WO2009125677A1

WO2009125677A1 - Method for producing wafer lens and wafer lens

Info

Publication number: WO2009125677A1
Application number: PCT/JP2009/056094
Authority: WO
Inventors: 明子原
Original assignee: コニカミノルタオプト株式会社
Priority date: 2008-04-08
Filing date: 2009-03-26
Publication date: 2009-10-15

Abstract

Disclosed is a method for producing a wafer lens (1) comprising a glass substrate (3) and, provided thereon, lens portions (5) made of a first curable resin (5A). When, from a master (10) having plural positive mold surfaces corresponding to the shape of optical surfaces of the lens portions (5), a submaster mold portion (22) having plural negative mold surfaces corresponding to the shape of the optical surfaces is molded with a second curable resin (22A), the submaster mold portion (22) is lined with a submaster substrate (26) to form a submaster (20), and a first curable resin (5A) is filled between the submaster (20) and the glass substrate (3) and cured to form the lens portions (5), an epoxy compound represented by Formula (A) is used as the first curable resin.

Description

Wafer lens manufacturing method and wafer lens

The present invention relates to a wafer lens manufacturing method and a wafer lens.

In the field of manufacturing optical lenses, a technique for obtaining an optical lens having high heat resistance by providing a lens portion (optical member) made of a curable resin on a glass flat plate has been studied (see, for example, Patent Document 1). .

Curing resins can be broadly classified into photo-curing resins and thermosetting resins. Examples of the photocurable resin include an acrylic resin, an allyl resin, an epoxy resin, and the like. If the acrylic resin and the allyl resin are used, they can be cured by radical polymerization. Any epoxy resin can be cured by cationic polymerization. On the other hand, the thermosetting resin can be cured by addition polymerization such as silicone in addition to radical polymerization and cationic polymerization.

Recently, as a method of manufacturing an optical lens to which the above technique is applied, a plurality of lenses are integrated by forming a so-called “wafer lens” in which a plurality of optical members made of a curable resin are provided on a glass flat plate. A method has been developed in which a glass flat plate portion is cut at the same time and the glass flat plate portion is cut after the forming. According to this manufacturing method, since a large number of optical lenses can be mass-produced by a single cutting process, the manufacturing cost of the optical lens can be reduced.
Japanese Patent No. 3926380

For the wafer lens, it is preferable to use a UV curable resin as a constituent material of the optical member because of its high curing speed. As the UV curable resin, a radical polymerization type and a cation polymerization type are mainly known. In the case of a radical polymerization system such as an acrylic resin, since it is affected by the inhibition of curing by oxygen, it is necessary to devise purging with an inert gas such as nitrogen. In addition, since the acrylic resin has a very large shrinkage due to curing (about 10%), it cannot be molded into a desired fine shape, and the surface is uneven.

On the other hand, since epoxy resin has a small shrinkage due to curing (about 2 to 3%), it can be neatly molded even in a fine shape. However, many of the monomers of the epoxy resin (Ames positive) have high skin sensitization, and the current situation is that the environment in which they can be used is restricted at a high rate.

Therefore, a main object of the present invention is to provide a wafer lens using an epoxy resin and a method for manufacturing the same, and a highly safe wafer lens with reduced skin sensitization and a method for manufacturing the same. .

A method for manufacturing a wafer lens according to the present invention includes:
A wafer lens manufacturing method in which an optical member made of a first curable resin is provided on a substrate,
From a master mold having a plurality of positive molding surfaces corresponding to the optical surface shape of the optical member, a sub master molding part having a plurality of negative molding surfaces corresponding to the optical surface shape is formed by the second curable resin. And forming a sub master mold by backing the sub master molding part with a sub master substrate,
When the optical member is molded by filling the first curable resin between the sub-master mold and the substrate and curing the mold,
As the first curable resin, an epoxy compound represented by the following general formula (A) is used.

[In the formula (A), R ₁₀₀ represents a substituent, m0 represents an integer of 0 to 2, and r0 represents an integer of 1 to 3. L ₀ represents an r0 + 1-valent linking group or a single bond having 1 to 15 carbon atoms, which may contain an oxygen atom or a sulfur atom in the main chain. ]
Further, the wafer lens according to the present invention,
It contains an epoxy compound represented by the following general formula (A).

[In the formula (A), R ₁₀₀ represents a substituent, m0 represents an integer of 0 to 2, and r0 represents an integer of 1 to 3. L ₀ represents an r0 + 1-valent linking group or a single bond having 1 to 15 carbon atoms, which may contain an oxygen atom or a sulfur atom in the main chain. ]
Further, the wafer lens according to the present invention is:
It contains an epoxy compound represented by the following general formula (I).

[In the formula (I), R ₁₀₁ represents a substituent, m1 represents an integer of 0 to 2, p1 and q1 each represents 0 or 1, and r1 represents an integer of 1 to 3. L ₁ represents an r1 + 1 valent linking group having 1 to 15 carbon atoms or a single bond which may contain an oxygen atom or a sulfur atom in the main chain. ]
Further, the wafer lens according to the present invention is:
It contains an epoxy compound represented by the following general formula (II).

[In the formula (II), R ₁₀₂ represents a substituent, m2 represents an integer of 0 to 2, p2 and q2 each represents 0 or 1, and r2 represents an integer of 1 to 3. L ₂ represents an r2 + 1 valent linking group or a single bond having 1 to 15 carbon atoms, which may contain an oxygen atom or a sulfur atom in the main chain. ]
Further, the wafer lens according to the present invention is:
It contains at least one epoxy compound represented by the following general formulas (III) to (VI).

[In the formula (III), R ₁₀₃ represents a substituent, m3 represents an integer of 0 to 2, and p3 represents 0 or 1. L ₃ represents a C 1-8 divalent linking group or single bond which may contain an oxygen atom or a sulfur atom in the main chain. ]

[In the formula (IV), R ₁₀₄ represents a substituent, m4 represents an integer of 0 to 2, and p4 represents 0 or 1. L ₄ represents a C 1-8 divalent linking group or single bond that may contain an oxygen atom or a sulfur atom in the main chain. ]

[In Formula (V), R ₁₀₅ represents a substituent, and m5 represents 1 or 2. ]

[In the formula (VI), R ₁₀₆ represents a substituent, and m6 represents an integer of 0 to 2. ]
The wafer lens of a preferred embodiment contains a photoacid generator that generates an acid by ultraviolet irradiation, and more preferably, the photoacid generator is a sulfonium salt compound.

Further, the wafer lens according to a preferred embodiment contains an oxetane compound.

According to the present invention, an epoxy compound (epoxy resin) having a special structure represented by the general formula (A) or the general formulas (I) to (VI) described above is used as the first curable resin, Since it contains the epoxy compound, skin sensitization can be suppressed, and a highly safe wafer lens can be produced.

It is a perspective view which shows schematic structure of a wafer lens. It is a perspective view which shows schematic structure of a master and a submaster. It is drawing for demonstrating the manufacturing method of a wafer lens. It is drawing which shows schematic structure of a master, a submaster, and a subsubmaster. It is drawing for demonstrating the manufacturing method of a wafer lens. FIG. 6 is a view for explaining a manufacturing method subsequent to FIG. 5. It is a top view which shows schematic structure of a large diameter submaster. It is a top view which shows schematic structure of a normal submaster. It is drawing for demonstrating a mode that a lens part is formed in the front and back both surfaces of a glass substrate using a large diameter submaster and a normal submaster. It is drawing for demonstrating the inconvenience at the time of using a large diameter submaster. It is drawing which shows the modification of a large diameter submaster. It is a reaction diagram of a release agent using an alkoxysilane group as an example of a functional group capable of being hydrolyzed at the terminal and an OH group on a master surface.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Wafer lens 3 Glass substrate 5 Lens part 5A Resin 10 (10A, 10B) Master 12 Base part 14 Convex part 16 Concave part 20 Submaster 22 Submaster molding part 22A Resin 24 Concave part 25 Convex part 26 Submaster board 30 Submaster 32 Sub Master molding part 32A Resin 34 Convex part 36 Sub master substrate 40 Sub sub master 42 Sub sub master molding part 42A Resin 44 Concave part 46 Sub

sub master substrate

50, 52, 54 Light source 60 Tension white 200 Large diameter sub master 210 Stress relaxation part

Hereinafter, embodiments of the present invention will be described with reference to the drawings.
[First Embodiment]
As shown in FIG. 1, the wafer lens 1 has a circular glass substrate (substrate) 3 and a plurality of lens portions (optical members) 5, and the plurality of lens portions 5 are arranged in an array on the glass substrate 3. It is an arranged configuration. The lens unit 5 may be formed on the surface of the glass substrate 3 or may be formed on both front and back surfaces.
<Lens part>
The lens unit 5 is formed of a resin 5A (first curable resin). As the resin 5A, an epoxy curable resin can be used. The curable resin can be roughly classified into a photocurable resin and a thermosetting resin. Any photo-curable epoxy resin can be cured by cationic polymerization. On the other hand, the thermosetting resin can be cured by radical polymerization or cationic polymerization.

Specifically, as the resin 5A constituting the lens unit 5, any of the alicyclic epoxide compounds represented by the general formula (A), the general formula (I) to the general formula (VI) can be used. . The resin 5A may be composed of one type of alicyclic epoxide compound, or may be composed of a combination of a plurality of types of alicyclic epoxide compounds.

In the general formula (A) and the general formulas (I) to (VI), R ₁₀₀ , R ₁₀₁ , R ₁₀₂ , R ₁₀₃ , R ₁₀₄ , R ₁₀₅ , and R ₁₀₆ each represent a substituent. Examples of the substituent include a halogen atom (eg, a chlorine atom, a bromine atom, a fluorine atom, etc.), an alkyl group having 1 to 6 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group). Etc.), an alkoxy group having 1 to 6 carbon atoms (for example, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, tert-butoxy group, etc.), acyl group (for example, acetyl group) , Propionyl group, trifluoroacetyl group, etc.), acyloxy group (eg, acetoxy group, propionyloxy group, trifluoroacetoxy group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, tert-butoxycarbonyl group, etc.) ) And the like. Among the above substituents, an alkyl group, an alkoxy group, or an alkoxycarbonyl group is preferable.

In the general formula (A), general formula (I) to general formula (VI), m0, m1, m2, m3, m4, and m6 each represents an integer of 0 to 2, and 0 or 1 is preferable. M5 represents 1 or 2.

In formula (A), L ₀ is the main chain of r0 + 1 valent connecting group or a single bond contain an oxygen atom or a sulfur atom which may having 1 to 15 carbon atoms, the general formula (I), L ₁ Is an r1 + 1 valent linking group or a single bond having 1 to 15 carbon atoms which may contain an oxygen atom or a sulfur atom in the main chain. In the general formula (II), L ₂ contains an oxygen atom or a sulfur atom in the main chain. In the general formula (III) and the general formula (IV), L ₃ and L ₄ each may contain an oxygen atom or a sulfur atom in the main chain. However, it represents a divalent linking group having a carbon number of 8 or a single bond.

Examples of the divalent linking group which may contain an oxygen atom or a sulfur atom in the main chain include the groups listed below, and these groups and —O— group, —S— group, —CO— group, —CS A group formed by combining a plurality of groups.
A methylene group [—CH ₂ —],
An ethylidene group [> CHCH ₃ ],
Isopropylidene [> C (CH ₃ ) ₂ ]
1,2-ethylene group [—CH ₂ CH ₂ —],
1,2-propylene group [—CH (CH ₃ ) CH ₂ —],
1,3-propanediyl group [—CH ₂ CH ₂ CH ₂ —],
2,2-dimethyl-1,3-propanediyl group [—CH ₂ C (CH ₃ ) ₂ CH ₂ —],
2,2-dimethoxy-1,3-propanediyl group [—CH ₂ C (OCH ₃ ) ₂ CH ₂ —],
2,2-dimethoxymethyl-1,3-propanediyl group [—CH ₂ C (CH ₂ OCH ₃ ) ₂ CH ₂ —],
1-methyl-1,3-propanediyl group [—CH (CH ₃ ) CH ₂ CH ₂ —],
1,4-butanediyl group [—CH ₂ CH ₂ CH ₂ CH ₂ —],
1,5-pentanediyl group [—CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ —],
An oxydiethylene group [—CH ₂ CH ₂ OCH ₂ CH ₂ —],
A thiodiethylene group [—CH ₂ CH ₂ SCH ₂ CH ₂ —],
3-oxothiodiethylene group [—CH ₂ CH ₂ SOCH ₂ CH ₂ —],
3,3-dioxothiodiethylene group [—CH ₂ CH ₂ SO ₂ CH ₂ CH ₂ —],
1,4-dimethyl-3-oxa-1,5-pentanediyl group [—CH (CH ₃ ) CH ₂ OCH (CH ₃ ) CH ₂ —],
3-oxopentanediyl group [—CH ₂ CH ₂ COCH ₂ CH ₂ —],
1,5-dioxo-3-oxapentanediyl group [—COCH ₂ OCH ₂ CO—],
4-oxa-1,7-heptanediyl group [—CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ —],
3,6-dioxa-1,8-octanediyl group [—CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ —],
1,4,7-trimethyl-3,6-dioxa-1,8-octanediyl group [—CH (CH ₃ ) CH ₂ OCH (CH ₃ ) CH ₂ OCH (CH ₃ ) CH ₂ —],
5,5-dimethyl-3,7-dioxa-1,9-nonanediyl group [—CH ₂ CH ₂ OCH ₂ C (CH ₃ ) ₂ CH ₂ OCH ₂ CH ₂ —],
5,5-dimethoxy-3,7-dioxa-1,9-nonanediyl group [—CH ₂ CH ₂ OCH ₂ C (OCH ₃ ) ₂ CH ₂ OCH ₂ CH ₂ —],
5,5-dimethoxymethyl-3,7-dioxa-1,9-nonanediyl group [—CH ₂ CH ₂ OCH ₂ C (CH ₂ OCH ₃ ) ₂ CH ₂ OCH ₂ CH ₂ —],
4,7-dioxo-3,8-dioxa-1,10-decandiyl group [—CH ₂ CH ₂ O—COCH ₂ CH ₂ CO—OCH ₂ CH ₂ —],
3,8-dioxo-4,7-dioxa-1,10-decandiyl group [—CH ₂ CH ₂ CO—OCH ₂ CH ₂ O—COCH ₂ CH ₂ —],
1,3-cyclopentanediyl group [-1,3-C ₅ H ₈ —],
1,2-cyclohexanediyl group [-1,2-C ₆ H _10- ],
1,3-cyclohexanediyl group [-1,3-C ₆ H _10- ],
1,4-cyclohexanediyl group [-1,4-C ₆ H _10- ],
2,5-tetrahydrofurandiyl group [2,5-C ₄ H ₆ O—]
p- phenylene _{_{[-p-C 6 H 4 -}} ],
m- phenylene group _{_{[-m-C 6 H 4 -}} ],
α, α'-o-xylylene group [-o-CH ₂ -C ₆ H ₄ -CH _2- ],
α, α'-m-xylylene group [-m-CH ₂ -C ₆ H ₄ -CH _2- ],
α, α'-p-xylylene group [-p-CH ₂ -C ₆ H ₄ -CH _2- ],
Furan-2,5-diyl-bismethylene group [2,5-CH ₂ —C ₄ H ₂ O—CH ₂ —]
Thiophene-2,5-diyl-bismethylene group [2,5-CH ₂ —C ₄ H ₂ S—CH ₂ —]
Isopropylidenebis -p- phenylene group _{_{_{_{[-p-C 6 H 4 -C}}}} (CH 3) 2 -p-C 6 H 4 -]
Examples of the trivalent or higher linking group include groups formed by removing as many hydrogen atoms as necessary from the divalent linking groups listed above, an —O— group, an —S— group, —CO— And a group formed by combining a plurality of groups and —CS— groups.

