COMPOSITION

Information

  • Patent Application
  • 20170072601
  • Publication Number
    20170072601
  • Date Filed
    September 12, 2016
    7 years ago
  • Date Published
    March 16, 2017
    7 years ago
Abstract
A suitable combination of a composition for formation of a resin mold with a pattern and a composition for formation of resin to which the pattern is transferred from the resin mold is found.
Description
TECHNICAL FIELD

Several aspects of this patent application relate to the fields of chemical compositions and associated manufacturing components and methods, particularly as they relate to nanoimprinting technologies.


BACKGROUND

Improving releasability of a film formed by curing a composition from a resin mold is an important technical problem for nanoimprinting technologies. One way to improve releasability is disclosed in JP 2014-076557 (laid-open disclosure date: May 1, 2014), the contents of which are incorporated herein by this reference.


BRIEF SUMMARY

When a film with a pattern is manufactured by transferring the pattern preliminarily formed in a resin mold to the film, damage in the resin mold or the film to which the pattern is transferred from the resin mold often occurs. In particular, such a tendency becomes prominent for larger patterns.


Disclosed herein are, among other things, combinations of a composition for formation of a resin mold with a pattern and a composition for formation of a film to which the pattern is transferred from the resin mold, which improve releasability of the film from the resin mold.


A method of manufacturing a component relating to an aspect of the disclosure includes:

    • providing a first composition;
    • providing a resin mold with a pattern;
    • curing the first composition to form a film to which the pattern is transferred from the resin mold; and
    • separating the film from the resin mold.


Examples of such components are lens, waveguides, and diffusers.


With regard to the method, it is preferred that the Shore hardness of the resin mold ranges from 1 to 50 when the Shore hardness of the film formed from the first composition ranges from 1 to 100.


With regard to the method, it is preferred that a size of the pattern is greater than or equal to 50 μm, 100 μm, 200 μm or 600 μm. “Size of the pattern” means typically the width of recess portions constituting the pattern. The shore hardness becomes important for releasability of a hardened body from a resin mold that transfers a pattern to the hardened body as the pattern size becomes larger


With regard to the method, it is preferred that the Shore hardness of the resin mold ranges from 51 to 60 when the Shore hardness of the film formed from the first composition ranges from 1 to 60.


If the size of pattern formed on the surface of a resin mold formed by curing a composition is 600 it is preferred that the Shore hardness of the film formed from the first composition range from 1 to 50 when the Shore hardness of the resin mold ranges from 51 to 60.


With regard to the method, when the Shore hardness of a resin mold formed by curing a composition for formation of the resin mold ranges from 1 to 50, it is preferred that the Shore hardness of a resin that is formed from another composition and is to be separated from the resin mold ranges from 1 to 100.


With regard to the method, when the Shore hardness of a resin mold formed by curing a composition for formation of the resin mold ranges from 51 to 60, it is preferred that the Shore hardness of a resin that is formed from another composition and is be separated from the resin mold ranges from 1 to 50.


With regard to the method, if the Shore hardness of a resin mold formed by curing a composition for formation of the resin mold ranges from 76 to 100, it is preferred that the Shore hardness of a resin that is formed from another composition and is to be separated from the resin mold ranges from 1 to 40.


With regard to the method, if the Shore hardness of a resin mold formed by curing a composition for formation of the resin mold ranges from 61 to 75, it is preferred that the Shore hardness of a resin that is formed from another composition and is to be separated from the resin mold ranges from 1 to 45.


If the size of pattern formed on the surface a resin mold formed by curing a composition for the resin mold is 200 μm, it is preferred that it is preferred that, when the Shore hardness of a resin mold formed by curing a composition for formation of the resin mold ranges from 1 to 50, the Shore hardness of a resin that is formed from another composition and is to be separated from the resin mold ranges from 1 to 100.


If the size of pattern formed on the surface a resin mold formed by curing a composition for the resin mold is 200 μm, it is preferred that it is preferred that, when the Shore hardness of a resin mold formed by curing a composition for formation of the resin mold ranges from 51 to 60, the Shore hardness of a resin that is formed from another composition and is to be separated from the resin mold ranges from 1 to 60.


If the size of pattern formed on the surface a resin mold formed by curing a composition for the resin mold is 200 μm, it is preferred that it is preferred that, when the Shore hardness of a resin mold formed by curing a composition for formation of the resin mold ranges from 61 to 75, the Shore hardness of a resin that is formed from another composition and is to be separated from the resin mold ranges from 1 to 55.


If the size of pattern formed on the surface a resin mold formed by curing a composition for the resin mold is 200 μm, it is preferred that it is preferred that, when the Shore hardness of a resin mold formed by curing a composition for formation of the resin mold ranges from 76 to 100, the Shore hardness of a resin that is formed from another composition and is to be separated from the resin mold ranges from 1 to 45.


If the size of pattern formed on the surface a resin mold formed by curing a composition for the resin mold is 600 μm, it is preferred that it is preferred that, when the Shore hardness of a resin mold formed by curing a composition for formation of the resin mold ranges from 1 to 50, the Shore hardness of a resin that is formed from another composition and is to be separated from the resin mold ranges from 1 to 100.


If the size of pattern formed on the surface a resin mold formed by curing a composition for the resin mold is 600 μm, it is preferred that it is preferred that, when the Shore hardness of a resin mold formed by a composition for formation of the resin mold ranges from 51 to 60, the Shore hardness of a resin that is formed from another composition and is to be separated from the resin mold ranges from 1 to 50.


If the size of pattern formed on the surface a resin mold formed by curing a composition for the resin mold is 600 μm, it is preferred that it is preferred that, when the Shore hardness of a resin mold formed by a composition for formation of the resin mold ranges from 61 to 75, the Shore hardness of a resin that is formed from another composition and is to be separated from the resin mold ranges from 1 to 45.


If the size of pattern formed on the surface a resin mold formed by a composition for the resin mold is 600 μm, it is preferred that it is preferred that, when the Shore hardness of a resin mold formed by a composition for formation of the resin mold ranges from 76 to 100, the Shore hardness of a resin that is formed from another composition and is to be separated from the resin mold ranges from 1 to 40.


It is preferred that the reaction percentage of a resin mold estimated on the basis of the ratio of amounts of unreacted monomers remaining in the resin mold to those of monomers contained in a composition (“mold composition”) for formation of the resin mold before curing the mold composition is greater than or equal to 50% to ensure enough releasability of a film formed by hardening on the resin mold from the resin mold. If a resin mold of which the reaction percentage is less than 50% is used, unreacted monomers remaining in the resin mold reacts easily with monomers contained in a composition (“film composition”), which is to be a film by a light irradiation of the film composition when the film composition is cured by a light irradiation of the film composition in a state in which the film composition is placed on the resin mold and contacts the resin mold. Thus, the releasability of the film from the resin mold decreases or damage easily arises when the film formed from the film composition is separated from the resin mold.


It is preferred that the reaction percentage of a film formed from a film composition estimated on the basis of the ratio of amounts of unreacted monomers remaining in the film to those of monomers contained in the film composition before curing of the film composition is greater than or equal to 50% to ensure enough releasability of the film from a resin mold. If the reaction percentage for the film is less than 50%, the film does not typically have enough mechanical strength. Thus, damages or defects easily arise in the film when the film formed from the film composition is separated from the resin mold.


