JP2019081342A - Substrate laminate, and image sensor using the laminate - Google Patents

Abstract

To provide a substrate laminate for providing several hundreds to several thousands hollow structures without non-adhesion location, by using an alkali developable photosensitive adhesive as an adhesive layer, and a method for producing the substrate laminate.SOLUTION: There is provided a substrate laminate by laminating 2 substrates 1 and 3 of which at least one is a transparent substrate with a patterned resin 2, having a hollow cell structure of which pattern shapes are individually independent, in which the patterned resin 2 is manufactured by curing a negative type photosensitive resin having alkali-solubility and cation polymerizability.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a stacked body of semiconductor elements and semiconductor substrates, and a method of manufacturing the same.

In MEMS sensors such as image sensors, acceleration sensors, and pressure sensors, a hollow part is provided in the semiconductor package and a sealing substrate made of glass, metal, etc. is placed around the package in order to ensure optical transparency and movement of mechanical parts. It is necessary to adhere with the adhesive. Conventionally, an adhesive layer pattern is formed on each package by using a liquid adhesive by a dispensing method, and glass is bonded to form a hollow structure by bonding. However, since productivity is low in the conventional method of forming a hollow structure one by one, several hundred to several thousand cell patterns are formed of a resin having adhesiveness on a large substrate such as 12 inches φ, A method is known in which a large number of hollow structures are easily obtained by laminating glass of the same size to produce a substrate laminate and then dicing it into pieces.
The above-mentioned many cell patterns are formed by the dispensing method or the screen printing method in the same manner as in the conventional method of forming hollow cell structures one by one. Position accuracy and height and width dimensional accuracy can not be obtained.
In order to solve such problems, photosensitive adhesives that can be patterned by photolithography are known. (Patent Document 1)

Unexamined-Japanese-Patent No. 2011-116968

In the case where a large number of hollow cell structures of several hundred to several thousand are formed by large substrates such as 12 inches in diameter, it is difficult to obtain a substrate laminate having no unbonded portion.
Since patent document 1 forms a pattern by radical polymerization, adhesiveness is scarce. Also, no consideration has been given to the point of forming several thousand hollow cell structures with one substrate laminate.
The present invention has been made in view of the above-mentioned point, and is a substrate laminate using an alkali-developable cation-curable resin as an adhesive layer and having several hundred to several thousand hollow structures without unadhered parts. It is an object of the present invention to provide a method of manufacturing a substrate laminate.

MEANS TO SOLVE THE PROBLEM As a result of repeating earnest research in order to solve the said subject, this invention is the laminated body which bonded two board | substrates with resin patterned, and the hollow cell which the pattern shape became independent independently. By using a substrate laminate characterized by having a structure, the inventors have found that the above-mentioned problems can be solved, and have completed the invention.

That is, the present invention has the following constitution.
1). A laminate of two substrates bonded with a patterned resin,
A substrate laminate characterized in that the patterned resin is a cured curable resin having alkali solubility and cationic polymerization, and has a hollow cell structure in which the pattern shape is individually independent.
2). The laminate according to 1), wherein the curable resin contains a photoacid generator.
3). The substrate laminate according to 1) or 2), wherein at least one of the substrates is a transparent substrate.
4). The substrate laminate according to 3), wherein the transparent substrate is glass.
5). The substrate laminate according to any one of 1) to 4), wherein at least one of the substrates is a semiconductor element substrate.
6). The substrate laminate according to any one of 1) to 5), wherein the curable resin contains a glycidyl group or an alicyclic epoxy group.
7). The substrate laminate according to any one of 1) to 6), wherein the curable resin is a polysiloxane compound.
8). The said curable resin is a following formula (X1) or (X2) as an alkali-soluble group

It is a negative photosensitive resin composition comprising at least one selected from the group consisting of each structure represented by the following, a phenolic hydroxyl group and a carboxyl group: any one of 1) to 7) described in any one of 1) to 7) Substrate stack.
9). The image sensor obtained using the substrate laminated body of any one of 1)-8).
10). A curable resin having alkali solubility and cationic polymerizability is coated on a substrate (first substrate), dried and developed with an alkaline aqueous solution after exposure to form hollows having individual pattern shapes on the substrate (first substrate) Forming a pattern corresponding to the cell structure;
A method of manufacturing a substrate laminate, comprising the step of bonding another substrate (second substrate) to a surface different from the substrate (first substrate) via the pattern.

  In the case of forming a substrate laminate having several hundreds to several thousands of hollow structures, the present invention forms an independent cell pattern of an alkali-soluble and cationically polymerizable curable resin, which is an adhesive layer. By using as, it is effective in the ability to form a hollow cell structure without an unbonded part. Further, by using the substrate laminate of the present invention, a large number of hollow structures can be provided by a simple process, and in particular, it is suitable for manufacturing a hollow structure for a CMOS / CCD sensor and a hollow structure for a MEMS device. .

It is a schematic diagram of the board | substrate which formed the pattern for forming the hollow structure of this invention. It is a schematic diagram of the cross section of the board | substrate laminated body for forming the hollow structure of this invention. It is a negative photomask for forming individual cell patterns. It is a negative photomask for forming individual cell patterns. It is a negative photomask for forming a cell pattern in which each individual is not independent. It is a negative photomask for forming a cell pattern in which each individual is not independent.

