CN104995230A - Curable composition for wafer level lens, manufacturing method for wafer level lens, wafer level lens, and optical device - Google Patents

Curable composition for wafer level lens, manufacturing method for wafer level lens, wafer level lens, and optical device Download PDF

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Publication number
CN104995230A
CN104995230A CN201480007908.3A CN201480007908A CN104995230A CN 104995230 A CN104995230 A CN 104995230A CN 201480007908 A CN201480007908 A CN 201480007908A CN 104995230 A CN104995230 A CN 104995230A
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level lens
wafer
compound
solidification compound
solidification
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CN104995230B (en
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藤川武
久保隆司
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Daicel Corp
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Daicel Chemical Industries Ltd
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/041—Lenses
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C08G59/245—Di-epoxy compounds carbocyclic aromatic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/027—Thermal properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/687—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/418—Refractive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2551/00—Optical elements

Abstract

The purpose of the present invention is to provide a curable composition exhibiting excellent rapid-curing properties and shape stability during curing, and being cured to form a high-precision wafer level lens that has optical properties such as a low Abbe number, high refractivity, high transparency and high thermal resistance. The curable composition for a wafer level lens, according to the present invention, comprises: an alicyclic epoxy compound (A) that does not have an ester group; and a cationic polymeric compound (B) having an aromatic ring, wherein the alicyclic epoxy compound (A) that does not have an ester group comprises at least two epoxidized cyclic olefin groups.

Description

The manufacture method of wafer-level lens solidification compound, wafer-level lens and wafer-level lens and Optical devices
Technical field
The present invention relates to and be applicable to the shaping solidification compound of wafer-level lens (wafer-level lens solidification compound), employ the manufacture method of the wafer-level lens of this wafer-level lens solidification compound and the wafer-level lens that obtained by the method and Optical devices.No. 2013-029690, the Japanese Patent Application that the application filed an application in Japan based on February 19th, 2013 and No. 2013-029688, the Japanese Patent Application of filing an application in Japan on February 19th, 2013 require right of priority, and its content are incorporated herein.
Background technology
In recent years, take mobile phone, mobile computer, portable personal digital assistant terminal (PDA), digital still camera (DSC) etc. as the electronic products of representative, its miniaturization, lighting and high performance obtain the development leaped.With these market trends, the lens for the camera being equipped on electronic products are also strongly required to realize miniaturization, thin-walled property and lighting, thus use wafer-level lens.Further, from the aspect of high performance, require that at least there is the resolving power corresponding with the imaging apparatus of 8,000,000 ~ 1,000 ten thousand pixel degree, lamination can be used to have the cemented lens (stacked wafers level lens) of more than 2 lens.
As forming the material of wafer-level lens, expanding glass material that replacement used in the past and having used the research of resin material.For such wafer-level lens resin material, usually require to possess high transparent and thermotolerance, also require further with the various optical characteristics of specific balancing control (such as, high refractive index and low Abbe number etc.) etc.As the resin material for the formation of optical components such as wafer-level lens, there will be a known the resin combination of such as the following stated.
In patent documentation 1, as the resin combination for the formation of optical component, disclose the alicyclic epoxy resin compositions containing aromatic backbone comprising the specific cycloaliphatic epoxy containing aromatic backbone and cationic cure catalyst.It is reported: utilize above-mentioned resin combination, high refractive index and cationic curing reactivity (see patent documentation 1) can be taken into account.
In addition, Patent Document 2 discloses a kind of optical component formed body resin combination, it is the resin combination comprising organic resin constituent, wherein, this resin combination with specific ratio comprise its molecular weight distribution middle-molecular-weihydroxyethyl be more than 700 organic resin constituent and molecular weight lower than 700 organic resin constituent, this organic resin constituent comprises aromatic epoxy compound, molecular weight be more than 700 organic resin constituent and molecular weight lower than 700 organic resin constituent comprise respectively and be selected from cycloaliphatic epoxy, hydrogenated epoxy compound, and in aromatic epoxy compound at least a kind, this resin combination also comprises releasing agent.It is reported: above-mentioned resin combination is rich in processibility, and, make the cured article after resin composition be the cured article (see patent documentation 2) of operability excellence such as can not to break when having high strength, the demoulding.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2009-179568 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2010-13667 publication
Summary of the invention
The problem that invention will solve
But, although there is the record about making cationic curing reactivity improve in patent documentation 1, resin combination disclosed in the document still exist solidified nature insufficient, solidify bad problem when obtaining cured article.In addition, with regard to resin combination disclosed in patent documentation 2, because its solidified nature is not enough, therefore create the problem that solidification is bad too.Therefore, as the solidification compound (wafer-level lens solidification compound) in order to form wafer-level lens, require curing speed enough fast (quick solidification) and the solidification compound of the cured article with high heat resistance and the transparency can be formed.Particularly, curing speed is not yet obtained at present fast and the solidification compound of the hot cationic curing class of the cured article of low Abbe number can be formed.
For wafer-level lens solidification compound, except above-mentioned various characteristics (quick solidification, thermotolerance, the transparency, high refractive index and low Abbe number), particularly, in order to obtain high-precision wafer-level lens, also require that its cure shrinkage when forming cured article is little, shape stability is excellent.In addition, also require wafer-level lens solidification compound be cured and shaping after, gained wafer-level lens is excellent from release property during mold releasability.
Particularly, about shape stability, even if require when such as wafer-level lens is placed in hot environment because of anneal etc., lens shape also can not have problems.Specifically, when utilizing mould molding solidification compound, usually can cause the existence strained due to the internal residual stresses of gained cured article (forming composition).In order to remove this strain, what often implement is carry out (heating) process of annealing after being taken out from mould by cured article.But, because carrying out anneal, probably cause following problems: the shape of cured article easily occurs " turned-down edge ", particularly for the situation of wafer-level lens, the Centre position deviation of lens can be caused, when lamination multi-disc lens, the problem that not fogging clear equally accurate reduces can be caused.
Therefore, the object of the present invention is to provide solidification compound, its quick solidification when solidifying and shape stability excellent, and by making this solidification compound solidify, the high-precision wafer-level lens that thermotolerance is high, have the optical characteristics of high transparent, high refractive index and low Abbe number concurrently can be obtained.
In addition, other object of the present invention is to provide the method using above-mentioned wafer-level lens solidification compound to manufacture wafer-level lens, and the thermotolerance utilizing the method to obtain high, have the high-precision wafer-level lens of the optical characteristics of high transparent, high refractive index and low Abbe number concurrently and possess the Optical devices of this wafer-level lens.
The method of dealing with problems
The present inventor etc. conduct in-depth research for solving above-mentioned problem, found that, comprise the alicyclic ring epoxy compound with ad hoc structure and the solidification compound of cationically polymerizable compound as neccessary composition with ad hoc structure, quick solidification during solidification and shape stability excellence, and by making it solidify, the high-precision cured article that thermotolerance is high, have the optical characteristics of high transparent, high refractive index and low Abbe number concurrently can be formed, suitable to wafer-level lens material, and then complete the present invention.
Namely, the invention provides a kind of wafer-level lens solidification compound, and comprise the alicyclic ring epoxy compound (A) without ester group and the cationically polymerizable compound (B) with aromatic ring, wherein, the alicyclic ring epoxy compound (A) without ester group has the compound that at least 2 have passed through epoxidised cyclic olefin base.
Further, provide above-mentioned wafer-level lens solidification compound, wherein, have passed through the group of cyclic olefin base through epoxidation that epoxidised cyclic olefin base is carbonatoms 5 ~ 12.
Further, above-mentioned wafer-level lens solidification compound is provided, wherein, the alicyclic ring epoxy compound (A) without ester group has to have passed through in epoxidised cyclic olefin base at least 2 compounds through the structure of singly-bound or divalent alkyl bonding.
Further, provide above-mentioned wafer-level lens solidification compound, wherein, the alicyclic ring epoxy compound (A) without ester group is the compound shown in following formula (a2).
[chemical formula 1]
[in formula (a2), X represents singly-bound or divalent alkyl.]
Further, provide above-mentioned wafer-level lens solidification compound, wherein, relative to the total amount (100 % by weight) of solidification compound, the content without the alicyclic ring epoxy compound (A) of ester group is 10 ~ 60 % by weight.
Further, above-mentioned wafer-level lens solidification compound is provided, wherein, the cationically polymerizable compound (B) with aromatic ring has at least a kind of cation-curable functional group be selected from alicyclic epoxy group, glycidyl and oxetanylmethoxy.
Further, provide above-mentioned wafer-level lens solidification compound, wherein, relative to the total amount (100 % by weight) of solidification compound, the content with the cationically polymerizable compound (B) of aromatic ring is 40 ~ 90 % by weight.
Further, provide above-mentioned wafer-level lens solidification compound, it also comprises hot cation curing agent (C).
Further, provide above-mentioned wafer-level lens solidification compound, its curing initiation temperature is 60 ~ 150 DEG C.
Further, provide above-mentioned wafer-level lens solidification compound, wherein, this solidification compound is solidified and the Abbe number of cured article that obtains is less than 35.
Further, provide above-mentioned wafer-level lens solidification compound, it also comprises the releasing agent with cation-curable functional group.
In addition, the invention provides the manufacture method of wafer-level lens, it comprises: utilize casting moulding or injection molding method to process above-mentioned wafer-level lens solidification compound.
Further, provide the manufacture method of above-mentioned wafer-level lens, wherein, above-mentioned casting moulding comprises following operation.
Operation 1a: prepare the operation with the wafer-level lens mold for forming of more than 1 lens die
Operation 2a: make the operation that wafer-level lens solidification compound contacts with above-mentioned wafer-level lens mold for forming
Operation 3a: the operation above-mentioned wafer-level lens solidification compound being solidified by heating and/or illumination
Further, provide the manufacture method of above-mentioned wafer-level lens, wherein, above-mentioned casting moulding also comprises following operation.
Operation 4a: the operation of the wafer-level lens solidification compound after solidification being carried out to anneal
Further, provide the manufacture method of above-mentioned wafer-level lens, wherein, above-mentioned casting moulding also comprises following operation.
Operation 5a: the operation that the wafer-level lens solidification compound after solidification is cut
Further, provide the manufacture method of above-mentioned wafer-level lens, wherein, above-mentioned injection molding method comprises following operation.
Operation 1b: prepare the operation with the wafer-level lens mold for forming of more than 1 lens die
Operation 2b: operation wafer-level lens solidification compound being injected to above-mentioned wafer-level lens mold for forming
Operation 3b: the operation above-mentioned wafer-level lens solidification compound being solidified by heating and/or illumination
Further, provide the manufacture method of above-mentioned wafer-level lens, wherein, above-mentioned injection molding method also comprises following operation.
Operation 4b: the operation of the wafer-level lens solidification compound after solidification being carried out to anneal
In addition, the invention provides a kind of wafer-level lens sheet, it is obtained by the manufacture method of above-mentioned wafer-level lens.
In addition, the invention provides a kind of wafer-level lens, it is obtained by the manufacture method of above-mentioned wafer-level lens.
In addition, the invention provides a kind of Optical devices, it is equipped with above-mentioned wafer-level lens.
In addition, the invention provides a kind of stacked wafers level lens, it is the multilayer body of more wafers level lens, wherein, as forming the wafer-level lens of this multilayer body, at least having and above-mentioned wafer-level lens solidification compound being cured and shaping and wafer-level lens that is that obtain.