If the Shore hardness of a resin mold formed by curing a mold composition for formation of the resin mold ranges from 1 to 50, it is preferred that the Shore hardness of a patterned resin that is formed by hardening or curing a film composition by in a state in which the film composition is placed on the resin mold and contacts the resin mold ranges from 1 to 100.


If the Shore hardness of a resin mold formed by curing a composition for formation of the resin mold ranges from 51 to 60, it is preferred that the Shore hardness of a patterned resin that is formed by hardening or curing a film composition by in a state in which the film composition is placed on the resin mold and contacts the resin mold ranges from 1 to 50.


If the Shore hardness of a resin mold formed by a curing composition for formation of the resin mold ranges from 61 to 75, it is preferred that the Shore hardness of a patterned resin that is formed by hardening or curing a film composition by in a state in which the film composition is placed on the resin mold and contacts the resin mold ranges from 1 to45.


If the Shore hardness of a resin mold formed by curing a composition for formation of the resin mold ranges from 76 to 100, it is preferred that the Shore hardness of a patterned resin that is formed by hardening or curing a film composition by in a state in which the film composition is placed on the resin mold and contacts the resin mold ranges from 1 to 40.


Composition for Formation of Resin Mold

It is preferred that a composition for formation of a resin mold contains at least one of a compound (Compound A) expressed by the chemical formula (1) and a compound (Compound B) expressed by the chemical formula (II). Both Compounds A and B have fluorine atoms and at least one polymerizable group. Fluorine atoms can improve releasability of a film that is formed by curing a film composition in a state in which the film composition contacts a patterned surface of the resin mold from the resin mold. It is more preferable that both Compounds A and B have at least two polymerizable groups to accelerate polymerization.




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In the above chemical formula, each of R1, R2 and R3 and R4 represents a substituent including at least one of the group consisting of hydrogen atom, carbon atom, nitrogen atom, and sulfur atom. “n” denotes integer from 1 to 10.


It is preferred that each of R1 and R2 is hydrogen atom or methyl group with regard to Compound A.




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In the above chemical formula, each of R5, R6, R7 and R8 represents a substituent including at least one of the group consisting of hydrogen atom, carbon atom, nitrogen atom and sulphur atom. Each of “m” and “r” denotes integer from 1 to 30.


It is preferred that each of R5 and R6 is hydrogen atom or methyl group with regard to Compound B.


In any one of the above compositions, it is preferred that each of R1 and R2 represents any one of hydrogen atom and methyl group.


In any one of the above compositions, it is preferred that each of R5 and R6 represents any one of hydrogen atom and methyl group.


It is preferred that the compound represented by the chemical formula 1 has at least one of moieties represented by formulae 3 and 4. Each of the moieties may have any one of chemical structures represented by the chemical formulae 5, 6 and 7.




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“j” of the chemical structure represented by the chemical formula 5 denotes 1 or 2. Each of R9, R10, R11 and R12 of the chemical formula 6 represents any one of hydrogen atom and methyl group and a moiety represented by the chemical formula 8.




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In the above chemical formula, R13 denotes hydrogen atom or methyl group.


It is preferred that, if the R9 is a substituent represented by the chemical formula 8, is any one of hydrogen atom and methyl group and each of the R10 and R12 is a hydrogen atom.


It is preferred that, if R10 is a substituent represented by the chemical formula 8, R12 is one of hydrogen atom and the methyl group and each of the R9 and is a hydrogen atom.


It is preferred that, if is a substituent represented by the chemical formula 8, R9 is one of hydrogen atom and methyl group and each of the R10 and R12 is a hydrogen atom.


It is preferred that, if the R12 is a substituent is represented by the chemical formula 8, R10 is one of hydrogen atom and methyl group and each of R9 and may be a hydrogen atom.


Alternatively, each of R9, R10, R11 and R12 may be a hydrogen atom.


It is preferred that the compound represented by the chemical formula 2 has at least one of moieties represented by formulae 9 and 10. Each of the moieties may have any one of chemical structures represented by formulae 11, 12 and 13.




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“k” of the chemical formula 11 is 1 or 2. Each of R14, R15, R16 and R17 is any one of hydrogen atom, methyl group and a moiety represented by the chemical formula 14.




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R18 of the chemical formula 14 denotes hydrogen atom or methyl group.


It is preferred that, if R14 includes the moiety represented by the chemical formula 14, R16 is hydrogen atom or methyl group and each of R15 and R17 is a hydrogen atom.


It is preferred that, if R15 includes the moiety represented by the chemical formula 14, R17 is one of hydrogen atom and methyl group and each of R14 and R16 is a hydrogen atom.


It is preferred that, if R16 includes the moiety represented by the chemical formula 14, R14 is one of hydrogen atoms methyl group and each of the R15 and R17 is a hydrogen atom.


It is preferred that, if R17 includes the moiety represented by the chemical formula 14, R15 is one of hydrogen atoms methyl group and each of the R14 and R16 is a hydrogen atom.


Alternatively, each of R14, R15, R16 and R17 may be a hydrogen atom.


The content amount of Compound A in the composition for formation of resin mold may range from 0 wt % to 99.9 wt %.


It is preferred that the content amount of Compound A in the composition for formation of resin mold ranges from 10 wt % to 99.9 wt %.


It is more preferred that the content amount of Compound A in the composition for formation of resin mold ranges from 35 wt % to 99.9 wt %.


The content amount of Compound B in the composition for formation of resin mold may range from 0 wt % to 80 wt %.


It is preferred that the content amount of Compound B in the composition for formation of resin mold ranges from 0 wt % to 65 wt %.


Such composition for formation of resin mold may further contain a monomer having only one polymerizable group such as acryloyl group and methacryloyl group.


The molecular weight of such monomer may range from 80 to 600.


It is preferred that the molecular weight of such monomer ranges from 86 to 450 due to greater solubility in the composition.


The content amount of such monomer may range from 0 wt % to 70 wt %. It is preferred that the content amount of such monomer ranges from 0 wt % to 50 wt %.


Such monomer may contain at least one fluorine atom due to improvement of mold releasability.


Such composition for formation of resin mold may further contain a monomer having plural polymerizable groups such as acryloyl group and methacryloyl group.


The molecular weight of such monomer may range from 170 to 500.


It is preferred that the molecular weight of such monomer ranges from 170 to 400 due to greater solubility in the composition.


The content amount of such monomer may range from 0 wt % to 50 wt %. It is preferred that the content amount of such monomer ranges from 0 wt % to 40 wt %.


It is preferred that such composition for formation of resin mold further contain a photoinitiator.


The content amount of such photoinitiator may range from 0.005 wt % to 20 wt %. It is preferred that the content amount of such monomer ranges from 0.01 wt % to 15 wt %.


Such composition for formation of resin mold may further contain antioxidant, light stabilizer, surfactant, UV absorber, sensitizer, colorant, filler, polymer and solvent.


Composition for Formation of a Patterned Resin of which Shore Hardness Ranges from 1 to 50


The patterned resin is formed by an irradiation of a composition with a light in a state in which the composition contacts a patterned surface of the resin mold. Further, the patterned resin is separated from the resin mold.


It is preferred that such composition for formation of a patterned resin contains at least one kind of monomers. Such monomer is at least one of the following monomers:

    • (i) urethane acrylate or urethane methacrylate with plural polymerizable groups of which molecular weight ranges from 400 to 35000;
    • (ii) acrylate or methacrylate with a main chain including ether group of which molecular weight ranges from 300 to 4000; and
    • (iii) acrylate or methacrylate with a main chain including ester group of which molecular weight ranges from 500 to 3000.


