Manufacturing method for substrate laminates

Abstract

To provide a method for manufacturing a substrate laminate having an adhesive layer having high adhesive reliability.SOLUTION: A method for manufacturing a substrate laminate includes (a) a step of forming a pattern 1 of a first curable resin composition on a first substrate 2 by using a printing method, (b) a step of semi-curing the pattern of the first curable resin composition, (c) a step of forming a pattern 1'of a second curable resin composition on the pattern of the semi-cured first curable resin composition by using the printing method, (d) a step of molding, in the form of a flat package type, the pattern of the first curable resin composition in which the pattern of the semi-cured first curable resin composition and the pattern of the second curable resin composition are formed, thereby forming a pattern 5 of a laminate of the curable resin composition, and (e) a step of arranging a first substrate and a second substrate 7 through the pattern of the laminate of the curable resin composition after the pattern of the laminate of the curable resin composition is semi-cured, and curing the pattern of the laminate of the curable resin composition.SELECTED DRAWING: Figure 2

Description

[Technical Field]

[0001] This invention relates to a method for manufacturing a substrate laminate. [Background technology]

[0002] In MEMS sensors such as image sensors, acceleration sensors, and pressure sensors, it is necessary to create a hollow space by bonding a semiconductor element substrate and a sealing substrate made of glass, metal, ceramic, etc., with an adhesive placed around the semiconductor element, in order to adjust light transmittance and ensure the movement of mechanical parts. In this case, a method is used in which a pattern of the adhesive layer is formed using a liquid adhesive by a dispensing method or a screen printing method (Patent Document 1). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2013-115104 [Overview of the project] [Problems that the invention aims to solve]

[0004] However, in conventional dispensing methods using liquid adhesives, as described in Patent Document 1, it is difficult to apply the adhesive to a uniform height. In the case of screen printing, the mesh marks of the screen remain on the upper surface of the adhesive layer, making it difficult to flatten. As a result, it is difficult to maintain a constant distance between substrates when bonded, leading to variations in the height of the laminate and uneven bonding surfaces, which has resulted in individual differences in the reliability of the resulting substrate laminates.

[0005] The present invention has been made in view of the above points, and aims to provide a method for manufacturing a substrate laminate having an adhesive layer with high adhesive reliability by forming a pattern of curable resin that has excellent uniformity in height and a good shape. [Means for solving the problem]

[0006] The inventors of the present invention have conducted extensive research to solve the above problems and have found that the above problems can be solved by a method of laminated printing using a printing method, which involves molding in a predetermined flat shape, and have completed the invention. That is, the present invention relates to the following.

[0007] A method for manufacturing a substrate laminate, comprising: step A, forming a pattern of a first curable resin composition on a first substrate using a printing method; step B, partially curing the pattern of the first curable resin composition; step C, forming a pattern of a second curable resin composition on the partially cured pattern of the first curable resin composition using a printing method; step D, forming a pattern of a laminate of curable resin compositions by flat molding the pattern of the first curable resin composition formed in step B and the pattern of the second curable resin composition formed in step C; and step E, arranging the first substrate and the second substrate via the pattern of the laminate of curable resin compositions to cure the pattern of the laminate of curable resin compositions, wherein the pattern of the laminate of curable resin compositions is partially cured before step E.

[0008] The process further includes step F for semi-curing the pattern of the second curable resin composition formed in step C, and after repeating steps C and F multiple times, step D is performed, with the option to omit step F in the last cycle of the multiple repeating cycles.

[0009] In at least one of the steps F described above, it is preferable that the semi-curing is performed while the molding is carried out in a flat form.

[0010] It is preferable that the step of partially curing the pattern of the laminate of the curable resin composition is carried out in step D.

[0011] In step B, it is preferable that the first curable resin composition is partially cured while being molded in a flat mold to form a pattern.

[0012] It is preferable that the printing method is screen printing.

[0013] It is preferable that the flat surface roughness Ra2 is 5 μm or less.

[0014] It is preferable that either the first substrate or the second substrate is a transparent substrate.

[0015] It is preferable that the other substrate is a semiconductor element substrate.

[0016] It is preferable that either the first substrate or the flat one is transparent.

[0017] It is preferable that the first curable resin composition and / or the second curable resin composition contains at least one of a glycidyl group or an alicyclic epoxy group.

[0018] It is preferable that the first curable resin composition and / or the second curable resin composition is a polysiloxane-based compound.

[0019] It is preferable that the first curable resin composition and / or the second curable resin composition is a photosensitive resin. [Advantages of the Invention]

[0020] By using the manufacturing method of the present invention, a stabilized adhesive surface can be obtained, resulting in excellent adhesive reliability. In addition, a substrate laminate that suppresses individual differences in semiconductors due to differences in the distance between substrates can be obtained. Further, since a substrate laminate with pattern control with high precision in a simple process can be obtained, it is particularly suitable for manufacturing hollow structures for CMOS / CCD sensors and MEMS devices. [Brief Description of the Drawings]

[0021] [Figure 1] It is a diagram showing step A of forming a pattern on a first substrate according to an embodiment of the present invention. [Figure 2]This figure shows steps A to E according to one embodiment of the present invention. [Modes for carrying out the invention]

[0022] (1. Stacked substrates) The substrate laminate according to the present invention is obtained by going through the following steps: step A (Figure 2(a)) of forming a pattern of a first curable resin composition on a first substrate using a printing method; step B (Figure 2(b)) of partially curing the pattern of the first curable resin composition; step C (Figure 2(c)) of forming a pattern of a second curable resin composition on the partially cured pattern of the first curable resin composition using a printing method; step D (Figure 2(d)) of forming a pattern of a laminate of curable resin compositions by flat molding the pattern of the first curable resin composition on which the pattern of the second curable resin composition is formed; and step E (Figure 2(e)) of bonding the first substrate and the second substrate via the pattern of the laminate of curable resin compositions and curing them. In step D, after forming a pattern of the second curable resin composition (before semi-curing), it is preferable to mold the pattern of the laminate of curable resin composition with a flat mold and semi-cur it while pressing with the flat mold (Figure 2(d')). Semi-curing may be done before step E or after molding with a flat mold, but it is preferable to semi-cur it while molding with a flat mold in step D.