In addition, the invention provides a kind of manufacture method of stacked wafers level lens, it is the method manufacturing above-mentioned stacked wafers level lens, and wherein, the method comprises following operation.
Operation 1c: prepare the operation with the wafer-level lens mold for forming of more than 1 lens die
Operation 2c: make the operation that above-mentioned wafer-level lens solidification compound contacts with above-mentioned wafer-level lens mold for forming
Operation 3c: by heating and/or illumination, above-mentioned wafer-level lens solidification compound solidified and obtain the operation of wafer-level lens sheet
Operation 4c: will the more wafers level lens lamination of above-mentioned wafer-level lens sheet be comprised and obtain the operation of wafer-level lens sheet laminate
Operation 5c: the operation of cutting above-mentioned wafer-level lens sheet laminate
Further, provide the manufacture method of above-mentioned stacked wafers level lens, it comprises following operation between operation 3c and operation 4c.
Operation 6c: the operation of above-mentioned wafer-level lens sheet being carried out to anneal
In addition, the invention provides a kind of wafer-level lens sheet laminate, the more wafers level lens lamination comprising above-mentioned wafer-level lens sheet obtains by it.
In addition, the invention provides a kind of Optical devices, it is equipped with above-mentioned stacked wafers level lens.
That is, the present invention relates to following technical proposals.
[1] a kind of wafer-level lens solidification compound, it comprises: do not have the alicyclic ring epoxy compound (A) of ester group and have the cationically polymerizable compound (B) of aromatic ring, wherein, the alicyclic ring epoxy compound (A) without ester group has the compound that at least 2 have passed through epoxidised cyclic olefin base.
[2] the wafer-level lens solidification compound Gen Ju [1], wherein, have passed through the group of cyclic olefin base through epoxidation that epoxidised cyclic olefin base is carbonatoms 5 ~ 12.
[3] according to [1] or the wafer-level lens solidification compound described in [2], wherein, the alicyclic ring epoxy compound (A) without ester group is the compound with following structure, and described structure has been through in epoxidised cyclic olefin base at least 2 structures through singly-bound or divalent alkyl bonding.
[4] according to the wafer-level lens solidification compound according to any one of [1] ~ [3], wherein, the alicyclic ring epoxy compound (A) without ester group is that [in formula (a2), X represents singly-bound or divalent alkyl to the compound shown in above-mentioned formula (a2).]。
[5] according to the wafer-level lens solidification compound according to any one of [1] ~ [4], wherein, relative to the total amount (100 % by weight) of solidification compound, the content without the alicyclic ring epoxy compound (A) of ester group is 10 ~ 60 % by weight.
[6] according to the wafer-level lens solidification compound according to any one of [1] ~ [5], wherein, relative to not having the alicyclic ring epoxy compound (A) of ester group and having the total amount (100 % by weight) of cationically polymerizable compound (B) of aromatic ring, the ratio without the alicyclic ring epoxy compound (A) of ester group is 10 ~ 60 % by weight.
[7] according to the wafer-level lens solidification compound according to any one of [1] ~ [6], wherein, the aromatic ring that the cationically polymerizable compound (B) with aromatic ring has is aromatic hydrocarbons ring.
[8] according to the wafer-level lens solidification compound according to any one of [1] ~ [7], wherein, having the aromatic ring number had in the molecule of the cationically polymerizable compound (B) of aromatic ring is 1 ~ 10.
[9] according to the wafer-level lens solidification compound according to any one of [1] ~ [8], wherein, the cationically polymerizable compound (B) with aromatic ring has at least a kind of cation-curable functional group be selected from alicyclic epoxy group, glycidyl and oxetanylmethoxy.
[10] according to the wafer-level lens solidification compound according to any one of [1] ~ [9], wherein, having the cation-curable functional group number had in the molecule of the cationically polymerizable compound (B) of aromatic ring is 1 ~ 10.
[11] according to the wafer-level lens solidification compound according to any one of [1] ~ [10], wherein, the cationically polymerizable compound (B) with aromatic ring is the compound shown in following formula (b1).
[chemical formula 2]
[in formula (b1), R 1~ R 5, R 7~ R 11identical or different, represent the alkyl of hydrogen atom or carbonatoms 1 ~ 6.Ring Z 1, ring Z 2identical or different, represent aromatic carbon ring (aromatic hydrocarbons ring).R 6, R 12identical or different, represent the alkylidene group of carbonatoms 1 ~ 10.P1, p2 are identical or different, are the integer of more than 0.]
[12] according to the wafer-level lens solidification compound according to any one of [1] ~ [11], wherein, relative to the total amount (100 % by weight) of solidification compound, the content with the cationically polymerizable compound (B) of aromatic ring is 40 ~ 90 % by weight.
[13] according to the wafer-level lens solidification compound according to any one of [1] ~ [12], wherein, relative to the total amount (100 % by weight) of solidification compound, the ratio of the total amount of the alicyclic ring epoxy compound (A) without ester group and the cationically polymerizable compound (B) with aromatic ring is more than 80 % by weight and lower than 100 % by weight.
[14] according to the wafer-level lens solidification compound according to any one of [1] ~ [13], it also comprises hot cation curing agent (C).
[15] the wafer-level lens solidification compound Gen Ju [14], wherein, hot cation curing agent (C) is hot cationic polymerization initiators.
[16] according to [14] or the wafer-level lens solidification compound described in [15], wherein, relative to total amount 100 weight part of the cation-curable compound comprised in solidification compound, the content (use level) of hot cation curing agent (C) is 0.001 ~ 10 weight part.
[17] according to the wafer-level lens solidification compound according to any one of [14] ~ [16], its curing initiation temperature is 60 ~ 150 DEG C.
[18] according to the wafer-level lens solidification compound according to any one of [1] ~ [17], it also comprises antioxidant.
[19] the wafer-level lens solidification compound Gen Ju [18], wherein, antioxidant is phenol system antioxidant.
[20] according to [18] or the wafer-level lens solidification compound described in [19], relative to total amount 100 weight part of the cation-curable compound comprised in solidification compound, the content (use level) of antioxidant is 0.001 ~ 15 weight part.
[21] according to wafer-level lens solidification compound according to any one of [1] ~ [20], wherein, this solidification compound is made to solidify and the Abbe number of cured article that obtains is less than 35.
[22] according to the wafer-level lens solidification compound according to any one of [1] ~ [21], it also comprises the releasing agent with cation-curable functional group.
[23] the wafer-level lens solidification compound Gen Ju [22], wherein, the cation-curable functional group number that above-mentioned releasing agent has is 1 ~ 4.
[24] according to [22] or the wafer-level lens solidification compound described in [23], wherein, above-mentioned releasing agent is that the fluorine with epoxy group(ing) replaces hydrocarbon.
[25] the wafer-level lens solidification compound Gen Ju [24], wherein, it is the compound shown in following formula (i) that the above-mentioned fluorine with epoxy group(ing) replaces hydrocarbon.
[chemical formula 3]
[r in formula (i) represents the integer of 1 ~ 15.S represents the integer of 1 ~ 5.Y represents hydrogen atom, fluorine atom or fluoro-alkyl.In formula (i)-(CH 2) r-be the group that part hydrogen atom is optionally substituted by a hydroxyl group, in addition, also can be the group that midway comprises ehter bond.]
[26] according to the wafer-level lens solidification compound according to any one of [22] ~ [25], wherein, relative to not having the alicyclic ring epoxy compound (A) of ester group and having total amount 100 weight part of cationically polymerizable compound (B) of aromatic ring, the content (use level) of above-mentioned releasing agent is 0.01 ~ 10 weight part.
[27] according to the wafer-level lens solidification compound according to any one of [1] ~ [26], wherein, relative to the total amount (100 % by weight) of the solidified nature compound comprised in solidification compound, the ratio of the total amount of cationically polymerizable compound is 80 ~ 100 % by weight.
[28] according to wafer-level lens solidification compound according to any one of [1] ~ [27], wherein, make this solidification compound solidify and the cured article that obtains in the inside transmitance [converting with thickness 0.5mm] of 400nm for 70 ~ 100%.
[29] according to wafer-level lens solidification compound according to any one of [1] ~ [28], wherein, this solidification compound is made to solidify and the cured article that obtains is more than 1.58 in the specific refractory power (25 DEG C) of 589nm.
[30] according to wafer-level lens solidification compound according to any one of [1] ~ [29], wherein, this solidification compound is made to solidify and the second-order transition temperature of cured article that obtains is 100 ~ 200 DEG C.
[31] according to the wafer-level lens solidification compound according to any one of [1] ~ [30], wherein, this solidification compound is made to solidify and the coefficient of linear expansion of cured article below second-order transition temperature (α 1) that obtain is 40 ~ 100ppm/K.
[32] according to the wafer-level lens solidification compound according to any one of [1] ~ [31], wherein, this solidification compound is made to solidify and the coefficient of linear expansion of cured article more than second-order transition temperature (α 2) that obtain is 90 ~ 150ppm/K.
[33] cured article, it makes [1] ~ [32] according to any one of wafer-level lens solidification compound solidification obtain.
[34] cured article Gen Ju [33], its inside transmitance at 400nm [converting with thickness 0.5mm] is for 70 ~ 100%.
[35] according to [33] or the cured article described in [34], its specific refractory power at 589nm (25 DEG C) is more than 1.58.
[36] according to the cured article according to any one of [33] ~ [35], its second-order transition temperature is 100 ~ 200 DEG C.
[37] according to cured article according to any one of [33] ~ [36], its coefficient of linear expansion (α 1) below second-order transition temperature is 40 ~ 100ppm/K.
[38] according to cured article according to any one of [33] ~ [37], its coefficient of linear expansion (α 2) more than second-order transition temperature is 90 ~ 150ppm/K.
[39] according to the cured article according to any one of [33] ~ [38], its Abbe number is less than 35.
[40] manufacture method for wafer-level lens, it comprises: utilize casting moulding or injection molding method to process the wafer-level lens solidification compound according to any one of [1] ~ [32].
The manufacture method of the wafer-level lens [41] Gen Ju [40], wherein, above-mentioned casting moulding comprises following operation.
Operation 1a: prepare the operation with the wafer-level lens mold for forming of more than 1 lens die
Operation 2a: make the operation that wafer-level lens solidification compound contacts with above-mentioned wafer-level lens mold for forming
Operation 3a: the operation above-mentioned wafer-level lens solidification compound being solidified by heating and/or illumination
The manufacture method of the wafer-level lens [42] Gen Ju [41], wherein, above-mentioned casting moulding also comprises following operation.
Operation 4a: the operation of the wafer-level lens solidification compound after solidification being carried out to anneal
[43] manufacture method of basis [41] or the wafer-level lens described in [42], wherein, above-mentioned casting moulding also comprises following operation.
Operation 5a: the operation that the wafer-level lens solidification compound after solidification is cut
The manufacture method of the wafer-level lens [44] Gen Ju [40], wherein, above-mentioned injection molding method comprises following operation.
Operation 1b: prepare the operation with the wafer-level lens mold for forming of more than 1 lens die
Operation 2b: operation wafer-level lens solidification compound being injected to above-mentioned wafer-level lens mold for forming
Operation 3b: the operation above-mentioned wafer-level lens solidification compound being solidified by heating and/or illumination
The manufacture method of the wafer-level lens [45] Gen Ju [44], wherein, above-mentioned injection molding method also comprises following operation.