The content amount of such monomers may be range from 20 wt % to 99.9 wt %. It is preferred that the content amount of such monomers range from 30 wt % to 99.9 wt %.


Such urethane acrylate or urethane methacrylate may be a polyol compound. Such urethane acrylate or urethane methacrylate may have a polyester framework, polycarbonate framework or alkyl carbonate.


Typical examples of Such urethane acrylate or urethane methacrylate are UN-333, UN-350, UN-1255, UN-2600, UN-2700, UN-5590, UN-6200, UN-6202, UN-6300, UN-6301, UN-7600, UN-7700, UN-9000PEP, UN-9200A (Negami Chemical Industrial Co., Ltd.), U-200PA, UA-160TM, UA-290TM, UA-4200, UA-4400 (SHIN-NAKAMURA CHEMICAL Co., Ltd.), UX-3204, UX-4101, UX-7101, UX-0937, UXF-4001-M35, UXF-4002 (Nippon Kayaku Co., Ltd), UV-2000B, UV-2750B, UV-3000B, UV-3200B, UV-3300B, UV-3310B, UV-3700B and UV-6640B (The Nippon Synthetic Chemical Industry Co., Ltd.).


Typical examples of (ii) acrylate or methacrylate with a main chain including ether group are A-200, A-400, A-600, A-1000, APG-100, APG-200, APG-400, APG-700, A-PTMG-65, A-1206PE, A-0612PE, A-0412PE, A-1000PER, A-3000PER, A-TMPT-3EO, A-TMPT-9EO, AT-20E, AT-30E, A-TMPT-3PO, A-TMPT-6PO, A-GLY-3E, A-GLY-6E, A-GLY-9E, A-GLY-20E, A-GLY-3 P, A-GLY-6 P, A-GLY-9 P, ATM-4EL, ATM-8EL, ATM-4PL, ATM-4E, ATM-35E, ATM-4 P, ATM-10 P, AD-TMP-4E, AD-TMP-4 P, A-DPH-6E, A-DPH-12E, A-DPH-6EL, A-DPH-12EL, A-DPH-6 P, A-PG5027E, A-PG5054E, 4G, 9G, 14G, 3PG, 9PG, 1206PE, 1000PER, TMPT-3EO, TMPT-9EO, TMPT-3PO, GLY-3E, GLY-6E, GLY-9E, GLY-20E, TM-4EL, TM-4PL, TM-4E, TM-35E, TM-4 P, TM-10 P, D-TMP-4E, D-TMP-4 P, M-DPH-6E, M-DPH-12E, M-DPH-6 P, M-PG5027E and M-PG5054E(SHIN-NAKAMURA CHEMICAL Co., Ltd.).


Typical examples of (iii) acrylate or methacrylate with a main chain including ester group are KAYARAD HX-220, KAYARADHX-620, KAYARAD DPCA-20, KAYARADDPCA-30, KAYARAD DPCA-60 and KAYARADDPCA-120(Nippon Kayaku Co., Ltd).


Such composition for formation of resin to be separated from resin may further contain an acrylate or methacrylate having only one polymerizable group. It is preferred that such an acrylate or methacrylate has an ether group due to its higher flexibility. It is preferred that the molecular weight of such an acrylate or methacrylate with the ether group ranges from 130 to 700. Alternatively, an acrylate or methacrylate having only one polymerizable group contained in such composition may have alkyl group. Molecular weight of such acrylate or methacrylate may range from 86 to 400.


Typical examples of such an acrylate or methacrylate with the ether group are AM-30G, AM-90G, AM-130G, AM30PG, M-20G, M-30G, M-40G, M-90G, M-130G, M-30PG and EH-4E, B-20G(SHIN-NAKAMURA CHEMICAL Co., Ltd.).


Typical examples of such acrylate or methacrylate with the alkyl group are methyl(meth) acrylate, ethyl(meth) acrylate, n-buthyl(meth) acrylate, isobuthyl(meth) acrylate, t-butyl(meth) acrylate, 2-ethyl hexyl(meth) acrylate, isodecyl(meth) acrylate, n-lauryl(meth) acrylate, isoamylacrylate, isotetradecyl(meth) acrylate, n-stearyl(meth) acrylate, bihenyl(meth) acrylate are isostearyl(meth) acrylate.


It is preferred that the content amount of such acrylate or methacrylate with the ether group or alkyl group ranges from 0 wt % to 79.9 wt %. It is more preferred that the content amount of such acrylate or methacrylate with the ether group or alkyl group ranges from 0 wt % to 69.9 wt %.


It is preferred that such composition for formation of the patterned resin to which the pattern is transferred from the resin mold further contains photoinitiator. The content amount of such photoinitiator may be from 0.005 wt % to 20 wt %. It is preferred that the content amount of such photoinitiator ranges from 0.01 wt % to 15 wt %.


Such composition may further contain antioxidant, light stabilizer, surfactant, UV absorber, sensitizer, colorant, filler, polymer or solvent.


Composition for Formation of a Patterned Resin of which Shore Hardness Ranges from 51 to 100


The patterned resin is formed by an irradiation of a composition with a light in a state in which the composition contacts a patterned surface of the resin mold. Further, the patterned resin is separated from the resin mold.


It is preferred that such composition contains at least one of acrylate or methacrylate having plural polymerizable groups and alicyclic group and urethane acrylate or urethane methacrylate having plural polymerizable groups and alicyclic group.


Such composition may further contain at least one of (a) acrylate or methacrylate with only one polymerizable group, (b) acrylate or methacrylate having plural polymerizable groups and no alicyclic group of which molecular weight is from 170 to 700 and (c) urethane acrylate or urethane methacrylate having plural polymerizable groups and no alicyclic group of which molecular weight is from 400 to 25000.


It is preferred that such a composition for formation of resin to be separated from resin further contains photoinitiator. The content amount of such photoinitiator may be from 0.005 wt % to 20 wt %. It is preferred that the content amount of such photoinitiator ranges from 0.01 wt % to 6 wt %.


Such composition may further contain antioxidant, light stabilizer, surfactant, UV absorber, sensitizer, colorant, filler, polymer or solvent.







DETAILED DESCRIPTION
Experimental Procedures:

Table 1 shows compositions for the formation of resin mold(s) with a pattern with size of 200 μm and for formation of resin to which the pattern is transferred from resin mold and shore hardness. Table 2 shows compositions for formation of resin mold with a pattern with size of 600 μm and for formation of resin to which the pattern is transferred from resin mold and shore hardness. The phrase “a pattern with size of 200 μm” typically means that, when a pattern formed by the recess and convex portions, each of the recess portions has a width of 200 μm while the phrase “a pattern with size of 600 μm” typically means each of recess portions has a width of 600 μm.


Compositions for formation of a resin mold contains constituents A to E while compositions of formation of a resin (“pattern-transferred resin”) to which the pattern of the resin mold is transferred from the resin mold contains F to M and E.


Constituents A to M are following compounds.




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TABLE 1





Compositions for formation of resin mold having a pattern with size of 200 μm and for formation of resin


(“pattern-transferred resin”) to which the pattern is transferred from resin mold and Shore hardness.




