[0023] Examples of substrates that can be used include semiconductor element substrates, silicon wafers, glass substrates, transparent resin substrates, colored resin substrates, and ceramic substrates. In the manufacturing of the image sensor described later, a semiconductor element substrate is used as the first or second substrate, and a glass substrate is used as the other substrate.

[0024] The substrate can be round or square. From a productivity standpoint, it is preferable to use a square substrate of 100mm x 100mm or larger, a substrate created by rearranging substrates that have been individually pieced into an area of ​​100mm x 100mm or larger, or a round substrate of 4 inches to 12 inches. The size and shape of the first and second substrates may be the same or different.

[0025] The curable resin used to form a pattern on the substrate of the substrate laminate of the present invention functions as an adhesive layer that bonds the first substrate and the second substrate. The width and height of the adhesive layer can be set as appropriate, and by selecting them appropriately, a substrate laminate having a hollow structure can be easily obtained. In particular, when using the substrate laminate for CMOS / CCD sensors, if the adhesive layer is too low, the sensor substrate may be damaged during assembly. Also, if the adhesive layer is too high, a good pattern may not be obtained. From these points of view, the height of the adhesive layer is 1 μm to 1000 μm, preferably 50 μm to 500 μm, and more preferably 50 μm to 300 μm. The height of the adhesive layer may also be 200 μm or less, or 150 μm or less. Regarding the width of the adhesive layer, if it is too narrow, sufficient adhesive strength may not be obtained, and if the width of the adhesive layer is too wide, there may be no space to place the sensor substrate. From these points of view, the width of the adhesive layer is 1 μm to 1000 μm, preferably 50 μm to 300 μm.

[0026] Furthermore, the surface roughness Ra1 of the upper surface of the adhesive layer formed on the first substrate, i.e., the surface in contact with the second substrate, is preferably 5 μm or less, more preferably 3 μm or less, and even more preferably 1 μm or less. Setting it to 5 μm or less improves bonding performance and enhances adhesive reliability, and is also effective in reducing height variations. Surface roughness can be measured using a 3D measuring laser microscope.

[0027] (2. Method for manufacturing a substrate laminate) (First Embodiment) An embodiment of the method for manufacturing the substrate laminate of the present invention will be described in detail below.

[0028] The method for preparing the curable resin used as the adhesive layer is not particularly limited and can be prepared by various methods. The various components may be mixed and prepared immediately before use, or all components may be mixed in advance and stored at low temperature in a single-liquid state. From the viewpoint of handling ease, it is preferable that it be in liquid form. The viscosity of the composition containing the curable resin is preferably 1 Pa·s or more at a 25°C environment from the viewpoint of suppressing bleeding. Furthermore, from the viewpoint of performing coating using a printing method, it is preferable to have a viscosity of 500 Pa·s or less. The viscosity can be measured using a rheometer. In addition, the resins used for each layer in laminated printing may be the same or different.

[0029] First, in step A, a pattern of the first curable resin composition is formed on the first substrate using a printing method (Figure 2(a)). The pattern shape can be appropriately set depending on the desired application. Printing methods include dispenser printing, inkjet printing, letterpress printing, flexographic printing, offset printing, gravure printing, and screen printing, but among these, screen printing is preferred from the viewpoint of simplicity and good patternability. The screen used for screen printing is not particularly limited as long as the curable resin composition can pass through it.

[0030] Next, in step B, the pattern of the first curable resin composition is partially cured (Figure 2(b)), and then in step C, the pattern of the second curable resin composition is formed on top of the pattern of the first curable resin composition by screen printing (Figure 2(c)).

[0031] To further control the pattern shape after printing, in step D, after step C, the first substrate and the flat mold are made parallel, and the flat mold is pressed against the pattern of the first curable resin composition that was semi-cured in step B and the pattern of the second curable resin composition formed in step C to form a laminate pattern of curable resin compositions (Figure 2(d)). By semi-curing and demolding, a pattern with a smooth top surface is formed (Figure 2(d'')). At this time, the laminate pattern of curable resin compositions is semi-cured while the flat mold is pressed against it, or after the flat mold is pressed against it. In particular, in order to create the desired pattern shape with high precision, it is preferable to semi-cure while the flat mold is pressed against it, that is, to semi-cure the laminate pattern of curable resin compositions in step D (Figure 2(d')). In this way, a first substrate having a semi-cured laminate pattern of curable resin compositions is created (Figure 2(d'')).

[0032] When molding in a flat mold, from the viewpoint of not crushing the pattern and not widening the pattern width, it is preferable to mold with a positional accuracy of 30% to 99% of the pattern height, and more preferably with a positional accuracy of 50% to 98%, when the height at the time of pattern molding is set to 100%.

[0033] The material used for the flat mold is not particularly limited, but examples include metals such as stainless steel, inorganic materials such as glass, organic materials such as rubber and resin, or combinations thereof. In addition, the mold surface may be treated to improve the release properties and durability of the pattern. For example, organic coatings such as fluorine, silicone, and PEEK, or metallic coatings such as cemented carbide, hard chromium, and DLC may be applied, and the surface may also be given a matte finish.

[0034] From the viewpoint of reducing the surface roughness of the upper surface of the pattern, i.e., the surface in contact with the second substrate, and improving adhesion and bonding, the surface roughness Ra2 of the mold is preferably 5 μm or less, preferably 3 μm or less, and more preferably 1 μm or less. The surface roughness Ra2 of the mold can be measured, for example, using a 3D measuring laser microscope.

[0035] Furthermore, the mold and substrate may be heated from before the mold is pressed against the substrate until demolding. The heating temperature is preferably 40°C to 300°C, and more preferably 40°C to 150°C from the viewpoint of solvent removal and adjustment of the physical properties of the cured product.