L ₀ , L ₁ , L ₂ , L ₃ and L ₄ may each have a substituent. Examples of the substituent include a halogen atom (eg, chlorine atom, bromine atom, fluorine atom), an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, propyl group, isopropyl group, butyl group, etc.) ), An alkoxy group having 1 to 6 carbon atoms (for example, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, tert-butoxy group, etc.), acyl group (for example, acetyl group, Propionyl group, trifluoroacetyl group, etc.), acyloxy group (eg, acetoxy group, propionyloxy group, trifluoroacetoxy group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, tert-butoxycarbonyl group, etc.) Etc. Preferred as a substituent is an alkyl group, an alkoxy group, or an alkoxycarbonyl group.

L ₀ , L ₁ and L ₂ are preferably divalent linking groups having 1 to 8 carbon atoms which may contain an oxygen atom or a sulfur atom in the main chain, or L ₀ , L ₁ , L ₂ , L ₃ , L ₄ is more preferably a divalent linking group having 1 to 5 carbon atoms each having a main chain composed of only carbon.

P1 and q1 each represents 0 or 1, and p1 + q1 is preferably 1 or more. p2 and q2 each represents 0 or 1, each preferably 1; p3 and p4 each represents 0 or 1.

Specific examples of preferred alicyclic epoxides are shown below, but the present invention is not limited thereto.

In each of the above alicyclic epoxide compounds according to the present invention, a value obtained by dividing the molecular weight by the total number of epoxy groups in the molecule is preferably 160 or more and 300 or less.

The synthesis of the alicyclic epoxide compounds represented by the general formula (A), the general formula (I) to the general formula (VI) according to the present invention is performed, for example, according to the methods described in the patent specifications listed below. Can be done.
A: US Pat. No. 2,745,847 B: US Pat. No. 2,750,395 C: US Pat. No. 2,853,498 D: US Pat. No. 2,853,499 Specification E: US Pat. No. 2,863,881 In the following, examples of the synthesis of the above exemplified compounds are shown below according to the methods described in the above patent specifications, but the present invention is not limited thereto. is not.
[Synthesis Example 1]
Exemplary Compound EP-9: Synthesis of Ethylglycol-bis- (4-methyl-3,4-epoxy-cyclohexanecarboxylate) <Synthesis of Methyl- (4-methyl-3-cyclocarboxylate)>
Methyl- (4-methyl-3-cyclohexanecarbylate) was synthesized from isoprene and methyl acrylate by known Diels-Alder reactions. Reactions are described in the literature (J. Organomet. Chem., 285, 1985, 333-342, J. Phys. Chem., 95, 5, 1992, 2293-2297, Acta. Chem. Scand., 47, 6, 1993, 581-591) or reaction conditions according to the conditions described in US Pat. No. 1,944,731, etc., and the target compound was obtained in high yield.
<Synthesis of Ethyleneglycol-bis- (4-methyl-3-cyclohexanecarbylate)>
1 g of toluenesulfonic acid monohydrate was added to 340 g (2 mol) of methyl- (4-methyl-3-cyclohexanecarboxylate) and 62 g (1 mol) of ethylene glycol, and reacted at 80 to 90 ° C. for 8 hours. The reaction solution was washed with aqueous sodium bicarbonate and then distilled under reduced pressure to obtain the target compound. The yield was 92%.
<Synthesis of Exemplified Compound EP-9>
306 g (1 mol) of ethylglycol-bis- (4-methyl-3-cyclohexanecarbylate) is placed in a 2 L three-headed flask, and an acetone solution with a peracetic acid content of 25% by mass is maintained at 35-40 ° C. 770 g (192 g (2.5 mol) peracetic acid) was added dropwise over 4 hours. After completion of the dropwise addition, the reaction was carried out after 4 hours at the same temperature. The reaction solution was stored at −11 ° C. overnight, and the remaining amount of peracetic acid was examined to confirm that 98% or more of the theoretical amount had reacted.

Next, the reaction solution was diluted with 1 L of toluene, heated to 50 ° C. under reduced pressure using a water aspirator, and the low-boiling components were distilled off and removed until the distillate disappeared. The remaining reaction composition was distilled under reduced pressure to obtain the target exemplified compound EP-9. The yield was 78%.

The structure of the obtained exemplary compound EP-9 was confirmed by NMR and MASS analysis.
1H NMR (CDCl ₃ ) δ (ppm): 1.31 (s, 6H, CH ₃ —), 1.45 to 2.50 (m, 14H, cyclohexane ring), 3.10 (m, 2H, epoxy root) ), 4.10 (s, 4H, —CH ₂ —O—)
[Synthesis Example 2]
Exemplary Compound EP-12: Synthesis of Propane-1,2-diol-bis- (4-methyl-3,4-epoxy-cyclohexanecarboxylate) <Propane-1,2-diol-bis- (4-methyl-3-cyclohexanecarboxylate) )
1 g of toluenesulfonic acid monohydrate was added to 340 g (2 mol) of Methyl- (4-methyl-3-cyclohexanecarboxylate) and 76 g (1 mol) of Propane-1,2-diol at 80 to 90 ° C. for 8 hours. Reacted. The reaction solution was washed with aqueous sodium bicarbonate, and then distilled under reduced pressure to obtain the target compound. The yield was 90%.
<Synthesis of Exemplified Compound EP-12>
Propane-1,2-diol-bis- (4-methyl-3-cyclohexenecarboxylate) 320 g (1 mol) was put into a 2 L three-headed flask, and the peracetic acid content was kept at 35 to 40 ° C. 770 g of a 25 mass% acetone solution (192 g (2.5 mol) of peracetic acid) was added dropwise over 4 hours. After completion of the dropwise addition, the reaction was carried out after 4 hours at the same temperature. The reaction solution was stored at −11 ° C. overnight, and the remaining amount of peracetic acid was examined to confirm that 98% or more of the theoretical amount had reacted.

Next, the reaction solution was diluted with 1 L of toluene, heated to 50 ° C. under reduced pressure using a water aspirator, and the low-boiling components were distilled off and removed until the distillate disappeared.

The remaining reaction composition was distilled under reduced pressure to obtain the target exemplified compound EP-12. The yield was 75%.

The structure of the obtained exemplary compound EP-12 was confirmed by NMR and MASS analysis. 1HNMR (CDCl ₃ ) δ (ppm): 1.23 (d, 3H, CH ₃ —), 1.31 (s, 6H, CH ₃ —), 1.45 to 2.50 (m, 14H, cyclohexane ring) ), 3.15 (m, 2H, epoxy base), 4.03 (m, 1H, —O—CH ₂ —), 4.18 (m, 1H, —O—CH ₂ —), 5.15 ( m, 1H,> CH-O-)
[Synthesis Example 3]
Synthesis of Exemplified Compound EP-17: 2,2-Dimethyl-propane-1,3-diol-bis- (4-methyl-3,4-epoxy-cyclohexanecarboxylate) <2,2-Dimethyl-propane-1,3- Synthesis of diol-bis- (4-methyl-3-cyclohexenecarboxylate)>
1 g of toluenesulfonic acid monohydrate was added to 340 g (2 mol) of methyl- (4-methyl-3-cyclohexanecarboxylate) and 104 g (1 mol) of 2,2-dimethyl-propane-1,3-diol. The reaction was carried out at 80 to 90 ° C. for 12 hours. The reaction solution was washed with aqueous sodium bicarbonate, and then distilled under reduced pressure to obtain the target compound. The yield was 86%.
<Synthesis of Exemplified Compound EP-17>
348 g (1 mol) of 2,2-Dimethyl-propane-1,3-diol-bis- (4-methyl-3-cyclohexanecarbylate) was placed in a 2 L three-headed flask, and the internal temperature was kept at 40 ° C. 770 g of an acetone solution having an acetic acid content of 25% by mass (192 g (2.5 mol) of peracetic acid) was added dropwise over 4 hours. After completion of the dropwise addition, the reaction was carried out after 4 hours at the same temperature. The reaction solution was stored at −11 ° C. overnight, and the remaining amount of peracetic acid was examined to confirm that 98% or more of the theoretical amount had reacted.

The remaining reaction composition was distilled under reduced pressure to obtain the target exemplified compound EP-17. The yield was 70%.

The structure of Exemplified Compound EP-17 was confirmed by NMR and MASS analysis.
1H NMR (CDCl ₃ ) δ (ppm): 0.96 (s, 6H, CH ₃ —), 1.31 (s, 6H, CH ₃ —), 1.45 to 2.50 (m, 14H, cyclohexane) Ring), 3.00 (m, 2H, epoxy root), 3.87 (s, 4H, —O—CH ₂ —)
[Synthesis Example 4]
Synthesis of Exemplary Compound EP-31: 1,3-Bis- (4-methyl-3,4-epoxy-cyclohexylmethyl) -2-propanol <Synthesis of 4-Methyl-3-cyclohexenylmethyl>
4-Methyl-3-cyclohexenyldehydride was synthesized from isoprene and acrolein by known Diels-Alder reactions. The reaction is performed under the reaction conditions according to the conditions described in the literature (J. Amer. Chem. Soc., 119, 15, 1997, 3507-3512, Tetrahedron Lett., 40, 32, 1999, 5817-5822). The target compound was obtained in a high yield. Subsequently, 4-methyl-3-cyclohexenyl methanol was synthesized in high yield by reducing this compound.
<Synthesis of 1,2-Bis- (4-methyl-3-cyclohexylmethyl) -2-propanol>
284 g (2 mol) of 4-methyl-3-cyclohexenylethanol and 305 g (2.2 mol) of potassium carbonate were added to 1 L of acetone containing 92 g (1 mol) of epichlorohydrin, and reacted at 50 ° C. for 8 hours. The precipitated salt was removed by filtration, the reaction solution was concentrated under reduced pressure, and the remaining crude product was distilled under reduced pressure to obtain the desired compound. The yield was 90%.
<Synthesis of Exemplified Compound EP-31>
308 g (1 mol) of 1,2-Bis- (4-methyl-3-cyclomethylyloxy) -2-propanol was placed in a 2 L three-headed flask, and the peracetic acid content was maintained while maintaining the internal temperature at 35-40 ° C. 770 g of a 25 mass% acetone solution (192 g (2.5 mol) of peracetic acid) was added dropwise over 4 hours. After completion of the dropwise addition, the reaction was carried out after 4 hours at the same temperature. The reaction solution was stored at −11 ° C. overnight, and the remaining amount of peracetic acid was examined to confirm that 98% or more of the theoretical amount had reacted.

The remaining reaction composition was distilled under reduced pressure to obtain the target exemplified compound EP-31. The yield was 83%.

The structure of Exemplified Compound EP-31 was confirmed by NMR and MASS analysis.