Operation 4b: the operation of the wafer-level lens solidification compound after solidification being carried out to anneal
[46] a wafer-level lens sheet, it is obtained by the manufacture method of the wafer-level lens described in [41] or [42].
[47] wafer-level lens, it is obtained by the manufacture method of the wafer-level lens according to any one of [40] ~ [45].
[48] wafer-level lens Gen Ju [47], its inside transmitance at 400nm [converting with thickness 0.5mm] is for 70 ~ 100%.
[49] according to [47] or the wafer-level lens described in [48], its specific refractory power at 589nm (25 DEG C) is more than 1.58.
[50] according to the wafer-level lens according to any one of [47] ~ [49], its second-order transition temperature is 100 ~ 200 DEG C.
[51] according to wafer-level lens according to any one of [47] ~ [50], its coefficient of linear expansion (α 1) below second-order transition temperature is 40 ~ 100ppm/K.
[52] according to wafer-level lens according to any one of [47] ~ [51], its coefficient of linear expansion (α 2) more than second-order transition temperature is 90 ~ 150ppm/K.
[53] according to the wafer-level lens according to any one of [47] ~ [52], its Abbe number is less than 35.
[54] Optical devices, it is equipped with [47] ~ [53] according to any one of wafer-level lens.
[55] a kind of stacked wafers level lens, it is the multilayer body of more wafers level lens, wherein, as forming the wafer-level lens of this multilayer body, at least having and the wafer-level lens solidification compound according to any one of [1] ~ [32] being cured and shaping and wafer-level lens that is that obtain.
[56] the stacked wafers level lens Gen Ju [55], wherein, the sheet number forming the wafer-level lens of these stacked wafers level lens is 2 ~ 5.
[57] manufacture method for stacked wafers level lens, it is the method manufacturing [55] or the stacked wafers level lens described in [56], and wherein, the method comprises following operation.
Operation 1c: prepare the operation with the wafer-level lens mold for forming of more than 1 lens die
Operation 2c: make [1] ~ [32] according to any one of the operation that contacts with above-mentioned wafer-level lens mold for forming of wafer-level lens solidification compound
Operation 3c: by heating and/or illumination, above-mentioned wafer-level lens solidification compound solidified and obtain the operation of wafer-level lens sheet
Operation 4c: will the more wafers level lens lamination of above-mentioned wafer-level lens sheet be comprised and obtain the operation of wafer-level lens sheet laminate
Operation 5c: the operation of cutting above-mentioned wafer-level lens sheet laminate
The manufacture method of the stacked wafers level lens [58] Gen Ju [57], it comprises following operation further between operation 3c and operation 4c.
Operation 6c: the operation of above-mentioned wafer-level lens sheet being carried out to anneal
[59] a wafer-level lens sheet laminate, the more wafers level lens lamination of the wafer-level lens sheet comprised described in [46] obtains by it.
[60] Optical devices, it is equipped with [55] or stacked wafers level lens described in [56].
The effect of invention
Wafer-level lens solidification compound of the present invention is owing to having above-mentioned formation, therefore quick solidification during its solidification and shape stability excellence, and by making it solidify, can form that thermotolerance is high, the cured article (wafer-level lens) of the optical characteristics that has high transparent, high refractive index and low Abbe number concurrently.Particularly, because the cure shrinkage of wafer-level lens solidification compound of the present invention is little, shape stability is excellent, therefore by using this solidification compound, the design of the high wafer-level lens of precision can be conducive to.In addition, when alicyclic ring epoxy compound (A) in solidification compound of the present invention is liquid, without the need to adding diluted composition (such branch that is diluted to causes detrimentally affect to the specific refractory power of cured article, Abbe number) in addition, therefore, it is possible to when keep the high refractive index of cured article and the optical characteristics of low Abbe number realize quick solidification, the productivity being conducive to wafer-level lens improves.The use of such wafer-level lens is conducive to the miniaturization, lighting, high performance etc. of the Optical devices realizing employing this wafer-level lens.
It should be noted that, described " wafer-level lens " in this specification sheets refers to, the lens used when being used for the camera of mobile phone etc. with wafer-level manufacture, and with regard to its size, such as, diameter is about 1 ~ 10mm, is preferably about 3 ~ 5mm.In addition, with regard to its thickness, such as, be about 100 ~ 1500 μm, be preferably about 500 ~ 800 μm.
Embodiment
< wafer-level lens solidification compound >
Wafer-level lens solidification compound of the present invention (also referred to as " solidification compound of the present invention ") comprises the alicyclic ring epoxy compound (A) without ester group and the cationically polymerizable compound (B) with the aromatic ring solidification compound as neccessary composition.In solidification compound of the present invention except above-mentioned neccessary composition, other compositions such as such as hot cation curing agent (C) described later, light cation curing agent (D), antioxidant, releasing agent, various additives can also be comprised.It should be noted that, with regard to solidification compound of the present invention, such as, by selecting the kind of solidifying agent, can be and to solidify by heating thus to form the thermoset composition of cured article (resin cured matter), also can be the solidification by light (illumination) thus form the Photocurable composition of cured article.
[alicyclic ring epoxy compound (A)]
The alicyclic ring epoxy compound (A) (hereinafter also referred to as " alicyclic ring epoxy compound (A) ", " composition (A) ") without ester group (ester bond) in solidification compound of the present invention does not have ester group (ester bond) in molecule and has the compound that at least 2 have passed through epoxidised cyclic olefin base in molecule.Described " have passed through epoxidised cyclic olefin base " that alicyclic ring epoxy compound (A) has, that at least 1 of the carbon-to-carbon unsaturated bond had from cyclic olefin (forming the annular aliphatic hydrocarbon that at least 1 of C-C of ring be carbon-to-carbon unsaturated bond) have passed through removal 1 hydrogen atom epoxidised structure and the group (1 valency group) that formed, hereinafter also referred to " epoxidation cyclic olefin base ", " alicyclic epoxy group ".That is, above-mentioned epoxidation cyclic olefin base comprises aliphatic hydrocarbon ring structure and epoxy group(ing) and this epoxy group(ing) is the group of the epoxy group(ing) be made up of adjacent 2 carbon atoms and Sauerstoffatom that form above-mentioned aliphatic hydrocarbon ring.
As the cyclic olefin base (form before epoxidation) in above-mentioned epoxidation cyclic olefin base, can enumerate: cyclopropenyl radical (such as, 2-cyclopropylene-1-base etc.), cyclobutene base (such as, 2-cyclobutene-1-base etc.), cyclopentenyl (such as, 2-cyclopentenes-1-base, 3-cyclopentenes-1-base etc.), the cycloalkenyl group such as cyclohexenyl (such as, 2-tetrahydrobenzene-1-base, 3-tetrahydrobenzene-1-base etc.); The cycloalkadienyls such as 2,4-cyclopentadiene-1-base, 2,4-cyclohexadiene-1-bases, 2,5-cyclohexadiene-1-bases; The polycycle groups etc. such as dicyclopentenyl, dicyclohexenyl, norbornene.
It should be noted that, on the aliphatic hydrocarbon ring forming the cyclic olefin base in above-mentioned epoxidation cyclic olefin base, also can be bonded with the substituting group of more than 1.As above-mentioned substituting group, the substituting group etc. of such as carbonatoms 0 ~ 20 (being more preferably carbonatoms 0 ~ 10) can be enumerated, more specifically, can enumerate: the halogen atoms such as fluorine atom, chlorine atom, bromine atoms, atomic iodine; Hydroxyl; The alkoxyl groups such as methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, isobutoxy (are preferably C 1-6alkoxyl group, be more preferably C 1-4alkoxyl group); The alkene oxygen bases such as allyloxy (are preferably C 2-6alkene oxygen base, be more preferably C 2-4alkene oxygen base); The aromatic rings such as phenoxy group, tolyloxy, naphthyloxy optionally has C 1-4alkyl, C 2-4thiazolinyl, halogen atom, C 1-4the substituent aryloxy such as alkoxyl group (is preferably C 6-14aryloxy); The aralkoxies such as benzyloxy, benzene oxyethyl group (are preferably C 7-18aralkoxy); Acetoxyl group, propionyloxy, acyloxy such as (methyl) acryloxy, benzoyloxy etc. (are preferably C 1-12acyloxy); Sulfydryl; The alkylthio such as methylthio group, ethylmercapto group (is preferably C 1-6alkylthio, be more preferably C 1-4alkylthio); The alkenylthio groups such as allyl sulfenyl (are preferably C 2-6alkenylthio group, be more preferably C 2-4alkenylthio group); The aromatic rings such as thiophenyl, Tolylsulfanvl, naphthalene sulfenyl optionally has C 1-4alkyl, C 2-4thiazolinyl, halogen atom, C 1-4the substituent arylthio such as alkoxyl group (is preferably C 6-14arylthio); The aromatic alkylthios such as benzylthio-, benzene ethylmercapto group (are preferably C 7-18aromatic alkylthio); Carboxyl; The alkoxy carbonyls such as methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl, butoxy carbonyl (are preferably C 1-6alkoxy-carbonyl); The aryloxycarbonyl such as phenyloxycarbonyl, tolyloxy carbonyl, naphthoxycarbonyl (are preferably C 6-14aryloxy-carbonyl); The aromatic alkoxy carbonyls such as benzyloxycarbonyl (are preferably C 7-18aralkoxy-carbonyl); Amino; The lists such as methylamino, ethylamino, dimethylamino, diethylamino or dialkyl amido (are preferably single or two-C 1-6alkylamino); The acyl aminos such as acetylamino, propanoylamino, benzoyl-amido (are preferably C 1-11acyl amino); The group containing oxetanylmethoxy such as ethyl oxa-cyclobutoxy group; The acyl groups such as ethanoyl, propionyl, benzoyl; Oxo base; By more than 2 in these as required via C 1-6the group etc. of alkylene.
Wherein, as above-mentioned cyclic olefin base, the cyclic olefin base of preferred carbonatoms 5 ~ 12, be more preferably cycloalkenyl group, the more preferably cyclohexenyl of carbonatoms 5 ~ 12.Namely, as above-mentioned epoxidation cyclic olefin base, be preferably the group of cyclic olefin base through epoxidation of carbonatoms 5 ~ 12, be more preferably the group of cycloalkenyl group through epoxidation of carbonatoms 5 ~ 12, more preferably cyclohexenyl is through the group (cyclohexene oxide base) of epoxidation.It should be noted that, alicyclic ring epoxy compound (A) can have a kind of epoxidation cyclic olefin base, also can have two or more epoxidation cyclic olefin base.
The number of the epoxidation cyclic olefin base that alicyclic ring epoxy compound (A) has in molecule is more than 2, is not particularly limited, but be preferably 2 ~ 4, be more preferably 2.
As alicyclic ring epoxy compound (A), preferably there are at least 2 of the epoxidation cyclic olefin base compounds via the structure of singly-bound or divalent alkyl bonding.As above-mentioned divalent alkyl, can enumerate such as: divalent aliphatic alkyl, divalent ester ring type alkyl and the group etc. by the multiple bondings in them.As above-mentioned divalent aliphatic alkyl, can enumerate such as: the alkylidene group (such as, the alkylidene group of carbonatoms 1 ~ 6) etc. of the straight or brancheds such as methylene radical, methylmethylene, dimethylated methylene base, ethylidene, propylidene, trimethylene, tetramethylene.In addition, as divalent ester ring type alkyl, can enumerate such as: the divalent cycloalkylidenes etc. such as 1,2-cyclopentylidene, 1,3-cyclopentylidene, 1,2-cyclohexylidene, 1,3-cyclohexylidene, Isosorbide-5-Nitrae-cyclohexylidene.