[0036] When the curable resin used as the adhesive layer is a photosensitive resin, it is preferable to include a step of exposure through the mold and substrate from before pressing the mold to before demolding. Including an exposure step can suppress changes in the pattern shape over time.

[0037] For photocuring (exposure), any light source that emits light at the absorption wavelength of the polymerization initiator and sensitizer used should be used. Typically, light sources containing wavelengths in the range of 200 nm to 450 nm (for example, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, high-power metal halide lamps, xenon lamps, carbon arc lamps, or light-emitting diodes) can be used.

[0038] Furthermore, for the purpose of solvent removal and adjustment of the physical properties of the cured product, heat may be applied before and after photocuring to pre-bake and after-bake the pattern resin, to the extent that the adhesion of the pattern resin does not decrease. The temperature at this time can be set as appropriate, but is preferably 40°C to 300°C, more preferably 40°C to 150°C.

[0039] Next, the process includes step E, in which a first substrate and a second substrate are placed via the pattern of the laminate of the curable resin composition, and the pattern of the laminate of the curable resin composition is cured (Figure 2(e)). At this time, the first substrate and the second substrate are pressed together via the pattern of the laminate of the curable resin composition and cured to obtain a substrate laminate. The curing temperature during pressing is usually 25°C to 350°C, preferably 60°C to 300°C, and more preferably 80°C to 250°C. The pressure applied to the bonding surface during pressing is usually 0 MPa to 50 MPa, preferably 0 MPa to 40 MPa, and more preferably 0 MPa to 30 MPa. From the viewpoint of improving adhesive strength, it is preferable to cure at 80°C to 350°C after pressing. After that, the substrate laminate is obtained by dicing each pattern to create individual pieces.

[0040] (Second embodiment) The above explanation describes an example of bonding a first substrate and a second substrate, each having a two-layer pattern, but this method is not the only one that can be used. The process further includes step F for semi-curing the pattern of the second curable resin composition formed in step C, and after repeating steps C and F multiple times, step D is performed, and the pattern of the laminate of the curable resin composition may be formed by omitting step F in the last cycle of the multiple repeated cycles.

[0041] (Other embodiments) In step B, partial curing may be performed while the pattern of the first curable resin composition is molded in a flat mold. Furthermore, for example, if the process involves repeating steps C and F multiple times, as in the second embodiment, it is sufficient to perform flat molding in at least step D, but flat molding may be performed in at least one step of step F, or flat molding may be performed in each step F. As for the method of creating each element, for example, after forming a pattern of multiple second curable resin compositions on a first substrate, the first substrate pieces on which the second curable resin composition patterns have been formed may be diced and then individually bonded to a second substrate that has been pre-partitioned. Alternatively, the pre-partitioned first substrate pieces may be rearranged to form multiple patterns, and then bonded to the second substrate all at once or piece by piece.

[0042] (3. Curable resin composition) The curable resin composition in this invention can be a curable resin that hardens with heat, light, or both. If the curable resin composition is a photosensitive resin that hardens with heat and light, it can be brought to a B-stage (semi-cured) state by a photoreaction, and is preferable because it can be easily used as an adhesive layer to constitute a substrate laminate.

[0043] (Cationically polymerizable) The adhesive layer of the present invention can use compounds having cationic polymerizable functional groups such as epoxy groups, oxetane groups, and vinyl ether groups. Specifically, novolacphenol type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, cyclohexyl epoxy group-containing polyorganosiloxane (cyclic or chain), glycidyl group-containing polyorganosiloxane (cyclic or chain), bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, 2,2'-bis(4-glycidyloxycyclohexyl)propane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carbonate, vinylcyclohexene dioxide, 2-(3,4-epoxycyclohexyl)-5, Examples include 5-spiro-(3,4-epoxycyclohexane)-1,3-dioxane, bis(3,4-epoxycyclohexyl)adipate, bisglycidyl ester of 1,2-cyclopropanedicarboxylic acid, triglycidyl isocyanurate, monoallyl diglycidyl isocyanurate, diallyl monoglycidyl isocyanurate, 1,4-bis{(3-ethyl-3-oxetanyl)methoxy}methyl}benzene, bis{1-ethyl(3-oxetanyl)}methyl ether, 3-ethyl-3-(phenoxymethyl)oxetane, and 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane.

[0044] From the viewpoint of stability, it is preferable to have epoxy groups, and among epoxy groups, it is more preferable to have at least one glycidyl group or an alicyclic epoxy group, and it is even more preferable to have an alicyclic epoxy group in particular in terms of excellent cationic polymerization by light and heat. Furthermore, it is sufficient to have at least one cationic polymerizable functional group in one molecule, but it is preferable to have two or more, and more preferable to have three or more. If there are three or more cationic polymerizable functional groups, a cured product with a high crosslink density can be obtained, and the cured product has the advantage of excellent heat resistance. Each cationic polymerizable functional group may be the same, or there may be two or more different functional groups. The amount of cationic polymerizable groups in the curable resin composition is preferably 1 to 99 parts by weight, and more preferably 5 to 90 parts by weight, of the curable resin excluding the solvent.

[0045] (Polysiloxane compounds) In this specification, the curable resin is preferably a polysiloxane-based compound from the viewpoint of heat resistance during reflow and reduction of outgassing. In this specification, the polysiloxane-based compound is not particularly limited as long as it is a compound having siloxane units Si-O-Si. Among the siloxane units in the polysiloxane-based compound, the T unit (XSiO 3 / 2 ) or Q units (SiO 4 / 2 The higher the content of ) the harder the resulting cured product will be and the better the heat resistance reliability. Also, among the siloxane units in the polysiloxane compound, the M unit (X3SiO 1 / 2 ) or D units (X2SiO 2 / 2 The higher the content of ), the more flexible and low-stress the resulting cured product will be. The polysiloxane compound in the curable resin preferably has a cationic polymerization group within its molecule from the viewpoint of compatibility with other components.

[0046] (4. Other additives) (Crosslinking agent) To adjust the workability, reactivity, adhesion, and cured product strength of the above-mentioned curable resin, a crosslinking agent having two or more photopolymerizable functional groups other than cationic polymerizable functional groups per molecule may be added. The above-mentioned crosslinking agent is not particularly limited as long as it is selected according to the curing reaction type, and examples include alkoxysilane compounds and (meth)acrylate compounds.