1H NMR (CDCl ₃ ) δ (ppm): 1.31 (s, 6H, CH ₃ —), 1.4 to 2.0 (m, 14H, cyclohexane ring), 2.7 (s, 1H, —OH ), 3.10 (m, 2H, epoxy base), 3.45 (d, 4H, —CH ₂ —O—), 3.50 (m, 4H, —CH ₂ —O—), 3.92 ( m, 1H,> CH-)
[Synthesis Example 5]
Exemplary Compound EP-35: Synthesis of Bis- (4-methyl-3,4-epoxy-cyclomethylmethyl) oxalate <Synthesis of Bis- (4-methyl-3-methylmethyl) succinate>
To 284 g (2 mol) of 4-methyl-3-cyclohexenyl methanol and 1 L of toluene containing 100 g (1 mol) of succinic anhydride, 5 g of toluenesulfonic acid monohydrate was added, and the water produced was separated with a water separator. The reaction was carried out at 110 to 120 ° C. for 8 hours while removing. The reaction solution was washed with an aqueous sodium bicarbonate solution, and toluene was distilled off by concentration under reduced pressure. The remaining crude product was distilled under reduced pressure to obtain the target compound. The yield was 90%.
<Synthesis of Exemplified Compound EP-35>
335 g (1 mol) of Bis- (4-methyl-3-cyclohexylmethyl) succinate was placed in a 2 L three-headed flask, and 770 g of an acetone solution having a peracetic acid content of 25% by mass while maintaining the internal temperature at 35 to 40 ° C. (192 g (2.5 mol) of peracetic acid) was added dropwise over 4 hours. After completion of the dropwise addition, the reaction was carried out after 4 hours at the same temperature. The reaction solution was stored at −11 ° C. overnight, and the remaining amount of peracetic acid was examined to confirm that 98% or more of the theoretical amount had reacted.

Next, the reaction solution was diluted with 1 L of toluene, heated to 50 ° C. under reduced pressure using a water aspirator, and low-boiling components were distilled off and removed until the distillate disappeared.

The remaining reaction composition was distilled under reduced pressure to obtain Exemplified Compound EP-35. The yield was 75%.

The structure of Exemplified Compound EP-35 was confirmed by NMR and MASS analysis.
1H NMR (CDCl3) δ (ppm): 1.31 (s, 6H, CH _3- ), 1.4 to 2.0 (m, 14H, cyclohexane ring), 3.10 (m, 2H, epoxy root) 2.62 (s, 4H, —CH ₂ —CO—), 4.05 (d, 4H, —CH ₂ —O—) and other alicyclic epoxide compounds according to the present invention listed above, Similar to the above method, the compound can be synthesized with good yield.

The alicyclic epoxide compounds represented by the general formula (A) and the general formulas (I) to (VI) may contain (add) a photoacid generator that generates an acid upon irradiation with ultraviolet rays. preferable.

As the photoacid generator, for example, a chemical amplification type photoresist or a compound used for photocationic polymerization is used (Organic Materials Research Group, “Organic Material for Imaging”, Bunshin Publishing (1993), See pages 187-192). Examples of compounds suitable for the present invention are listed below.

First, B (C ₆ F ₅ ) ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , p-CH ₃ C ₆ H ₄ of aromatic onium compounds such as diazonium, ammonium, iodonium, sulfonium, and phosphonium. SO ₃ ^- salt, _CF 3 SO ₃ ^- and sulfonic acid salts such as salts.

Those having a borate compound as a counter anion and PF ₆ ^- salt acid generation capability higher preferred. Specific examples of the onium compound are shown below.

Secondly, sulfonated products that generate sulfonic acid can be mentioned. Specific compounds are exemplified below.

Thirdly, a halide that generates hydrogen halide can also be used. Specific compounds are exemplified below.

Fourthly, iron allene complexes can be mentioned.

Examples of the photoacid generator used in the present invention include arylsulfonium salt derivatives (for example, Cyracure UVI-6990, Cyracure UVI-6974, manufactured by Union Carbide, Adekaoptomer SP-150, Adekaopter, manufactured by Asahi Denka Kogyo Co., Ltd. Merp SP-152, Adekaoptomer SP-170, Adekaoptomer SP-172), allyl iodonium salt derivatives (for example, RP-2074 manufactured by Rhodia), allene-ion complex derivatives (for example, Irgacure 261 manufactured by Ciba Geigy) ), Acid generators such as diazonium salt derivatives, triazine initiators and other halides. The photoacid generator is preferably contained in a ratio of 0.2 to 20 parts by mass with respect to 100 parts by mass of the compound having cationic polymerizability. When the content of the photoacid generator is less than 0.2 parts by mass, it is difficult to obtain a cured product, and even if the content exceeds 20 parts by mass, there is no further effect of improving curability. These photoacid generators can be used alone or in combination of two or more.

Preferred as the photoacid generator used in the present invention are onium salts such as sulfonium salts, iodonium salts, ammonium salts, phosphonium salts, etc. Among them, sulfonium salt compounds are preferred.

More preferable sulfonium salt compounds include sulfonium salts represented by the following general formulas (I-1), (I-2), and (I-3).

In the general formula (I-1), R ₁₁ , R ₁₂ , and R ₁₃ represent substituents, and m, n, and p represent integers of 0 to 2. X ₁₁ ⁻ represents a counter ion.

In the above general formula (I-2), R ₁₄ represents a substituent, and q represents an integer of 0 to 2. R ₁₅ and R _{16 each} represents a substituted, unsubstituted alkyl group, a substituted, unsubstituted alkenyl group, a substituted, unsubstituted alkynyl group, or a substituted, unsubstituted aryl group. X ₁₂ ⁻ represents a counter ion.

In the general formula (I-3), R ₁₇ represents a substituent, and r represents an integer of 0 to 3. R ₁₈ represents a hydrogen atom or a substituted or unsubstituted alkyl group, and R ₁₉ and R ₂₀ represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted group. Represents a substituted aryl group. X ₁₃ ^- is a counter ion.

Further, the sulfonium salts represented by the general formulas (I-1), (I-2), and (I-3) will be described. In the general formula (I-1), R ₁₁ , R ₁₂ and R ₁₃ each represent a substituent. Examples of the substituent include a halogen atom (eg, chlorine atom, bromine atom, fluorine atom), an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, propyl group, isopropyl group, butyl group, etc.) ), A cycloalkyl group having 3 to 6 carbon atoms (for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc.), an alkenyl group having 1 to 6 carbon atoms (for example, vinyl group, 1-propenyl group, 2-propenyl group, 2-butenyl group, etc.), alkynyl group having 1 to 6 carbon atoms (for example, acetylenyl group, 1-propynyl group, 2-propynyl group, 2-butynyl group, etc.), 1 to 6 carbon atoms Alkoxy groups (for example, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, tert-butoxy group, etc.), having 1 to 6 carbon atoms Alkylthio group (eg, methylthio group, ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, tert-butylthio group, etc.), aryl group having 6 to 14 carbon atoms (eg, phenyl group, naphthyl group, Anthracenyl group, etc.), aryloxy groups having 6 to 10 carbon atoms (eg, phenoxy group, naphthoxy group, etc.), arylthio groups having 6 to 10 carbon atoms (eg, phenylthio group, naphthylthio group, etc.), acyl groups (eg, acetyl) Group, propionyl group, trifluoroacetyl group, benzoyl group, etc.), acyloxy group (eg, acetoxy group, propionyloxy group, trifluoroacetoxy group, benzoyloxy group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl) Group, tert-butoxy Carbonyl group and the like), hetero atom-containing aromatic Hajime Tamaki having 4 to 8 carbon atoms (e.g., furyl group, a thienyl group, etc.), a nitro group, a cyano group, and the like.

Preferred examples of the substituent include a halogen atom, an alkyl group, an alkyloxy group, an aryl group, an aryloxy group, an arylthio group, and an acyl group. Of these substituents, possible ones may be further substituted. m, n and p each represents an integer of 0 to 2, and each is preferably 1 or more. X ₁₁ ^- is a counter anion. Counter anions include complex ions such as BF ₄ ⁻ , B (C ₆ F ₅ ) ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ^— , p-CH ₃ C ₆ H ₄ SO ₃ ⁻ , CF ₃ SO ₃ ^- can be given sulfonate ion such. As the counter anion, borate ion and PF ₆ ^- are preferable because of their high acid generation ability.

In the general formula (I-2), R ₁₄ represents a substituent. Examples of the substituent include a halogen atom (for example, chlorine atom, bromine atom, fluorine atom, etc.) and an alkyl group having 1 to 6 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, etc.) A cycloalkyl group having 3 to 6 carbon atoms (for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, etc.), an alkenyl group having 1 to 6 carbon atoms (for example, a vinyl group, a 1-propenyl group, 2 -Propenyl group, 2-butenyl group, etc.), alkynyl groups having 1 to 6 carbon atoms (for example, acetylenyl group, 1-propynyl group, 2-propynyl group, 2-butynyl group, etc.), 1 to 6 carbon atoms An alkoxy group (for example, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, a tert-butoxy group), an aryl group having 1 to 6 carbon atoms Kirthio group (for example, methylthio group, ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, tert-butylthio group, etc.), aryl group having 6 to 14 carbon atoms (for example, phenyl group, naphthyl group, Anthracenyl group, etc.), aryloxy groups having 6 to 10 carbon atoms (eg, phenoxy group, naphthoxy group, etc.), arylthio groups having 6 to 10 carbon atoms (eg, phenylthio group, naphthylthio group, etc.), acyl groups (eg, acetyl) Group, propionyl group, trifluoroacetyl group, benzoyl group, etc.), acyloxy group (eg, acetoxy group, propionyloxy group, trifluoroacetoxy group, benzoyloxy group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl) Group, tert-butoxyca Boniru group), hetero atom-containing aromatic Hajime Tamaki having 4 to 8 carbon atoms (e.g., furyl group, a thienyl group, etc.), a nitro group, a cyano group, and the like. Preferably, they are a halogen atom, an alkyl group, an aryl group, an alkoxy group, and an aryloxy group. Of these substituents, possible ones may be further substituted. q represents an integer of 0 to 2, preferably 1 or more, and more preferably 2.

R ₁₅ and R ₁₆ represent a substituted, unsubstituted alkyl group, a substituted, unsubstituted alkenyl group, a substituted, unsubstituted alkynyl group, or a substituted, unsubstituted aryl group. Examples of the substituent include a halogen atom (eg, chlorine atom, bromine atom, fluorine atom), an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, propyl group, isopropyl group, butyl group, etc.) ), A cycloalkyl group having 3 to 6 carbon atoms (for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc.), an alkenyl group having 1 to 6 carbon atoms (for example, vinyl group, 1-propenyl group, 2-propenyl group, 2-butenyl group, etc.), alkynyl group having 1 to 6 carbon atoms (for example, acetylenyl group, 1-propynyl group, 2-propynyl group, 2-butynyl group, etc.), 1 to 6 carbon atoms Alkoxy groups (for example, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, tert-butoxy group, etc.), having 1 to 6 carbon atoms Alkylthio group (eg, methylthio group, ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, tert-butylthio group, etc.), aryl group having 6 to 14 carbon atoms (eg, phenyl group, naphthyl group, Anthracenyl group, etc.), aryloxy groups having 6 to 10 carbon atoms (eg, phenoxy group, naphthoxy group, etc.), arylthio groups having 6 to 10 carbon atoms (eg, phenylthio group, naphthylthio group, etc.), acyl groups (eg, acetyl) Group, propionyl group, trifluoroacetyl group, benzoyl group, etc.), acyloxy group (eg, acetoxy group, propionyloxy group, trifluoroacetoxy group, benzoyloxy group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl) Group, tert-butoxy Carbonyl group and the like), hetero atom-containing aromatic Hajime Tamaki having 4 to 8 carbon atoms (e.g., furyl group, a thienyl group, etc.), a nitro group, a cyano group, and a hydroxyl group. Preferred are a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, and an acyl group.

R ₁₅ and R ₁₆ are preferably a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and the substituent is preferably a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, An acyl group and a hydroxyl group.

X ₁₂ ^- is a counter anion. Counter anions include complex ions such as BF ₄ ⁻ , B (C ₆ F ₅ ) ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ^— , p-CH ₃ C ₆ H ₄ SO ₃ ⁻ , CF ₃ SO ₃ ^- can be given sulfonate ion such. As the counter anion, borate ion and PF ₆ ^- are preferable because of their high acid generation ability.

In the general formula (I-3), R ₁₇ represents a substituent. Examples of the substituent include a halogen atom (eg, chlorine atom, bromine atom, fluorine atom), an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, propyl group, isopropyl group, butyl group, etc.) ), A cycloalkyl group having 3 to 6 carbon atoms (for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc.), an alkenyl group having 1 to 6 carbon atoms (for example, vinyl group, 1-propenyl group, 2-propenyl group, 2-butenyl group, etc.), alkynyl group having 1 to 6 carbon atoms (for example, acetylenyl group, 1-propynyl group, 2-propynyl group, 2-butynyl group, etc.), 1 to 6 carbon atoms Alkoxy groups (for example, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, tert-butoxy group, etc.), having 6 to 14 carbon atoms Reel group (for example, phenyl group, naphthyl group, anthracenyl group, etc.), acyl group (for example, acetyl group, propionyl group, trifluoroacetyl group, benzoyl group, etc.), acyloxy group (for example, acetoxy group, propionyloxy group, tri Fluoroacetoxy group, benzoyloxy group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, tert-butoxycarbonyl group, etc.), aryl group having 6 to 10 carbon atoms (eg, phenyl group, naphthyl group, anthracenyl group) Group), a hetero atom-containing aromatic ring group having 4 to 8 carbon atoms (for example, furyl group, thienyl group, etc.), nitro group, cyano group, and the like. A halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, and an acyl group are preferable. r represents an integer of 0 to 3, preferably 1 or more, more preferably 2.

