, polybutadiene acrylate, and silicone acrylate. Here, as the polyester acrylate oligomer, for example, by esterifying hydroxyl groups of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol with (meth) acrylic acid, It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding alkylene oxide to a polyvalent carboxylic acid with (meth) acrylic acid. The epoxy acrylate oligomer can be obtained, for example, by reacting (meth) acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin and esterifying it. A carboxyl-modified epoxy acrylate oligomer obtained by partially modifying this epoxy acrylate oligomer with a dibasic carboxylic acid anhydride can also be used. The urethane acrylate oligomer can be obtained, for example, by esterifying a polyurethane oligomer obtained by reaction of polyether polyol or polyester polyol with polyisocyanate with (meth) acrylic acid. It can be obtained by esterifying the hydroxyl group of ether polyol with (meth) acrylic acid.
The weight average molecular weight of the oligomer is a value in terms of standard polystyrene measured by the GPC method, preferably 500 to 100,000, more preferably 1,000 to 70,000, and still more preferably 3,000 to 40,000. Selected by range.
This oligomer may be used individually by 1 type, and may be used in combination of 2 or more type.

On the other hand, examples of the active energy ray-curable monomer include cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and isobornyl (meth) acrylate. Monofunctional acrylic acid esters, di (meth) acrylic acid 1,4-butanediol ester, di (meth) acrylic acid 1,6-hexanediol ester, di (meth) acrylic acid neopentyl glycol ester, di (meth) ) Acrylic acid polyethylene glycol ester, di (meth) acrylic acid neopentyl glycol adipate ester, di (meth) acrylic acid hydroxypivalic acid neopentyl glycol ester, di (meth) acrylic acid dicyclopentanyl, di (meth) acrylic acid Caprolactone-modified dicyclopentenyl, di (meth) acrylic Ethylene oxide modified phosphate ester, di (meth) acrylate allylated cyclohexyl, di (meth) acrylic acid isocyanurate, dimethylol tricyclodecane di (meth) acrylate, tri (meth) acrylic acid trimethylolpropane ester, tri (meth) ) Acrylic acid dipentaerythritol ester, tri (meth) acrylic acid propionic acid modified dipentaerythritol ester, tri (meth) acrylic acid pentaerythritol ester, tri (meth) acrylic acid propylene oxide modified trimethylolpropane ester, isocyanuric acid tris ( Acryloxyethyl), penta (meth) acrylic acid propionic acid modified dipentaerythritol ester, hexa (meth) acrylic acid dipentaerythritol ester, hexa (meth) acrylic acid caprolactone modified dipe Such as data pentaerythritol ester, and the like. These monomers may be used alone or in combination of two or more.
The amount of these oligomers and monomers used is usually 3 to 300 parts by mass with respect to 100 parts by mass of the solid content of the (meth) acrylic acid ester copolymer.

Moreover, although an ultraviolet-ray or an electron beam is normally irradiated as an active energy ray, when irradiating an ultraviolet-ray, a photoinitiator can be used. Examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenyl Ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 4- (2-hydroxyethoxy) phenyl-2 (hydroxy-2-propyl) ketone, benzophenone, p -Feni Benzophenone, 4,4′-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyldimethyl ketal, acetophenone dimethyl ketal, p-dimethylamine benzoate, oligo (2-hydroxy-2-methyl-1- [4- (1-propenyl) Phenyl] propanone) and the like. These may be used alone or in combination of two or more.
A compounding quantity is 0.1-10 mass parts normally with respect to 100 mass parts of solid content of the above-mentioned active energy ray hardening-type polymeric material.

Next, in the polymer material of (2), the adhesive acrylic polymer having an active energy ray-curable group in the side chain is, for example, the adhesive acrylic polymer described in the polymer material of (1) described above. An active site such as —COOH, —NCO, epoxy group, —OH, —NH ₂ is introduced into the polymer chain of the polymer, and this active site reacts with a compound having an active energy ray-curable group to produce the adhesive property. The thing formed by introduce | transducing an active energy ray hardening group into the side chain of an acrylic polymer can be mentioned. As the active energy ray-curable group, a (meth) acryloyl group is preferable.
To introduce the active sites in the adhesive acrylic polymer, a functional group in preparing the tacky acrylic polymer, -COOH, -NCO, epoxy groups, -OH, etc. -NH _2, A monomer or oligomer having an active energy ray-curable group may be present in the reaction system.
Specifically, when the -acrylic polymer described in the polymer material (1) described above is produced, when a -COOH group is introduced, (meth) acrylic acid or the like is substituted with -NCO group. In the case of introducing 2- (meth) acryloyloxyethyl isocyanate, etc., in the case of introducing an epoxy group, glycidyl (meth) acrylate, etc., in the case of introducing an —OH group, (meth) N-methyl (meth) acrylamide or the like may be used when -NH ₂ group is introduced into 2-hydroxyethyl acrylate, mono (meth) acrylic acid 1,6-hexanediol ester or the like.