As alicyclic ring epoxy compound (A), the such as compound shown in following formula (a1) specifically can be enumerated.
[chemical formula 4]
R-X-R (a1)
In above-mentioned formula (a1), R representative ring oxidation cyclic olefin base.2 R can be the same or different.X represents singly-bound or divalent alkyl.As the epoxidation cyclic olefin base of R, the divalent alkyl as X, group same as described above can be enumerated.Such as, be the compound shown in formula (a1) of cyclohexene oxide base as 2 R, the such as compound etc. shown in following formula (a2) can be enumerated.
[chemical formula 5]
[in formula (a2), X is the same.]
It should be noted that, in solidification compound of the present invention, alicyclic ring epoxy compound (A) can be used alone a kind, also two or more can be combinationally used.
The content (use level) of the alicyclic ring epoxy compound (A) in solidification compound of the present invention is not particularly limited, but is preferably 10 ~ 60 % by weight relative to the total amount (whole amount) (100 % by weight) of solidification compound, is more preferably 15 ~ 55 % by weight, more preferably 20 ~ 50 % by weight.If the content of alicyclic ring epoxy compound (A) is lower than 10 % by weight, then the solidified nature of solidification compound may be caused insufficient.On the other hand, if the content of alicyclic ring epoxy compound (A) is more than 60 % by weight, then may cause being difficult to for cured article gives high refractive index and the optical characteristics of low Abbe number.
Be not particularly limited relative to the ratio of alicyclic ring epoxy compound (A) of total amount (100 % by weight) of alicyclic ring epoxy compound (A) and the cationically polymerizable compound (B) with aromatic ring, be preferably 10 ~ 60 % by weight, be more preferably 15 ~ 55 % by weight, more preferably 20 ~ 50 % by weight.If aforementioned proportion is lower than 10 % by weight, then the solidified nature of solidification compound may be caused insufficient.On the other hand, if aforementioned proportion is more than 60 % by weight, then may cause being difficult to for cured article gives high refractive index and the optical characteristics of low Abbe number.
[there is the cationically polymerizable compound (B) of aromatic ring]
The cationically polymerizable compound (B) (hereinafter also referred to as " cationically polymerizable compound (B) ", " composition (B) ") with aromatic ring in solidification compound of the present invention is the compound in molecule with at least 1 aromatic ring and at least 1 cation-curable functional group (cationically polymerizable functional group).By containing cationically polymerizable compound (B), there is following tendency: can effectively for the cured article making solidification compound of the present invention solidification obtain gives the optical characteristics of particularly thermotolerance and high transparent, high refractive index and low Abbe number.
As the aromatic ring that cationically polymerizable compound (B) has, be not particularly limited, can enumerate such as: the aromatic monocyclic hydrocarbon ring that phenyl ring is such; The aromatic hydrocarbons rings etc. such as aromatic series fused polycycle hydrocarbon ring such as naphthalene nucleus, anthracene nucleus, fluorenes ring, pyrene ring.In addition, as above-mentioned aromatic ring, the heteroaromatics etc. such as pyridine ring, furan nucleus, pyrrole ring, cumarone ring, indole ring, carbazole ring, quinoline ring, benzoglyoxaline ring, quinoxaline ring can also be enumerated.Wherein, as above-mentioned aromatic ring, optimization aromatic hydrocarbon ring, is more preferably phenyl ring, fluorenes ring, further, from the view point of being easy to give high refractive index and the optical characteristics of low Abbe number, particularly preferably fluorenes ring to cured article.
It should be noted that, on the aromatic ring that cationically polymerizable compound (B) has, also can be bonded with the substituting group of more than 1.As above-mentioned substituting group, can enumerate such as: form the identical group of the substituting group of the aliphatic hydrocarbon ring of cyclic olefin base with above-mentioned being optionally bonded to.It should be noted that, cationically polymerizable compound (B) can have a kind of aromatic ring, also can have aromatic ring of more than two kinds.
The number of the aromatic ring that cationically polymerizable compound (B) has in molecule is more than 1, is not particularly limited, but be preferably 1 ~ 10, be more preferably 2 ~ 8.
As the cation-curable functional group that cationically polymerizable compound (B) has, known or the usual functional group with cation-curable (cationically polymerizable) can be enumerated, be not particularly limited, can enumerate such as: the cyclic ether group such as epoxy group(ing), oxetanylmethoxy, tetrahydrofuran base, oxazolinyl; The group containing vinyl such as vinyl ether group, styryl; At least comprise the group etc. of these groups.Wherein, as above-mentioned cation-curable functional group, consider from the reactive viewpoint with alicyclic ring epoxy compound (A), preferred alicyclic epoxy group (epoxidation cyclic olefin base), glycidyl, oxetanylmethoxy.It should be noted that, cationically polymerizable compound (B) can have a kind of cation-curable functional group, also can have cation-curable functional group of more than two kinds.
The number of the cation-curable functional group that cationically polymerizable compound (B) has in molecule is more than 1, is not particularly limited, but be preferably 2 ~ 10, be more preferably 2 ~ 4.
In cationically polymerizable compound (B), as the epoxy compounds with aromatic ring, can enumerate such as: bisphenol A type epoxy compound (diglycidyl ether etc. of dihydroxyphenyl propane or its alkylene oxide adduct), bisphenol F type epoxy compound (diglycidyl ether etc. of Bisphenol F or its alkylene oxide adduct), biphenol type epoxy compound, phenol novolak-type epoxy compound, cresol novolak type epoxy compound, cresols type epoxy compounds, the cresol novolak type epoxy compound of dihydroxyphenyl propane, polyphenol type epoxy compounds, bmminated bisphenol-A type epoxy compounds, brominated bisphenol F type epoxy compounds, quinhydrones diglycidyl ether, Resorcinol diglycidyl ether, terephthalic acid diglycidyl ester, o-phthalic acid diglycidyl ester, the addition reaction of terminal carboxylic's polyhutadiene and bisphenol A type epoxy resin, naphthalene type epoxy compounds (there is the epoxy compounds of naphthalene nucleus), there is the epoxy compounds etc. of fluorenes ring.In addition, as the above-mentioned epoxy compounds with aromatic ring, the cycloaliphatic epoxy etc. such as disclosed in Japanese Unexamined Patent Publication 2009-179568 with aromatic backbone can also be used.
As the epoxy compounds with aromatic ring, particularly from the view point of high refractive index, the low Abbe number of cured article, the compound shown in preferred following formula (b1).
[chemical formula 6]
In formula (b1), R 1~ R 5, R 7~ R 11identical or different, represent the alkyl of hydrogen atom or carbonatoms 1 ~ 6.As the alkyl of described carbonatoms 1 ~ 6, can enumerate such as: methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, hexyl etc.Wherein, as R 1~ R 5, R 7~ R 11, be preferably the alkyl of hydrogen atom, carbonatoms 1 ~ 3, be more preferably hydrogen atom.
In formula (b1), ring Z 1, ring Z 2identical or different, represent aromatic carbon ring (aromatic hydrocarbons ring).As ring Z 1, ring Z 2in aromatic carbon ring, the aromatic carbon ring of 1 ~ 4 round trip degree such as phenyl ring, naphthalene nucleus, anthracene nucleus can be enumerated.Wherein, as above-mentioned aromatic carbon ring, preferred phenyl ring, naphthalene nucleus etc.
In formula (b1), the fluorenes ring shown in formula (b1), ring Z 1, ring Z 2also substituting group can be had.As above-mentioned substituting group, can enumerate such as: alkyl (such as, the C such as methyl, ethyl, propyl group, sec.-propyl 1-6alkyl, preferably methyl); The cycloalkyl such as cyclopentyl, cyclohexyl (such as, C 5-8cycloalkyl etc.); The aryl such as phenyl, naphthyl (such as, C 6-15aryl etc.); The aralkyl such as benzyl (such as, C 7-16aralkyl etc.); Acyl group (such as, the C such as ethanoyl, propionyl, benzoyl 1-10acyl group etc.); Alkoxyl group (such as, the C such as methoxyl group, oxyethyl group, propoxy-, isopropoxy 1-6alkoxyl group etc.); The alkoxy carbonyl such as methoxycarbonyl, ethoxy carbonyl (such as, C 1-4alkoxy-carbonyl etc.); Cyano group; Carboxyl; Nitro; Amino; Substituted-amino (such as, single or two C 1-4alkylamino etc.); The halogen atoms etc. such as fluorine atom, chlorine atom.
In formula (b1), R 6, R 12identical or different, represent the alkylidene group of carbonatoms 1 ~ 10.As R 6, R 12in alkylidene group, can enumerate such as: the alkylidene group etc. of the straight or branched of the carbonatomss 1 ~ 10 such as methylene radical, ethylidene, propylidene, trimethylene, tetramethylene, hexa-methylene.Wherein, as above-mentioned alkylidene group, the alkylidene group of the carbonatomss 2 ~ 6 such as preferred ethylidene, propylidene, trimethylene, is more preferably the alkylidene group of carbonatoms 2 or 3.
In formula (b1), p1, p2 are identical or different, are the integer of more than 0, are preferably the integer of 0 ~ 4, lower from the view point of viscosity, mobility is more excellent, is more preferably the integer of 1 ~ 4.
It should be noted that, as the compound shown in formula (b1), the commercially available product of such as commodity " PG-100 ", " EG-200 " by name (being made by Osaka Gas Chemicals (strain) above) etc. can also be used.
In cationically polymerizable compound (B), as the oxetane compound with aromatic ring, can enumerate such as: 1, two { [(3-ethyl-3-oxetanylmethoxy) methoxyl group] methyl } benzene of 4-, 3-ethyl-3-[(phenoxy group) methyl] trimethylene oxide, 4,4'-two [3-ethyl-(3-oxetanylmethoxy) methoxymethyl] biphenyl, phenolic varnish type oxetane resins etc.
As cationically polymerizable compound (B), commercially available product can also be used.As the commercially available product of the bisphenol A type epoxy compound in cationically polymerizable compound (B), can enumerate such as: trade(brand)name " jER827 ", " jER828 ", " jER828EL ", " jER828XA ", " jER834 " (being made by Mitsubishi Chemical's (strain) above); Trade(brand)name " EPICLON 840 ", " EPICLON 840-S ", " EPICLON 850 ", " EPICLON 850-S ", " EPICLON 850-LC " (being made by DIC (strain) above) etc.In addition, as the commercially available product in the molecule in cationically polymerizable compound (B) with the epoxy compounds of naphthalene nucleus, can enumerate such as: trade(brand)name " EPICLON HP4032 ", " HP4032D ", " HP4700 ", " HP4710 ", " HP4770 ", " HP5000 " (being made by DIC (strain) above) etc.Further, as the commercially available product in the molecule in cationically polymerizable compound (B) with the epoxy compounds of fluorenes ring, can enumerate such as: trade(brand)name " PG-100 ", " EG-200 ", " EG-250 " (being made by Osaka Gas Chemicals (strain) above); Trade(brand)name " ONCOAT EX-1010 ", " ONCOATEX-1011 ", " ONCOAT EX-1012 ", " ONCOAT EX-1020 ", " ONCOATEX-1030 ", " ONCOAT EX-1040 ", " ONCOAT EX-1050 ", " ONCOATEX-1051 " (above by long rapids industry (strain) Inc.) etc.Further, as the commercially available product in the molecule in cationically polymerizable compound (B) with the oxetane compound of aromatic ring, can enumerate such as: trade(brand)name " OXT-121 ", " OXT-211 " (synthesizing (strain) by East Asia above to make); Trade(brand)name " ETERNACOLL OXBP " (the emerging product in space portion (strain) system) etc.