R ₁₈ represents a hydrogen atom or a substituted or unsubstituted alkyl group, and R ₁₉ and R ₂₀ represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted group. Represents a substituted aryl group. Examples of the substituent include a halogen atom (eg, chlorine atom, bromine atom, fluorine atom), an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, propyl group, isopropyl group, butyl group, etc.) ), A cycloalkyl group having 3 to 6 carbon atoms (for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc.), an alkenyl group having 1 to 6 carbon atoms (for example, vinyl group, 1-propenyl group, 2-propenyl group, 2-butenyl group, etc.), alkynyl group having 1 to 6 carbon atoms (for example, acetylenyl group, 1-propynyl group, 2-propynyl group, 2-butynyl group, etc.), 1 to 6 carbon atoms Alkoxy groups (for example, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, tert-butoxy group, etc.), having 6 to 14 carbon atoms Reel group (for example, phenyl group, naphthyl group, anthracenyl group, etc.), acyl group (for example, acetyl group, propionyl group, trifluoroacetyl group, benzoyl group, etc.), acyloxy group (for example, acetoxy group, propionyloxy group, tri Fluoroacetoxy group, benzoyloxy group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, tert-butoxycarbonyl group, etc.), aryl group having 6 to 10 carbon atoms (eg, phenyl group, naphthyl group, anthracenyl group) Group), a hetero atom-containing aromatic ring group having 4 to 8 carbon atoms (for example, furyl group, thienyl group, etc.), nitro group, cyano group and the like. A halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, and an acyl group are preferable.

R ₁₈ is preferably a hydrogen atom or an unsubstituted lower alkyl group (methyl group, ethyl group, propyl group), and R ₁₉ and R ₂₀ are preferably a substituted or unsubstituted alkyl group, or a substituted or unsubstituted group. The substituent is preferably a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, or an acyl group. X ₁₃ ^- is a counter anion. Counter anions include complex ions such as BF ₄ ⁻ , B (C ₆ F ₅ ) ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ^— , p-CH ₃ C ₆ H ₄ SO ₃ ⁻ , CF ₃ SO ₃ ^- can be given sulfonate ion such. As the counter anion, borate ion and PF ₆ ^- are preferable because of their high acid generation ability.

Specific examples of the sulfonium salts represented by the general formulas (I-1), (I-2), and (I-3) are shown below, but the present invention is not limited thereto.

Examples of the photopolymerization accelerator include anthracene, anthracene derivatives (for example, Adekaoptomer SP-100 manufactured by Asahi Denka Kogyo Co., Ltd.), phenothiazine (10H-phenothiazine), phenothiazine derivatives (for example, 10-methylphenothiazine, 10-ethylphenothiazine, 10-decylphenothiazine, 10-acetylphenothiazine, 10-decylphenothiazine-5-oxide, 10-decylphenothiazine-5,5-dioxide, 10-acetylphenothiazine-5,5-dioxide). These photopolymerization accelerators can be used alone or in combination.

The alicyclic epoxide compound represented by the general formula (A), general formula (I) to general formula (VI) preferably contains (adds) an oxetane compound.

As the oxetane compound, a conventionally known oxetane compound can be used, and in particular, when an oxetane compound not substituted at the 2-position is used in combination, a sensitivity improving effect or a cured film property improving effect can be obtained. .

Hereinafter, the oxetane compound in which the 2-position is not substituted will be described.

An example of an oxetane compound in which the 2-position is not substituted is a compound represented by the following general formula (101).

In the general formula (101), R ¹ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group, a fluoroalkyl group having 1 to 6 carbon atoms, an allyl group, or an aryl group. , Furyl group or thienyl group. R ² represents an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group, a 1-propenyl group, a 2-propenyl group, a 2-methyl-1-propenyl group, or 2-methyl-2. -Alkenyl groups having 2 to 6 carbon atoms such as propenyl group, 1-butenyl group, 2-butenyl group and 3-butenyl group, fragrances such as phenyl group, benzyl group, fluorobenzyl group, methoxybenzyl group and phenoxyethyl group A group having a ring, an alkylcarbonyl group having 2 to 6 carbon atoms such as an ethylcarbonyl group, a propylcarbonyl group and a butylcarbonyl group, an alkoxy having 2 to 6 carbon atoms such as an ethoxycarbonyl group, a propoxycarbonyl group and a butoxycarbonyl group Carbonyl group, ethylcarbamoyl group, propylcarbamoyl group, butylcarbamoyl group, pentylcarbamoyl group An N-alkylcarbamoyl group having 2 to 6 carbon atoms, and the like. As the oxetane compound used in the present invention, it is particularly preferable to use a compound having one oxetane ring because the resulting composition has excellent tackiness, low viscosity and excellent workability.

Examples of the compound having two oxetane rings include a compound represented by the following general formula (102).

In General Formula (102), R ¹ is the same group as that in General Formula (101). R ³ is, for example, a linear or branched poly (alkyleneoxy) group such as a linear or branched alkylene group such as an ethylene group, a propylene group or a butylene group, a poly (ethyleneoxy) group or a poly (propyleneoxy) group. ) Group, propenylene group, methylpropenylene group, butenylene group or other linear or branched unsaturated hydrocarbon group, alkylene group containing carbonyl group or carbonyl group, alkylene group containing carboxyl group, alkylene containing carbamoyl group Group.

As the ^{R 3,} the following general formula (103) can also include polyvalent group selected from groups represented by (104) and (105).

In the general formula (103), R ⁴ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group, or a carbon such as a methoxy group, an ethoxy group, a propoxy group, or a butoxy group. A C 1-4 alkoxy group, a halogen atom such as a chlorine atom or a bromine atom, a nitro group, a cyano group, a mercapto group, a lower alkyl carboxyl group, a carboxyl group, or a carbamoyl group.

In General Formula (104), R ⁵ represents an oxygen atom, a sulfur atom, a methylene group, NH, SO, SO ₂ , C (CF ₃ ) ₂ , or C (CH ₃ ) ₂ .

In General Formula (105), R ⁶ is an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group, or an aryl group. n is an integer of 0 to 2000. R ⁷ is a methyl group, an ethyl group, a propyl group, a butyl group having 1 to 4 carbon atoms, or an aryl group. R ^{7 can also} include a group selected from the group represented by the following general formula (106).

In General Formula (106), R ⁸ is an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group, or an aryl group. m is an integer from 0 to 100.

Specific examples of the compound having two oxetane rings include the following compounds.

The exemplified compound 11 is a compound in which R ¹ is an ethyl group and R ³ is a carboxyl group in the general formula (102). The exemplified compound 12 is a compound in which, in the general formula (102), R ¹ is an ethyl group, R ³ is the general formula (105), R ⁶ and R ⁷ are methyl groups, and n is 1.

Among the compounds having two oxetane rings, a preferred example other than the above compound is a compound represented by the following general formula (107).

In formula (107), ^{R 1} has the same meaning as ^{R 1} in the general formula (101). An example of a compound having 3 to 4 oxetane rings is a compound represented by the following general formula (108).

In formula (108), ^{R 1} has the same meaning as ^{R 1} in the general formula (101). As R ⁹ , for example, a branched alkylene group having 1 to 12 carbon atoms such as groups represented by the following A to C, a branched poly (alkyleneoxy) group such as a group represented by the following D, or the following E And branched polysiloxy groups such as those shown. j is 3 or 4.

In A above, R ¹⁰ is a lower alkyl group such as a methyl group, an ethyl group or a propyl group. In D, p is an integer of 1 to 10.

Example compound 13 is an example of a compound having 3 to 4 oxetane rings.

Furthermore, examples of compounds having 1 to 4 oxetane rings other than those described above include compounds represented by the following general formula (109).

In formula (109), ^{R 8} has the same meaning as ^{R 8} in the general formula (106). R ¹¹ is an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group or a butyl group, or a trialkylsilyl group, and r is 1 to 4.

Preferred examples of the oxetane compound used in the present invention include the following compounds.

The production method of each compound having an oxetane ring described above is not particularly limited, and may be a conventionally known method, for example, Pattisson (DB Pattison, J. Am. Chem. Soc., 3455, 79). (1957)) discloses a method for synthesizing an oxetane ring from a diol. In addition to these, compounds having 1 to 4 oxetane rings having a high molecular weight of about 1000 to 5000 are also exemplified. Examples of these specific compounds include the following compounds.

The resin 5A as described above includes an alicyclic epoxide compound represented by the general formula (A), the general formula (I) to the general formula (VI), a photoacid generator that generates an acid by ultraviolet irradiation, and oxetane. In addition to the compound, various conventionally known additives may be contained.

An example of the additive is a color material. As the color material, a color material that can be dissolved or dispersed in the main component of the polymerizable compound can be used, but a pigment is preferable from the viewpoint of weather resistance.

When the wafer lens 1 is manufactured, a master mold (hereinafter simply referred to as “master”) 10 and a sub master mold (hereinafter simply referred to as “submaster”) 20 shown in FIG. 2 are used as molds for molding. Is done.
<Master>
As shown in FIG. 2, the master 10 has a plurality of convex portions 14 formed in an array with respect to a rectangular parallelepiped base portion 12. The convex portion 14 is a portion corresponding to the lens portion 5 of the wafer lens 1 and protrudes from the base portion 12 in a substantially hemispherical shape.

The optical surface shape (surface shape) of the master 10 may have a convex shape in which convex portions 14 are formed as shown in FIG. 2, or a plurality of concave portions 16 are formed as shown in FIG. You may have a concave shape. However, the surface (molding surface) shape of these convex portions 14 and concave portions 16 is positive corresponding to the optical surface shape (the shape of the surface opposite to the glass substrate 3) of the lens portion 5 molded and transferred onto the glass substrate 3. It has a shape. In the following description, the master 10 in FIG. 2 is distinguished as “master 10A”, and the master 10 in FIG. 4 is distinguished as “master 10B”.

As the molding material of the master 10A, metal or metal glass can be used. The classification includes ferrous materials and other alloys. Examples of the iron system include hot dies, cold dies, plastic dies, high-speed tool steel, general structural rolled steel, carbon steel for mechanical structure, chromium / molybdenum steel, and stainless steel. Among them, plastic molds include pre-hardened steel, quenched and tempered steel, and aging treated steel. Examples of pre-hardened steel include SC, SCM, and SUS. More specifically, the SC system is PXZ. SCM systems include HPM2, HPM7, PX5, and IMPAX. Examples of the SUS system include HPM38, HPM77, S-STAR, G-STAR, STAVAX, RAMAX-S, and PSL. Examples of the iron-based alloy include JP-A-2005-113161 and JP-A-2005-206913. As the non-ferrous alloys, copper alloys, aluminum alloys and zinc alloys are well known. Examples thereof include alloys disclosed in JP-A-10-219373 and JP-A-2000-176970.

Also, glass can be used as a molding material for the master 10A. If glass is used for master 10A, the merit of letting UV light pass is also obtained. If it is the glass generally used, it will not specifically limit.

Particularly, as the molding material of the master 10A, there can be mentioned materials that can easily ensure fluidity at a low temperature, such as low melting point glass and metallic glass. Use of the low melting point glass is advantageous because it enables irradiation from the mold side of the sample when molding a UV curable material. Examples of the low melting point glass include glass having a glass transition point of about 600 ° C. or lower and a glass composition of ZnO—PbO— B2O3, PbO—SiO2—B2O3, PbO—P2O5-SnF2, and the like. Examples of the glass that melts at 400 ° C. or less include PbF2-SnF2-SnO—P2O5 and similar structures. Specific materials include S-FPL51, S-FPL53, S-FSL-5, S-BSL-7, S-BSM-2, S-BSM-4, S-BSM-9, S-BSM10, S-BSM14, S-BSM15 , S-BSM16, S-BSM18, S-BSM22, S-BSM25, S-BSM28, S-BSM71, S-BSM81, S-NSL 3, S-NSL 5, S-NSL36, S-BAL 2, S- BAL 3, S-BAL11, S-BAL12, S-BAL14, S-BAL35, S-BAL41, S-BAL42, S-BAM 3, S-BAM 4, S-BAM12, S-BAH10, S-BAH11, S -BAH27, S-BAH28, S-BAH32, S-PHM52, S-PHM53, S-TIL 1, S-TIL 2, S-TIL 6, S-TIL25, S-TIL26, S-TIL27, S-TIM 1 , S-TIM 2, S-TIM 3, S-TIM 5, S-TIM 8, S-TIM22, S-TIM25, S-TIM27, S-TIM28, S-TIM35, S-TIM39, S-TIH 1, S-TIH 3, S-TIH 4, S-TIH 6, S-TIH10, S-TIH11, S-TIH13, S-TIH14, S-TIH18, S-TIH23, S-TIH53, S-LAL 7, S- LAL 8, S-LAL 9, S-LAL10, S-LAL12, S-LAL13, S-LAL14, S-LAL18, S-LAL54, S-LAL56, S-LAL58, S-LAL59, S-LAL61, S-L LAM 2, S-LAM 3, S-LAM 7, S-LAM51, S-LAM52, S-LAM54, S-LAM55, S-LAM58, S-LAM59, S-LAM60, S-LAM61, S-LAM66, S -LAH51, S-LAH52, S-LAH53, S -LAH55, S-LAH58, S-LAH59, S-LAH60, S-LAH63, S-LAH64, S-LAH65, S-LAH66, S-LAH71, S-LAH79, S-YGH51, S-FTM16, S-NBM51 , S-NBH 5, S-NBH 8, S-NBH51, S-NBH52, S-NBH53, S-NBH55, S-NPH 1, S-NPH 2, S-NPH53, P-FK01S, P-FKH2S, P -SK5S, P-SK12S, P-LAK13S, P-LASF03S, P-LASFH11S, P-LASFH12S and the like are mentioned, but it is not necessary to be limited to these.