Examples of the compound having an active energy ray-curable group to be reacted with these active sites include 2- (meth) acryloyloxyethyl isocyanate, glycidyl (meth) acrylate, mono (meth) acrylate pentaerythritol ester, mono ( It can be used by appropriately selecting from dimethacrylic acid dipentaerythritol ester, mono (meth) acrylic acid trimethylolpropane ester and the like according to the type of active site.
In this way, an adhesive acrylic polymer having an active energy ray-curable group on the side chain of the adhesive acrylic polymer via the active site, that is, a (meth) acrylic acid ester copolymer is obtained. .
The (meth) acrylic acid ester copolymer introduced with the active energy ray-curable group preferably has a weight average molecular weight of 50,000 or more, more preferably 100,000 to 2,000,000. In addition, the said weight average molecular weight is the value of polystyrene conversion measured by GPC method.
Moreover, as a photoinitiator used as needed, the photoinitiator illustrated in description of the polymeric material of the above-mentioned (1) can be used.

In the active energy ray-curable polymer materials (1) and (2), a crosslinking agent, a tackifier, an antioxidant, an ultraviolet absorber, and the like, as long as the effects of the present invention are not impaired. Light stabilizers, softeners, fillers and the like can be added.
Examples of the crosslinking agent include polyisocyanate compounds, epoxy resins, melamine resins, urea resins, dialdehydes, methylol polymers, aziridine compounds, metal chelate compounds, metal alkoxides, metal salts, and the like. A compound is preferably used. This crosslinking agent can be blended in an amount of 0 to 30 parts by mass with respect to 100 parts by mass of the solid content of the (meth) acrylic acid ester copolymer.
Examples of polyisocyanate compounds include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, and isophorone diisocyanate. Nalto, cycloaliphatic polyisocyanates such as hydrogenated diphenylmethane diisocyanate, etc., and their biurets, isocyanurates, and low molecules such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, castor oil The adduct body etc. which are a reaction material with an active hydrogen containing compound can be mentioned. These crosslinking agents may be used individually by 1 type, and may be used in combination of 2 or more type.

The active energy ray-curable polymer material (1) and (2) described above has a side chain (2) with respect to the active energy ray-curable polymer material (1) in order to control the elastic modulus. A (meth) acrylic acid ester copolymer having an active energy ray-curable group can be added to. Similarly, the adhesive acrylic polymer (1), the active energy ray curable oligomer or the active energy ray curable monomer (1) can be added to the active energy ray curable polymer material (2).
Moreover, although the thickness of the resin layer in which this semiconductor chip is embedded depends on the size of the semiconductor chip, it is usually about 30 to 1000 μm, preferably 40 to 500 μm, from the viewpoint of chip embedding property and retention property. .

(Adhesion layer to the support substrate)
In the resin sheet for a substrate of the present invention, an active energy ray curable resin material (hereinafter referred to as an active energy ray curable resin) is used as a resin constituting an adhesion layer (hereinafter sometimes referred to as a support substrate adhesion layer) to a support substrate. (Referred to as resin material B).
From the viewpoint of adhesion to a support substrate (glass or the like), the adhesion layer to the support substrate made of this active energy ray-curable resin material B has an adhesive force to the glass plate after being cured by active energy ray irradiation of the resin sheet for substrate. 0.3 N / 25 mm or more is preferable, and 0.35 N / 25 mm or more is more preferable. Although there is no restriction | limiting in particular about the upper limit, Usually, it is about 20N / 25mm.
In addition, from the viewpoint of solvent resistance, the support substrate adhesion layer preferably has a swelling ratio (soaked in ethanol at 23 ° C. for 5 minutes) of 60% or less after curing by irradiation with active energy rays. % Or less is more preferable. The lower limit is not particularly limited, but is usually about 1%.
In addition, the measuring method of the adhesive force with respect to the said glass plate and the swelling rate with respect to ethanol is demonstrated later.