[1. Substrate laminate]
The substrate laminate in the present invention comprises the steps of: coating and drying a curable resin having alkali solubility and cationic polymerization on a substrate, developing it with an alkaline aqueous solution after exposure, and forming a pattern on a substrate (first substrate); It is obtained by passing through the step of bonding another substrate (second substrate) to a surface different from the substrate (first substrate) through the pattern.
In the substrate laminate of the present invention, a hollow structure can be easily obtained by appropriately selecting the width and height of the adhesive layer.

Examples of substrates that can be used include semiconductor element substrates, silicon wafers, transparent substrates (eg, glass substrates, transparent resin substrates) resin substrates, ceramic substrates, and the like. In the production of an image sensor described later, a sensor substrate is used as a first substrate, a glass substrate as a second substrate, or a glass substrate as a first substrate, and a sensor substrate as a second substrate.
The shape of the substrate may be round or square. It is preferable to use a 4-inch to 12-inch round substrate from the viewpoint that an existing semiconductor manufacturing apparatus can be used, and a substrate with a size of 12 inches or so or so from which a large number of hollow structures can be formed at one time. Is preferred. Further, the sizes of the first substrate and the second substrate may be the same or different.
[2. Hollow structure independent of each other]
The substrate on which a pattern for forming an independent hollow structure can be exemplified, for example, as shown in FIG.
By bonding the substrate of FIG. 1 to another substrate, the individually independent hollow structures of FIG. 2 are formed.

The distance between a large number of independent hollow cells on one substrate may be 1 μm or more, but in order to form a good pattern, 5 μm or more is preferable. The pattern for forming the hollow cell structure may be other than a quadrangle, may be a polygon such as a triangle or a hexagon, or may be a structure including a curve such as a circle.
In the case of using a hollow structure substrate laminate for a CMOS / CCD sensor, a rectangle having a side of 1 to 50 mm is preferable, and it may be spread as much as possible on one substrate. (For example, when a cell size of 4 mm × 5 mm is spread at 12 μm with a cell spacing of 100 μm, more than 2000 hollow structures are obtained.)
In the case of using a hollow structure substrate laminate for a CMOS / CCD sensor, if the adhesive layer is too low, the sensor substrate may be damaged during assembly. If the adhesive layer is too high, a good pattern can not be obtained. From these points, the height of the adhesive layer is 1 μm to 200 μm, preferably 50 to 150 μm. When the adhesive layer is too thin, sufficient adhesive strength can not be obtained. In addition, when the adhesive layer is too thick, the space for disposing the sensor substrate is lost. From these points, the width of the adhesive layer is 1 μm to 1000 μm, preferably 100 to 250 μm.

  As an example of a negative photomask for forming a pattern for forming an independent hollow structure, FIGS. 3 and 4 can be exemplified.

[3. Alkaline soluble]
Since the curable resin in the present invention has alkali solubility, in the pattern formation step by photolithography, a developing solution of an aqueous alkaline solution, not an organic solvent, can be used. As an alkali-soluble group which expresses alkali solubility, for example, the said curable resin is following formula (X1) or (X2) as an alkali-soluble group.

Each structure represented by these, a phenolic hydroxyl group, a carboxyl group, etc. are considered. From the viewpoint of being able to reduce the swelling of the pattern by heat resistance and alkali development, it is preferable that the structures are each represented by Formula (X1) or (X2).

[4. Cationic polymerization property]
As resin which shows cationic polymerization property, resin which has cationically polymerizable functional groups, such as an epoxy group, an oxetane group, vinyl ether group, is considered. Specifically, novolac phenol type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, cyclohexyl epoxy group-containing polyorganosiloxane (cyclic or linear), glycidyl group-containing polyorganosiloxane (cyclic or linear), Bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, 2,2′-bis (4-glycidyloxycyclohexyl) propane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide, 2- (3,4-epoxycyclohexyl) -5,5-spiro- (3,4-epoxycyclohexane) -1,3-dioxane, bis (3,4-epoxycyclohexyl) adipate, 1,2-cyclohexane Cropropanedicarboxylic acid bisglycidyl ester, triglycidyl isocyanurate, monoallyl diglycidyl isocyanurate, diallyl monoglycidyl isocyanurate, 1,4-bis {(3-ethyl-3-oxetanyl) methoxy} methyl} benzene, bis {1 And -ethyl (3-oxetanyl)} methyl ether, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane and the like. Among the epoxy groups, an alicyclic epoxy group or a glycidyl group is preferable from the viewpoint of stability, and in particular, an alicyclic epoxy group is preferable in that it is excellent in cationic polymerizability by light and heat. As a resin exhibiting cationic polymerization, at least one cationically polymerizable functional group may be contained in one molecule, but it is preferable to have two or more, and more preferable to have three or more. When the number of cationically polymerizable functional groups is 3 or more, a cured product having a high crosslinking density can be obtained, and the cured product has an advantage of being excellent in heat resistance. Each cationically polymerizable functional group may be the same or may be two or more different functional groups.

[5. Curable resin having alkali solubility and cationic polymerization property]
The curable resin in the present invention is a resin that is cured by light or light and heat. The negative photosensitive resin is irradiated with light through a photomask to cause a cationic polymerization reaction only in the exposed area. Thereafter, by immersing in an alkaline aqueous solution, the unexposed area is removed, and the pattern resin is formed only in the exposed area. The pattern resin is a B-stage state by light reaction and is not completely cured, and thus can function as an adhesive layer constituting the substrate laminate.