It should be noted that, in solidification compound of the present invention, cationically polymerizable compound (B) can be used alone a kind, also two or more can be combinationally used.
The content (use level) of the cationically polymerizable compound (B) in solidification compound of the present invention is not particularly limited, but is preferably 40 ~ 90 % by weight relative to the total amount (100 % by weight) of solidification compound, is more preferably 40 ~ 80 % by weight, more preferably 45 ~ 75 % by weight.If the content of cationically polymerizable compound (B) is lower than 40 % by weight, be then sometimes difficult to for cured article gives high refractive index and the optical characteristics of low Abbe number.On the other hand, if the content of cationically polymerizable compound (B) is more than 90 % by weight, then may be difficult to the effect of quick solidification when obtaining solidification, shape stability raising.
Be not particularly limited relative to the composition (A) of total amount (100 % by weight) of solidification compound of the present invention and the ratio of the total amount of composition (B), be preferably more than 80 % by weight (such as, more than 80 % by weight and lower than 100 % by weight), be more preferably more than 90 % by weight (such as, 90 ~ 98 % by weight).If aforementioned proportion is lower than 80 % by weight, be then sometimes difficult to quick solidification when balancing the solidification controlling solidification compound well and shape stability, the thermotolerance of cured article and the various characteristics of optics physical property (high transparent, high refractive index, low Abbe number).
[hot cation curing agent (C)]
Also hot cation curing agent (C) (hereinafter also referred to " composition (C) ") can be comprised in solidification compound of the present invention.Hot cation curing agent (C) has to cause by heating or to promote that the cation-curable compound comprised in solidification compound (has the compound of cation-curable functional group; Such as, there is in alicyclic ring epoxy compound (A), cationically polymerizable compound (B), molecule the releasing agent etc. of more than 1 cation-curable functional group) the compound of effect of polyreaction (curing reaction).As hot cation curing agent (C), known or the usual compound with above-mentioned effect can be used, being not particularly limited, can enumerating such as: producing positively charged ion kind by heating and the hot cationic polymerization initiators etc. of the polymerization (solidification) of initiation solidified nature compound thus.
As hot cation curing agent (C), can enumerate such as: the hot cationic polymerization initiators such as aryl diazonium salts, aryl salt, aryl sulfonium salt, propadiene (ア レ Application)-ionic complex.In addition, as hot cation curing agent (C), can enumerate such as: the compound that the silanols such as the chelate compound of the metal such as aluminium, titanium and etheric acid or diones and tri-phenyl-silane alcohol are formed; Or the hot cationic polymerization initiators such as the compound that formed of the phenols such as the chelate compound of the metal such as aluminium, titanium and etheric acid or diones and bisphenol S.As hot cation curing agent (C), such as trade(brand)name " PP-33 ", " CP-66 ", " CP-77 " (above by (strain) ADEKA system) can also be used; Trade(brand)name " FC-509 " (3M system); Trade(brand)name " UVE1014 " (G.E. system); Trade(brand)name " Sun Aid SI-60L ", " Sun Aid SI-80L ", " Sun Aid SI-100L ", " Sun Aid SI-110L ", " Sun Aid SI-150L " (being made by three new chemical industry (strain) above); The commercially available products such as trade(brand)name " CG-24-61 " (BASF system).
Wherein, as hot cation curing agent (C), preferably use the solidifying agent that the curing initiation temperature of solidification compound of the present invention described later can be controlled in 60 ~ 150 DEG C (being more preferably 80 ~ 120 DEG C).
It should be noted that, in solidification compound of the present invention, hot cation curing agent (C) can be used alone a kind, also two or more can be combinationally used.
The content (use level) of the hot cation curing agent (C) in solidification compound of the present invention is not particularly limited, but is preferably 0.001 ~ 10 weight part relative to total amount 100 weight part of the cation-curable compound comprised in solidification compound, is more preferably 0.01 ~ 5 weight part, more preferably 0.1 ~ 3 weight part.If content is lower than 0.001 weight part, then particularly in the situation etc. that will form thicker cured article, sometimes easily there is solidification bad.On the other hand, if content is more than 10 weight parts, then the physical property such as the thermotolerance of cured article may be caused to reduce or exist in cost unfavorable.
[light cation curing agent (D)]
(such as, replace hot cation curing agent (C) and comprise) light cation curing agent (D) (hereinafter also referred to " composition (D) ") can also be comprised further in solidification compound of the present invention.Light cation curing agent (D) has the cation-curable compound being caused by light (illumination) or comprise in promotion solidification compound (to have the compound of cation-curable functional group; Such as, there is in alicyclic ring epoxy compound (A), cationically polymerizable compound (B), molecule the releasing agent etc. of more than 1 cation-curable functional group) the compound of effect of polyreaction (curing reaction).As light cation curing agent (D), known or the usual compound with above-mentioned effect can be used, be not particularly limited, can enumerate such as: positively charged ion kind can be produced by illumination, and cause the light cationic polymerization initiators etc. of the polymerization (solidification) of solidified nature compound thus.
As the cationic catalyst being produced positively charged ion kind by illumination (particularly uviolizing), can enumerate such as: hexafluoro antimonate, five fluorine hydroxyl stibnates, hexafluorophosphate, hexafluoro arsenate etc.As above-mentioned cationic catalyst, also can preferably use such as: trade(brand)name " UVACURE1590 " (DAICEL-CYTEC (strain) system); Trade(brand)name " CD-1010 ", " CD-1011 ", " CD-1012 " (above by Sartomer Americas system); Trade(brand)name " IRGACURE 264 " (BASF system); Trade(brand)name " CIT-1682 " (Japanese Cao Da (strain) system); The commercially available products such as trade(brand)name " CPI-101A " (SAN-APRO (strain) system).
It should be noted that, in solidification compound of the present invention, light cation curing agent (D) can be used alone a kind, also two or more can be combinationally used.
The content (use level) of the light cation curing agent (D) in solidification compound of the present invention is not particularly limited, but is preferably 0.001 ~ 10 weight part relative to total amount 100 weight part of the cation-curable compound comprised in solidification compound, is more preferably 0.01 ~ 5 weight part, more preferably 0.1 ~ 3 weight part.If content is lower than 0.001 weight part, then particularly in the situation etc. that will form thicker cured article, sometimes easily there is solidification bad.On the other hand, if content is more than 10 weight parts, then the physical property such as the thermotolerance of cured article may be caused to reduce or exist in cost unfavorable.
[antioxidant]
Antioxidant can also be comprised further in solidification compound of the present invention.As above-mentioned antioxidant, known or the usual compound that can use as antioxidant can be used, be not particularly limited, can enumerate such as: phenol system antioxidant (phenol system compound), phosphorous antioxidant (phosphorus series compound), sulphur system antioxidant (chalcogenide compound) etc.
As above-mentioned phenol system antioxidant, can enumerate such as: the unitary phenols such as 2,6 ditertiary butyl p cresol, butylated hydroxyanisol, 2,6-di-t-butyl p-ethyl phenols, β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid stearyl ester; 2,2'-methylene-bis (4-methyl-6-tert-butylphenol), 2,2'-methylene-bis(4-ethyl-6-t-butyl phenol), 4,4'-thiobis (3 methy 6 tert butyl phenol), 4,4'-fourth forks two (3 methy 6 tert butyl phenol), 3,9-two [1,1-dimethyl-2-{ β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy } ethyl] 2, the bisphenols such as 4,8,10-tetra-oxaspiro [5.5] hendecane; 1,1,3-tri-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, 1,3,5-trimethylammonium-2,4,6-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) benzene, four [methylene radical-3-(3', 5'-di-t-butyl-4'-hydroxy phenyl) propionic ester] methane, two [3,3'-two (4'-hydroxyl-3'-tert-butyl-phenyl) butyric acid] glycol ester, 1,3,5-tri-(3', 5'-di-t-butyl-4'-hydroxybenzyl)-guanamine, 4,6-(1H, 3H, 5H) polymer such as triketone, tocopherol phenols etc.
As above-mentioned phosphorous antioxidant, can enumerate such as: triphenyl phosphite, diphenylisodecyl ester, phenyl two isodecyl ester, tricresyl phosphite (nonyl phenyl) ester, diiso decyl pentaerythritol phosphite, tricresyl phosphite (2, 4-di-tert-butyl-phenyl) ester, two (octadecyl) phosphorous acid ester of ring neopentane four base, ring neopentane four base two (2, 4-di-tert-butyl-phenyl) phosphorous acid ester, ring neopentane four base two (2, 4-di-t-butyl-4-aminomethyl phenyl) phosphorous acid ester, the phosphorous acid esters such as two [the 2-tertiary butyl-6-methyl-4-{2-(octadecane oxygen base carbonyl) ethyl } phenyl] phosphorous acid hydrogen ester, the oxa-phospho hetero phenanthrenes such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(3,5-di-tert-butyl-4-hydroxyl benzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide are oxide-based.
As above-mentioned sulphur system antioxidant, can enumerate such as: 3,3 '-Tyox B, 3,3 '-thio-2 acid two myristin, 3,3 '-distearylthiodi-propionate etc.
Wherein, as antioxidant, preferred phenol system antioxidant.It should be noted that, in solidification compound of the present invention, antioxidant can be used alone a kind, also two or more can be combinationally used.
The content (use level) of the antioxidant in solidification compound of the present invention is not particularly limited, but is preferably 0.001 ~ 15 weight part relative to total amount 100 weight part of the cation-curable compound comprised in solidification compound, is more preferably 0.01 ~ 10 weight part, more preferably 0.1 ~ 5 weight part.If its content is lower than 0.001 weight part, then different according to purposes, cause the suppression of the deteriorations such as oxidation insufficient sometimes.On the other hand, if content is more than 15 weight parts, then the physical property such as the thermotolerance of cured article may be caused to reduce or exist in cost unfavorable.
[releasing agent]
Releasing agent can also be comprised further in solidification compound of the present invention.As described releasing agent, known or the usual compound that can use as releasing agent can be used, be not particularly limited, can enumerate such as: (gathering) oxyalkylene alkyl phosphonic acid compound, fluorine cpd (fluorine system releasing agent), silicon-type compound, the compound with chain alkyl, polyolefin-wax, amide waxe, polytetrafluorethylepowder powder etc.Wherein, the viewpoint always can not destroying the transparency is set out, and has the releasing agent of more than 1 cation-curable functional group, more preferably have the fluorine cpd (fluorine system releasing agent) of more than 1 cation-curable functional group in molecule in preferred molecule.
As the cation-curable functional group that the fluorine cpd having more than 1 cation-curable functional group in above-mentioned molecule have, can enumerate: the cyclic ether group such as epoxy group(ing), oxetanylmethoxy, tetrahydrofuran base, oxazolinyl; The group containing vinyl such as vinyl ether group, styryl; At least comprise the group etc. of these groups.Wherein, as above-mentioned cation-curable functional group, preferred cyclic ether group, is more preferably epoxy group(ing).It should be noted that, the number of the cation-curable functional group that the fluorine cpd in above-mentioned molecule with more than 1 cation-curable functional group have is more than 1 (such as, 1 ~ 4), is not particularly limited.In addition, when there is multiple cation-curable functional group, only can have a kind of cation-curable functional group, also can have two or more cation-curable functional group.