<Active energy ray-curable resin material B>
In the present invention, as the active energy ray-curable resin material B used for the adhesion layer to the support substrate, as shown in the description of the active energy ray-curable resin material A, (1) an adhesive acrylic polymer, A polymeric material containing an active energy ray-curable oligomer and / or monomer and, if desired, a photopolymerization initiator; (2) an adhesive acrylic polymer having active energy ray curability in the side chain; and optionally a photopolymerization initiator. The high molecular weight material can be used, but from the viewpoint of adhesion after curing with active energy rays, the adhesive acrylic polymer in the above (1) and (2) is composed of (meth) acrylic acid units and (meta It is essential to have acrylate units. 1-40 mass% is preferable, as for content of the (meth) acrylic acid unit in this adhesive acrylic polymer, 2-30 mass% is more preferable, and 3-25 mass% is more preferable.

Although there is no restriction | limiting in particular in the thickness of the said support substrate contact | adherence layer, Usually, about 1-100 micrometers, Preferably it is 3-80 micrometers.
The resin sheet for a substrate of the present invention may have a two-layer structure including a resin layer in which a semiconductor chip is embedded and a support substrate adhesion layer, or a resin layer in which the semiconductor chip is embedded, It may have a multilayer structure of three or more layers in which one or more other resin layers are interposed between the supporting substrate adhesion layer.

(Production of resin sheet for substrates)
Hereinafter, a method for producing the resin sheet for a substrate of the present invention will be described by taking a two-layer structure as an example. However, the present invention is not particularly limited thereby.
On the release agent layer of the heavy release release sheet, a coating solution adjusted to an appropriate concentration containing the active energy ray-curable resin material A is applied to a known method such as knife coating, roll coating, bar coating. The resin layer in which the semiconductor chip is embedded is formed by applying and drying to a predetermined thickness by a method, a blade coating method, a die coating method, a gravure coating method, or the like.
On the other hand, on the release agent layer of the light release type release sheet, the coating liquid adjusted to an appropriate concentration containing the active energy ray-curable resin material B is made to have a predetermined thickness in the same manner as described above. The substrate is coated and dried, and an energy ray is irradiated as desired to form an adhesion layer to the supporting substrate. As the active energy ray, an ultraviolet ray or an electron beam is usually used. Ultraviolet rays are obtained with a high-pressure mercury lamp, a fusion H lamp, a xenon lamp or the like, while an electron beam is obtained with an electron beam accelerator or the like. Among these active energy rays, ultraviolet rays are particularly preferable. The irradiation amount of the active energy ray is appropriately selected. For example, in the case of ultraviolet rays, the amount of light is preferably 100 to 5000 mJ / cm ² , and in the case of an electron beam, it is preferably about 10 to 1000 krad.
Next, by laminating the adhesion layer for supporting substrate formed on the light release type release sheet on the resin layer in which the semiconductor chip formed on the above heavy release type release sheet is embedded, the heavy release type release sheet, the semiconductor A resin sheet for a substrate comprising a resin layer in which chips are embedded, a support substrate adhesion layer, and a light release type release sheet in this order is obtained.
The release sheet is not particularly limited, and examples thereof include a polyolefin film such as a polyethylene film and a polypropylene film, and a polyester film such as polyethylene terephthalate coated with a release agent such as a silicone resin to provide a release agent layer. . The thickness of this release sheet is usually about 20 to 150 μm.

Next, the board | substrate sheet | seat of this invention is demonstrated.
[Substrate sheet]
In the substrate sheet of the present invention, one surface of the substrate resin sheet may be formed on a support substrate.
There is no restriction | limiting in particular about the said support substrate, From the transparent support substrate normally used as a support substrate for a display, arbitrary things can be selected suitably and can be used. Examples of such a support substrate include a glass substrate, a plate-like or film-like plastic support substrate, and the like. As the glass substrate, for example, a support substrate made of soda lime glass, barium / strontium-containing glass, aluminosilicate glass, lead glass, borosilicate glass, barium borosilicate glass, quartz, or the like can be used. On the other hand, as the plate-like or film-like plastic support substrate, for example, a support substrate made of polycarbonate resin, acrylic resin, polyethylene terephthalate resin, polyether sulfide resin, polysulfone resin, polycycloolefin resin, or the like can be used. The thickness of these supporting substrates is appropriately selected depending on the application, but is usually about 20 μm to 5 mm, preferably 50 μm to 2 mm.
In the present invention, among these supporting substrates, a glass substrate is particularly preferably used.