Also, metallic glass can be easily formed by molding as well. The metal glass has a structure such as JP-A-8-109419, JP-A-8-333660, JP-A-10-81944, JP-A-10-92619, JP-A-2001-140047, JP-A-2001-303218, and JP-T-2003-534925. Although mentioned, it is not necessary to specifically limit to these.

The optical surface of the master 10A may be a surface on which a single convex portion 14 is formed, or may be a surface on which a plurality of convex portions 14 are formed in an array as shown in FIG. As a method for creating the optical surface of the master 10A, there is diamond cutting.

If the optical surface of the master 10A is a surface on which a single convex portion 14 is formed, it is realized by turning with a diamond tool using a material such as nickel phosphorus, aluminum alloy or free-cutting true casting as a mold material. it can.

If the optical surface of the master 10A is a surface on which a plurality of convex portions 14 are formed in an array, the shape of the optical surface is cut using a ball end mill having a cutting edge made of diamond. At this time, the cutting edge of the tool is not a complete arc, and an error occurs in the machining shape depending on the location where the cutting edge is used. Therefore, when cutting any part of the optical surface shape, the position of the cutting edge used is the same. Thus, it is desirable to work while adjusting the tilt of the tool.

In order to perform such processing, the processing machine needs at least 3 translational degrees of freedom and 2 rotational degrees of freedom, and can only be realized by a processing machine having a total of 5 or more degrees of freedom, so the optical surface of the master 10A is formed. In this case, a processing machine having 5 or more degrees of freedom is used.
<Submaster>
As shown in FIG. 2, the sub master 20 includes a sub master molding portion 22 and a sub master substrate 26. A plurality of concave portions 24 are formed in the sub master molding portion 22 in an array. The surface (molding surface) shape of the recess 24 is a negative shape corresponding to the lens portion 5 in the wafer lens 1, and is recessed in a substantially hemispherical shape in FIG. 2.
≪Submaster molding part≫
The sub master molding part 22 is formed of a resin 22A (second curable resin). As the resin 22A, a resin having good releasability, particularly a transparent resin is preferable. It is excellent in that it can be released without applying a release agent. As the resin, any of a photo-curing resin, a thermosetting resin, and a thermoplastic resin may be used.

Examples of the photo-curable resin include a fluorine-based resin, and examples of the thermosetting resin include a fluorine-based resin and a silicone-based resin. Among them, a resin having good releasability, that is, a resin having a low surface energy when cured is preferable. Examples of the thermoplastic resin include transparent and relatively good releasable olefin resins such as polycarbonate and cycloolefin polymer. In addition, the release property is improved in the order of fluorine resin, silicone resin, and olefin resin. In this case, the sub master substrate 26 may be omitted. By using such a resin, it can be bent, so that it becomes more advantageous at the time of mold release.

Hereinafter, the fluorine resin, the silicone resin, and the thermoplastic resin will be described in detail.
(Fluorine resin)
As fluororesin, PTFE (polytetrafluoroethylene), PFA (tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer), FEP (tetrafluoroethylene / hexafluoropropylene copolymer (4,6 fluorinated)), ETFE (tetrafluoroethylene / ethylene copolymer), PVDF (polyvinylidene fluoride (difluoride)), PCTFE (polychlorotrifluoroethylene (trifluoride)), ECTFE (chlorotrifluoroethylene / ethylene copolymer) ), PVF (polyvinyl fluoride) and the like.

Fluorine-based resin has advantages such as releasability, heat resistance, chemical resistance, insulation, and low friction, but the disadvantage is that it is inferior in transparency because it is crystalline. Since the melting point is high, a high temperature (about 300 ° C.) is required during molding.

Also, the molding method is injection molding, extrusion molding, blow molding, transfer molding, etc. Among them, FEP, PFA, PVDF, etc., which are excellent in light transmittance and can be injection molding and extrusion molding, are particularly preferable.

Examples of melt moldable grades include Asahi Glass Fluon PFA, Sumitomo 3M Dyneon PFA, Dyneon THV, and the like. In particular, the Dyneon THV series is preferable because it has a low melting point (about 120 ° C.) and can be molded at a relatively low temperature and is highly transparent.

As a thermosetting amorphous fluororesin, CYTOP Grade S manufactured by Asahi Glass is preferable because of its high transmittance and good releasability.
(Silicone resin)
Silicone resins include one-part moisture curing type and two-part addition reaction type and two-part condensation type.

Advantages include releasability, flexibility, heat resistance, flame resistance, moisture permeability, low water absorption, and many transparent grades, but disadvantages include large linear expansion.

In particular, a silicone resin for mold making that contains a PDMS (polydimethylsiloxane) structure is preferable because of good release properties, and a highly transparent grade of RTV elastomer is desirable. For example, TSE3450 manufactured by Momentive Performance Materials (two-component mixed, additive type), ELASTOSIL M 4647 (two-component RTV silicone rubber) manufactured by Asahi Kasei Wacker Silicone, and KE-1603 manufactured by Shin-Etsu Silicone (added two-component mixed, added) Type RTV rubber), SH-9555 manufactured by Toray Dow Corning (two-component mixed, addition type RTV rubber), SYLGARD 184, Sylpot 184, WL-5000 series (photosensitive silicone buffer material, which can be patterned by UV) and the like are preferable.

In the case of a two-component RTV rubber, the molding method is room temperature curing or heat curing.
(Thermoplastic resin)
Examples of the thermoplastic resin include transparent resins such as alicyclic hydrocarbon resins, acrylic resins, polycarbonate resins, polyester resins, polyether resins, polyamide resins, and polyimide resins. A hydrocarbon-based resin is preferably used. If the submaster 20 is made of a thermoplastic resin, the injection molding technique that has been conventionally performed can be used as it is, and the submaster 20 can be easily manufactured. If the thermoplastic resin is an alicyclic hydrocarbon-based resin, the hygroscopic property is low, so the life of the submaster 20 is extended. In addition, since cycloaliphatic hydrocarbon resins such as cycloolefin resins are excellent in light resistance and light transmittance, in order to cure actinic ray curable resins, light having a short wavelength such as a UV light source may be used. There is little deterioration and it can be used as a mold for a long time.

Examples of the alicyclic hydrocarbon-based resin include those represented by the following formula (1).

In the formula (1), “x” and “y” represent copolymerization ratios and are real numbers satisfying 0/100 ≦ y / x ≦ 95/5. “N” is 0, 1 or 2, and represents the number of substitutions of the substituent Q. “R ¹ ” is one or more (2 + n) -valent groups selected from a hydrocarbon group having 2 to 20 carbon atoms. “R ² ” is a hydrogen atom or a monovalent group of one or more selected from the group consisting of carbon and hydrogen and having 1 to 10 carbon atoms. “R ³ ” is one or two or more divalent groups selected from a hydrocarbon group having 2 to 20 carbon atoms. “Q” is COOR ₄ (R ₄ is a hydrogen atom or a hydrocarbon, and is one or more monovalent groups selected from a structural group having 1 to 10 carbon atoms). It is 1 type or 2 or more types of monovalent group chosen from the structural group made.

In the formula (1), R ¹ is preferably one or more divalent groups selected from the group of hydrocarbon groups having 2 to 12 carbon atoms, more preferably the following formula (2) (formula ( In 2), p is an integer of 0 to 2.);

And more preferably a divalent group in which p is 0 or 1 in the formula (2). The structure of R ¹ may be used alone or in combination of two or more. Examples of R ² include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and a 2-methylpropyl group, preferably a hydrogen atom and / or Or a methyl group, and most preferably a hydrogen atom. As an example of R ³ , as a preferred example of a structural unit containing this group, when n = 0, for example, the following formula (a), formula (b), formula (c) (provided formulas (a) to ( c) wherein R ¹ is as described above;

Etc. N is preferably 0.

In this embodiment, the type of copolymerization is not particularly limited, and known copolymerization types such as random copolymerization, block copolymerization, and alternating copolymerization can be applied, but random copolymerization is preferable. is there.

In addition, the polymer used in the present embodiment has a repeating structural unit derived from another copolymerizable monomer as required, as long as the physical properties of the product obtained by the molding method of the present embodiment are not impaired. You may do it. The copolymerization ratio is not particularly limited, but is preferably 20 mol% or less, more preferably 10 mol% or less. When the copolymerization is further performed, the optical characteristics are impaired and a high-precision optical component is obtained. May not be obtained. The type of copolymerization at this time is not particularly limited, but random copolymerization is preferred.

As another example of a preferable thermoplastic alicyclic hydrocarbon polymer applied to the submaster 20, the repeating unit having an alicyclic structure has an alicyclic structure represented by the following formula (4). The total content of the repeating unit (a) and the repeating unit (b) having a chain structure represented by the following formula (5) and / or the following formula (6) and / or the following formula (7) is 90 mass. Examples thereof include a polymer that is contained so as to be at least% and the content of the repeating unit (b) is 1% by mass or more and less than 10% by mass.

In formula (4), formula (5), formula (6) and formula (7), R21 to R33 each independently represent a hydrogen atom, a chain hydrocarbon group, a halogen atom, an alkoxy group, a hydroxy group, an ether group, Chains substituted with ester groups, cyano groups, amino groups, imide groups, silyl groups, and polar groups (halogen atoms, alkoxy groups, hydroxy groups, ester groups, cyano groups, amide groups, imide groups, or silyl groups) Represents a hydrocarbon group or the like. Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the chain hydrocarbon group substituted with a polar group include, for example, 1 to 20 carbon atoms, preferably Examples thereof include 1 to 10, more preferably 1 to 6 halogenated alkyl groups. As the chain hydrocarbon group, for example, an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms: 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms. 6 alkenyl groups.

X in the formula (4) represents an alicyclic hydrocarbon group, and the number of carbon atoms constituting the group is usually 4 to 20, preferably 4 to 10, more preferably 5 to 7. is there. Birefringence can be reduced by setting the number of carbon atoms constituting the alicyclic structure within this range. The alicyclic structure is not limited to a monocyclic structure, and may be a polycyclic structure such as a norbornane ring.

The alicyclic hydrocarbon group may have a carbon-carbon unsaturated bond, but the content thereof is 10% or less, preferably 5% or less, more preferably 3% or less of the total carbon-carbon bonds. is there. By setting the carbon-carbon unsaturated bond of the alicyclic hydrocarbon group within this range, transparency and heat resistance are improved. The carbon constituting the alicyclic hydrocarbon group includes a hydrogen atom, hydrocarbon group, halogen atom, alkoxy group, hydroxy group, ester group, cyano group, amide group, imide group, silyl group, and polar group ( A chain hydrocarbon group substituted with a halogen atom, an alkoxy group, a hydroxy group, an ester group, a cyano group, an amide group, an imide group, or a silyl group) may be bonded,
Among these, a hydrogen atom or a chain hydrocarbon group having 1 to 6 carbon atoms is preferable in terms of heat resistance and low water absorption.

Further, formula (6) has a carbon-carbon unsaturated bond in the main chain, and formula (7) has a carbon-carbon saturated bond in the main chain. Is strongly required, the content of unsaturated bonds is usually 10% or less, preferably 5% or less, more preferably 3% or less, of all carbon-carbon bonds constituting the main chain.

In the present embodiment, the repeating unit (a) having an alicyclic structure represented by the formula (4) in the alicyclic hydrocarbon copolymer, the formula (5) and / or the formula (6). And / or the total content of the chain-structured repeating unit (b) represented by the general formula (7) is usually 90% or more, preferably 95% or more, more preferably 97% or more, on a mass basis. is there. By setting the total content within the above range, low birefringence, heat resistance, low water absorption, and mechanical strength are highly balanced.

As a production method for producing the alicyclic hydrocarbon copolymer, an aromatic vinyl compound is copolymerized with another monomer that can be copolymerized, and a carbon-carbon unsaturated bond of the main chain and the aromatic ring is formed. The method of hydrogenating is mentioned.

The molecular weight of the copolymer before hydrogenation is 1,000 to 1,000,000, preferably 5,000 to 500,000 in terms of polystyrene (or polyisoprene) equivalent weight average molecular weight (Mw) measured by GPC. More preferably, it is in the range of 10,000 to 300,000. When the mass average molecular weight (Mw) of the copolymer is excessively small, the strength characteristics of the molded product of the alicyclic hydrocarbon copolymer obtained therefrom are inferior, and conversely when it is excessively large, the hydrogenation reactivity is inferior.

Specific examples of the aromatic vinyl compound used in the above method include, for example, styrene, α-methylstyrene, α-ethylstyrene, α-propylstyrene, α-isopropylstyrene, α-t-butylstyrene, 2- Methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-diisopropylstyrene, 2,4-dimethylstyrene, 4-t-butylstyrene, 5-t-butyl-2-methylstyrene, monochlorostyrene, dichlorostyrene Monofluorostyrene, 4-phenylstyrene and the like, and styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene and the like are preferable. These aromatic vinyl compounds can be used alone or in combination of two or more.