  The curable resin in the present invention is not particularly limited as long as it has an alkali soluble group and a cationically polymerizable group in the cured resin. The curable resin may have both an alkali-soluble group and a cationically polymerizable group in one molecule or as another molecule, but from the viewpoint of patternability, the alkali-soluble group and the cation are preferable. It is preferable to have both of the polymerizable groups in one molecule.

  The amount of the alkali soluble group in the curable resin is preferably 1 to 90 parts by weight of the curable resin excluding the solvent, and more preferably 5 to 60 parts by weight at the time of patterning.

  The cationically polymerizable group in the curable resin is preferably 1 to 90 parts by weight of the curable resin excluding the solvent, and more preferably 5 to 60 parts by weight.

[6. Polysiloxane compound]
The curable resin in the present invention preferably contains a polysiloxane compound from the viewpoint of heat resistance at reflow and reduction of outgassing. In the present invention, the polysiloxane compound is not particularly limited as long as it is a compound having a siloxane unit Si-O-Si. The higher the content of T units (XSiO _3/2 ) or Q units (SiO _4/2 ) among the siloxane units in the polysiloxane compound, the higher the hardness of the obtained cured product and the more excellent the heat resistance reliability. . In addition, the higher the content of M units (X ₃ SiO _1/2 ) or D units (X ₂ SiO _2/2 ) among the siloxane units in the polysiloxane compound, the softer and lower the cured product obtained. It is stress.
The polysiloxane compound in the curable resin preferably has a cationically polymerizable group in the molecule from the viewpoint of compatibility with other components and patterning properties, and a cationically polymerizable group and an alkali-soluble group are preferably used. It is more preferable to have it inside.

[7. Other additives]
(Crosslinking agent)
The above-mentioned curable resin is added with a cross-linking agent having one or more photopolymerizable functional groups other than cationically polymerizable functional groups in one molecule in order to adjust workability, reactivity, adhesiveness and cured product strength. can do. The crosslinking agent is not particularly limited as long as it is selected depending on the curing reaction type, and examples include alkoxysilane compounds and (meth) acrylate compounds.

(Photo acid generator)
The curable resin preferably contains a photoacid generator. The photoacid generator is not particularly limited as long as it is a compound capable of releasing an acidic active substance capable of crosslinking the photopolymerizable functional group possessed by the curable resin by being irradiated with active energy rays.

  The pKa of the acid generated by the photoacid generator is preferably, but not limited to, less than 3, and more preferably less than 1.

  A well-known photo-acid generator can be used as said photo-acid generator. For example, as the photoacid generator, various compounds suitable as described in JP-A-2000-1648, JP-A-2001-515533 and WO 2002/83764 may be mentioned, but are not particularly limited. The photoacid generator is preferably a sulfonate ester, a carboxylic acid ester or an onium salt, and more preferably an onium salt.

  As the sulfonate esters, various sulfonic acid derivatives can be used. For example, imidosulfonates such as disulfones, disulfonyldiazomethanes, disulfonylmethanes, sulfonylbenzoylmethanes, trifluoromethylsulfonate derivatives, etc. Benzoin sulfonates, sulfonates of 1-oxy-2-hydroxy-3-propyl alcohol, pyrogallol trisulfonates and benzyl sulfonates can be mentioned.

  Specific examples of the sulfonate esters include diphenyldisulfone, ditosyldisulfone, bis (phenylsulfonyl) diazomethane, bis (chlorophenylsulfonyl) diazomethane, bis (xylylsulfonyl) diazomethane, phenylsulfonylbenzoyldiazomethane, bis (cyclohexylsulfonyl) ) Methane, 1,8-naphthalenedicarboximide methyl sulfonate, 1,8-naphthalenedicarboximido tosyl sulfonate, 1,8-naphthalenedicarboximide trifluoromethylsulfonate, 1,8-naphthalenedicarboximide camphorsulfonate, succinic acid Acid imide phenyl sulfonate, succinimide imidosyl tosyl sulfonate, succinimide trifluoromethyl sulfonate, succinimide Fermyl sulfonate, phthalimido imide trifluorosulfonate, cis-5-norbornene-endo-2,3-dicarboximide trifluoromethylsulfonate, benzoin tosylate, 1,2-diphenyl-2-hydroxypropyl tosylate, 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 Etc.

  These can be used alone or in combination of two or more. In the present invention, carboxylic acid esters can be similarly used as a photoacid generator.

  In general, sulfonic acid esters and carboxylic acid esters may require a heating step (50 ° C. to 100 ° C.) to liberate the acid.

As the above onium salt, tetrafluoroborate (BF ₄ ⁻ ), hexafluorophosphate (PF ₆ ⁻ ), hexafluoroantimonate (SbF ₆ ⁻ ), hexafluoroarsenate (AsF ₆ ⁻ ), hexachloroantimonate (SbCl 2) ₆ ⁻ ), tetraphenyl borate, tetrakis (trifluoromethylphenyl) borate, tetrakis (pentafluoromethylphenyl) borate, fluoroalkyl fluorophosphate, perchlorate ion (ClO ₄ ⁻ ), trifluoromethanesulfonate ion (CF ₃ SO ₄ ) ₃ ^-), fluorosulfonic acid ion (FSO 3 ^_-), sulfo having toluenesulfonate ion, an anion such as trinitrobenzene sulfonate anion and trinitrotoluene sulfonate anion Um salts and iodonium salts. The photoacid generator is preferably an aromatic sulfonium salt from the viewpoint of absorption wavelength.