(Manufacturing method of sheet for substrate)
The method for producing this substrate sheet will be exemplified below. However, the present invention is not particularly limited thereby.
First, the light release type release sheet of the resin sheet for substrates obtained by producing the resin sheet for substrates described above is peeled off, and the peeled surface is bonded to the support substrate. Next, the heavy release type release sheet is peeled off, the semiconductor chip is placed on the resin layer in which the exposed semiconductor chip is embedded, a glass plate or the like is pressed against the semiconductor chip, and the load is about 0.05 to 2.0 MPa. The substrate sheet is obtained by embedding the chip at a temperature of preferably 0 to 150 ° C., more preferably 5 to 100 ° C., and irradiating an active energy ray as necessary to cure the substrate resin sheet. In addition, when the circuit chip is embedded by heating, the irradiation with the active energy ray may be performed in a state where the resin sheet for substrate is heated or after being cooled to room temperature.
As the active energy ray, an ultraviolet ray or an electron beam is usually used. Ultraviolet rays are obtained with a high-pressure mercury lamp, a fusion H lamp, a xenon lamp or the like, while an electron beam is obtained with an electron beam accelerator or the like. Among these active energy rays, ultraviolet rays are particularly preferable. The irradiation amount of the active energy ray is appropriately selected. For example, in the case of ultraviolet rays, the amount of light is preferably 100 to 5000 mJ / cm ² , and in the case of an electron beam, it is preferably about 10 to 1000 krad.

(Wiring formation)
In this way, a display circuit board or the like in which a semiconductor chip is embedded and fixed by being cured is usually provided with wiring (circuit) on the surface thereof.
There is no particular limitation on the method of forming the wiring, and any method can be appropriately selected from the conventionally performed methods. For example, the wiring can be formed using a photolithography technique. As an example, a positive or negative photoresist solution is first applied on a substrate sheet in which a semiconductor chip is embedded and cured, thereby forming a photoresist layer. Next, after exposing the photoresist layer through a predetermined mask pattern, the photoresist layer is developed using an alkaline developer such as an aqueous tetramethylammonium hydroxide solution to form a resist pattern.
Next, after forming a chromium film of a predetermined thickness on the resist pattern by sputtering using a chromium target as a wiring material, for example, the substrate sheet is immersed in an etching solution such as ethanol, Desired wiring can be formed by etching the resist.
In this invention, since the hardened | cured material uses the thing excellent in solvent resistance as a resin sheet for board | substrates, drop-off | omission and peeling of wiring can be prevented in this wiring formation.
FIG. 1 is a schematic cross-sectional view showing an example of a display substrate produced using the substrate resin sheet of the present invention. The display substrate 10 includes a resin layer 2 and a support substrate adhesion layer 3. The two-layer structure substrate resin sheet 4 to the supporting substrate adhesion layer 3 is bonded to the glass substrate 1, and the semiconductor layer 5 is embedded in the resin layer 2 to form a substrate sheet. Has a structure in which wiring 6 is formed on the surface.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
Various characteristics in each example were determined by the following methods.
(1) Adhesiveness with the support substrate Before the wiring is formed on the substrate sheet and after the wiring is formed on the substrate sheet, the substrate sheet is checked for peeling or lifting from the support substrate, and peeling or lifting is confirmed. The case where there was no peeling was marked as ◯, and the case where peeling or floating occurred was marked as x.

(2) Measurement of adhesive strength A resin sheet for a substrate is cut to 25 mm and a length of 250 mm, a light release type release sheet is peeled off, and a non-alkali glass [made by Corning, trade name “ # 1737 "]. Next, the heavy release type release sheet was peeled off and an adhesive sheet having a width of 25 mm and a length of 250 mm (a strong adhesive agent with a thickness of 20 μm [trade name “PA-T1”, manufactured by Lintec Corporation) with a thickness of 25 μm was applied. Polyethylene terephthalate film) was bonded using a rubber roller weighing 2 kg. The substrate sheet was cured by irradiating with ultraviolet light using a fusion H bulb as a light source through an alkali-free glass under the conditions of an illuminance of 400 mW / cm ² and a light amount of 315 mJ / cm ² . Using an all-purpose tensile tester [Orientec Co., Ltd., “Tensilon”], the substrate sheet to which the adhesive sheet is bonded at a peeling angle of 180 ° and a peeling speed of 300 mm / min is peeled off from the alkali-free glass, and the adhesive strength Was measured.