Entry
Entry
Entry
Entry
Entry
Entry
Entry
Entry
Entry
Entry




1
2
3
4
5
6
7
8
9
10





Composition for
Constituent A
99.5%
99.5%
99.5%
49.75% 
49.75% 
49.75% 
20.7%
20.7%
20.7%
20.7%


formation of resin
Constituent B



49.75% 
49.75% 
49.75% 
78.8%
78.8%
78.8%
78.8%


mold with a pattern
Constituent C



Constituent D



Constituent E
 0.5%
 0.5%
 0.5%
 0.5%
 0.5%
 0.5%
 0.5%
 0.5%
 0.5%
 0.5%


Composition for
Constituent F
62.0%


62.0%


62.0%


formation of pattern-
Constituent G
37.8%


37.8%


37.8%


transferred resin
Constituent H

49.9%
37.8%

49.9%
37.8%



37.8%



Constituent I

49.9%


49.9%



Constituent J


62.0%


62.0%

99.8%
89.8%
62.0%



Constituent K








10.0%



Constituent L



Constituent M



Constituent E
 0.2%
 0.2%
 0.2%
 0.2%
 0.2%
 0.2%
 0.2%
 0.2%
 0.2%
 0.2%

















Shore hardness of resin mold with a
28
28
28
48
48
48
58
58
58
58


pattern


Shore hardness of pattern-transferred
11
78
70
11
78
70
11
48
56
70


resin


Pattern size
200 m
200 μm
200 μm
200 μm
200 μm
200 μm
200 μm
200 μm
200 μm
200 μm


Presence of damage of resin mold or
A
A
A
A
A
A
A
A
A
P


pattern-transferred resin
























Entry
Entry
Entry
Entry
Entry
Entry
Entry
Entry
Entry





11
12
13
14
15
16
17
18
19







Composition for
Constituent A



formation of resin
Constituent B
99.5%
87.1%
99.5%
99.5%
99.5%
68.4%
68.4%
68.4%
68.4%



mold with a pattern
Constituent C

12.4%




Constituent D





31.1%
31.1%
31.1%
31.1%




Constituent E
 0.5%
 0.5%
 0.5%
 0.5%
 0.5%
 0.5%
 0.5%
 0.5%
 0.5%



Composition for
Constituent F
62.0%
62.0%

62%



62.0%
62.0%
62.0%



formation of pattern-
Constituent G
37.8%
37.8%



37.8%



transferred resin
Constituent H




Constituent I




Constituent J



98.8%
89.8%



98.8%




Constituent K




10.0%




Constituent L






37.8%




Constituent M


37.8%




37.8%




Constituent E
 0.2%
 0.2%
 0.2%
 0.2%
 0.2%
 0.2%
 0.2%
 0.2%
 0.2%


















Shore hardness of resin mold with a
65
69
65
65
65
78
78
78
78



pattern



Shore hardness of pattern-transferred
11
11
41
48
56
11
35
41
48



resin



Pattern size
200 μm
200 μm
200 μm
200 μm
200 μm
200 μm
200 μm
200 μm
200 μm



Presence of damage of resin mold or
A
A
A
A
P
A
A
A
P



pattern-transferred resin

















TABLE 2





Compositions for formation of resin mold having a pattern with size of 600 μm and for formation


resin (“pattern-transferred resin”) to which the pattern is transferred and Shore hardness


























Entry
Entry
Entry
Entry
Entry
Entry
Entry
Entry




20
21
22
23
24
25
26
27





Composition for
Constituent A
99.5%
99.5%
99.5%
49.75% 
49.75% 
49.75% 
20.7%
20.7%


formation of resin
Constituent B



49.75% 
49.75% 
49.75% 
78.8%
78.8%


mold with a pattern
Constituent C



Constituent D



Constituent E
 0.5%
 0.5%
 0.5%
 0.5%
 0.5%
 0.5%
 0.5%
 0.5%


Composition for
Constituent F
62.0%


62.0%


62.0%


formation of pattern-
Constituent G
37.8%


37.8%


37.8%


transferred resin
Constituent H

49.9%
37.8%

49.9%
37.8%



Constituent I

49.9%


49.9%



Constituent J


62.0%


62.0%

99.8%



Constituent K



Constituent L



Constituent M



Constituent E
 0.2%
 0.2%
 0.2%
 0.2%
 0.2%
 0.2%
 0.2%
 0.2%















Shore hardness of resin mold with a
28
28
28
48
48
48
58
58


pattern


Shore hardness of pattern-transferred
11
78
70
11
78
70
11
48


resin


Pattern size
600 μm
600 μm
600 μm
600 μm
600 μm
600 μm
600 μm
600 μm


Presence of damage of resin mold or
A
A
A
A
A
A
A
A


pattern-transferred resin























Entry
Entry
Entry
Entry
Entry
Entry
Entry
Entry





28
29
30
31
32
33
34
35







Composition for
Constituent A
20.7%



formation of resin
Constituent B
78.8%
99.5%
87.1%
99.5%
99.5%
68.4%
68.4%
68.4%



mold with a pattern
Constituent C


12.4%




Constituent D





31.1%
31.1%
31.1%




Constituent E
 0.5%
 0.5%
 0.5%
 0.5%
 0.5%
 0.5%
 0.5%
 0.5%



Composition for
Constituent F

62.0%
62.0%

62%


62.0%
62.0%
62.0%



formation of pattern-
Constituent G

37.8%
37.8%


37.8%



transferred resin
Constituent H




Constituent I




Constituent J
89.8%



98.8%




Constituent K
10.0%




Constituent L






37.8%




Constituent M



37.8%



37.8%




Constituent E
 0.2%
 0.2%
 0.2%
 0.2%
 0.2%
 0.2%
 0.2%
 0.2%

















Shore hardness of resin mold with a
58
65
69
65
65
78
78
78



pattern



Shore hardness of pattern-transferred
56
11
11
41
48
11
35
41



resin



Pattern size
600 μm
600 μm
600 μm
600 μm
600 μm
600 μm
600 μm
600 μm



Presence of damage of resin mold or
P
A
A
A
P
A
A
P



pattern-transferred resin










If damage or a deficit is found for resin mold or pattern-transferred resin when pattern-transferred resin is separated from resin mold, or if pattern-transferred resin cannot be separated from resin mold, the combination of compositions is designated as “P” as shown in Tables 1 and 2. If damage or deficit is not found in either of the resin mold and the pattern-transferred resin when pattern-transferred resin is separated from resin mold, the combination of compositions is designated as “A” as shown in Tables 1 and 2.


Blends of the Shore hardness of resin molds and the Shore hardness of pattern-transferred resin observed. As shown in Tables 1 and 2, when the Shore hardness of a resin mold formed from the composition for formation of resin mold with the pattern ranges from 1 to 50 and the Shore hardness of a pattern-transferred resin ranges from 1 to 100, damage is not found for either the resin mold or the pattern-transferred resin when the pattern-transferred resin is separated from the resin mold.


If the pattern size is 200 as shown in Table 1, when the Shore hardness of a resin mold formed from the composition for formation of resin mold with the pattern ranges from 51 to 60 and the Shore hardness of a pattern-transferred resin ranges from 1 to 60, damage is not found for either the resin mold or the pattern-transferred resin when the pattern-transferred resin is separated from the resin mold.


If the pattern size is 200 as shown in Table 1, when the Shore hardness of a resin mold formed from the composition for formation of resin mold with the pattern ranges from 61 to 75 and the Shore hardness of a pattern-transferred resin ranges from 1 to 55, damage is not found for either the resin mold or the pattern-transferred resin when the pattern-transferred resin is separated from the resin mold.