[0047] (Photoacid generator) The above curable resin composition preferably contains a photoacid generator. The photoacid generator is not particularly limited as long as it is a compound that can release an acidic active substance that can crosslink the photopolymerizable functional groups of the curable resin composition when irradiated with active energy rays. The pKa of the acid generated by the photoacid generator is not limited, but is preferably less than 3, and more preferably less than 1.

[0048] As the above-mentioned photoacid generator, known photoacid generators can be used. For example, various compounds that are preferred as photoacid generators in Japanese Patent Publication No. 2000-1648, Japanese Patent Publication No. 2001-515533, and International Publication No. 2002 / 83764 can be used, but are not particularly limited. The above-mentioned photoacid generator is preferably a sulfonate ester, a carboxylic acid ester, or an onium salt, and more preferably an onium salt.

[0049] Various sulfonic acid derivatives can be used as the above-mentioned sulfonate esters, for example, disulfones, disulfonyl diazomethanes, disulfonylmethanes, sulfonyl benzoylmethanes, imidosulfonates such as trifluoromethylsulfonate derivatives, benzoin sulfonates, sulfonates of 1-oxy-2-hydroxy-3-propyl alcohol, pyrogallol trisulfonates, and benzyl sulfonates.

[0050] The above sulfonate esters specifically include diphenyl disulfone, ditosyl disulfone, bis(phenylsulfonyl) diazomethane, bis(chlorophenylsulfonyl) diazomethane, bis(xylylsulfonyl) diazomethane, phenylsulfonylbenzoyl diazomethane, bis(cyclohexylsulfonyl) methane, 1,8-naphthalenedicarboxylic acid imide methyl sulfonate, 1,8-naphthalenedicarboxylic acid imide tosyl sulfonate, 1,8-naphthalenedicarboxylic acid imide trifluoromethyl sulfonate, 1,8-naphthalenedicarboxylic acid imide camphor sulfonate, succinide imide phenyl sulfonate, succinate imide Examples include dotosyl sulfonate, succinimide trifluoromethyl sulfonate, succinimide camphor sulfonate, phthalimide trifluorosulfonate, cis-5-norbornene-endo-2,3-dicarboxylate imide trifluoromethyl sulfonate, benzoin tosylate, 1,2-diphenyl-2-hydroxypropyl tosylate, 1,2-di(4-methylmercaptophenyl)-2-hydroxypropyl tosylate, pyrogallol methyl sulfonate, pyrogallol ethyl sulfonate, 2,6-dinitrophenyl methyl tosylate, ortho-nitrophenyl methyl tosylate, and para-nitrophenyl tosylate.

[0051] These can be used individually or in combination of two or more. In the present invention, carboxylic acid esters can also be used as photoacid generators.

[0052] Generally, sulfonate esters and carboxylic acid esters may require a heating step (50°C to 100°C) to release the acid.

[0053] The above onium salt is tetrafluoroborate (BF4 - ), hexafluorophosphate (PF6 - ), hexafluoroantimonate (SbF6 - ), hexafluoroarsenate (AsF6 -) Hexachloroantimonate (SbCl6 - )、tetraphenylborate, tetrakis(trifluoromethylphenyl)borate, tetrakis(pentafluoromethylphenyl)borate, fluoroalkyl fluorophosphate, perchlorate ion (ClO4 - )、trifluoromethanesulfonate ion (CF3SO3 - )、fluorosulfonate ion (FSO3 - )、sulfonium salts and iodonium salts having anions such as toluenesulfonate ion, trinitrobenzenesulfonate anion and trinitrotoluenesulfonate anion. From the viewpoint of absorption wavelength, aromatic sulfonium salts are preferred as the photoacid generator.

[0054] When arranging the anions in the photoacid generator in order of decreasing acid strength, it is SbF6 - 、B(C6F5)4 - 、PF6 - 、CF3SO3 - 、HSO4 - It becomes like this. The higher the acid strength of the anion of the photoacid generator, the higher the residual film rate tends to be.

[0055] There is no particular limitation on the content of the photoacid generator contained in the curable resin composition. From the viewpoints of curing rate and balance of physical properties of the cured product, the content of the photoacid generator is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the compound (A).

[0056] If the amount of the photoacid generator is small, it may take a long time to cure or a sufficiently cured product may not be obtained. Also, if there is too much photoacid generator, it may remain in the cured product, or coloring, heat resistance or light resistance may be impaired due to rapid curing, which may not be preferable.

[0057] (Basic compound) The above curable resin composition may contain a basic compound from the viewpoints of controlling the curing rate and improving the storage stability.

[0058] The amount of basic compound is preferably 0.001 to 2.0 parts by weight, and more preferably 0.01 to 1.0 parts by weight, per 100 parts by weight of the compound having a cationic polymerizable functional group. If the amount of basic compound is 0.001 parts by weight or more, the effect can be sufficiently achieved. If the amount of basic compound is 2.0 parts by weight or less, the sensitivity can be improved.

[0059] The weight ratio of the basic compound (B) to the photoacid generator (A) (B) / (A) is 0.001 to 0.2, preferably 0.01 to 0.15. If the weight ratio is 0.001 or higher, the effect of the basic compound can be fully realized. If the weight ratio is 0.2 or lower, sufficient crosslinking can be achieved.

[0060] There are no particular restrictions on the basic compounds, but examples include primary, secondary, and tertiary aliphatic amines, hybrid amines, aromatic amines, heterocyclic amines, amide derivatives, and imide derivatives. Among these, aromatic amines and heterocyclic amines can be suitably used as basic compounds.