(3) Measurement of swelling rate From the light release sheet side of the resin sheet for substrates, ultraviolet light was irradiated using a Fusion H bulb as a light source under the conditions of illuminance of 400 mW / cm ² and light amount of 300 mJ / cm ^{2 in} a nitrogen atmosphere. Then, the light release type release sheet and the heavy release type release sheet were peeled off and immersed in ethanol at 23 ° C. for 5 minutes, and the film thickness of the adhesion layer to the supporting substrate before and after immersion was measured and calculated. The swelling ratio was calculated from [((film thickness after immersion) − (film thickness before immersion)) / (film thickness before immersion)] × 100, and the average value of 5 times of the above measurement was defined as the swelling ratio.

Example 1
(1) Formation of resin layer in which semiconductor chip is embedded Obtained by reacting 97 parts by weight of methyl methacrylate and 3 parts by weight of 2-hydroxyethyl methacrylate in a mixed solvent of ethyl acetate / methyl ethyl ketone (mass ratio 50:50). 2,2-dimethoxy-1,2-diphenylethane, which is a photopolymerization initiator, with respect to 100 parts by mass of the solid content of the methacrylic acid ester copolymer solution (solid content concentration 35 mass%, weight average molecular weight 100,000). -1-one [Ciba Specialty Chemicals, trade name “Irgacure 651”] 5.0 parts by mass and active energy ray-curable polyfunctional monomer [Kyoeisha Chemical Co., trade name “Light” Acrylate DCP-A "] 200 parts by mass and a polyisocyanate compound cross-linking agent [Mitsui Chemical Polyurethanes, trade name" Takenai " D-140N "] 5.0 parts by mass (solid part 3.8 parts by mass), and finally, methyl ethyl ketone is added to adjust the solids concentration to 40% by mass, followed by stirring until a uniform solution is obtained. Coating solution.
The prepared coating solution was applied by a knife coater to the release-treated surface of a heavy release type release sheet [trade name “PET3811” manufactured by Lintec Corporation] in which a silicone release agent layer was provided on one side of a polyethylene terephthalate film. A resin layer in which a semiconductor chip made of an active energy ray-curable resin material A having a thickness of 50 μm was embedded was formed by heating and drying at 90 ° C. for 90 seconds.

(2) Formation of adhesion layer for supporting substrate Acrylate ester copolymer obtained by reacting 80 parts by mass of butyl acrylate and 20 parts by mass of acrylic acid in a mixed solvent of ethyl acetate / methyl ethyl ketone (mass ratio 50:50) 2-Methacryloyloxyethyl isocyanate is added to the solution (solid content concentration: 35% by mass) so as to be 30 equivalents with respect to 100 equivalents of acrylic acid units in the copolymer, and the reaction is carried out at 40 ° C. for 48 hours in a nitrogen atmosphere. As a result, a (meth) acrylic acid ester copolymer having an active energy ray-curable group in the side chain and a weight average molecular weight of 850,000 was obtained. The photopolymerization initiator 2,2-dimethoxy-1,2-diphenylethane-1-based on 100 parts by mass of the solid content of the copolymer solution into which the obtained active energy ray-curable functional group has been introduced. ON [Ciba Specialty Chemicals, trade name “Irgacure 651”] 3.0 parts by mass, active energy ray-curable polyfunctional monomer and oligomer [Daiichi Seika Kogyo, trade name “ 14-29B (NPI) "] 100 parts by mass (solid content 80 parts by mass) and a cross-linking agent comprising a polyisocyanate compound [manufactured by Toyo Ink Mfg. Co., Ltd., trade name" Olivein BHS-8515 "] 1.2 parts by mass ( 0.45 parts by mass of solids) was dissolved, and finally methyl ethyl ketone was added to adjust the solids concentration to 40% by mass, followed by stirring until a uniform solution was obtained.
The prepared coating solution was applied by a knife coater to the release-treated surface of a light release-type release sheet [trade name “PET3801” manufactured by Lintec Co., Ltd.] having a silicone release agent layer on one side of a polyethylene terephthalate film. The substrate was heat-dried at 90 ° C. for 90 seconds to form a contact substrate adhesion layer made of an active energy ray-curable resin material having a thickness of 50 μm.