As the fluorine cpd in above-mentioned molecule with more than 1 cation-curable functional group, specifically can enumerate the fluorine such as with epoxy group(ing) and replace hydrocarbon (fluorine containing epoxy group(ing) replaces hydrocarbon) etc., more specifically, the compound (there is the monofunctional epoxy compound of fluoro-alkyl) etc. such as shown in following formula (i) can be enumerated.
[chemical formula 7]
R in above-mentioned formula (i) represents the integer of 1 ~ 15.In addition, s represents the integer of 1 ~ 5.Y represents hydrogen atom, fluorine atom or fluoro-alkyl.As above-mentioned fluoro-alkyl, can enumerate such as: the alkyl [such as, trifluoromethyl, perfluoroisopropyl etc.] etc. of the carbonatoms 1 ~ 20 (being preferably 1 ~ 10) that part or all of hydrogen atom is replaced by fluorine atoms.It should be noted that, in formula (i)-(CH 2) r-can be the group that part hydrogen atom is optionally substituted by a hydroxyl group, in addition, also can be the group that midway comprises ehter bond.As the compound shown in formula (i), more specifically, 3-perfluoro hexyl-1,2 epoxy prapane etc. can be enumerated.
As above-mentioned releasing agent, also can use such as: the commercially available product such as trade(brand)name " E-1430 ", " E-1630 ", " E-1830 ", " E-2030 ", " E-3430 ", " E-3630 ", " E-3830 ", " E-4030 ", " E-5244 ", " E-5444 ", " E-5644 ", " E-5844 " (fluorine system releasing agent, above by DAIKIN INDUSTRIES (strain) system).It should be noted that, in solidification compound of the present invention, releasing agent can be used alone a kind, also two or more can be combinationally used.
The content (use level) of the releasing agent in solidification compound of the present invention is not particularly limited, but is preferably 0.01 ~ 10 weight part relative to total amount 100 weight part of alicyclic ring epoxy compound (A) and cationically polymerizable compound (B), is more preferably 0.1 ~ 5 weight part.If the content of releasing agent is lower than 0.01 weight part, then may cause cannot from mold releasability when shaping.On the other hand, if the content of releasing agent is more than 10 weight parts, then the transparency of solidification compound may be destroyed.
[additive]
In solidification compound of the present invention except mentioned component, other compositions such as additive can also be comprised as required.As above-mentioned additive, known or usual additive can be enumerated, be not particularly limited, can enumerate such as: the defoamer, silane coupling agent, weighting agent, softening agent, flow agent, static inhibitor, fire retardant, tinting material, UV light absorber, ionic adsorption body, pigment etc. of metal oxide particle, rubber particles, silicon-type or fluorine system.The content (use level) of above-mentioned various additive is not particularly limited, but is preferably less than 5 % by weight (such as, 0 ~ 5 % by weight) relative to solidification compound (100 % by weight).In addition, also solvent can be comprised in solidification compound of the present invention, but if cured article too much may be caused to produce bubble, therefore preferably it is less than 10 % by weight (such as relative to solidification compound (100 % by weight), 0 ~ 10 % by weight), less than 1 % by weight is more preferably.
Relative to the total amount (100 % by weight) of solidified nature compound (have the compound of radically curing functional group, have the compound of cation-curable functional group) contained in solidification compound of the present invention, cationically polymerizable compound (has the compound of cation-curable functional group; Such as, there is in alicyclic ring epoxy compound (A), cationically polymerizable compound (B), molecule the releasing agent etc. of more than 1 cation-curable functional group) the ratio of total amount be not particularly limited, be preferably more than 80 % by weight (such as, 80 ~ 100 % by weight), be more preferably more than 90 % by weight.If aforementioned proportion is lower than 80 % by weight, then cure shrinkage when solidifying may be caused to become excessive or be difficult to guarantee the transparency of cured article.
Though be not particularly limited, but solidification compound of the present invention such as can be prepared as follows: coordinate the alicyclic ring epoxy compound (A) of specified rate, cationically polymerizable compound (B) and hot cation curing agent (C) and the antioxidant, releasing agent, various additives etc. that add as required, as required, stirring/mixing is carried out while removing bubble under vacuo.Temperature when carrying out stirring/mixing is preferably such as about 10 ~ 60 DEG C.It should be noted that, stirring/mixing can use known or usual device, such as rotation-revolution type mixing tank, singe screw or multiple screw extruder, planetary-type mixer, kneader, dissolver etc.
The curing initiation temperature (particularly when comprising hot cation curing agent (C)) of solidification compound of the present invention is not particularly limited, and is preferably 60 ~ 150 DEG C, is more preferably 80 ~ 120 DEG C.If the curing initiation temperature of solidification compound of the present invention is lower than 60 DEG C, then storage stability may be caused to be deteriorated, be not suitable in room temperature environment (25 DEG C) and use.It should be noted that, described " curing initiation temperature of solidification compound " refers to, the ascending temperature (starting the temperature risen relative to baseline) when using DSC (means of differential scanning calorimetry determinator) thermalmeasurement under the following conditions to solidification compound of the present invention.
(condition determination of DSC)
Mensurated gas composition atmosphere: nitrogen (flow: 50mL/ minute)
Measure temperature: 30 ~ 300 DEG C
Elevated Temperature Conditions: 20 DEG C/min
It should be noted that, the curing initiation temperature of solidification compound of the present invention can according to the composition of such as solidification compound (such as, the kind of hot cation curing agent (C); Particularly, the combination of alicyclic ring epoxy compound (A) and cationically polymerizable compound (B) and hot cation curing agent (C)) control.
By making solidification compound of the present invention solidify, cured article (also referred to as " cured article of the present invention ") can be obtained.Cured article of the present invention is not particularly limited inside transmitance (the inside transmitance of the light of wavelength 400nm) [the converting with thickness 0.5mm] of 400nm, be preferably more than 70% (such as, 70 ~ 100%), be more preferably more than 75%, more preferably more than 80%, be particularly preferably more than 85%.
Cured article of the present invention is not particularly limited at specific refractory power (specific refractory power of the light of wavelength 589nm) (25 DEG C) of 589nm, is preferably more than 1.58, is more preferably more than 1.60.
The Abbe number of cured article of the present invention is not particularly limited, and is preferably less than 35, is more preferably less than 30, more preferably less than 27.
Second-order transition temperature (glass transition point) (Tg) of cured article of the present invention is not particularly limited, and is preferably more than 100 DEG C (such as, 100 ~ 200 DEG C), is more preferably more than 140 DEG C.If second-order transition temperature is lower than 100 DEG C, then different according to use-pattern, its thermotolerance may be caused not enough.The second-order transition temperature of cured article such as measures by various thermal analyses [DSC (differential scanning calorimeter), TMA (thermo-mechanical analysis device) etc.], Measurement of Dynamic Viscoelasticity etc., more specifically, the measuring method by recording in embodiment measures.
The coefficient of linear expansion of cured article of the present invention below second-order transition temperature (α 1) is not particularly limited, and is preferably 40 ~ 100ppm/K, is more preferably 40 ~ 90ppm/K.In addition, the coefficient of linear expansion of cured article of the present invention more than second-order transition temperature (α 2) is not particularly limited, and is preferably 90 ~ 150ppm/K, is more preferably 90 ~ 130ppm/K.It should be noted that, coefficient of linear expansion α 1, the α 2 of cured article measure by such as TMA etc., more specifically, measure by the measuring method recorded in embodiment.
The manufacture method > of < wafer-level lens
By solidification compound of the present invention solidification is shaping, wafer-level lens (also referred to as " wafer-level lens of the present invention ") can be obtained.That is, wafer-level lens of the present invention is the wafer-level lens formed by the cured article of solidification compound of the present invention.Therefore, wafer-level lens of the present invention preferably has the characteristic (inner transmitance, specific refractory power, Abbe number, second-order transition temperature, coefficient of linear expansion (α 1, α 2)) same with above-mentioned cured article.Specifically, wafer-level lens of the present invention obtains by the method (also referred to as " manufacture method of wafer-level lens of the present invention ") that utilizes casting moulding or injection molding method and process solidification compound of the present invention.
It should be noted that, the material for the shaping mould (wafer-level lens mold for forming) for wafer-level lens is not particularly limited, and can be any material in such as metal, glass, plastics etc.
[casting moulding]
As above-mentioned casting moulding, can enumerate such as: the method comprising following operation 1a ~ operation 3a.
Operation 1a: prepare the operation with the wafer-level lens mold for forming of more than 1 lens die
Operation 2a: after operation 1a, makes the operation that solidification compound of the present invention contacts with above-mentioned wafer-level lens mold for forming
Operation 3a: after operation 2a, operation solidification compound of the present invention being solidified by heating and/or illumination
The solidification of solidification compound of the present invention is undertaken (operation 3a) by heating and/or illumination (in heating and illumination any one or both).When carrying out heat treated, as its temperature, according to suitably adjustment such as the kinds of the composition for reacting, catalyzer, can be not particularly limited, being preferably 100 ~ 200 DEG C, being more preferably about 120 ~ 160 DEG C.When carrying out illumination, as its light source, can use such as: mercuryvapour lamp, xenon lamp, carbon arc lamp, metal halid lamp, sunlight, electron beam source, LASER Light Source etc.In addition, can also after illumination, at the temperature of such as about 50 ~ 180 DEG C, implement heat treated and make curing reaction carry out further.
Above-mentioned casting moulding also can comprise following operation 4a further after operation 3a.
Operation 4a: the operation of the solidification compound of the present invention after solidification being carried out to anneal
Above-mentioned anneal is not particularly limited, by such as 100 ~ 200 DEG C heating temperatures 30 minutes ~ 1 hours and carry out.It should be noted that, anneal can be implemented, also can not remove mould and implement after removing wafer-level lens mold for forming.
Above-mentioned casting moulding particularly state afterwards while method of forming when implementing, usually obtain the cured article (wafer-level lens sheet) of the morphogenetic sheet of shape connected with one or more wafer-level lens by above-mentioned operation 3a or operation 4a.When above-mentioned wafer-level lens sheet has multiple wafer-level lens, these wafer-level lens can arrange in an orderly manner (piling up (permutation)), also can randomly arrange.Removing unnecessary part by cutting above-mentioned wafer-level lens sheet, wafer-level lens of the present invention can be obtained.
That is, above-mentioned casting moulding particularly state afterwards while the method for forming implement when, above-mentioned casting moulding can comprise following operation 5a further after operation 3a or operation 4a.
Operation 5a: the operation that the solidification compound of the present invention (being generally wafer-level lens sheet) after solidification is cut
The cutting of the solidification compound of the present invention after solidification can utilize the enforcements such as known or usual processing means.
More specifically, above-mentioned casting moulding comprises: the method for forming while comprising following operation 1-1 ~ operation 1-3, comprise the monolithic method of forming etc. of following operation 2-1 and operation 2-2.