When the anions in the photoacid generator are arranged in the order of acid strength, the anions become SbF ₆ ⁻ , B (C ₆ F ₅ ) ₄ ⁻ , PF ₆ ⁻ , CF ₃ SO ₃ ⁻ , HSO ₄ ⁻ . As the acid strength of the anion of the photoacid generator is stronger, the residual film ratio tends to be higher. The pKa of the acid generated from the photoacid generator is preferably less than 3, more preferably less than 1.

  The content of the photoacid generator in the photosensitive composition is not particularly limited. The content of the photoacid generator is preferably 0.1 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the compound (A), from the viewpoint of curing speed and balance of physical properties of the cured product. preferable.

  When the amount of the photoacid generator is small, it may take a long time to cure, or a sufficiently cured cured product may not be obtained. In addition, when the amount of the photoacid generator is large, the color may remain in the cured product, or it may unfavorably cause coloring or damage to heat resistance or light resistance due to rapid curing.

(Basic compound)
The curable resin may contain a basic compound to improve the residual film rate and resolution. The above basic compound acts as a quencher. That is, by blending the basic compound in the curable resin in an appropriate amount, it is possible to prevent the cross-linking by the photoacid generator from reaching the unexposed portion. As a result, the residual film rate is improved, and the contrast between the exposed part and the unexposed part is clarified to improve the resolution.

  The compounding amount of the basic compound is preferably 0.001 to 2.0 parts by weight, more preferably 0.01 to 1.0 parts by weight with respect to 100 parts by weight of the compound having a cationically polymerizable functional group. It is. When the amount of the basic compound is 0.001 parts by weight or more, the effect as a quencher can be sufficiently exhibited. When the amount of the basic compound is 2.0 parts by weight or less, the sensitivity can be improved.

  The weight ratio ((B) / (A)) of the basic compound (B) to the photoacid generator (A) is 0.001 to 0.2, preferably 0.01 to 0.15. If the said weight ratio is 0.001 or more, a basic compound can fully show the effect as a quencher. If the said weight ratio is 0.2 or less, bridge | crosslinking can fully be performed.

  The basic compound is not particularly limited, but primary, secondary and tertiary aliphatic amines, mixed amines, aromatic amines, heterocyclic amines, amide derivatives and imide derivatives, etc. Can be mentioned. Among these, aromatic amines and heterocyclic amines can be suitably used as the basic compound.

  Examples of the above aromatic amines and the above heterocyclic amines include aniline, pyrrole, oxazole, thiazole, imidazole, pyrazole, furazan, pyrroline, pyrrolidine, imidazoline, imidazolidine, pyridine, pyridazine, pyrimidine, pyrazine, pyrazoline, pyrazolidine, piperidine , Piperazine, morpholine, indole, isoindole, 1H-indazole, indoline, quinoline, cinnoline, quinazoline, quinoxaline, quinoxaline, phthalazine, purine, pteridine, carbazole, phenanthridine, acridine, phenazine, 1,10-phenanthroline, adenine, adenosine, Examples include guanine, guanosine, uracil and uridine, and derivatives thereof. Moreover, as said heterocyclic amine, 2, 6- lutidine is also mentioned.

Among them, morpholine derivatives can be suitably used as the basic compound. Specific examples of morpholine derivatives include bis (2-morpholinoethyl) ether, 4,4'-carbonyldimorpholine, 4- [2- (ethoxycarbonyl) ethyl] morpholine, 4- (p-tolyl) morpholine and the like. It is illustrated.
Is represented by

As the above-mentioned basic compound, 1 type may be used and 2 or more types may be used together.
(Sensitizer)
The curable resin may contain a sensitizer. According to the sensitizer, the sensitivity to visible light and the like can be improved in the curable resin, and furthermore, high wavelength light such as g-line (436 nm), h-line (405 nm) and i-line (365 nm) Light can be made sensitive. The curability of the curable resin can be adjusted by using these sensitizers in combination with the above-described photoacid generator.

  Examples of the sensitizer include anthracene compounds and thioxanthone compounds.

  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, 9,10-diphenyl-2,6-di -Tert- butylanthracene etc. are mentioned. From the viewpoint of easy availability, anthracene, 9,10-dimethylanthracene, 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene, 9,10-diethoxyanthracene and the like are preferable as the above anthracene compound.

  Anthracene is preferable as the above anthracene compound from the viewpoint of excellent transparency of a cured product, and from the viewpoint of excellent compatibility with the photosensitive composition, 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene and 9 , 10-diethoxyanthracene and the like are preferable.

  As a specific example of the said thioxanthone type-compound, thioxanthone, 2-chloro thioxanthone, 2, 5- diethyldioxane ton etc. are mentioned.

  As these sensitizers, 1 type may be used and 2 or more types may be used together.