[0061] Examples of the above aromatic amines and heterocyclic amines include aniline, pyrrole, oxazole, thiazole, imidazole, pyrazole, furazan, pyrroline, pyrrolidine, imidazoline, imidazolidine, pyridine, pyridazine, pyrimidine, pyrazine, pyrazolin, pyrazolidine, piperidine, piperazine, morpholine, indole, isoindole, 1H-indazole, indoline, quinoline, cinnoline, quinazoline, quinoxaline, phthalazine, purine, pteridine, carbazole, phenanthidine, acridine, phenazine, 1,10-phenanthroline, adenine, adenosine, guanine, guanosine, uracil, and uridine, as well as their derivatives. Furthermore, 2,6-lutidine can also be cited as a heterocyclic amine.

[0062] In particular, morpholine derivatives can be suitably used as basic compounds. Examples of morpholine derivatives include bis(2-morpholinoethyl) ether, 4,4'-carbonyldimorpholine, 4-[2-(ethoxycarbonyl)ethyl]morpholine, and 4-(p-tolyl)morpholine.

[0063] The above basic compound may be used as one type, or two or more types may be used in combination.

[0064] (Sensitizer) The above-mentioned curable resin composition may contain a sensitizer. The sensitizer can improve the sensitivity of the curable resin to visible light and other wavelengths, and further enhance its sensitivity to high-wavelength light such as the g-line (436 nm), h-line (405 nm), and i-line (365 nm). By using these sensitizers in combination with the above-mentioned photoacid generator, the curability of the curable resin composition can be adjusted.

[0065] Examples of the sensitizers mentioned above include anthracene compounds and thioxanthone compounds.

[0066] Specific examples of the above anthracene compounds include anthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-dimethylanthracene, 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene, 9,10-diethoxyanthracene, 1,4-dimethoxyanthracene, 9-methylanthracene, 2-ethylanthracene, 2-tert-butylanthracene, 2,6-di-tert-butylanthracene, and 9,10-diphenyl-2,6-di-tert-butylanthracene. Particularly from the viewpoint of availability, anthracene, 9,10-dimethylanthracene, 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene, and 9,10-diethoxyanthracene are preferred as the above anthracene compounds.

[0067] As the above anthracene-based compound, anthracene is preferred from the viewpoint of excellent transparency of the cured product, and 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene, and 9,10-diethoxyanthracene are preferred from the viewpoint of excellent compatibility with curable resins.

[0068] Specific examples of the thioxanthone compounds mentioned above include thioxanthone, 2-chlorothioxanthone, and 2,5-diethyldioxantone.

[0069] These sensitizers may be used individually or in combination of two or more.

[0070] The amount of the sensitizer described above is not particularly limited as long as it is sufficient to exert a sensitizing effect, but is preferably 0.01 to 300 moles, and more preferably 0.01 to 100 moles, per mole of added photoacid generator. If the amount of sensitizer is too small, the sensitizing effect will not be obtained, curing may take a long time, or it may have an undesirable effect on developability. On the other hand, if the amount of sensitizer is too large, the color may remain on the cured product, discoloration may occur due to rapid curing, or heat resistance or light resistance may be impaired.

[0071] (Adhesion modifier) The above curable resin composition may contain an adhesion modifier. Examples of adhesion modifiers include commonly used adhesives, as well as various coupling agents, epoxy compounds, oxetane compounds, phenolic resins, coumarone-indene resins, rosin ester resins, terpene-phenolic resins, α-methylstyrene-vinyltoluene copolymers, polyethylmethylstyrene, and aromatic polyisocyanates.

[0072] Examples of coupling agents include silane coupling agents. Silane coupling agents are not particularly limited as long as they are compounds having at least one functional group reactive with an organic group and at least one hydrolyzable silicon group in their molecule. From the viewpoint of handling ease, at least one functional group selected from epoxy, methacrylic, acrylic, isocyanate, isocyanurate, vinyl, and carbamate groups is preferred as the reactive group with the organic group, and epoxy, methacrylic, or acrylic groups are particularly preferred from the viewpoint of curability and adhesion. From the viewpoint of handling ease, an alkoxysilyl group is preferred as the hydrolyzable silicon group, and from the viewpoint of reactivity, a methoxysilyl or ethoxysilyl group is particularly preferred.

[0073] Examples of preferred silane coupling agents include alkoxysilanes having epoxy functional groups such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane; alkoxysilanes having methacryl or acrylic groups such as 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acryloxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane and acryloxymethyltriethoxysilane; tris[3-(trimethoxysilylpropyl)]isocyanurate; γ-isocyanatetopropyltrimethoxysilane; and others.

[0074] The amount of silane coupling agent added can be set as appropriate, but is preferably 0.1 to 20 parts by weight, more preferably 0.3 to 10 parts by weight, and even more preferably 0.5 to 5 parts by weight, per 100 parts by weight of the compound having a cationic polymerizable functional group. If the amount added is too small, the adhesion improvement effect will not be observed, and if the amount added is too large, it may adversely affect the curability and the physical properties of the cured product.

[0075] Furthermore, one of these coupling agents, silane coupling agents, and epoxy compounds may be used, or two or more may be used in combination.

[0076] (thermoplastic resin) It is also possible to add various thermoplastic resins to the above-mentioned curable resin for purposes such as modifying the properties of the above-mentioned curable resin. Examples of the above-mentioned thermoplastic resins include acrylic resins such as polymethyl methacrylate-based resins such as homopolymers of methyl methacrylate or random, block, or graft polymers of methyl methacrylate and other monomers (e.g., Optrets from Hitachi Chemical Co., Ltd.) and polybutyl acrylate-based resins such as homopolymers of butyl acrylate or random, block, or graft polymers of butyl acrylate and other monomers; polycarbonate-based resins such as polycarbonate resins containing bisphenol A, 3,3,5-trimethylcyclohexylidenebisphenol, etc. as monomer structures (e.g., APEC from Teijin Corporation); resins obtained by single or copolymerization of norbornene derivatives, vinyl monomers, etc.; resins obtained by ring-opening metathesis polymerization of norbornene derivatives; or hydrogenated thereof; and cycloolefin-based resins. Examples include, but are not limited to, APEL (manufactured by Mitsui Chemicals, Inc.), ZEONOR and ZEONEX (manufactured by Nippon Zeon Co., Ltd.), olefin-maleimide resins such as copolymers of ethylene and maleimide (e.g., TI-PAS (manufactured by Tosoh Corporation)), polyester resins such as polyesters obtained by polycondensation of bisphenols (bisphenol A and bis(4-(2-hydroxyethoxy)phenyl)fluorene, or diols (diethylene glycol, etc.) with phthalates (terephthalic acid and isophthalic acid, etc.) or aliphatic dicarboxylic acids (e.g., O-PET (manufactured by Kanebo Co., Ltd.)), polyethersulfone resins, polyarylate resins, polyvinyl acetal resins, polyethylene resins, polypropylene resins, polystyrene resins, polyamide resins, silicone resins, fluororesins, and rubber-like resins such as natural rubber and EPDM. These thermoplastic resins may be used individually or in combination.