Other monomers that can be copolymerized are not particularly limited, but chain vinyl compounds and chain conjugated diene compounds are used. When chain conjugated dienes are used, the operability in the production process is excellent. The resulting alicyclic hydrocarbon copolymer is excellent in strength properties.

Specific examples of the chain vinyl compound include chain olefin monomers such as ethylene, propylene, 1-butene, 1-pentene and 4-methyl-1-pentene; 1-cyanoethylene (acrylonitrile), 1-cyano- Nitrile monomers such as 1-methylethylene (methacrylonitrile) and 1-cyano-1-chloroethylene (α-chloroacrylonitrile); 1- (methoxycarbonyl) -1-methylethylene (methacrylic acid methyl ester), 1- (Ethoxycarbonyl) -1-methylethylene (methacrylic acid ethyl ester), 1- (propoxycarbonyl) -1-methylethylene (methacrylic acid propyl ester), 1- (butoxycarbonyl) -1-methylethylene (methacrylic) Acid butyl ester), 1-methoxycarbo (Meth) acrylic acid such as ruethylene (acrylic acid methyl ester), 1-ethoxycarbonylethylene (acrylic acid ethyl ester), 1-propoxycarbonylethylene (acrylic acid propyl ester), 1-butoxycarbonylethylene (acrylic acid butyl ester) Examples include ester monomers, unsaturated fatty acid monomers such as 1-carboxyethylene (acrylic acid), 1-carboxy-1-methylethylene (methacrylic acid), and maleic anhydride, among which chain olefin monomers are preferred, Most preferred are ethylene, propylene and 1-butene.

Examples of the chain conjugated diene include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and the like. Of these chain vinyl compounds and chain conjugated dienes, chain conjugated dienes are preferable, and butadiene and isoprene are particularly preferable. These chain vinyl compounds and chain conjugated dienes can be used alone or in combination of two or more.

The polymerization reaction is not particularly limited, such as radical polymerization, anionic polymerization, and cationic polymerization. However, the polymerization operation, the ease of the hydrogenation reaction in the post-process, and the mechanical properties of the finally obtained hydrocarbon copolymer are not limited. In view of strength, the anionic polymerization method is preferable.

In the case of anionic polymerization, bulk polymerization, solution polymerization, slurry polymerization, etc. in the temperature range of usually 0 ° C. to 200 ° C., preferably 20 ° C. to 100 ° C., particularly preferably 20 ° C. to 80 ° C. in the presence of an initiator. However, solution polymerization is preferable in view of removal of reaction heat. In this case, an inert solvent capable of dissolving the polymer and its hydride is used. Examples of the inert solvent used in the solution reaction include aliphatic hydrocarbons such as n-butane, n-pentane, iso-pentane, n-hexane, n-heptane, and iso-octane; cyclopentane, cyclohexane, methylcyclopentane, Examples thereof include alicyclic hydrocarbons such as methylcyclohexane and decalin; aromatic hydrocarbons such as benzene and toluene. Examples of the initiator for anionic polymerization include monoorganolithium such as n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, and phenyllithium, dilithiomethane, 1,4-diobtan, 1,4-dilithiol. A polyfunctional organolithium compound such as 2-ethylcyclohexane can be used.

When carrying out hydrogenation reactions such as carbon-carbon double bonds of unsaturated rings such as aromatic rings and cycloalkene rings of the copolymer before hydrogenation, and unsaturated bonds of the main chain, the reaction method and reaction form are special. There is no particular limitation, and it may be carried out according to a known method, but a hydrogenation method that can increase the hydrogenation rate and has little polymer chain scission reaction that occurs simultaneously with the hydrogenation reaction is preferable, for example, in an organic solvent, nickel, The method is performed using a catalyst containing at least one metal selected from cobalt, iron, titanium, rhodium, palladium, platinum, ruthenium, and rhenium. The hydrogenation reaction is usually from 10 ° C. to 250 ° C., but preferably from 50 ° C. to 200 ° C. because the hydrogenation rate can be increased and the polymer chain scission reaction that occurs simultaneously with the hydrogenation reaction can be reduced. More preferably, it is 80 ° C to 180 ° C. The hydrogen pressure is usually 0.1 MPa to 30 MPa, but in addition to the above reasons, it is preferably 1 MPa to 20 MPa, more preferably 2 MPa to 10 MPa from the viewpoint of operability.

The hydrogenation rate of the hydride obtained in this way is determined by ¹ H-NMR as measured by the main chain carbon-carbon unsaturated bond, aromatic ring carbon-carbon double bond, unsaturated ring carbon- All of the carbon double bonds are usually 90% or more, preferably 95% or more, more preferably 97% or more. When the hydrogenation rate is low, the low birefringence, thermal stability, etc. of the resulting copolymer are lowered.

The method for recovering the hydride after completion of the hydrogenation reaction is not particularly limited. Usually, after removing the hydrogenation catalyst residue by a method such as filtration or centrifugation, the solvent is removed directly from the hydride solution by drying, the hydride solution is poured into a poor solvent for the hydride, and the hydride A method of coagulating can be used.
≪Sub-master board≫
Even if the submaster substrate 26 is inferior in strength only by the submaster molding portion 22 of the submaster 20, the strength of the submaster 20 can be increased by pasting resin on the substrate, and the submaster substrate 26 can be molded many times. It is a material.

The sub-master substrate 26 may be any material that can produce high smoothness, such as quartz, silicone wafer, metal, glass, and resin.

From the viewpoint of transparency, considering that UV irradiation can be performed from above or below the submaster 20, a transparent mold such as quartz, glass, or transparent resin is preferable. The transparent resin may be any of a thermoplastic resin, a thermosetting resin, and a UV curable resin, and may have an effect of reducing the linear expansion coefficient by adding fine particles to the resin. By using a resin in this way, it is easier to release when it is released because it bends than glass. However, since the resin has a large coefficient of linear expansion, the shape is deformed when heat is generated during UV irradiation. It may not be possible to transfer clearly. Therefore, such a problem can also be avoided by using resin as the backing material. As the backing material, a glass material may be used from the viewpoint of strength. In that case, however, there is a difference in linear expansion between the resin constituting the submaster molding portion 22 and the material constituting the backing material from the above viewpoint. The difference is preferably small, and the difference in linear expansion coefficient is preferably 3 × 10 ⁻⁵ / K or less.

Next, a method for manufacturing the wafer lens 1 will be described with reference to FIG.

As shown in FIG. 3A, a resin 22A is applied on the master 10A, the convex portions 14 of the master 10A are transferred to the resin 22A, the resin 22A is cured, and a plurality of concave portions 24 are formed on the resin 22A. Thereby, the sub master molding part 22 is formed.

The resin 22A may be thermosetting, photocurable, or volatile curable (HSQ (hydrogensilsesquioxane or the like) that is cured by volatilization of the solvent). In the case where high-precision molding transferability is important, molding with UV curable or volatile curable resin, which is less affected by thermal expansion of resin 22A, is preferable because it does not apply heat to curing, but is not limited thereto. Since the resin 22A having good releasability from the master 10A after curing does not require a large force at the time of peeling, the molded optical surface shape and the like are more preferable without being inadvertently deformed.

In the case where the resin 22A (the material of the sub-master molding part 22) and the resin 5A (the material of the lens part 5) are curable resins, the optical surface shape (convex part 14) of the master 10A is preferably cure shrinkage of the resin 22A. And designed in anticipation of cure shrinkage of resin 5A.

When the resin 22A is applied on the master 10A, a technique such as spray coating or spin coating is used. In this case, the resin 22A may be applied while evacuating. If the resin 22A is applied while evacuating, the resin 22A can be cured without introducing bubbles into the resin 22A.

Further, when spray coating, spin coating or the like is not performed on the master 10A, it is preferable to apply a release agent to the surface of the master 10A.

When applying a release agent, the surface of the master 10A is modified. Specifically, an OH group is made to stand on the surface of the master 10A. The method for modifying the surface may be any method as long as OH groups are set on the surface of the master 10A, such as UV ozone cleaning and oxygen plasma ashing.

As the release agent, a material having a hydrolyzable functional group bonded to the end, such as a silane coupling agent structure, that is, dehydration condensation or hydrogen bonding with an OH group present on the metal surface is caused. And those having a structure that binds to each other. In the case of a release agent having a silane coupling structure at the end and a release function at the other end, the more OH groups are formed on the surface of the master 10A, the more covalently bonded sites are on the surface of the master 10A. Increases and allows stronger bonds. As a result, even if the molding operation is executed a plurality of times, the durability can be improved without diminishing the releasing effect. Moreover, since a primer (underlayer, SiO ₂ coat, etc.) is not required, the effect of improving the durability can be obtained while keeping the thin film.

The material having a hydrolyzable functional group bonded to the terminal preferably includes a material composed of an alkoxysilane group, a halogenated silane group, a quaternary ammonium salt, a phosphate ester group or the like as a functional group. Further, the terminal group may be a group that causes a strong bond with the mold, such as triazine thiol. Specifically, it has an alkoxysilane group (8) or a halogenated silane group (9) represented by the following general formula.

-Si (OR1) nR2 (3-n) (8)
-SiXmR3 (3-m) (9)
Here, R1 and R2 are alkyl groups (eg, methyl, ethyl, propyl, butyl, etc.), n and m are 1, 2 or 3, and R3 is an alkyl group (eg, methyl, ethyl, propyl) Group, butyl group, etc.) or alkoxy group (for example, methoxy group, ethoxy group, butoxy group, etc.). X is a halogen atom (for example, Cl, Br, I).

Further, when two or more of R1, R2, R3 or X are bonded to Si, they may be different within the above group or atom range, for example, so that two Rm are an alkyl group and an alkoxy group. Good.

The alkoxysilane group —SiOR1 and the halogenated silane group —SiX react with moisture to become —SiOH, which further undergoes dehydration condensation or hydrogen bonding with the OH group present on the surface of the mold material such as glass or metal. Wake up and join.

FIG. 12 shows a reaction diagram of a mold release agent using an alkoxysilane group as an example of a hydrolyzable functional group at the terminal and an OH group on the surface of the master 10A.

In FIG. 12A, —OR represents methoxy (—OCH ₃ ) or ethoxy (—OC ₂ H ₅ ), and generates methanol (CH ₃ OH) or ethanol (C ₂ H ₅ OH) by hydrolysis. Thus, silanol (-SiOH) in FIG. Thereafter, it is partially dehydrated and condensed to form a silanol condensate as shown in FIG. Further, as shown in FIG. 12 (d), it is adsorbed by OH groups and hydrogen bonds on the surface of the master 10 (inorganic material), and finally dehydrated as shown in FIG. 12 (e) to form —O—chemical bonds (covalent bonds). To do. FIG. 12 shows the case of an alkoxysilane group, but basically the same reaction occurs in the case of a halogenated silane group.

That is, the mold release agent used in the present invention is chemically bonded to the surface of the master 10A at one end and the functional group is oriented at the other end to cover the master 10A, and is thin and uniform in durability. A release layer can be formed.

A structure having a releasability function preferably has a low surface energy, such as a fluorine-substituted hydrocarbon group or a hydrocarbon group.
(Fluorine release agent)
Fluorine-substituted hydrocarbon groups include fluorine-substituted hydrocarbons that have a perfluoro group (a and b are integers) such as CF3 (CF2) a- and CF3 / CF3 / CF (CF2) b- groups at one end of the molecular structure. A hydrocarbon group is preferable, and the length of the perfluoro group is preferably 2 or more, and the number of CF2 groups following CF3 of CF3 (CF2) a- is 5 or more.

In addition, the perfluoro group does not need to be a straight chain and may have a branched structure. Furthermore, a structure such as CF3 (CF2) c- (CH2) d- (CF2) e- may be used in response to recent environmental problems. In this case, c is 3 or less, d is an integer (preferably 1), and e is 4 or less.

The above-mentioned fluorine release agent is usually a solid, but in order to apply it to the surface of the master 10A, it is necessary to make it a solution dissolved in an organic solvent. Depending on the molecular structure of the release agent, a fluorinated hydrocarbon solvent or a mixture of some organic solvent is suitable as the solvent. The concentration of the solvent is not particularly limited, but the required release film is characterized by being particularly thin. Therefore, a low concentration is sufficient, and it may be 1 to 3% by mass.

In order to apply this solution to the surface of the master 10A, a normal coating method such as dip coating, spray coating, brush coating, spin coating or the like can be used. After application, the solvent is evaporated by natural drying to obtain a dry coating film. The film thickness applied at this time is suitably 20 μm or less.

Specific examples include Optool DSX from Daikin Industries, Durasurf HD-1100, HD-2100, Novec EGC1720 from Sumitomo 3M, Triazine thiol deposition from Takeuchi's vacuum coating, Amorphous fluorine Cytop grade M from AGC, Antifouling from N Material Coat OPC-800 etc. are mentioned.
(Hydrocarbon release agent)
The hydrocarbon group may be linear, such as CnH2n + 1, or may be branched, and a silicone-based mold release agent is applicable.

Conventionally, a number of compositions are known as compositions having an organopolysiloxane resin as a main component and forming a cured film exhibiting water repellency. For example, JP-A-55-48245 discloses a hydroxyl group-containing methylpolysiloxane resin, α, ω-dihydroxydiorganopolysiloxane, and organosilane, which are cured to have excellent releasability and antifouling properties and water repellency. Compositions that form certain films have been proposed. Japanese Patent Application Laid-Open No. 59-140280 discloses a composition mainly composed of a partial cohydrolyzed condensate of an organosilane mainly composed of a perfluoroalkyl group-containing organosilane and an amino group-containing organosilane. A composition that forms a cured film excellent in oil repellency has been proposed.