If the pattern size is 200 as shown in Table 1, when the Shore hardness of a resin mold formed from the composition for formation of resin mold with the pattern ranges from 76 to 100 and the Shore hardness of a pattern-transferred resin ranges from 1 to 45, damage is not found for either the resin mold or the pattern-transferred resin when the pattern-transferred resin is separated from the resin mold.


If the pattern size is 600 as shown in Table 2, when the Shore hardness of a resin mold formed from the composition for formation of resin mold with the pattern ranges from 1 to 50 and the Shore hardness of a pattern-transferred resin ranges from 1 to 100, damage is not found for either the resin mold or the pattern-transferred resin when the pattern-transferred resin is separated from the resin mold.


If the pattern size is 600 μm, as shown in Table 2, if the Shore hardness of a resin mold formed from the composition for formation of resin mold with the pattern ranges from 51 to 60 and the Shore hardness of a pattern-transferred resin ranges from 1 to 50, then damage is not found for either the resin mold or the pattern-transferred resin when the pattern-transferred resin is separated from the resin mold.


If the pattern size is 600 μm, as shown in Table 2, if the Shore hardness of a resin mold formed from the composition for formation of resin mold with the pattern ranges from 61 to 75 and the Shore hardness of a pattern-transferred resin ranges from 1 to 45, then damage is not found for either the resin mold or the pattern-transferred resin when the pattern-transferred resin is separated from the resin mold.


If the pattern size is 600 μm, as shown in Table 2, if the Shore hardness of a resin mold formed from the composition for formation of resin mold with the pattern ranges from 76 to 100 and the Shore hardness of a pattern-transferred resin ranges from 1 to 40, then damage is not found for either the resin mold or the pattern-transferred resin when the pattern-transferred resin is separated from the resin mold.









TABLE 3







Compositions for formation of resin mold having a pattern with size of 200 μm and for formation of resin to which the pattern


is transferred (“pattern-transferred resin”) and Shore hardness, reaction percentages of resin mold and pattern-transferred resin


















Entry
Entry
Entry
Entry
Entry
Entry
Entry
Entry
Entry
Entry



36
37
38
39
40
41
42
43
44
45






















Composition for
Constituent A
49.75% 
49.75% 
20.7%
20.7%








formation of resin
Constituent B
49.75% 
49.75% 
78.8%
78.8%
99.5%
99.5%
68.4%
68.4%
68.4%
68.4%


mold with a pattern
Constituent C



Constituent D






31.1%
31.1%
31.1%
31.1%



Constituent E
 0.5%
 0.5%
 0.5%
 0.5%
 0.5%
 0.5%
 0.5%
 0.5%
 0.5%
 0.5%


Composition for
Constituent F






62.0%
62.0%


formation of pattern-
Constituent G


transferred resin
Constituent H
49.9%
49.9%
37.8%
37.8%



Constituent I
49.9%
49.9%



Constituent J


62.0%
62.0%
89.8%
89.8%


98.8%
98.8%



Constituent K




10.0%
10.0%



Constituent L



Constituent M






37.8%
37.8%



Constituent E
 0.2%
 0.2%
 0.2%
 0.2%
 0.2%
 0.2%
 0.2%
 0.2%
 0.2%
 0.2%

















Exposure time of resin mold
1200 
10
1200 
10
1200 
10
1200 
10
1200 
10


Reaction percentage of resin mold

80%


46%


76%


43%


68%


40%


65%


38%


65%


38%



Shore hardness of resin mold
48
12
58
15
65
22
78
40
78
40


Exposure time of pattern-transferred
400 
400 
400 
400 
400 
400 
400 
400 
400 
400 


resin


Reaction percentage of pattern-

63%


63%


70%


70%


78%


78%


82%


82%


75%


75%



transferred resin


Shore hardness of pattern-
78
78
70
70
56
56
41
41
48
48


transferred resin


Pattern size
200 μm
200 μm
200 μm
200 μm
200 μm
200 μm
200 μm
200 μm
200 μm
200 μm


Presence of damage of resin mold or
A
P
P
P
P
P
A
P
P
P


pattern-transferred resin









As shown in Entries 37, 39, 41, 43 and 45, if the reaction percentages of resin molds are less than 50%, damages arise in resin molds or pattern-transferred resins.


As shown in Entries 38, 40 and 44, if the reaction percentages of resin molds are greater than 50%, presence of absence of damages in resin molds or pattern-transferred resins depends on blends of the Shore hardness of resin molds and pattern-transferred resin as explained above.









TABLE 4





Compositions for formation of resin mold having a pattern with size of 600 μm and


for formation of resin to which the pattern is transferred (“pattern-transferred resin”) and


Shore hardness, reaction percentages of resin mold and pattern-transferred resin

























Entry
Entry
Entry
Entry
Entry
Entry
Entry




46
47
48
49
50
51
52





Composition for
Constituent A
49.75% 
49.75% 
20.7%
20.7%
20.7%
20.7%


Formation of resin
Constituent B
49.75% 
49.75% 
78.8%
78.8%
78.8%
78.8%
87.1%


mold with a pattern
Constituent C






12.4%



Constituent D



Constituent E
 0.5%
 0.5%
 0.5%
 0.5%
 0.5%
 0.5%
 0.5%


Composition for
Constituent F
62.0%
62.0%




62.0%


Formation of pattern-
Constituent G
37.8%
37.8%




37.8%


transferred resin
Constituent H



Constituent I



Constituent J


99.8%
99.8%
89.8%
89.8%



Constituent K




10.0%
10.0%



Constituent L



Constituent M



Constituent E
 0.2%
 0.2%
 0.2%
 0.2%
 0.2%
 0.2%
 0.2%














Exposure time of resin mold
1200 
10
1200 
10
1200 
10
1200 


Reaction percentage of resin mold

80%


46%


76%


43%


76%


43%


70%



Shore hardness of resin mold
48
12
58
15
58
15
69


Exposure time of pattern-transferred
400 
400 
400 
400 
400 
400 
400 


resin


Reaction percentage of pattern-

88%


88%


75%


75%


78%


78%


88%



transferred resin


Shore hardness of pattern-
11
11
48
48
56
56
11


transferred resin


Pattern size
600 μm
600 μm
600 μm
600 μm
600 μm
600 μm
600 μm


Presence of damage of resin mold or
A
P
A
P
P
P
A


pattern-transferred resin






















Entry
Entry
Entry
Entry
Entry
Entry
Entry





53
54
55
56
57
58
59







Composition for
Constituent A



Formation of resin
Constituent B
87.1%
99.5%
99.5%
68.4%
68.4%
68.4%
68.4%



mold with a pattern
Constituent C
12.4%




Constituent D



31.1%
31.1%
31.1%
31.1%




Constituent E
 0.5%
 0.5%
 0.5%
 0.5%
 0.5%
 0.5%
 0.5%



Composition for
Constituent F
62.0%


62.0%
62.0%
62.0%
62.0%



Formation of pattern-
Constituent G
37.8%



transferred resin
Constituent H




Constituent I




Constituent J

98.8%
98.8%




Constituent K




Constituent L



37.8%
37.8%




Constituent M





37.8%
37.8%




Constituent E
 0.2%
 0.2%
 0.2%
 0.2%
 0.2%
 0.2%
 0.2%
















Exposure time of resin mold
10
1200 
10
1200 
10
1200 
10



Reaction percentage of resin mold

45%


68%


40%


65%


38%


65%


38%




Shore hardness of resin mold
25
65
22
78
40
78
40



Exposure time of pattern-transferred
400 
400 
400 
400 
400 
400 
400 



resin



Reaction percentage of pattern-

88%


75%


75%


82%


82%


82%


82%




transferred resin



Shore hardness of pattern-
11
48
48
35
35
41
41



transferred resin



Pattern size
600 μm
600 μm
600 μm
600 μm
600 μm
600 μm
600 μm



Presence of damage of resin mold or
P
P
P
A
P
P
P



pattern-transferred resin










As shown in Entries 47, 49, 51, 53 and 55, 57 and 59, if the reaction percentages of resin molds are lower than 50%, damages arise in resin molds or pattern-transferred resins.