(3) Production of resin sheet for substrate Laminating the resin layer in which the semiconductor chip formed on the above heavy release type release sheet is embedded, on the adhesion layer to the support substrate formed on the light release type release sheet, and finally A resin sheet for a substrate made of an active energy ray-curable resin material B having a thickness of 100 μm provided with a heavy release type release sheet, a layer in which a semiconductor chip is embedded, a support substrate adhesion layer, and a light release type release sheet in this order was obtained. .

(4) Production of Substrate Sheet After peeling off the light release release sheet of the produced resin sheet for substrate, and laminating it on a 5 cm × 5 cm glass substrate [manufactured by Corning, “# 1737”] as a support substrate, The release type release sheet was peeled off. Next, two semiconductor chips (circuit chip, length 1 mm × width 1 mm, thickness 50 μm) were arranged at an interval of 3 cm on the resin layer in which the semiconductor chip was embedded. Another 5 cm × 5 cm glass plate was prepared, pressed against the circuit chip on the substrate resin sheet, and pressed for 5 minutes at a pressure of 0.3 MPa using a flat press. After returning to normal pressure, the substrate resin sheet is cured by irradiating with ultraviolet light using a fusion H bulb as a light source under the conditions of an illuminance of 400 mW / cm ² and a light amount of 315 mJ / cm ² from the glass substrate side in a nitrogen atmosphere. A substrate sheet was produced.
(5) Wiring formation A positive resist solution [trade name “OFPR-800”, manufactured by Tokyo Ohka Kogyo Co., Ltd.] is applied to the surface of the substrate sheet on which the semiconductor chip is embedded with a spin coater at a rotation speed of 3000 rpm for 40 seconds. The coating was uniformly applied to the entire surface, and then dried at 100 ° C. for 5 minutes. Since wiring was formed only between circuit chips, exposure was performed using a photomask so that the wiring width was 1 mm. After exposure, the substrate sheet was immersed in a developer [trade name “NMD-3” manufactured by Tokyo Ohka Kogyo Co., Ltd.] for 1 minute, washed with purified water, and dried at 120 ° C. for 5 minutes for development. Thereafter, a chromium (Cr) film having a thickness of 25 nm was formed on the substrate sheet by sputtering using a chromium (Cr) target. Finally, it was immersed in ethanol at 23 ° C. for 5 minutes, and the resist was etched to form a Cr wiring between the chips.
The evaluation results of various properties are shown in Table 1.

Example 2
In Example 1, a resin sheet for a substrate and a sheet for a substrate were prepared and wired in the same manner as in Example 1 except that the adhesion layer to the supporting substrate was changed as follows.
<Formation of adhesion layer for supporting substrate>
Acrylic ester copolymer solution (solid) having a weight average molecular weight of 1.5 million obtained by reacting 95 parts by mass of butyl acrylate with 5 parts by mass of acrylic acid in a mixed solvent of ethyl acetate / methyl ethyl ketone (mass ratio 50:50) A partial concentration of 35% by weight). The photopolymerization initiator 2,2-dimethoxy-1,2-diphenylethane-1-one [trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.] with respect to 100 parts by mass of the solid content of the obtained copolymer solution. “Irgacure 651”] 1.0 part by mass, tris (acryloxyethyl) isocyanurate as an active energy ray-curable monomer [trade name “Aronix M-315” manufactured by Toagosei Co., Ltd.], and polyisocyanate A cross-linking agent composed of a compound [manufactured by Nippon Polyurethane, trade name “Coronate L”] 2.0 parts by mass (solid content 1.5 parts by mass) and a silane coupling agent [manufactured by Shin-Etsu Chemical Co., Ltd. 403 "] 0.2 parts by mass was dissolved, and finally methyl ethyl ketone was added to adjust the solid content concentration to 35% by mass, followed by stirring until a uniform solution was obtained.
The prepared coating solution was applied by a knife coater to the release-treated surface of a light release-type release sheet [trade name “PET3801” manufactured by Lintec Co., Ltd.] having a silicone release agent layer on one side of a polyethylene terephthalate film. Heat drying at 90 ° C. for 90 seconds to form a layer made of an active energy ray-curable resin material B having a thickness of 50 μm. Under a nitrogen atmosphere, the layer made of the active energy ray-curable resin material B was irradiated with ultraviolet rays using a fusion H bulb as a light source under the conditions of an illuminance of 400 mW / cm ² and a light amount of 315 mJ / cm ² from the light release sheet side.
The evaluation results of various properties are shown in Table 1.