Specific examples include AGC Seimi Chemical's mold spat, Matsumoto Fine Chemical's Olga Chicks SIC-330, 434, Toray Dow Chemical's SR-2410, and the like. Moreover, as a self-assembled monomolecular film, SAMLAY manufactured by Nippon Soda is cited.

As shown in FIG. 3A, when the resin 22A is a photocurable resin, the light source 50 disposed above the master 10A is turned on and irradiated with light.

Examples of the light source 50 include a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, a halogen lamp, a fluorescent lamp, a black light, a G lamp, and an F lamp, and may be a linear light source or a point light source. Good. The high-pressure mercury lamp is a lamp having a narrow spectrum at 365 nm and 436 nm. A metal halide lamp is a kind of mercury lamp, and its output in the ultraviolet region is several times higher than that of a high-pressure mercury lamp. A xenon lamp is a lamp having a spectrum closest to sunlight. Halogen lamps contain a lot of long-wavelength light and are mostly near-infrared light. A fluorescent lamp has an irradiation intensity equal to the three primary colors of light. Black light has a peak top at 351 nm and emits near-ultraviolet light from 300 nm to 400 nm.

When light is emitted from the light source 50, a plurality of linear or point light sources 50 may be arranged in a lattice shape so that light reaches the entire surface of the resin 22A at one time. The light source 50 may be scanned in parallel to the surface of the resin 22A so that the light sequentially reaches the resin 22A. In this case, preferably, the luminance distribution and the illuminance (intensity) distribution during light irradiation are measured, and the number of irradiations, the irradiation amount, the irradiation time, and the like are controlled based on the measurement results.

After photocuring the resin 22A (after the production of the submaster 20), the submaster 20 may be post-cured (heat treatment). If post cure is performed, the resin 22A of the submaster 20 can be completely cured, and the mold life of the submaster 20 can be extended.

When the resin 22A is a thermosetting resin, the resin 22A is heated while controlling the heating temperature and heating time within an optimal range. The resin 22A can also be molded by techniques such as injection molding, press molding, light irradiation and subsequent cooling.

3B, the sub master substrate 26 is mounted on the back surface (the surface opposite to the concave portion 24) of the sub master molding portion 22 (resin 22A), and the sub master molding portion 22 is lined.

The sub-master substrate 26 may be quartz or a glass plate, and it is important to have sufficient bending strength and UV transmittance. In order to improve the adhesion between the sub-master molding part 22 and the sub-master substrate 26, a treatment such as applying a silane coupling agent may be performed on the sub-master substrate 26.

As described above, after the convex portion 14 of the master 10A is transferred to the resin 22A and the resin 22A is cured (that is, after the submaster molding portion 22 is formed), the submaster substrate 26 is mounted (room temperature). Use an adhesive.

Conversely, the convex portion 14 of the master 10A may be transferred to the resin 22A, and the sub-master substrate 26 may be mounted (backed at room temperature) before the resin 22A is cured. In this case, without using an adhesive, the sub-master substrate 26 is attached by the adhesive force of the resin 22A, or a coupling agent is applied to the sub-master substrate 26 to increase the adhesive force and thereby apply the resin 22A to the resin 22A. On the other hand, the sub master substrate 26 is attached.

Further, when backing the sub master molding portion 22 (resin 22A) with the sub master substrate 26, a known vacuum chuck device 260 is used, and the sub master substrate 26 is sucked and held on the suction surface 260A of the vacuum chuck device 260. The sub master molding portion 22 is preferably lined with the sub master substrate 26 with the suction surface 260A parallel to the molding surface of the convex portion 14 in the master 10A. Thereby, the back surface 20A of the sub master 20 (surface on the sub master substrate 26 side) is parallel to the molding surface of the convex portion 14 in the master 10A, and the molding surface of the recess 24 in the sub master 20 is parallel to the back surface 20A. . Therefore, when the lens unit 5 is molded by the submaster 20 as will be described later, the reference surface of the submaster 20, that is, the back surface 20 </ b> A can be made parallel to the molding surface of the recess 24. And variation in thickness can be prevented, and the shape accuracy of the lens unit 5 can be improved. Further, since the sub master 20 is sucked and held by the vacuum chuck device 260, the sub master 20 can be attached and detached only by turning on / off the vacuum exhaust. Therefore, the sub master 20 can be easily arranged.

Here, that the back surface 20A is parallel to the molding surface of the recess 24 specifically means that the back surface 20A is perpendicular to the central axis of the molding surface of the recess 24.

The sub master 20 is preferably formed by being cured while being lined with the sub master substrate 26, but may be formed by being cured before being lined. As a method of curing while backing the sub master substrate 26, for example, a thermosetting resin is used as the resin 22A, and these are put into a baking furnace in a state where the resin 22A is filled between the master 10A and the sub master substrate 26. Method, and using a UV curable resin as the resin 22A, using a UV transmissive substrate as the sub master substrate 26, and filling the resin 22A between the master 10A and the sub master substrate 26, the sub master substrate 26 There is a method of irradiating the resin 22A with UV light from the side.

Further, the suction surface 260A of the vacuum chuck device 260 is preferably made of a ceramic material. In this case, the hardness of the suction surface 260A is increased, and the suction surface 260A is not easily damaged by the attachment / detachment of the submaster 20 (submaster substrate 26), so that the surface accuracy of the suction surface 260A can be maintained high. Moreover, it is preferable to use silicon nitride or sialon as such a ceramic material. In this case, since the linear expansion coefficient is as small as 1.3 ppm, the flatness of the suction surface 260A can be kept high with respect to the temperature change.

In the present embodiment, the following method is used as a method for bringing the suction surface 260A in parallel with the molding surface of the convex portion 14 in the master 10A.

First, the front and back surfaces of the master 10A are parallelized with high accuracy. Thereby, in the master 10A, the shaping | molding surface and back surface of the convex part 14 become parallel.

Further,

reference members

260C and 260D are provided so as to protrude from the support surface 260B that supports the master 10A from the back surface (surface opposite to the convex portion 14) and the suction surface 260A, respectively. Here, the shapes of these

reference members

260C and 260D are such that there is no backlash when the master 10A and the sub-master 20 come into contact with each other with the support surface 260B and the suction surface 260A in parallel with each other.

Thereby, by bringing the

reference members

260C and 260D into contact with each other, the support surface 260B of the master 10A, and consequently the molding surface of the convex portion 14 in the master 10, becomes parallel to the suction surface 260A.

However, in such a method, the reference member may be provided on at least one of the support surface 260B and the suction surface 260A. For example, when the reference member is provided only on the support surface 260B, the shape of the reference member is the support surface. When the master 10A and the sub master 20 are in contact with each other in a state where the 260B and the suction surface 260A are parallel to each other, the shape may be such that the suction surface 260A contacts with no backlash. Similarly, when the reference member is provided only on the suction surface 260A, the shape of the reference member is such that the support surface 260B and the suction surface 260A are supported when the master 10A and the sub master 20 are in contact with each other. What is necessary is just to make it the shape which does not rattle with respect to the surface 260B, and contact | abuts.

As shown in FIG. 3C, the sub master 20 is formed by releasing the sub master molding portion 22 and the sub master substrate 26 from the master 10A.

If a resin such as PDMS (polydimethylsiloxane) is used as the resin 22A, the releasability from the master 10 is good, so that a large force is not required for peeling from the master 10, and the molding optical surface may be distorted. There is no need.

As shown in FIG. 3D, a resin 5A is filled between the sub-master 20 and the glass substrate 3 and cured. More specifically, the resin 5A is filled in the recess 24 of the submaster 20, and the resin 5A is cured while pressing the glass substrate 3 from above.

When filling the concave portion 24 of the sub master 20 with the resin 5A, the resin 5A is sprayed on the sub master 20 using a technique such as spray coating or spin coating. In this case, the resin 5A may be filled while evacuating. If the resin 5A is filled while evacuating, the resin 5A can be cured without introducing bubbles into the resin 5A.

Instead of filling the concave portion 24 of the submaster 20 with the resin 5A, the resin 5A may be applied to the glass substrate 3, and the glass substrate 3 coated with the resin 5A may be pressed against the submaster 20.

When the glass substrate 3 is pressed, the glass substrate 3 is preferably provided with a structure for axial alignment with the submaster 20. When the glass substrate 3 has a circular shape, for example, it is preferable to form a D cut, an I cut, a marking, a notch, or the like. The glass substrate 3 may have a polygonal shape, and in this case, the axis alignment with the submaster 20 is easy.

When the resin 5A is to be cured, the light source 52 disposed below the sub master 20 may be turned on to emit light from the sub master 20 side, or the light source 54 disposed above the glass substrate 3 may be turned on to turn on the glass substrate. The light may be irradiated from the 3 side, or both the

light sources

52 and 54 may be turned on simultaneously and the light may be irradiated from both the sub master 20 side and the glass substrate 3 side.

As the

light sources

52 and 54, the same high pressure mercury lamp, metal halide lamp, xenon lamp, halogen lamp, fluorescent lamp, black light, G lamp, and F lamp as the light source 50 described above can be used. It may be a point light source.

When irradiating light from the

light sources

52 and 54, a plurality of linear or point

light sources

52 and 54 may be arranged in a lattice shape so that the light reaches the resin 5A at a time. The point

light sources

52 and 54 may be scanned in parallel to the sub master 20 and the glass substrate 3 so that the light sequentially reaches the resin 5A. In this case, preferably, the luminance distribution and the illuminance (intensity) distribution during light irradiation are measured, and the number of irradiations, the irradiation amount, the irradiation time, and the like are controlled based on the measurement results.

When the resin 5A is cured, the lens portion 5 is formed. Thereafter, the lens unit 5 and the glass substrate 3 are released from the sub-master 20 to manufacture the wafer lens 1 (the wafer lens 1 has the lens unit 5 formed only on the surface of the glass substrate 3). .

When the wafer lens 1 is released from the sub master 20, a tension white 60 is provided between the wafer lens 1 (glass substrate 3) and the sub master 20 in advance (see FIG. 3B). The wafer lens 1 may be released from the sub master 20 by pulling.

When the sub-master substrate 26 of the sub-master 20 is an elastic material (resin), the wafer lens 1 may be released from the sub-master 20 by bending it slightly, or the glass substrate 3 is replaced with glass. Even in the case of an elastic material (resin), the wafer lens 1 may be released from the sub master 20 by slightly bending it.

When the wafer lens 1 is slightly separated from the sub master 20 and a gap is formed between both members, air or pure water may be pumped into the gap and the wafer lens 1 may be released from the sub master 20.

In the above description, the method of providing the lens unit 5 on one side of the glass substrate 3 has been described. However, when the lens unit 5 is provided on both sides, first, it corresponds to the optical surface shape of the lens unit 5 on one side of the glass substrate 3. A master (not shown) having a plurality of positive molding surfaces and a master having a plurality of positive molding surfaces corresponding to the optical surface shape of the lens portion 5 on the other surface are prepared, and each of these masters is used. Thus, the

sub masters

20C and 20D (see FIGS. 3E and 3F) are formed. Accordingly, the sub master 20C has a negative molding surface corresponding to the optical surface shape of the lens portion 5 on one surface of the glass substrate 3, and the sub master 20D corresponds to the optical surface shape of the lens portion 5 on the other surface. Will have a negative shaped molding surface. And after filling resin 5A between each submaster 20C and 20D and the glass substrate 3, the resin 5A is hardened and the lens part 5 is shape | molded on both surfaces of the glass substrate 3. FIG. According to this, the resin 5A does not cure and shrink on only one side of the glass substrate 3, and the resin 5A cures and shrinks simultaneously on both sides to become the lens portions 5, respectively. Unlike the case where it provides, since the curvature of the glass substrate 3 can be prevented, the shape accuracy of the lens part 5 can be improved.

Further, when the lens portions 5 are formed on both surfaces of the glass substrate 3, a heating step (post-cure step) may be provided after the resin 5A is cured by irradiating light on both surfaces. By providing the post-cure process, it is possible to suppress a decrease in accuracy due to the curing and shrinkage of the lens unit 5 after taking out from the sub master, and the transfer accuracy is further improved. Moreover, the process which once heats in the state which provided each

submaster

20C and 20D in the both surfaces of the glass substrate 3, releases from a submaster, and heats again may be provided. According to such a configuration, curing shrinkage can be suppressed to some extent in the first heating step, and the hardness of the lens can be increased by heating again, and the time for using the submaster mold can be increased. Since it becomes possible to shorten, manufacturing efficiency can be improved. It is also preferable to provide a plurality of heating steps at different temperatures in a state where the

sub-master molds

20C and 20D are provided on both surfaces of the glass substrate 3. In the first heating process, it is possible to accelerate curing by heating at a relatively low temperature, and to suppress curing shrinkage after removal, and in the second heating process, it is relatively higher than the first heating process. By heating at a temperature, it becomes possible to improve the releasability from the submaster.

Here, in order to fill the resin 5A between the sub-masters 20C and 20D and the glass substrate 3, two methods can be used.