(simultaneously the method for forming)
Operation 1-1: solidification compound of the present invention is injected the wafer-level lens mold for forming with the shape that multiple lens die arranges in a certain direction, and carry out heating and/or illumination with the operation making it solidify
Operation 1-2: after operation 1-1, removes wafer-level lens mold for forming and carries out anneal, thus obtains the operation of the cured article (wafer-level lens sheet) with the shape be combined into by multiple wafer-level lens
Operation 1-3: after operation 1-2, cutting gained cured article and obtain the operation of wafer-level lens
(the monolithic method of forming)
Operation 2-1: solidification compound of the present invention is injected the wafer-level lens mold for forming with 1 lens die, and carry out heating and/or illumination with the operation making it solidify
Operation 2-2: after operation 2-1, removes wafer-level lens shape die for forming and carries out anneal, thus obtaining the operation of wafer-level lens
[injection molding method]
As above-mentioned injection molding method, can enumerate such as: the method comprising following operation 1b ~ operation 3b.
Operation 1b: prepare the operation with the wafer-level lens mold for forming of more than 1 lens die
Operation 2b: after operation 1b, is injected to the operation of above-mentioned wafer-level lens mold for forming by solidification compound of the present invention
Operation 3b: after operation 2b, operation solidification compound of the present invention being solidified by heating and/or illumination
The solidification of the solidification compound of the present invention in above-mentioned injection molding method is undertaken by heating and/or illumination, more specifically, can implement in the same manner as the solidification in above-mentioned casting moulding.
Above-mentioned injection molding method also can comprise following operation 4b further after operation 3b.
Operation 4b: the operation of the solidification compound of the present invention after solidification being carried out to anneal
Above-mentioned anneal is not particularly limited, by such as 100 ~ 200 DEG C heating temperatures 30 minutes ~ 1 hours and carry out.It should be noted that, anneal can be implemented after removing wafer-level lens mold for forming, also can not remove mould and implement.
Above-mentioned injection molding method also can comprise the operation etc. of removing flash further after operation 3b or operation 4b.
While in above-mentioned casting moulding in the method for forming, solidification compound of the present invention is low viscosity and mobility is excellent, and this is being preferred in the fillibility excellence of wafer-level lens mold for forming.Viscosity during for the solidification compound of the present invention used in the method for forming above-mentioned while 25 DEG C is not particularly limited, and is preferably below 5000mPas, is more preferably below 2500mPas.By the viscosity of solidification compound of the present invention is adjusted to above-mentioned scope, mobility improves, not easily residual bubble, can carry out the filling to wafer-level lens mold for forming while suppressing injection to press liter.That is, coating and fillibility can be improved, can in the whole operations for forming of solidification compound of the present invention, workability be improved.
The cured article of solidification compound of the present invention also has excellent thermotolerance in the hot environment of about 100 ~ 200 DEG C, and shape-holding property is excellent.Thus, even if implement anneal after taking out from wafer-level lens mold for forming, the wafer-level lens with excellent lens centre positional precision can also effectively be manufactured.As lens centre positional precision, the deviation of preferred lens central position is less than such as ± 2 μm degree, is more preferably ± less than 1 μm degree.For the wafer-level lens utilizing the manufacture method of wafer-level lens of the present invention to obtain, by multi-disc lamination is bonding, the cemented lens (stacked wafers level lens) with high pixel count, optical characteristics excellence can be formed.
In addition, as mentioned above, even if the cured article of solidification compound of the present invention also has excellent shape-holding property in hot environment, even if therefore implement anneal, lenticular spacing (レ Application ズ ピ ッ チ) also can not produce deviation, above-mentioned while the method for forming operation 1-3 in, by by superimposed for multi-disc cured article and cut for the position of benchmark determination line of cut with the cured article of topmost, it can be made to be separated when not causing multiple wafer-level lens breakage, thus the reduction of cost and the efficient activity of operation can be realized.
Wafer-level lens of the present invention also can use as the member of formation of the multilayer body of more wafers level lens (also referred to as " stacked wafers level lens ").That is, stacked wafers level lens of the present invention at least have the stacked wafers level lens of wafer-level lens of the present invention as the wafer-level lens of these stacked wafers level lens of formation.It should be noted that, the wafer-level lens forming stacked wafers level lens of the present invention can be all wafer-level lens of the present invention, also can be wafer-level lens of the present invention and other wafer-level lens.The sheet number forming the wafer-level lens of stacked wafers level lens of the present invention is not particularly limited, and can be such as 2 ~ 5 (particularly 2 ~ 3).
Stacked wafers level lens of the present invention can utilize known or customary way manufacture, be not particularly limited, such as manufacture by will the more wafers level lens stack of wafer-level lens of the present invention be comprised, also can by by comprise utilize above-mentioned while the more wafers level lens lamination of wafer-level lens sheet that obtains of the method for forming and after obtaining wafer-level lens sheet laminate (multilayer body of wafer-level lens sheet), this wafer-level lens sheet is cut and manufactures.It should be noted that, in stacked wafers level lens of the present invention (or above-mentioned wafer-level lens sheet laminate), between each wafer-level lens, (or between each wafer-level lens sheet) can utilize known or usual adhering method to engage, and also can not engage.
More specifically, the method for stacked wafers level lens of the present invention such as by least comprising following operation 1c ~ operation 5c manufactures.
Operation 1c: prepare the operation with the wafer-level lens mold for forming of more than 1 lens die
Operation 2c: after operation 1c, makes the operation that solidification compound of the present invention contacts with above-mentioned wafer-level lens mold for forming
Operation 3c: after operation 2c, makes solidification compound of the present invention solidify by heating and/or illumination and obtains the operation of wafer-level lens sheet
Operation 4c: after operation 3c, will comprise the more wafers level lens lamination of above-mentioned wafer-level lens sheet and obtain the operation of wafer-level lens sheet laminate
Operation 5c: after operation 4c, cuts the operation of above-mentioned wafer-level lens sheet laminate
The manufacture method of above-mentioned stacked wafers level lens also can comprise following operation further between operation 3c and operation 4c.
Operation 6c: the operation of above-mentioned wafer-level lens sheet being carried out to anneal
Wafer-level lens of the present invention or stacked wafers level lens have excellent thermotolerance and optical characteristics, also can give play to excellent shape-holding property even if be exposed in hot environment, and can keep excellent optical characteristics.Thus, can preferably as the use such as pinch picture camera lens, glasses lens, beam condenser lens, light diffusion lens of the camera (vehicle-mounted camera, digital camera, PC camera, mobile phone camera, monitoring camera are first-class) in such as various Optical devices.The above-mentioned Optical devices being equipped with wafer-level lens of the present invention or stacked wafers level lens have high-quality.
Further, when wafer-level lens of the present invention or stacked wafers level lens are installed on circuit substrate, Reflow Soldering can be utilized to carry out soldering installation.Thus, the solder reflow soldering process identical with the surface mounting of other electronic unit can be utilized to be equipped with the photomoduel of wafer-level lens of the present invention or stacked wafers level lens, directly effectively be installed on PCB (the PrintedCircuit Board of mobile phone etc., printed circuit board (PCB)) on substrate, the manufacture of very effective Optical devices can be realized.
Embodiment
Below, more specific detail is carried out to the present invention, but the present invention is not by the restriction of these embodiments in conjunction with the embodiments.
Embodiment 1 ~ 3, comparative example 1 ~ 3
For each composition recorded in table 1, utilize rotation-revolution type mixing tank to carry out stirring/mixing under normal temperature (25 DEG C), resulting in solidification compound (wafer-level lens solidification compound).It should be noted that, the unit of the use level recorded in table 1 is weight part.
Be described for the abbreviation in table 1.
[solidified nature compound]
PG-100: fluorenes system epoxy compounds (Osaka Gas Chemicals (strain) system, trade(brand)name " PG-100 ")
EG-200: fluorenes system epoxy compounds (Osaka Gas Chemicals (strain) system, trade(brand)name " EG-200 ")
827: bisphenol A type epoxy compound (Mitsubishi Chemical's (strain) system, trade(brand)name " jER827 ")
C1:3,4-epoxycyclohexyl-methyl (3,4-epoxy) cyclohexane carboxylate
C2:3,4,3', 4'-diepoxy connection hexanaphthene
EA-F5503: fluorenes system acrylic compound (Osaka Gas Chemicals (strain) system, trade(brand)name " OGSOL EA-F5503 ")
IRR-214K: alicyclic ring acrylic compound (DAICEL-CYTEC (strain) system, trade(brand)name " IRR-214K ")
[hot cationic polymerization initiators]
SI-100L: aromatic series sulfonium salt (three new chemical industry (strain) systems, trade(brand)name " Sun Aid SI-100L)
[hot radical polymerization starter]
PERHEXA C:1,1-bis-(tert-butyl hydroperoxide) hexanaphthene (day oil (strain) system, trade(brand)name " PERHEXA C ", 1 minute half life temperature: 153.8 DEG C)
[antioxidant]
IRG1010: tetramethylolmethane four [3-(3,5-di-t-butyl-4-hydroxyl phenol) propionic ester] (BASF AG's system, trade(brand)name " IRGANOX1010 ")
[releasing agent]
E-1630:3-perfluoro hexyl-1,2 epoxy prapane (DAIKIN INDUSTRIES (strain) system, trade(brand)name " E-1630 ")
[preparation of cured article]
Cured article has been prepared according to following program.
For the solidification compound obtained in embodiment and comparative example, use marking forming machine (bright prosperous machine work (strain) system " NANOIMPRINTER NM-0501 ") after 25 DEG C are carried out being coated with (casting), adjustment last item position makes thickness be 0.5mm, 180 DEG C are warming up to heat-up rate 20 DEG C/min, then keep 5 minutes in 180 DEG C, the demoulding after being cooled to 80 DEG C.By gained cured article (it can be used as " one-step solidification thing ") after being heated in advance heat 30 minutes in the baking oven of 180 DEG C, obtain cured article (it can be used as " regelate thing ").
It should be noted that, in the making of release property and lens position offset sample for evaluation, employ the mould that mould central authorities have 7 aspheric lens shape, in the making of other sample for evaluation, employ the mould of the plane without lens shape.
For the solidification compound obtained in embodiment and comparative example and cured article thereof, following various mensuration are carried out.
[viscosity]
For the solidification compound obtained in embodiment and comparative example, the viscosity (Pas) when using rheometer (Paar Physica Inc. " PHYSICA UDS200 ") to determine temperature 25 DEG C, rotating speed 20/ second.
[curing degree]
For the solidification compound obtained in embodiment and comparative example, curing exotherm amount under using differential scanning calorimeter (TAInstruments Inc. " Q2000 ") to determine following temperature condition in nitrogen atmosphere, and it can be used as the curing exotherm amount of solidification compound.Then, for one-step solidification thing obtained above, curing exotherm amount under the central part of one-step solidification thing and periphery (utilizing cutter to cut respectively and to obtain corresponding site) determine uniform temp condition, using the curing exotherm amount of its mean value as one-step solidification thing.Then, following formula is utilized to calculate curing degree.
Temperature condition: after 50 DEG C keep 3 minutes, be warming up to 250 DEG C with heat-up rate 20 DEG C/min, and keep 3 minutes in 250 DEG C
Curing degree (%)={ 1-(the curing exotherm amount of one-step solidification thing)/(the curing exotherm amount of solidification compound) } × 100
[curing initiation temperature]
For the solidification compound obtained in embodiment and comparative example, the curing exotherm amount (reaction heat) when heating under using differential scanning calorimeter (TAInstruments Inc. " Q2000 ") to observe the condition when above-mentioned curing initiation temperature measures in nitrogen atmosphere.In the curve of gained curing exotherm amount, the ascending temperature (starting the temperature risen relative to baseline) of curing exotherm is measured as curing initiation temperature.