[0077] The above thermoplastic resin may have crosslinkable groups. Examples of such crosslinkable groups include epoxy groups, amino groups, radical polymerizable unsaturated groups, carboxyl groups, isocyanate groups, hydroxyl groups, and alkoxysilyl groups. From the viewpoint of easily increasing the heat resistance of the resulting cured product, it is preferable that the above thermoplastic resin has at least one crosslinkable group per molecule on average.

[0078] While there are no particular limitations on the molecular weight of the thermoplastic resin described above, from the viewpoint of good compatibility with polysiloxane compounds, a number-average molecular weight of 10,000 or less is preferred, and more preferably 5,000 or less. On the other hand, from the viewpoint of the resulting cured product being tough, a number-average molecular weight of 10,000 or more is preferred, and more preferably 100,000 or more. While there are no particular limitations on the molecular weight distribution, from the viewpoint of lowering the viscosity of the mixture and improving moldability, a molecular weight distribution of 3 or less is preferred, more preferably 2 or less, and even more preferably 1.5 or less.

[0079] There are no particular limitations on the amount of the thermoplastic resin added, but it is preferably 5 to 50% by weight, more preferably 10 to 30% by weight, relative to the total curable resin composition. If the amount of thermoplastic resin added is too small, the resulting cured product may become brittle. If the amount of thermoplastic resin added is too large, the heat resistance (elastic modulus at high temperatures) tends to be low.

[0080] The thermoplastic resin may be dissolved in the curable resin and mixed in a homogeneous state, crushed and mixed in a granular state, or dissolved in a solvent and mixed in a dispersed state. In terms of the fact that the resulting cured product tends to be more transparent, it is preferable to dissolve it in the curable resin and mix it in a homogeneous state. In this case as well, the thermoplastic resin may be directly dissolved in the curable resin, or it may be uniformly mixed using a solvent, or the solvent may be removed afterward to obtain a uniform dispersed or mixed state.

[0081] When using a dispersed thermoplastic resin, the average particle size of the thermoplastic resin can be set as appropriate, but the preferred lower limit of the average particle size is 10 nm and the preferred upper limit is 10 μm. The particle system may have a distribution, and may have a single dispersion or multiple peak particle sizes, but from the viewpoint of having a low viscosity and good moldability in the curable resin composition, it is preferable that the coefficient of variation of the particle size is 10% or less.

[0082] (filling material) Fillers may be added to the above-mentioned curable resin as needed. Various types of fillers can be used, but examples include silica-based fillers (quartz, fumed silica, precipitated silica, anhydrous silicic acid, fused silica, crystalline silica, and ultrafine amorphous silica, etc.), silicon nitride, silver powder, alumina, aluminum hydroxide, titanium oxide, glass fiber, carbon fiber, mica, carbon black, graphite, diatomaceous earth, white clay, clay, talc, calcium carbonate, magnesium carbonate, barium sulfate, and inorganic balloons, as well as epoxy-based fillers and other fillers that are commonly used or proposed as fillers for conventional sealing materials. The fillers may also be subjected to various surface treatments.

[0083] (Anti-aging agent) Antioxidants may be added to the above-mentioned curable resin. Examples of antioxidants include commonly used antioxidants such as hindered phenol-based antioxidants, as well as citric acid, phosphoric acid, and sulfur-based antioxidants.

[0084] Various hindered phenol-based antioxidants can be used, including Irganox 1010, which is available from BASF.

[0085] Examples of the above-mentioned sulfur-based antioxidants include mercaptans, mercaptan salts, sulfides (sulfide carboxylic acid esters and hindered phenolic sulfides, etc.), polysulfides, dithiocarboxylic acid salts, thioureas, thiophosphates, sulfonium compounds, thioaldehydes, thioketones, mercaptals, mercaptols, monothio acids, polythio acids, thioamides, and sulfoxides. Furthermore, one of these antioxidants may be used, or two or more may be used in combination.

[0086] (Radical inhibitor) Radical inhibitors may be added to the above-mentioned curable resin. Examples of radical inhibitors include phenolic radical inhibitors such as 2,6-di-t-butyl-3-methylphenol (BHT), 2,2'-methylene-bis(4-methyl-6-t-butylphenol), and tetrakis(methylene-3(3,5-di-t-butyl-4-hydroxyphenyl)propionate)methane, as well as amine-based radical inhibitors such as phenyl-β-naphthylamine, α-naphthylamine, N,N'-second-butyl-p-phenylenediamine, phenothiazine, and N,N'-diphenyl-p-phenylenediamine. Furthermore, one of these radical inhibitors may be used, or two or more may be used in combination.

[0087] (solvent) If the above-mentioned curable resin has high viscosity, it can also be used dissolved in a solvent. The solvent is not particularly limited, and specifically includes hydrocarbon solvents such as benzene, toluene, hexane, and heptane; ether solvents such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, and diethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; glycol solvents such as propylene glycol-1-monomethyl ether-2-acetate (PGMEA), ethylene glycol diethyl ether, and diethylene glycol diethyl ether; halogen solvents such as chloroform, methylene chloride, and 1,2-dichloroethane; ester solvents such as butyl acetate and isobutyl isobutyrate; and lactone solvents such as γ-butyrolactone, ε-caprolactone, and δ-valerolactone. One of these solvents may be used, or a mixture of two or more solvents may be used.