As shown in Entries 50, 54 and 58, if the reaction percentages of resin molds are higher than 50%, presence of absence of damages in resin molds or pattern-transferred resins depends on blends of the Shore hardness of resin molds and pattern-transferred resin as explained above.









TABLE 5





Compositions for formation of resin mold having a pattern with size of 600 μm and for formation of resin to which the pattern


is transferred (“pattern-transferred resin”) and Shore hardness, reaction percentages of resin mold and pattern-transferred resin





























Entry
Entry
Entry
Entry
Entry
Entry
Entry
Entry
Entry
Entry
Entry




60
61
62
63
64
65
66
67
68
69
70





Composition for
Constituent A
99.5%
99.5%
49.75% 
49.75% 
20.7%
20.7%
20.7%
20.7%
20.7%
20.7%


formation of resin
Constituent B


49.75% 
49.75% 
78.8%
78.8%
78.8%
78.8%
78.8%
78.8%
99.5%


mold with a pattern
Constituent C



Constituent D



Constituent E
 0.5%
 0.5%
 0.5%
 0.5%
 0.5%
 0.5%
 0.5%
 0.5%
 0.5%
 0.5%
 0.5%


Composition for
Constituent F
62.0%
62.0%


62.0%
62.0%




62.0%


formation of pattern-
Constituent G
37.8%
37.8%


37.8%
37.8%




37.8%


transferred resin
Constituent H


49.9%
49.9%




37.8%
37.8%



Constituent I


49.9%
49.9%



Constituent J






89.8%
89.8%
62.0%
62.0%



Constituent K






10.0%
10.0%



Constituent L



Constituent M



Constituent E
 0.2%
 0.2%
 0.2%
 0.2%
 0.2%
 0.2%
 0.2%
 0.2%
 0.2%
 0.2%
 0.2%


















Exposure time of resin mold
1200 
1200 
1200 
1200 
1200 
1200 
1200 
1200 
1200 
1200 
1200 


Reaction percentage of resin mold

85%


85%


80%


80%


76%


76%


76%


76%


76%


76%


68%



Shore hardness of resin mold
28
28
48
48
58
58
58
58
58
58
65


Exposure time of pattern-transferred
400 
10
400 
10
400 
10
400 
10
400 
10
400 


resin


Reaction percentage of pattern-

88%


45%


63%


42%


88%


45%


78%


46%


70%


45%


88%



transferred resin


Shore hardness of pattern-
11
5
78
51
11
5
56
25
70
40
11


transferred resin


Pattern size
200 μm
200 μm
200 μm
200 μm
200 μm
200 μm
200 μm
200 μm
200 μm
200 μm
200 μm


Presence of damage of resin mold or
A
P
A
P
A
P
A
P
P
P
A


pattern-transferred resin


























Entry
Entry
Entry
Entry
Entry
Entry
Entry
Entry
Entry
Entry
Entry





71
72
73
74
75
76
77
78
79
80
81







Composition for
Constituent A



formation of resin
Constituent B
99.5%
99.5%
99.5%
99.5%
99.5%
68.4%
68.4%
68.4%
68.4%
68.4%
68.4%



mold with a pattern
Constituent C




Constituent D





31.1%
31.1%
31.1%
31.1%
31.1%
31.1%




Constituent E
 0.5%
 0.5%
 0.5%
 0.5%
 0.5%
 0.5%
 0.5%
 0.5%
 0.5%
 0.5%
 0.5%



Composition for
Constituent F
62.0%




62.0%
62.0%
62.0%
62.0%



formation of pattern-
Constituent G
37.8%




37.8%
37.8%



transferred resin
Constituent H




Constituent I




Constituent J

98.8%
98.8%
89.8%
89.8%




98.8%
98.8%




Constituent K



10.0%
10.0%




Constituent L




Constituent M







37.8%
37.8%




Constituent E
 0.2%
 0.2%
 0.2%
 0.2%
 0.2%
 0.2%
 0.2%
 0.2%
 0.2%
 0.2%
 0.2%




















Exposure time of resin mold
1200 
1200 
1200 
1200 
1200 
1200 
1200 
1200 
1200 
1200 
1200 



Reaction percentage of resin mold

68%


68%


68%


68%


68%


65%


65%


65%


65%


65%


65%




Shore hardness of resin mold
65
65
65
65
65
78
78
78
78
78
78



Exposure time of pattern-transferred
10
400 
10
400 
10
400 
10
400 
10
400 
10



resin



Reaction percentage of pattern-

45%


75%


38%


78%


46%


88%


45%


82%


42%


75%


38%




transferred resin



Shore hardness of pattern-
5
48
20
56
25
11
5
41
22
48
20



transferred resin



Pattern size
200 μm
200 μm
200 μm
200 μm
200 μm
200 μm
200 μm
200 μm
200 μm
200 μm
200 μm



Presence of damage of resin mold or
P
A
P
P
P
A
P
A
P
P
P



pattern-transferred resin










As shown in Entries 61, 63, 65, 67, 69, 71, 73, 75, 77, 79 and 81, if the reaction percentages of pattern-transferred resins are lower than 50%, damages arise in resin molds or pattern-transferred resins.


As shown in Entries 68, 74 and 80, if the reaction percentages of pattern-transferred resins are higher than 50%, presence of absence of damages in resin molds or pattern-transferred resins depends on blends of the Shore hardness of resin molds and pattern-transferred resin as explained above.









TABLE 6





Compositions for formation of resin mold having a pattern with size of 600 μm and for formation of resin to which the pattern


is transferred (“pattern-transferred resin”) and Shore hardness, reaction percentages of resin mold and pattern-transferred resin



























Entry
Entry
Entry
Entry
Entry
Entry
Entry
Entry
Entry




82
83
84
85
86
87
88
89
90





Composition for
Constituent A
99.5%
99.5%
99.5%
99.5%
49.75% 
49.75% 
20.7%
20.7%
20.7%