  The content of the sensitizer is not particularly limited as long as the sensitizing effect can be exhibited, but preferably 0.01 to 300 moles, more preferably 1 mole to 1 mole of the added photo acid generator. Is 0.01 mol to 100 mol. When the amount of the sensitizer is small, the sensitizing effect can not be obtained, and a long time may be required for curing, and the developability may be adversely affected. On the other hand, when the amount of the sensitizer is large, the color may remain in the cured product, may be colored due to rapid curing, or may be damaged in heat resistance or light resistance.

(Adhesive modifier)
The curable resin may contain an adhesion improver. As adhesion improvers, in addition to commonly used adhesives, for example, various coupling agents, epoxy compounds, oxetane compounds, phenol resins, coumarone-indene resins, rosin ester resins, terpene-phenol resins, α-methylstyrene -Vinyl toluene copolymer, polyethyl methyl styrene, aromatic polyisocyanate etc. can be mentioned.

  As a coupling agent, a silane coupling agent is mentioned, for example. The silane coupling agent is not particularly limited as long as it is a compound having at least one functional group having reactivity with an organic group and at least one hydrolyzable silicon group in the molecule. From the viewpoint of handleability, at least one functional group selected from an epoxy group, a methacryl group, an acryl group, an isocyanate group, an isocyanurate group, a vinyl group and a carbamate group is preferable as the group reactive with an organic group, From the viewpoint of properties and adhesion, epoxy group, methacryl group or acryl group is particularly preferable. The hydrolyzable silicon group is preferably an alkoxysilyl group from the viewpoint of handleability, and is preferably a methoxysilyl group or an ethoxysilyl group from the viewpoint of reactivity.

  Preferred silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and 2- (3,4-) Epoxy-functional alkoxysilanes such as epoxycyclohexyl) ethyltriethoxysilane: 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyl Methacryl groups such as triethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane and acryloxymethyltriethoxysilane, or Alkoxysilanes having a Lil groups, tris [3- (trimethoxysilylpropyl)] isocyanurate, .gamma. isocyanate propyl trimethoxysilane and the like.

Although the addition amount of the silane coupling agent can be set appropriately, it is preferably 0.1 to 20 parts by weight, more preferably 0.3 to 10 parts by weight, with respect to 100 parts by weight of the compound having a cationically polymerizable functional group. More preferably, it is 0.5 to 5 parts by weight. When the addition amount is small, the adhesive improvement effect does not appear, and when the addition amount is large, the curability and physical properties of the cured product may be adversely affected.
Moreover, as these coupling agents, a silane coupling agent, an epoxy compound, etc., 1 type may be used and 2 or more types may be used together.

(Thermoplastic resin)
It is also possible to add various thermoplastic resins to the curable resin for the purpose of, for example, modifying the properties of the curable resin. Examples of the thermoplastic resin include polymethyl methacrylate resins such as homopolymers of methyl methacrylate or random, block or graft polymers of methyl methacrylate and another monomer (for example, Optorets manufactured by Hitachi Chemical Co., Ltd.) Acrylic resins represented by polybutyl acrylate resins such as homopolymers of butyl acrylate or random, block or graft polymers of butyl acrylate and other monomers, bisphenol A, 3,3,5-trimethylcyclohexene Polycarbonate resins such as polycarbonate resins containing silylidene bisphenol or the like as a monomer structure (for example, APEC manufactured by Teijin Ltd.), norbornene derivative, resin obtained by homopolymerizing or copolymerizing vinyl monomer or the like, norbornene derivative Ring-opening metathesis polymerized resins or cycloolefin resins such as hydrogenated products thereof (for example, APEL manufactured by Mitsui Chemicals, Inc., ZEONOR manufactured by Nippon Zeon, ZEONEX, ARTON manufactured by JSR, etc.), Copolymer of ethylene and maleimide And olefin-maleimide based resins (eg, TI-PAS manufactured by Tosoh Corporation), bisphenols (such as bisphenol A and bis (4- (2-hydroxyethoxy) phenyl) fluorene) or diols (such as diethylene glycol); Polyester resins (such as O-PET manufactured by Kanebo Co., Ltd.) such as polyesters obtained by polycondensing acids (such as terephthalic acid and isophthalic acid) or aliphatic dicarboxylic acids, polyether sulfone resin, polyarylate resin, polyvinyl acetal resin, Polyethylene tree , Polypropylene resins, polystyrene resins, polyamide resins, silicone resins, other like fluorine resin, natural rubber, but the rubber-like resins such as EPDM, but is not limited thereto.

  The thermoplastic resin may have a crosslinkable group. Examples of the crosslinkable group include epoxy group, amino group, radically polymerizable unsaturated group, carboxyl group, isocyanate group, hydroxyl group and alkoxysilyl group. From the viewpoint that the heat resistance of the resulting cured product tends to be high, it is preferable that the thermoplastic resin has one or more crosslinkable groups in one molecule on average.

  The molecular weight of the thermoplastic resin is not particularly limited, but the number average molecular weight is preferably 10000 or less and 5000 or less from the viewpoint that the compatibility with the polysiloxane compound tends to be good. Is more preferred. On the other hand, the number average molecular weight is preferably 10000 or more, more preferably 100000 or more, from the viewpoint that the resulting cured product tends to be tough. The molecular weight distribution is also not particularly limited, but the molecular weight distribution is preferably 3 or less, more preferably 2 or less, from the viewpoint that the viscosity of the mixture is low and formability is likely to be good. It is more preferable that it is the following.