In the first method, as shown in FIGS. 3E and 3F, after the resin 5A is dropped or discharged onto the upper surface of the submaster 20C, the submaster 20C and the glass substrate disposed above the submaster 20C are disposed. 3 and the glass substrate 3 and the sub-master 20C are filled with the resin 5A, and then the glass substrate 3 and the sub-master 20C are integrally turned upside down in a state of contacting each other. And after dripping or discharging the resin 5A onto the upper surface of the sub master 20D, the sub master 20D is brought into contact with the glass substrate 3 disposed above the sub master 20D, and the glass substrate 3 and the sub master 20D are brought into contact with each other. The resin 5A is filled.

In the second method, after the resin 5A is dropped or discharged onto the upper surface of the glass substrate 3, the glass substrate 3 and the sub master 20C disposed above the glass substrate 3 are brought into contact with each other. The resin 5A is filled between the masters 20C, and after the resin 5A is dropped or discharged onto the upper surface of the submaster 20D, the submaster 20D is brought into contact with the glass substrate 3 disposed thereabove. Then, the resin 5A is filled between the glass substrate 3 and the sub master 20D.

It should be noted that when the glass substrate 3 and the sub-masters 20C and 20D are brought into contact with each other, it is preferable that no bubbles remain. The resin 5A used here may be a thermosetting resin, a UV curable resin, or a volatile curable resin (HSQ or the like). When a UV curable resin is used, at least one of the sub-masters 20C and 20D is made to be UV transmissive so that the UV light is irradiated on the resin 5A on both surfaces of the glass substrate 3 from one sub-master side at a time. be able to.

Here, when the lens portions 5 are formed on both the front and back surfaces of the glass substrate 3, as shown in FIG. 7, the sub master 20 is doubled vertically and horizontally (magnification can be changed). The diameter submaster 200 and the normal submaster 20 of FIG. 8 are prepared. When the lens unit 5 is formed on the surface of the glass substrate 3, the sub master 200 is used, and when the lens unit 5 is formed on the reverse side, the sub master 20 is used a plurality of times. May be.

Specifically, the lens portion 5 is formed in a lump on the surface of the glass substrate 3 using the large-diameter submaster 200. On the back surface of the glass substrate 3 thereafter, as shown in FIG. 9, the lens unit 5 is formed by using the submaster 20 four times while shifting the submaster 20 by a quarter of the large-diameter submaster 200. To do. According to such a configuration, the axis alignment of the sub master 20 is easy with respect to the glass substrate 3 having the lens portion 5 formed using the large-diameter submaster 200, and the lens formed using the large-diameter submaster 200. It is possible to suppress a situation in which the portion 5 and the lens portion 5 formed using the sub master 20 are misaligned on the front and back of the glass substrate 3.

However, when using the large-diameter submaster 200, as shown in the upper to lower stages of FIG. 10, there is a possibility that the submaster molding portion 22 may be slightly warped, so that the original function as a mold is exhibited. May not be possible. Therefore, as shown in FIG. 11, a region (stress relaxation portion 210) in which the resin 22 </ b> A does not exist in a cross shape is provided in the center so as to divide the large-diameter submaster 200, and the submaster molding portion 22 of the large-diameter submaster 200 It is preferable to adopt a configuration that suppresses the occurrence of warping (relaxes stress with the glass substrate 3). The stress relaxation unit 210 may be a region where the resin 22A does not exist as in the present embodiment, or the resin may be formed thin. Moreover, the stress relaxation part 210 may be provided every several lens shaping | molding parts, and may be provided so that each lens shaping | molding part may be enclosed. When such a stress relieving part is provided, in addition to suppressing the warpage of the submaster 20, it is also possible to suppress a displacement in the surface direction and a decrease in molding accuracy due to shrinkage.

In the case where the stress relieving portion 210 is provided, for example, when the resin 22A is a photocurable resin, the glass substrate 3 or the sub master substrate 26 is masked to form an unirradiated portion, or the

light sources

52 and 54 are masked. Thus, an unirradiated portion of light may be formed.

Note that the master 10B may be used in place of the master 10A, and the wafer lens 1 may be manufactured directly from the master 10B without manufacturing the sub-master 20.

In this case, the recess 5 of the master 10B is filled with the resin 5A, the resin 5A is cured while pressing the glass substrate 3 from above, and then the glass substrate 3 and the lens unit 5 are released from the master 10B. .

The mold release for peeling the resin 5A from the master 10B is important, and two types of mold release methods are conceivable.

As a first method, a release agent is added to the resin 5A. In this case, the adhesion of the anti-reflection coating, which is a subsequent process, is lowered, or the adhesion to the glass substrate 3 is lowered. Preferably, a coupling agent or the like is applied to the glass substrate 3 to enhance the adhesion. To do.

As a second method, a release agent is coated on the surface of the master 10B. As the release agent, triazine dithiol, a release agent that forms a fluorine-based or silicon-based monomolecular layer can be used. By using a release agent, it is possible to coat the film to a thickness that does not affect the optical surface shape, with a film thickness of about 10 nm. In order to increase the adhesion so that the release agent does not peel off during molding, the coupling agent is applied to the master 10B, or the master 10B is coated with SiO ₂ or the like that creates a bridge between the release agent and the master 10B. If done, the adhesion may be increased.
[Second Embodiment]
The second embodiment is mainly different from the first embodiment in the following points, and is otherwise substantially the same.

When the wafer lens 1 is manufactured, a master 10, a sub master 30, and a sub sub master 40 shown in FIG. 4 are used as molds for molding. In the first embodiment, the sub-master 20 is used to manufacture the wafer lens 1 from the master 10 (10A), whereas in the second embodiment, the wafer lens 1 is mainly from the master 10 (10B). The difference is that two types of sub-master 30 and sub-sub-master 40 are used to manufacture the sub-master. In particular, the process of manufacturing the sub master 30 from the master 10B and the process of manufacturing the wafer lens 1 from the sub sub master 40 are substantially the same as in the first embodiment, and the first is that the sub sub master 40 is manufactured from the sub master 30. This is different from the embodiment.

As shown in FIG. 4, the master 10 </ b> B is a mold in which a plurality of concave portions 16 are formed in an array shape with respect to a rectangular parallelepiped base portion 12. The shape of the concave portion 16 is a negative shape corresponding to the lens portion 5 of the wafer lens 1, and is concave in a substantially hemispherical shape in this figure.

The master 10B may be formed by cutting an optical surface with high accuracy by diamond cutting of a material such as nickel phosphorus, aluminum alloy, free-cutting cast metal, or grinding a high-hardness material such as carbide. It may also have been created. The optical surface created by the master 10B is preferably one in which a plurality of recesses 16 are arranged in an array as shown in FIG. 4, and only a single recess 16 may be arranged.

As shown in FIG. 4, the submaster 30 includes a submaster molding portion 32 and a submaster substrate 36. A plurality of convex portions 34 are formed in an array on the sub master molding portion 32. The shape of the convex portion 34 is a positive shape corresponding to the lens portion 5 of the wafer lens 1 and protrudes in a substantially hemispherical shape in this figure. The sub master molding part 32 is formed of a resin 32A.

The resin 32A can basically use the same material as the resin 22A of the sub-master 20 of the first embodiment, but is particularly releasable and heat resistant, and has a small linear expansion coefficient (ie It is preferable to use a resin having a small surface energy. Specifically, any of the above-mentioned photo-curing resin, thermosetting resin, and thermoplastic resin may be used, and it may be transparent or opaque. For example, if it is a thermosetting resin, the above-mentioned fluorine-based resin may be used. is necessary. This is because when the silicone resin is used, the coefficient of linear expansion is large, so that it deforms when thermally transferred to the sub-submaster 40, and the fine structure cannot be accurately transferred.

The same material as the sub master substrate 26 can be used for the sub master substrate 36.

As shown in FIG. 4, the sub-sub master 40 includes a sub-sub master molding portion 42 and a sub-sub master substrate 46. A plurality of recesses 44 are formed in an array in the sub-submaster molding part 42. The concave portion 44 is a portion corresponding to the lens portion 5 of the wafer lens 1 and is concave in a substantially hemispherical shape. The sub-sub master molding part 42 is formed of a resin 42A.

The resin 42A can use the same material as the resin 22A of the submaster 20 of the first embodiment, but uses a silicone resin or an olefin resin because it can be bent and easily released. It is preferable to do.

The same material as the sub master substrate 26 can be used for the sub sub master substrate 46.

Next, a method for manufacturing the wafer lens 1 will be briefly described with reference to FIGS.

As shown in FIG. 5A, a resin 32A is applied on the master 10B, the resin 32A is cured, the concave portions 16 of the master 10B are transferred to the resin 32A, and a plurality of convex portions 34 are formed on the resin 32A. Thereby, the submaster molding part 32 is formed.

As shown in FIG. 5B, the sub master substrate 36 is bonded to the sub master molding portion 32.

Thereafter, as shown in FIG. 5C, the sub-master molding part 32 and the sub-master substrate 36 are released from the master 10B, and the sub-master 30 is manufactured.

Thereafter, as shown in FIG. 5D, a resin 42A is applied on the sub master 30, the resin 42A is cured, and the convex portions 34 of the sub master 30 are transferred to the resin 42A. Form. Thereby, the sub-submaster molding part 42 is formed.

Thereafter, as shown in FIG. 5 (e), the sub-sub master substrate 46 is mounted on the sub-sub master molding portion 42.

As shown in FIG. 6F, the sub-sub-master 40 is manufactured by releasing the sub-sub-master molding part 42 and the sub-sub-master substrate 46 from the sub-master 30.

As shown in FIG. 6G, the resin 5A is filled into the recess 44 of the sub-sub master 40, and the resin 5A is cured while pressing the glass substrate 3 from above. As a result, the lens portion 5 is formed from the resin 5A. Thereafter, the lens unit 5 and the glass substrate 3 are released from the sub-submaster 40, and the wafer lens 1 is manufactured (the wafer lens 1 has the lens unit 5 formed only on the surface of the glass substrate 3). .

When the lens unit 5 is formed on the back surface of the glass substrate 3 and the lens unit 5 is formed on both the front and back surfaces of the glass substrate 3, it corresponds to the optical surface shape of the lens unit 5 on one surface of the glass substrate 3. A master (not shown) having a plurality of negative-shaped molding surfaces and a master having a plurality of negative-shaped molding surfaces corresponding to the optical surface shape of the lens portion 5 on the other surface are prepared, and each of these masters is used. Then, a sub master having a positive molding surface is formed, and further, a sub sub master is formed using each of these sub masters. And after filling resin 5A between each sub-submaster and the glass substrate 3, the resin 5A is hardened and the lens part 5 is shape | molded on both surfaces of the glass substrate 3. FIG.

Claims

A wafer lens manufacturing method in which an optical member made of a first curable resin is provided on a substrate,
From a master mold having a plurality of positive molding surfaces corresponding to the optical surface shape of the optical member, a sub master molding part having a plurality of negative molding surfaces corresponding to the optical surface shape is formed by the second curable resin. And forming a sub master mold by backing the sub master molding part with a sub master substrate,
When the optical member is molded by filling the first curable resin between the sub-master mold and the substrate and curing the mold,
An epoxy compound represented by the following general formula (A) is used as the first curable resin.

[In the formula (A), R 100 represents a substituent, m0 represents an integer of 0 to 2, and r0 represents an integer of 1 to 3. L 0 represents an r0 + 1-valent linking group or a single bond having 1 to 15 carbon atoms, which may contain an oxygen atom or a sulfur atom in the main chain. ]
A wafer lens comprising an epoxy compound represented by the following general formula (A):

[In the formula (A), R 100 represents a substituent, m0 represents an integer of 0 to 2, and r0 represents an integer of 1 to 3. L 0 represents an r0 + 1-valent linking group or a single bond having 1 to 15 carbon atoms, which may contain an oxygen atom or a sulfur atom in the main chain. ]
A wafer lens comprising an epoxy compound represented by the following general formula (I):

[In the formula (I), R 101 represents a substituent, m1 represents an integer of 0 to 2, p1 and q1 each represents 0 or 1, and r1 represents an integer of 1 to 3. L 1 represents an r1 + 1 valent linking group having 1 to 15 carbon atoms or a single bond which may contain an oxygen atom or a sulfur atom in the main chain. ]
A wafer lens comprising an epoxy compound represented by the following general formula (II):

[In the formula (II), R 102 represents a substituent, m2 represents an integer of 0 to 2, p2 and q2 each represents 0 or 1, and r2 represents an integer of 1 to 3. L 2 represents an r2 + 1 valent linking group or a single bond having 1 to 15 carbon atoms, which may contain an oxygen atom or a sulfur atom in the main chain. ]
A wafer lens comprising at least one epoxy compound represented by the following general formulas (III) to (VI):

[In the formula (III), R 103 represents a substituent, m3 represents an integer of 0 to 2, and p3 represents 0 or 1. L 3 represents a C 1-8 divalent linking group or single bond which may contain an oxygen atom or a sulfur atom in the main chain. ]

[In the formula (IV), R 104 represents a substituent, m4 represents an integer of 0 to 2, and p4 represents 0 or 1. L 4 represents a C 1-8 divalent linking group or single bond that may contain an oxygen atom or a sulfur atom in the main chain. ]

[In Formula (V), R 105 represents a substituent, and m5 represents 1 or 2. ]

[In the formula (VI), R 106 represents a substituent, and m6 represents an integer of 0 to 2. ]
6. The wafer lens according to claim 2, further comprising a photoacid generator that generates an acid upon irradiation with ultraviolet rays.
The wafer lens according to claim 6, wherein the photoacid generator is a sulfonium salt compound.
The wafer lens according to any one of claims 2 to 7, further comprising an oxetane compound.