formation of resin
Constituent B




49.75% 
49.75% 
78.8%
78.8%
78.8%


mold with a pattern
Constituent C



Constituent D






 0.5%
 0.5%
 0.5%



Constituent E
 0.5%
 0.5%
 0.5%
 0.5%
 0.5%
 0.5%
 0.5%
 0.5%
 0.5%


Composition for
Constituent F
62.0%
62.0%


62.0%
62.0%


formation of pattern-
Constituent G
37.8%
37.8%


37.8%
37.8%


transferred resin
Constituent H


49.9%
49.9%



Constituent I


49.9%
49.9%



Constituent J






89.8%
89.8%
99.8%



Constituent K






10.0%
10.0%



Constituent L



Constituent M



Constituent E
 0.2%
 0.2%
 0.2%
 0.2%
 0.2%
 0.2%
 0.2%
 0.2%
 0.2%
















Exposure time of resin mold
1200 
1200 
1200 
1200 
1200 
1200 
1200 
1200 
1200 


Reaction percentage of resin mold

85%


85%


85%


85%


80%


80%


76%


76%


76%



Shore hardness of resin mold
28
28
28
28
48
48
58
58
58


Exposure time of pattern-transferred
400 
10
400 
10
400 
10
400 
10
400 


resin


Reaction percentage of pattern-

88%


45%


63%


42%


88%


45%


78%


45%


75%



transferred resin


Shore hardness of pattern-
11
5
78
51
11
5
56
25
48


transferred resin


Pattern size
600 μm
600 μm
600 μm
600 μm
600 μm
600 μm
600 μm
600 μm
600 μm


Presence of damage of resin mold or
A
P
A
P
A
P
P
P
A


pattern-transferred resin
























Entry
Entry
Entry
Entry
Entry
Entry
Entry
Entry
Entry





91
92
93
94
95
96
97
98
99







Composition for
Constituent A
20.7%



formation of resin
Constituent B
78.8%
99.5%
99.5%
99.5%
99.5%
68.4%
68.4%
68.4%
68.4%



mold with a pattern
Constituent C




Constituent D
 0.5%




31.1%
31.1%
31.1%
31.1%




Constituent E
 0.5%
 0.5%
 0.5%
 0.5%
 0.5%
 0.5%
 0.5%
 0.5%
 0.5%



Composition for
Constituent F

62.0%
62.0%


62.0%
62.0%
62.0%
62.0%



formation of pattern-
Constituent G



transferred resin
Constituent H




Constituent I




Constituent J
99.8%


98.8%
98.8%




Constituent K




Constituent L





37.8%
37.8%




Constituent M

37.8%
37.8%




37.8%
37.8%




Constituent E
 0.2%
 0.2%
 0.2%
 0.2%
 0.2%
 0.2%
 0.2%
 0.2%
 0.2%


















Exposure time of resin mold
1200 
1200 
1200 
1200 
1200 
1200 
1200 
1200 
1200 



Reaction percentage of resin mold

76%


68%


68%


68%


68%


65%


65%


65%


65%




Shore hardness of resin mold
58
65
65
65
65
78
78
78
78



Exposure time of pattern-transferred
10
400 
10
400 
10
400 
10
400 
10



resin



Reaction percentage of pattern-

38%


82%


42%


75%


38%


82%


43%


82%


42%




transferred resin



Shore hardness of pattern-
20
41
22
48
20
35
18
41
22



transferred resin



Pattern size
600 μm
600 μm
600 μm
600 μm
600 μm
600 μm
600 μm
600 μm
600 μm



Presence of damage of resin mold or
P
A
P
P
P
A
P
P
P



pattern-transferred resin










As shown in Entries 83, 85, 87, 89, 91, 93, 95, 97 and 99, if the reaction percentages of patter-transferred resin are lower than 50%, damages arise in resin molds or pattern-transferred resins.


As shown in Entries 88, 94 and 98, if the reaction percentages of pattern-transferred resin are higher than 50%, presence of absence of damages in resin molds or pattern-transferred resins depends on blends of the Shore hardness of resin molds and pattern-transferred resin as explained above.









TABLE 7







Compositions for formation of resin mold with patterns


with sizes of 1 μm and 50 μm and formation of resin


to which the pattern is transferred (“pattern-transferred


resin”) and Shore hardness











Entry 100
Entry 101
Entry 102















Composition for
Constituent A





formation of resin
Constituent B
68.4%
68.4%
68.4%


mold with a pattern
Constituent C



Constituent D
31.1%
31.1%
31.1%



Constituent E
 0.5%
 0.5%
 0.5%


Composition for
Constituent F

62.0%


formation of
Constituent G

37.8%


pattern-transferred
Constituent H
49.9%

49.9%


resin
Constituent I
49.9%

49.9%



Constituent J



Constituent K



Constituent L



Constituent M



Constituent E
 0.2%
 0.2%
 0.2%










Exposure time of resin mold
1200
1200
1200


Reaction percentage of resin mold
  65%
  65%
  65%


Shore hardness of resin mold
78
78
78


Exposure time of pattern-transferred
400
400
400


resin


Reaction percentage of pattern-
  63%
  88%
  63%


transferred resin


Shore hardness of pattern-
78
11
78


transferred resin


Pattern size
1 μm
50 μm
50 μm


Presence of damage of resin mold or
A
A
P


pattern-transferred resin









Such blend of the Shore hardness is not observed for a fine pattern such as a 1 μm pattern as shown in Entry 100 while such blend of the Shore hardness is observed for pattern of which size is greater than or equal to 50 μm as shown in Entries 101 and 102.


Presence or Absence of Damage Resins for Pattern Dimension of 200 μm

A Ni mold subjected to a treatment for improvement of mold releasablity with the treatment agent containing fluorine compound (DURASURF HD-2101Z, Daikin Industries, Ltd.) is prepared. The thickness and area of the Ni mold are 0.1 mm and 50 mm2, respectively. The Ni mold has a surface on which a pattern is formed by recesses and convex portions. The width and depth of each of the recess portions are 200 μm together while the width of each of the convex portions is 400 μm. A composition for formation of resin mold is deposited on the patterned surface of the Ni mold. Further a non-alkali glass of which thickness and area are 1.1 mm and 100 mm2, respectively, is disposed on the coating film of the composition such that the thickness of the coating film becomes approximately 1 mm. The coating film is irradiated under nitrogen atmosphere with a light from UV-LED lamp of which wavelength and intensity are 365 nm and 50 mW/cm2, respectively, for 1200 seconds or 10 seconds.


The resin mold formed by the light irradiation is separated from the Ni mold. A composition for formation of resin that the pattern is transferred from the resin mold is deposited on the surface of the resin mold with the pattern transferred from the Ni mold. Further a non-alkali glass of which thickness and area are 1.1 mm and 100 mm2, respectively, is disposed on the coating film of the composition such that the thickness of the coating film becomes approximately 1 mm. The coating film is irradiated under nitrogen atmosphere with a light from a UV-LED lamp of which wavelength and intensity are 365 nm and 20 mW/cm2, for 400 seconds or 10 seconds, in a state in which the coating film contacts the patterned surface of the resin mold. The patterned resin formed by the light irradiation is separated from the resin mold.


The presence or absence of damage of the patterned resin separated from the resin mold and the resin mold is checked by a confocal laser microscope (OLS3100, Olympus). If damage is found for either of the patterned resin separated from the resin mold or the resin mold, or if separation of the patterned resin from the resin mold is impossible, the combination of compositions is designated as “P” as shown in Tables. If damage is not found in either of the resins, the combination of compositions is designated as “A” as shown in Tables.


Presence or Absence of Damage Resins for Pattern Dimension of 600 μm

A Ni mold subjected to a treatment for improvement of mold releasability with the treatment agent containing fluorine compound (DURASURF HD-2101Z, Daikin Industries, Ltd.) is prepared. The thickness and area of the Ni mold are 0.2 mm and 50 mm2, respectively. The Ni mold has a surface on which a pattern formed by recess and convex portions. The width and depth of each of the recess portions are 600 μm together while the width of each of the convex portions is 900 μm. A composition for formation of resin mold is deposited on the patterned surface of the Ni mold. Further a non-alkali glass of which thickness and area are 1.1 mm and 100 mm2, respectively, is disposed on the coating film of the composition such that the thickness of the coating film becomes approximately 1 mm. The coating film is irradiated under nitrogen atmosphere with a light from UV-LED lamp of which wavelength and intensity are 365 nm and 50 mW/cm2, respectively, for 1200 seconds or 10 seconds. The resin mold formed by the light irradiation is separated from the Ni mold.