  Although there is no limitation in particular as a compounding quantity of the said thermoplastic resin, Preferably it is 5-50 weight% with respect to the said whole curable resin, More preferably, it is 10-30 weight%. When the amount of the thermoplastic resin added is small, the resulting cured product may become brittle. If the amount of the thermoplastic resin added is large, the heat resistance (elastic modulus at high temperature) tends to be low.

  A single thermoplastic resin may be used, or a plurality of thermoplastic resins may be used in combination.

  The thermoplastic resin may be dissolved in the curable resin and mixed in a uniform state, may be pulverized and mixed in a particle state, or may be dissolved in a solvent and mixed to be in a dispersed state. . From the viewpoint 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 uniform state. Also in this case, the thermoplastic resin may be directly dissolved in the curable resin, or may be uniformly mixed using a solvent or the like, and then the solvent may be removed to form a uniformly dispersed or mixed state. .

  When the thermoplastic resin is dispersed and used, the average particle diameter of the thermoplastic resin may be set appropriately, but the lower limit of the preferable average particle diameter is 10 nm, and the upper limit of the preferable average particle diameter is 10 μm. The particle system may have a distribution, and may have a single dispersion or a plurality of peak particle sizes, but from the viewpoint that the viscosity of the curable composition is low and the formability tends to be good, the particles The coefficient of variation of diameter is preferably 10% or less.

(Filling material)
A filler may be added to the curable resin as required.

  As the filler, various types of fillers can be used. For example, silica-based fillers (quartz, fume silica, precipitated silica, silicic anhydride, fused silica, crystalline silica, ultrafine powder amorphous silica, etc.), silicon nitride, Inorganic fillers such as silver powder, alumina, aluminum hydroxide, titanium oxide, glass fiber, carbon fiber, mica, carbon black, graphite, diatomaceous earth, clay, clay, talc, calcium carbonate, magnesium carbonate, barium sulfate and inorganic balloon As a start, a filler which is generally used or suggested as a filler of a conventional sealing material such as an epoxy-based filler can be mentioned.

(Anti-aging agent)
An anti-aging agent may be added to the curable resin. Examples of anti-aging agents include citric acid, phosphoric acid, sulfur-based anti-aging agents, etc., in addition to generally used anti-aging agents such as hindered phenolic anti-aging agents.

  As the above hindered phenolic anti-aging agent, various ones can be used including Irganox 1010 available from BASF.

  Examples of the sulfur-based anti-aging agent include mercaptans, salts of mercaptans, sulfides (sulfide carboxylic acid esters and hindered phenol sulfides, etc.), polysulfides, dithiocarboxylic acid salts, thioureas, thiophosphates, Sulfonium compounds, thioaldehydes, thioketones, mercaptals, mercaptols, monothio acids, polythio acids, thioamides, sulfoxides and the like can be mentioned.

  Moreover, as these anti-aging agents, 1 type may be used and 2 or more types may be used together.

(Radical inhibitor)
A radical inhibitor may be added to the curable resin. As a radical inhibitor, for example, 2,6-di-t-butyl-3-methylphenol (BHT), 2,2'-methylene-bis (4-methyl-6-t-butylphenol) and tetrakis (methylene-) Phenolic radical inhibitors such as 3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate) methane, and phenyl-β-naphthylamine, α-naphthylamine, N, N'-sec-butyl-p- And amine radical inhibitors such as phenylenediamine, phenothiazine and N, N'-diphenyl-p-phenylenediamine.

  Moreover, as these radical inhibitors, 1 type may be used and 2 or more types may be used together.

(solvent)
When the said curable resin is high viscosity, it is also possible to melt | dissolve in a solvent and to use. The above solvent is not particularly limited, and specifically, hydrocarbon solvents such as benzene, toluene, hexane and heptane; and ether solvents such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane and diethyl ether Solvents: 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) and ethylene glycol diethyl ether; chloroform, methylene chloride and 1,2 -Halogen solvents such as dichloroethane and the like can be mentioned.

  The use amount of the solvent can be set appropriately, but the lower limit of the preferable use amount with respect to 1 g of the curable resin to be used is 0.1 mL, and the upper limit of the preferable use amount is 10 mL. When the amount of the solvent used is small, the effect of using the solvent such as viscosity reduction may be difficult to obtain. In addition, when the amount of the solvent used is large, the solvent remains in the material to easily cause a problem such as a thermal crack, and it is also disadvantageous in cost and the industrial use value may be reduced.

  As these solvents, 1 type may be used and it may be used as 2 or more types of mixed solvents.

(Others)
Examples of the curable resin include a colorant, a mold release agent, a flame retardant, a flame retardant auxiliary, a surfactant, an antifoaming agent, an emulsifier, a leveling agent, an antiflushing agent, an ion trap agent (antimony-bismuth, etc.), thixo Additives, tackifiers, storage stability improvers, anti-ozonants, light stabilizers, thickeners, plasticizers, reactive diluents, antioxidants, heat stabilizers, conductivity-imparting agents, charging Inhibitor, radiation blocking agent, nucleating agent, phosphorus peroxide decomposer, lubricant, pigment, metal deactivator, thermal conductivity imparting agent, physical property modifier, etc., within the scope that does not impair the purpose and effect of the present invention Can be added at

[8. Method of manufacturing laminate]
(Method of preparing curable resin)
The preparation method of the said curable resin is not specifically limited, It can prepare by various methods. The various components may be mixed and prepared immediately before curing, or all the components may be stored at low temperature in the form of one component mixed in advance.