[0088] The amount of solvent used can be set as appropriate, but the preferred lower limit for the amount used per 1 g of the above-mentioned curable resin is 0.001 mL, and the preferred upper limit is 10 mL.

[0089] (others) The above-mentioned curable resin may contain, to the extent that it does not impair the objectives and effects of the present invention, colorants, mold release agents, flame retardants, flame retardant additives, surfactants, defoamers, emulsifiers, leveling agents, anti-repellent agents, ion trapping agents (such as antimony-bismuth), thixotropic agents, tackifiers, storage stability improvers, ozone degradation inhibitors, light stabilizers, thickeners, plasticizers, reactive diluents, antioxidants, thermal stabilizers, conductivity modifiers, antistatic agents, radiation shielding agents, nucleating agents, phosphorus-based peroxide decomposers, lubricants, pigments, metal deactivators, thermal conductivity modifiers, and property modifiers.

[0090] (Application) The substrate laminates described herein can be used in a variety of applications. They can be applied to various applications using conventional substrate laminates made with acrylic resin and epoxy resin adhesives.

[0091] For the above applications, applying the substrate laminate manufactured according to the present invention to hollow structures for CMOS / CCD sensors and hollow structures for MEMS devices is preferable because it enables stable adhesion of the wall material and reduces defects in the structure.

[0092] The present invention is not limited to the embodiments described above, and various modifications are possible within the scope of the claims. Embodiments obtained by appropriately combining the technical means disclosed in different embodiments are also included in the technical scope of the present invention. [Examples]

[0093] The present invention will be described in more detail below based on examples, but the present invention is not limited to the following examples.

[0094] (Patterned surface properties) The fabricated patterns were observed using a 3D measuring laser microscope (LEXT OLS4000, manufactured by Olympus Corporation), and the surface roughness Ra1 of the pattern surface was evaluated according to the following criteria. <Evaluation Criteria> ○: Very good level (Ra1 is 5 μm or less) ×: Not suitable for practical use (Ra1 exceeds 5 μm)

[0095] (Pattern height variation) The fabricated patterns were measured at 10 or more points using a 3D measuring laser microscope (LEXT OLS4000, manufactured by Olympus Corporation). The difference between the maximum and minimum heights of the measured patterns was calculated, and the height variation was evaluated according to the following criteria. <Evaluation Criteria> ○: Very good level (the difference between the maximum and minimum height of the pattern is less than 6 μm) ×: Not suitable for practical use (the difference between the maximum and minimum height of the pattern is 6 μm or more)

[0096] (Pattern adhesion) Using a 3D measuring laser microscope (LEXT OLS4000, manufactured by Olympus Corporation), the adhesion state between the second substrate and the adhesive layer was observed from the transparent substrate side, and evaluated according to the following criteria. The bonded and unbonded areas clearly have different contrasts, making it possible to determine this through observation. <Evaluation Criteria> ○: Very good level (adhered) ×: Not suitable for practical use (there are areas that are not glued)

[0097] (Synthesis Example 1) 50 g of diallylmonomethylisocyanuric acid was dissolved in 100 g of toluene, and 87 mg of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% platinum) was added. The resulting solution was then added dropwise over 3 hours to a solution of 94 g of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane and 186 g of toluene, heated to 105°C under a nitrogen atmosphere containing 3% oxygen. 30 minutes after the end of the dropwise addition... 1 After confirming that the reaction rate of alkenyl groups (the percentage of alkenyl groups reduced) was 95% or higher by 1H-NMR, a solution of 55 g of 1-vinyl-3,4-epoxycyclohexane and 55 g of toluene was added dropwise over 1 hour. 30 minutes after the end of the dropwise addition... 1 After confirming that the reaction rate of the alkenyl group was 95% or higher by 1H-NMR, the reaction was terminated by cooling. The solvents toluene and dioxane were removed by vacuum distillation to obtain "curable resin A".

[0098] (Manufacturing Example 1) A mixture was obtained by mixing 100 parts by weight of curable resin with 7 parts by weight of alicyclic epoxy compound CEL2021P (manufactured by Daicel Organic Synthesis Company), 2 parts by weight of photoacid generator CPI-210S (manufactured by Sunapro), and 0.5 parts by weight of antioxidant IRGANOX1010 (manufactured by BASF). Next, 15 g of thixotropic agent Aerosil R974 (manufactured by Nippon Aerosil) was added to 100 g of the mixture, and then the mixture was mixed using a three-roll mixer to obtain a curable resin composition.

[0099] (Example 1) A curable resin composition containing curable resin A obtained in Manufacturing Example 1 was screen printed onto a 100 mm x 100 mm glass substrate (D263, manufactured by Teco SCHOTT) using a screen printing apparatus (DP-320, manufactured by New Long Precision Industry Co., Ltd.) to form a pattern of the first curable resin composition with a width of 150 μm and a height of 15 μm (Step A). ​​The screen plate used had a mesh count of 500 (lines / inch), a wire diameter of 19 μm, and an emulsion thickness of 10 μm. After screen printing, the substrate with the pattern was subjected to an integrated light intensity of 3000 mJ / cm². 2 The first curable resin composition pattern was exposed to light to form a semi-cured pattern (Step B). Subsequently, a pattern of the second curable resin composition was formed on the pattern of the first curable resin composition (Step C). For the second curable resin composition, the same material and screen plate as the first curable resin composition were used, and a pattern of the second curable resin composition with a width of 150 μm and a height of 10 μm was formed by screen printing. Subsequently, the pattern of the second curable resin composition on the pattern of the first curable resin composition was exposed to light at an integrated light intensity of 3000 mJ / cm². 2 The material was exposed to light and partially cured (Step F). Steps C and F were repeated nine times, excluding the final Step F, to form a pattern with a height of 115 μm. After that, a metal flat die (flat die) was pressed against the material, and while pressing the flat die, an integrated light intensity of 3000 mJ / cm² was applied. 2 The laminate of the curable resin composition was exposed to light, and the pattern was partially cured to obtain a 110 μm pattern (Step D). After pattern formation, the pattern surface properties and pattern height were observed using the method described above. Subsequently, each pattern was separated into individual pieces, and a silicon substrate (second substrate) was laminated onto the glass substrate (first substrate) via the pattern of the laminate of the curable resin composition. A substrate laminate was obtained by heating and pressing on a hot plate at 120°C under a pressure of 1 MPa for 30 seconds (Step E). The pattern adhesion of the obtained substrate laminate was evaluated using the method described above.