[inner transmitance]
Following formula is utilized to calculate the inside transmitance of regelate thing obtained above (thickness: 0.5mm).It should be noted that, use spectrophotometer (Hitachi High-Technologies (strain) makes " U-3900 ") to measure at the transmittance (transmittance of regelate thing) of 400nm.N in following formula is the specific refractory power at 400nm, employs the value obtained based on detecting refractive index method described later.
Inner transmitance (400nm) (%)=at transmittance (%)/(1-r) of 400nm 2
r＝{(n-1)/(n+1)} 2
[specific refractory power]
For regelate thing obtained above, utilize based on JIS K7142 method, use refractive index measuring instrument (Metricon Inc. " Model 2010 ") determine 25 DEG C of specific refractory poweres at 589nm.
[Abbe number]
The Abbe number of the regelate thing obtained above that utilized following formula to calculate.
Abbe number=(nd-1)/(nF-nC)
(in formula, nd represents and to represent at the specific refractory power of 589.2nm, nF and represent specific refractory power at 656.3nm at the specific refractory power of 486.1nm, nC.It should be noted that, as the value of specific refractory power, employ the value of the specific refractory power utilizing aforesaid detecting refractive index method to obtain under above-mentioned each wavelength.)
[volumetric shrinkage]
For the volumetric shrinkage (%) of regelate thing obtained above, after proportion (G1) at using electronic hydrometer ((strain) Shimadzu Seisakusho Ltd. system " SD-200L ") to measure 25 DEG C of solidification compound and the proportion (G2) of regelate thing, following formula is utilized to calculate.
Volumetric shrinkage (%)={ (G2-G1)/G1 × 100}
[second-order transition temperature]
For the second-order transition temperature (glass transition point) (Tg, DEG C) of regelate thing obtained above, using TMA determinator (SII NanoTechnology Inc. " TMA/SS100 "), utilize based on the method for JIS K7197, in nitrogen atmosphere, determine the thermal expansivity that measures in temperature range 30 ~ 250 DEG C with heat-up rate 5 DEG C/min after, for curve cutting-up line before glass transition point and afterwards, obtain its second-order transition temperature by the intersection point of these tangent lines.
[coefficient of linear expansion]
For the coefficient of linear expansion of regelate thing obtained above, use TMA determinator (SIINanoTechnology Inc. " TMA/SS100 "), utilize based on the method for JIS K7197, in nitrogen atmosphere, determine the thermal expansivity measured in temperature range 30 ~ 250 DEG C with heat-up rate 5 DEG C/min, then the gradient of the straight line of the low temperature side for glass transition point is set to α 1, the gradient of the straight line of the high temperature side for glass transition point is set to α 2, they to be obtained respectively and as coefficient of linear expansion.
[thermal test (the yellowing resistance evaluation under Reflow Soldering condition)]
For regelate thing obtained above, use desk-top reflow soldering (Shinapex Inc.), based on the temperature distribution recorded in JEDEC standard, carry out the thermal test that 3 top temperatures are the Reflow Soldering condition of 270 DEG C continuously, then utilize above-mentioned measuring method to determine the transmittance at 400nm and the specific refractory power at 400nm, obtain the inside transmitance after thermal test.By the inside transmitance before and after thermal test, utilize following formula to calculate xanthochromia rate (%), have rated thermotolerance.It should be noted that, xanthochromia rate is less, then the thermotolerance of cured article is better.
Xanthochromia rate (%)={ (the inside transmitance before thermal test)-(the inside transmitance after thermal test) }/(the inside transmitance before thermal test) × 100
[release property]
Utilize following standard evaluation in the preparation of above-mentioned cured article (wafer-level lens), by cured article (one-step solidification thing) from release property during mold releasability.
Zero (release property is fabulous): when carrying out 5 times continuously and being shaping, the demouldings such as cured article (forming composition) breaks do not occur bad
△ (release property is good): when carrying out 5 times continuously and being shaping, there occurs the demoulding such as to break of 1 cured article bad
× (release property is bad): when carrying out 5 times continuously and being shaping, the cured article that there occurs more than the 2 times demoulding such as to break is bad
[lens position offset]
For lens 7 central positions in the upper formation of gained cured article (forming composition), picture size survey meter (trade(brand)name " IM-6020 ", (strain) KEYENCE system) is utilized to measure respectively, determine the Centre position deviation of the lens relative to die design value, and obtain its mean value.
Acquired results is as shown in table 2.
Compared with all situations employing the alicyclic ring epoxy compound with ester group as the comparative example 1, the quick solidification (curing degree is high) of the solidification compound obtained in embodiment and cured article thereof and excellent heat resistance, can confirm that it is excellent as lens material.In addition, such as comparative example 2 such not containing having in the hot Cationic curing systems of compound of alicyclic epoxy group, completely unconfirmed to solidification, thus cannot carry out the evaluation as lens material.In addition, compared with the hot radical curing system that such as comparative example 3 is such, the solidification compound obtained in embodiment and cured article thereof have not only confirmed the tendency that volumetric shrinkage is little, shape stability is excellent, and also do not have problems in release property, position skew, therefore can confirm it no matter in shaping workability or aspect of performance, be all excellent as lens material.
Industrial applicibility
By wafer-level lens solidification compound of the present invention solidification is shaping, wafer-level lens of the present invention can be obtained.Wafer-level lens of the present invention can preferably as the use such as pinch picture camera lens, glasses lens, beam condenser lens, light diffusion lens of the camera (vehicle-mounted camera, digital camera, PC camera, mobile phone camera, monitoring camera are first-class) in such as various Optical devices.

Claims (25)

1. a wafer-level lens solidification compound, it comprises: do not have the alicyclic ring epoxy compound (A) of ester group and have the cationically polymerizable compound (B) of aromatic ring,
Wherein, the alicyclic ring epoxy compound (A) without ester group has the compound that at least 2 have passed through epoxidised cyclic olefin base.
2. wafer-level lens solidification compound according to claim 1, wherein, have passed through the group of cyclic olefin base through epoxidation that epoxidised cyclic olefin base is carbonatoms 5 ~ 12.
3. wafer-level lens solidification compound according to claim 1 and 2, wherein, the alicyclic ring epoxy compound (A) without ester group is the compound with following structure, and described structure has been through in epoxidised cyclic olefin base at least 2 structures through singly-bound or divalent alkyl bonding.
4. the wafer-level lens solidification compound according to any one of claims 1 to 3, wherein, the alicyclic ring epoxy compound (A) without ester group is the compound shown in following formula (a2),
In formula (a2), X represents singly-bound or divalent alkyl.
5. the wafer-level lens solidification compound according to any one of Claims 1 to 4, wherein, relative to the total amount (100 % by weight) of solidification compound, the content without the alicyclic ring epoxy compound (A) of ester group is 10 ~ 60 % by weight.
6. the wafer-level lens solidification compound according to any one of Claims 1 to 5, wherein, the cationically polymerizable compound (B) with aromatic ring has at least a kind of cation-curable functional group be selected from alicyclic epoxy group, glycidyl and oxetanylmethoxy.
7. the wafer-level lens solidification compound according to any one of claim 1 ~ 6, wherein, relative to the total amount (100 % by weight) of solidification compound, the content with the cationically polymerizable compound (B) of aromatic ring is 40 ~ 90 % by weight.
8. the wafer-level lens solidification compound according to any one of claim 1 ~ 7, it also comprises hot cation curing agent (C).
9. wafer-level lens solidification compound according to claim 8, its curing initiation temperature is 60 ~ 150 DEG C.
10. the wafer-level lens solidification compound according to any one of claim 1 ~ 9, wherein, makes this solidification compound solidify and the Abbe number of cured article that obtains is less than 35.
11. wafer-level lens solidification compounds according to any one of claim 1 ~ 10, it also comprises the releasing agent with cation-curable functional group.
The manufacture method of 12. 1 kinds of wafer-level lens, it comprises: utilize casting moulding or injection molding method to process the wafer-level lens solidification compound according to any one of claim 1 ~ 11.
The manufacture method of 13. wafer-level lens according to claim 12, wherein, described casting moulding comprises following operation:
Operation 1a: prepare the operation with the wafer-level lens mold for forming of more than 1 lens die;
Operation 2a: make the operation that wafer-level lens solidification compound contacts with described wafer-level lens mold for forming;
Operation 3a: the operation described wafer-level lens solidification compound being solidified by heating and/or illumination.
The manufacture method of 14. wafer-level lens according to claim 13, wherein, described casting moulding also comprises following operation:
Operation 4a: the operation of the wafer-level lens solidification compound after solidification being carried out to anneal.
The manufacture method of 15. wafer-level lens according to claim 13 or 14, wherein, described casting moulding also comprises following operation:
Operation 5a: the operation that the wafer-level lens solidification compound after solidification is cut.
The manufacture method of 16. wafer-level lens according to claim 12, wherein, described injection molding method comprises following operation:
Operation 1b: prepare the operation with the wafer-level lens mold for forming of more than 1 lens die;
Operation 2b: operation wafer-level lens solidification compound being injected to described wafer-level lens mold for forming;
Operation 3b: the operation described wafer-level lens solidification compound being solidified by heating and/or illumination.
The manufacture method of 17. wafer-level lens according to claim 16, wherein, described injection molding method also comprises following operation:
Operation 4b: the operation of the wafer-level lens solidification compound after solidification being carried out to anneal.
18. 1 kinds of wafer-level lens sheets, it is obtained by the manufacture method of the wafer-level lens described in claim 13 or 14.
19. 1 kinds of wafer-level lens, it is obtained by the manufacture method of the wafer-level lens according to any one of claim 12 ~ 17.
20. 1 kinds of Optical devices, it is equipped with wafer-level lens according to claim 19.
21. 1 kinds of stacked wafers level lens, it is the multilayer body of more wafers level lens, wherein, as forming the wafer-level lens of this multilayer body, at least having and the wafer-level lens solidification compound according to any one of claim 1 ~ 11 being cured and shaping and wafer-level lens that is that obtain.
22. a manufacture method for stacked wafers level lens, it is the method for the stacked wafers level lens described in manufacturing claims 21, and wherein, the method comprises following operation:
Operation 1c: prepare the operation with the wafer-level lens mold for forming of more than 1 lens die;
Operation 2c: make the operation that the wafer-level lens solidification compound according to any one of claim 1 ~ 11 contacts with described wafer-level lens mold for forming;
Operation 3c: by heating and/or illumination, described wafer-level lens solidification compound solidified and obtain the operation of wafer-level lens sheet;
Operation 4c: will the more wafers level lens lamination of described wafer-level lens sheet be comprised and obtain the operation of wafer-level lens sheet laminate;
Operation 5c: the operation of cutting described wafer-level lens sheet laminate.
The manufacture method of 23. stacked wafers level lens according to claim 22, it comprises following operation further between operation 3c and operation 4c:
Operation 6c: the operation of described wafer-level lens sheet being carried out to anneal.
24. 1 kinds of wafer-level lens sheet laminates, the more wafers level lens lamination comprising wafer-level lens sheet according to claim 18 obtains by it.
25. 1 kinds of Optical devices, it is equipped with stacked wafers level lens according to claim 21.
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