Comparative Example 1
In Example 1, the same operation as in Example 1 was performed except that only the resin layer in which the semiconductor chip was embedded was used to form a resin sheet for a substrate made of an active energy ray-curable resin material A having a thickness of 100 μm.
The evaluation results of various properties are shown in Table 1.

Comparative Example 2
In Example 1, the same operation as in Example 1 was performed, except that the non-energy ray curable resin material was changed as follows to the support substrate adhesion layer.
<Formation of adhesion layer for supporting substrate>
Acrylate ester copolymer solution (solid) having a weight average molecular weight of 850,000 obtained by reacting 95 parts by mass of butyl acrylate with 5 parts by mass of acrylic acid in a mixed solvent of ethyl acetate / methyl ethyl ketone (mass ratio 50:50) A partial concentration of 35% by mass) was obtained. 1.2 parts by mass (solid content 0) of a cross-linking agent [trade name “Olivein BHS-8515” manufactured by Toyo Ink Co., Ltd.] consisting of a polyisocyanate compound with respect to 100 parts by mass of the solid content of the obtained copolymer solution. .45 parts by mass) was dissolved, and finally methyl ethyl ketone was added to adjust the solid content concentration to 30% by mass, followed by stirring until a uniform solution was obtained.
The prepared coating solution was applied by a knife coater to the release-treated surface of a light release-type release sheet [trade name “PET3801” manufactured by Lintec Co., Ltd.] having a silicone release agent layer on one side of a polyethylene terephthalate film. Heat drying at 90 ° C. for 90 seconds to form a 50 μm-thick adhesive layer for supporting substrate.
The evaluation results of various properties are shown in Table 1.

As is apparent from Table 1, in Examples 1 and 2 using the resin sheet for substrates of the present invention, the adhesive force is high and the swelling rate is low after irradiation with active energy rays and after wiring formation. Neither peeling nor floating of the circuit board sheet from the substrate was observed.
In contrast, in Comparative Example 1 in which the adhesion to the support substrate is not provided and in Comparative Example 2 in which the adhesion layer to the support substrate is not an active energy ray curable type, the circuit board sheet is peeled off from the support substrate after the wiring is formed. Both were recognized, and in Comparative Example 2, the swelling ratio of the adhesion layer to the support substrate exceeded 60%, and measurement was impossible.

  The resin sheet for a substrate of the present invention enables a substrate for a display embedded with a semiconductor chip such as a circuit chip or a light emitting diode for controlling each pixel for display to be efficiently produced with high quality and high productivity. Can be produced.

It is a cross-sectional schematic diagram of one example of the display substrate produced using the resin sheet for substrates of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Glass substrate 2 Resin layer 3 Adhesive layer for supporting substrates 4 Resin sheet for substrate 5 Semiconductor chip 6 Wiring 10 Display substrate

Claims (6)

  A resin sheet for a substrate, comprising: a resin layer in which a semiconductor chip is embedded; and an adhesion layer made of an active energy ray-curable resin material and / or a cured product thereof to a support substrate.   The resin sheet for a substrate according to claim 1, wherein the resin layer in which the semiconductor chip is embedded is made of an active energy ray-curable resin material.   The resin sheet for substrates according to claim 1 or 2, wherein the adhesive force to the glass plate after curing by irradiation with active energy rays is 0.3 N / 25 mm or more.   The resin for a substrate according to any one of claims 1 to 3, wherein a swelling ratio with respect to ethanol after being cured by active energy ray irradiation (soaked in ethanol at 23 ° C for 5 minutes) is 60% or less in the adhesion layer to the support substrate. Sheet.   In the adhesion layer to the support substrate, the active energy ray-curable resin material and / or the cured product thereof includes an acrylic copolymer having a (meth) acrylic acid unit and a (meth) acrylic acid ester unit. The resin sheet for substrates as described in any of the above.   The board | substrate sheet | seat by which a semiconductor chip is embedded in the resin sheet for board | substrates in any one of Claims 1-5.

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