(Laminated body 1 (substrate 1 / curable resin): step of applying and drying curable resin on substrate to form a film)
The curable resin can be handled in a liquid state, and a film can be easily formed by solution application. Therefore, a layered product (base 1 / photosensitive resin composition) can be easily formed by layer-coating the above-mentioned curable resin on a base (base 1) and drying it.

  Specifically, for example, the laminate may be produced by the following method. First, the negative photosensitive resin composition is applied onto a substrate. As the base material (base material 1), for example, glass, polycarbonates, films, silicon wafer on which an imaging device is formed, patterned colored resin film of color filter for LCD or CCD, printing paper, for printing Examples include fibers, ceramic substrates, and metal plates. Examples of the method of application include spin coating, roll coating, printing and bar coating. The film thickness to apply | coat is 0.05-1000 micrometers normally, Preferably it is 0.1-500 micrometers, More preferably, it is 1-300 micrometers. Next, a laminate can be obtained by performing exposure with active energy rays.

  The laminate obtained in this manner can then be developed with an alkali developer as described later.

(Alkali development method (pattern formation process))
The laminate (substrate 1 / photosensitive resin composition) obtained by layer-coating the above-mentioned curable resin on a substrate (substrate 1) and drying is exposed and then developed with an alkaline developer. , Can form a pattern.

  As a light source for photocuring (exposure) the above-mentioned curable resin, a light source which emits the absorption wavelength of the polymerization initiator and the sensitizer used may be used, and a light source containing a wavelength of usually 200 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, light emitting diodes, etc.) can be used.

Although the exposure amount in particular for photocuring the said curable resin is not restrict | limited, Preferably it is 1-10000 mJ / cm < ² >, More preferably, it is 1-4000 mJ / cm < ² >. When the exposure amount is small, the negative photosensitive resin composition may not be cured. If the amount of exposure is high, color change may occur due to rapid curing. The range of curing time is preferably 1 to 600 seconds, more preferably 1 to 150 seconds. If the curing time is long, the characteristic of quick curing which light curing has can not be utilized.
In order to accelerate the light reaction, after exposure to light, heat may be applied before development to allow post-exposure baking (PEB).

  Further, for the purpose of removing the solvent and adjusting the physical properties of the cured product, heat may be applied before and after the photocuring so that pre-baking and after-baking may be performed to such an extent that the adhesiveness of the pattern resin is not reduced. Although hardening temperature may be set suitably, preferably it is 40-300 ° C, more preferably 40-150 ° C.

  There is no particular limitation on the patterning with an alkaline developer, and the desired pattern may be formed by dissolving and removing the unexposed area by a commonly used development method such as immersion, paddle or spray. it can.

  Moreover, about the developing solution used in alkaline development, if it is generally used, it can be used without limitation. Specific examples of the developer include organic alkaline aqueous solutions such as tetramethyl ammonium hydroxide (TMAH) aqueous solution and choline aqueous solution, potassium hydroxide aqueous solution, sodium hydroxide aqueous solution, potassium carbonate aqueous solution, sodium carbonate aqueous solution and lithium carbonate aqueous solution Inorganic alkaline aqueous solution etc. are mentioned. The aqueous solution may contain an alcohol, a surfactant and the like to adjust the dissolution rate and the like.

  The concentration of the aqueous solution is preferably 25% by weight or less, more preferably 10% by weight or less, and still more preferably 5% by weight or less, from the viewpoint that the contrast between the exposed portion and the unexposed portion is easily obtained. .

(Laminated body 2 (base 1 / photosensitive resin composition / base 2): step of pressing on a pattern on which a base is formed) Laminated body obtained in the pattern forming step (base 1 / photosensitive resin) The substrate (substrate 2) is crimped to the pattern of the composition). The pressure bonding temperature is usually 25 ° C. to 350 ° C., preferably 60 ° C. to 300 ° C., more preferably 80 ° C. to 250 ° C. As pressure bonding conditions, the pressure applied to the adhesive surface is 0 to 20 MPa, preferably 0 to 10 MPa, and more preferably 0 to 5 MPa.

  It is preferable to harden | cure at 25 degreeC-350 degreeC after pressure bonding from a viewpoint of improving adhesiveness.

[9. Application]
The laminate can be used for various applications.

  As the above application, if the laminate of the present invention is applied to a hollow structure for a CMOS / CCD sensor or a hollow structure for a MEMS device, several hundreds to several thousands of sensor devices and vises without adhesion failure in one substrate laminate. Since it is obtained at one time, it is particularly suitable for image sensor applications. In addition, the thickness of the wall material can be reduced, and the structure can be miniaturized, which is preferable. The photosensitive resin composition can be used as an adhesive layer, which is preferable from the viewpoint of simplification of the manufacturing process.

  The present invention is not limited to the above-described embodiments, and various modifications can be made within the scope of the claims, and embodiments obtained by appropriately combining the technical means disclosed in the different embodiments. Is also included in the technical scope of the present invention.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to the following examples.