[0100] (Example 2) A curable resin composition containing curable resin A obtained in Manufacturing Example 1 was screen printed onto a 100mm x 100mm glass substrate (D263 Teco SCHOTT) using a screen printing device (DP-320 New Long Precision Industry Co., Ltd.) to form a pattern of the first curable resin composition with a width of 150 μm and a height of 15 μm (Step A). ​​The screen plate used had a mesh count of 500 (lines / inch), a wire diameter of 19 μm, and an emulsion thickness of 10 μm. A metal flat die was pressed against the substrate with the screen-printed pattern, and an integrated light intensity of 3000 mJ / cm² was applied. 2 The pattern was exposed to light and partially cured (Step B). Subsequently, a pattern of the second curable resin composition was formed on the flattened pattern of the first curable resin composition (Step C). For the second curable resin composition, the same material and screen plate as the first curable resin composition were used, and a pattern of the second curable resin composition with a width of 150 μm and a height of 10 μm was formed by screen printing. After that, the pattern of the second curable resin composition on the pattern of the first curable resin composition was exposed to light at an integrated light intensity of 3000 mJ / cm². 2 The material was exposed to light and partially cured (Step F). Steps C and F were repeated 10 times, excluding the final Step F, to form a pattern with a height of 110 μm. Then, a metal flat die was pressed against the material, and an integrated light intensity of 3000 mJ / cm² was applied. 2 The surface was exposed to light to form a 105 μm semi-cured pattern. After pattern formation, the surface properties and height of the pattern were observed using the method described above. Subsequently, each pattern was separated into individual pieces, and a silicon substrate was laminated via the pattern on the glass substrate. A substrate laminate was obtained by heating and pressing the laminate on a 120°C hot plate under a pressure of 1 MPa for 30 seconds. The pattern adhesion of the obtained substrate laminate was evaluated using the method described above.

[0101] (Comparative Example 1) The procedure was carried out in the same manner as in Example 1, except that the pattern was not formed in a flat mold (i.e., step D was not performed), and the pattern surface quality and pattern adhesion were evaluated.

[0102] [Table 1]

[0103] As shown in Examples 1 and 2, forming the pattern and then molding it with a mold resulted in an adhesive layer with a good shape, and a substrate laminate with good height variation and adhesion was obtained. Comparative Example 1, which was not molded with a mold, had insufficient surface properties, height variation, and adhesion. [Explanation of symbols]

[0104] 1. Pattern of the first curable resin composition (pattern before partial curing after step A) 1'. Pattern of the second curable resin composition (pattern before partial curing after step C) 2. First substrate 3. Pattern of the first curable resin composition (partially cured pattern after step B) 4.Flat type 5. Pattern of the laminate of the curable resin composition (semi-cured pattern before step E) 6. Pattern of the laminate of the curable resin composition (cured pattern after step E) 7. Second substrate

Claims

1. Step A involves forming a pattern of the first curable resin composition on a first substrate using a printing method, Step B involves partially curing the pattern of the first curable resin composition, Step C involves forming a pattern of the second curable resin composition on the pattern of the semi-cured first curable resin composition using a printing method, Step D involves forming a laminate pattern of the curable resin composition by flat molding the pattern of the first curable resin composition, which has been partially cured in step B and the pattern of the second curable resin composition formed in step C, The process includes step E, which involves arranging the first and second substrates through the pattern of the laminate of the curable resin composition and curing the pattern of the laminate of the curable resin composition, A method for manufacturing a substrate laminate, comprising partially curing the pattern of the laminate of the curable resin composition before step E.

2. The process further includes step F, which partially cures the pattern of the second curable resin composition formed in step C, The method for manufacturing a substrate laminate according to claim 1, wherein step C and step F are repeated multiple times, step D is performed, and step F is omitted in the last cycle of the multiple repeated cycles.

3. The method for manufacturing a substrate laminate according to claim 2, wherein in at least one of the steps F, the substrate is partially cured while being molded in a flat form.

4. A method for manufacturing a substrate laminate according to any one of claims 1 to 3, wherein the step of partially curing the pattern of the laminate of the curable resin composition is carried out in step D.

5. A method for manufacturing a substrate laminate according to any one of claims 1 to 4, wherein in step B, the pattern of the first curable resin composition is formed in a flat mold while semi-curing is performed.

6. A method for manufacturing a substrate laminate according to any one of claims 1 to 5, wherein the printing method is screen printing.

7. The surface roughness Ra of the flat type ２ A method for manufacturing a substrate laminate according to any one of claims 1 to 6, wherein the thickness is 5 μm or less.

8. A method for manufacturing a substrate laminate according to any one of claims 1 to 7, wherein either the first substrate or the second substrate is a transparent substrate.

9. The method for manufacturing a substrate laminate according to claim 8, wherein the other substrate of the first substrate and the second substrate is a semiconductor element substrate.

10. A method for manufacturing a substrate laminate according to any one of claims 1 to 9, wherein either the first substrate or the flat type is transparent.

11. A method for producing a substrate laminate according to any one of claims 1 to 10, wherein the first curable resin composition and / or the second curable resin composition comprises at least one of a glycidyl group or an alicyclic epoxy group.

12. A method for producing a substrate laminate according to any one of claims 1 to 11, wherein the first curable resin composition and / or the second curable resin composition is a polysiloxane compound.

13. A method for manufacturing a substrate laminate according to any one of claims 1 to 12, wherein the first curable resin composition and / or the second curable resin composition is a photosensitive resin.

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