(Production Example 1)
40 g of diallyl isocyanuric acid and 29 g of diallyl monomethyl isocyanuric acid are dissolved in 264 g of dioxane and a xylene solution of a platinum vinyl siloxane complex (a platinum vinyl siloxane complex containing 3% by weight of platinum, manufactured by Yumicore Precious Metals Japan, Pt-VTSC-3X) Add 143 μL. 1,3,5,7-Tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane heated to 105 ° C. in a nitrogen atmosphere containing 3% of the solution thus obtained Over a period of 3 hours, a solution of 88 g dissolved in 176 g of toluene was added dropwise.

Thirty minutes after completion of the dropwise addition, it was confirmed by ¹ H-NMR that the reaction rate of the alkenyl group was 95% or more. Thereafter, a solution in which 62 g of 1-vinyl-3,4-epoxycyclohexane was dissolved in 62 g of toluene was added dropwise to the above solution over 1 hour. Thirty minutes after completion of the dropwise addition, after confirming that the reaction rate of the alkenyl group is 95% or more by ¹ H-NMR, the reaction was completed by cooling. After the solvent toluene and dioxane were distilled off under reduced pressure, propylene glycol 1-monomethyl ether 2-acetate was substituted to obtain a colorless and clear 75 wt% alkali soluble and cationic curable compound solution.

  To 100 g of the above compound solution, 0.7 g of a photoacid generator CPI 210 S (manufactured by San-Apro Co., Ltd.) and 0.02 g of bis (2-morpholinoethyl) ether are added and mixed well, and a negative-working, alkali developable cationic curing Resin was obtained.

(Formation of an independent cell pattern)
Using the resin composition obtained in Production Example 1, the following substrate pressure evaluation evaluation sample was produced. First, the resin composition obtained in the production example was spin-coated to a film thickness of 50 μm on a glass substrate of 6 and 12 inches in diameter. The resulting substrate was heated on a hot plate heated to 120 ° C. for 10 minutes. Furthermore, using an exposure apparatus (high-pressure mercury lamp, manual exposure machine, Dainippon Kagaku Co., Ltd.), expose at a cumulative light quantity of 1500 mj / cm ² through the photomask of FIG. I left for a minute. Then, it was immersed in an alkaline developing solution (TMAH 2.38% aqueous solution) for 300 seconds, then washed with water for 30 seconds, and water on the surface was removed with compressed air or compressed nitrogen to form a pattern.

(Formation of a solid phase substrate having a hollow cell structure by bonding with a substrate)
A 12 inch φ silicon wafer was superposed on the surface of the adhesive layer of the 6 inch and 12 inch φ glass substrate on which the cell structure was formed. The lower press was placed on the lower plate of the precision press, and the lower plate was heated to 30 ° C., and the upper plate to 150 ° C. The load was set so that a pressure of 2.5 MPa was applied to the adhesive layer, and the press was started, and was held for 2 minutes and 30 seconds while reaching the predetermined load.

(result)
The obtained substrate laminate was observed with a microscope to count the number of unbonded portions (Table 1).

  FIG. 3 shows a negative photomask for forming cell patterns independent of one another. When cells spaced 0.11 mm are drawn on a 12-inch substrate, 2000 cells (Example 1), 6 When drawn on an inch substrate, 335 pieces (Example 2) can be drawn. Similarly, Examples 3 and 4 were carried out using negative type photomasks for forming individual cell patterns shown in FIG.

FIGS. 5 and 6 are negative photomasks for forming cell patterns which are not independent of one another, which form non-independent cells having the number of cells as shown in Table 1, and Comparative Examples 1 to 4 Did.
As shown in Table 1, in the cell patterns in which each of Examples 1 to 6 is independent, no unbonded portion is generated, and a substrate laminate having several hundred to several thousand hollow structures can be obtained.

  Although the comparative examples 1 and 2 are examples of the cell pattern in which each is not independent, the unbonded part has generate | occur | produced.

1. Substrate 2. Patterned curable resin3. substrate

Claims (10)

A laminate of two substrates bonded with a patterned resin,
A substrate laminate characterized in that the patterned resin is a cured curable resin having alkali solubility and cationic polymerization, and has a hollow cell structure in which the pattern shape is individually independent. The laminate according to claim 1, wherein the curable resin contains a photoacid generator. The substrate laminate according to claim 1, wherein at least one of the substrates is a transparent substrate. The said transparent substrate is glass, The board | substrate laminated body of Claim 3 characterized by the above-mentioned. The substrate laminate according to any one of claims 1 to 4, wherein at least one of the substrates is a semiconductor element substrate. The substrate laminate according to any one of claims 1 to 5, wherein the curable resin contains a glycidyl group or an alicyclic epoxy group. The substrate laminate according to any one of claims 1 to 6, wherein the curable resin is a polysiloxane compound. The said curable resin is a following formula (X1) or (X2) as an alkali-soluble group

The negative photosensitive resin composition according to any one of claims 1 to 7, which is a negative photosensitive resin composition containing at least one selected from the group consisting of each structure represented by the formula, a phenolic hydroxyl group and a carboxyl group. Substrate stack. An image sensor obtained using the substrate laminate according to any one of claims 1 to 8. A curable resin having alkali solubility and cationic polymerizability is coated on a substrate (first substrate), dried and developed with an alkaline aqueous solution after exposure to form hollows having individual pattern shapes on the substrate (first substrate) Forming a pattern corresponding to the cell structure;
A method of manufacturing a substrate laminate, comprising the step of bonding another substrate (second substrate) to a surface different from the substrate (first substrate) via the pattern.