A composition for formation of resin to be separated from the resin mold is deposited on the surface of the resin mold with the pattern transferred from the Ni mold. Further a non-alkali glass of which thickness and area are 1.1 mm and 100 mm2, respectively, is disposed on the coating film of the composition such that the thickness of the coating film becomes approximately 1 mm. The coating film is irradiated under nitrogen atmosphere with a light from UV-LED lamp of which wavelength and intensity are 365 nm and 20 mW/cm2, respectively, for 400 seconds or 10 seconds, in a state in which the coating film contacts the patterned surface of the resin mold. The patterned resin formed by the light irradiation is separated from the resin mold.


The presence or absence of damage of the patterned resin separated from the resin mold and the resin mold is checked by a confocal laser microscope (OLS3100, Olympus). If damage is found for either of the patterned resin separated from the resin mold and the resin mold, or if separation of the patterned resin from the resin mold is impossible, the combination of compositions is designated as “P” as shown in Tables. If damage not found in either of the resins after separation from the resin mold, the combination of compositions is designated as “A” as shown in Tables.


Measurement of Shore Hardness

A non-alkali glass subjected to a treatment for improvement of mold releasability with the treatment agent containing a fluorocompound (OPTOOL HD-1101Z, Daikin Industries, Ltd) is prepared. The thickness and area of the non-alkali glass are 1.1 mm and 100 mm2, respectively. A composition for formation of resin mold is deposited on the non-alkali glass. Further a non-alkali glass of which thickness and area are 1.1 mm and 100 mm2, respectively, is disposed on the coating film of the composition such that the thickness of the coating film becomes approximately 1 mm. The coating film is irradiated under nitrogen atmosphere with a light from UV-LED lamp of which wavelength and intensity are 365 nm and 50 mW/cm2, respectively, for 1200 seconds. The resin mold formed by the light irradiation is separated from the non-alkali glass. Six resin molds obtained by the above operation are stacked and Shore hardness is measured by a material hardness durometer Type D (GS-720G, TECLOCH).


A non-alkali glass subjected to a treatment for improvement of mold releasability with the treatment agent containing a fluorocompound (OPTOOL HD-1101Z, Daikin Industries, Ltd) is prepared. The thickness and area of the non-alkali glass are 1.1 mm and 100 mm2, respectively. A composition for formation of resin to which a pattern of the resin mold is transferred from the resin mold is deposited on the non-alkali glass. Further a non-alkali glass of which thickness and area are 1.1 mm and 100 mm2, respectively, is disposed on the coating film of the composition such that the thickness of the coating film becomes approximately 3 mm. The coating film is irradiated under nitrogen atmosphere with a light from UV-LED lamp of which wavelength and intensity are 365 nm and 20 mW/cm2, respectively, for 400 seconds. The resin formed by the light irradiation is separated from the non-alkali glass. Two resins obtained by the above operation are stacked and Shore hardness is measured by a material hardness durometer Type D (GS-720G, TECLOCH).


Presence or Absence of Damage Resins for Pattern Dimension of 1 μm

A Ni mold has been subjected to a treatment for improvement of mold releasability with the treatment agent containing fluorine compound (DURASURF HD-2101Z, Daikin Industries, Ltd.) is prepared. The thickness and area of the Ni mold are 1 mm and 50 mm2, respectively. The Ni mold has a surface on which a pattern formed by recess and convex portions. The width and depth of each of the recess portions are 1 μm together while the width of each of the convex portion is 2 μm. A composition for formation of resin mold is deposited on the patterned surface of the Ni mold. Further a non-alkali glass of which thickness and area are 1.1 mm and 100 mm2, respectively, is disposed on the coating film of the composition such that the thickness of the coating film becomes approximately 1 mm. The coating film is irradiated under nitrogen atmosphere with a light from UV-LED lamp of which wavelength and intensity are 365 nm and 50 mW/cm2, respectively, for 1200 seconds. The resin mold formed by the light irradiation is separated from the Ni mold.


A composition for formation of resin to which the pattern of the resin mold is transferred from the resin mold is deposited on the surface of the resin mold with the pattern transferred from the Ni mold. Further a non-alkali glass of which thickness and area are 1.1 mm and 100 mm2, respectively, is disposed on the coating film of the composition such that the thickness of the coating film becomes approximately 1 mm. The coating film is irradiated under nitrogen atmosphere with a light from a UV-LED lamp of which the wavelength and intensity are 365 nm and 20 mW/cm2, respectively, for 400 seconds, in a state in which the coating film contacts the patterned surface of the resin mold. The resin formed by the light irradiation is separated from the resin mold.


The presence or absence of damage of the resin separated from the resin mold and the resin mold is checked by a confocal laser microscope (OLS3100, Olympus). If damage is found for either of the patterned resin separated from the resin mold and the resin mold, or if separation of the patterned resin from the resin mold is impossible, the combination of compositions is designated as “P” as shown in Table 7. If damage not found in either of the resins after separation from the resin mold, the combination of compositions is designated as “A” as shown in Table 7.


Presence or Absence of Damage Resins for Pattern Dimension of 50 μm

A Ni mold has been subjected to a treatment for improvement of mold releasability with the treatment agent containing fluorine compound (DURASURF HD-2101Z, Daikin Industries, Ltd.) is prepared. The thickness and area of the Ni mold are 1 mm and 50 mm2, respectively. The Ni mold has a surface on which a pattern formed by recess and convex portions. The width and depth of each of the recess portions are 50 μm together while the width of each of the convex portion is 100 μm. A composition for formation of resin mold is deposited on the patterned surface of the Ni mold. Further a non-alkali glass of which thickness and area are 1.1 mm and 100 mm2, respectively, is disposed on the coating film of the composition such that the thickness of the coating film becomes approximately 1 mm. The coating film is irradiated under nitrogen atmosphere with a light from a UV-LED lamp of which wavelength and intensity are 365 nm and 50 mW/cm2, respectively, for 1200 seconds. The resin mold formed by the light irradiation is separated from the Ni mold.


A composition for formation of resin to which the pattern of the resin mold is transferred from the resin mold is deposited on the surface of the resin mold with the pattern transferred from the Ni mold. Further a non-alkali glass of which thickness and area are 1.1 mm and 100 mm2, respectively, is disposed on the coating film of the composition such that the thickness of the coating film becomes approximately 1 mm. The coating film is irradiated under nitrogen atmosphere with a light from a UV-LED lamp of which wavelength and intensity are 365 nm and 20 mW/cm2, respectively, for 400 seconds, in a state in which the coating film contacts the patterned surface of the resin mold. The patterned resin formed by the light irradiation is separated from the resin mold.


The presence or absence of damage of the resin separated from the resin mold and the resin mold is checked by a confocal laser microscope (OLS3100, Olympus).


If damage is found for either of the patterned resin separated from the resin mold and the resin mold, or if separation of the patterned resin from the resin mold is impossible, the combination of compositions is designated as “P” as shown in Table 7. If damage not found in either of the resins after separation from the resin mold, the combination of compositions is designated as “A” as shown in Table 7.


Estimation of Percentage of Reaction for Resin Mold and Patterned Resin

A peak at 810 cm−1, which is assigned to C═CH bending vibration observed by FT-IR spectroscopy is noted. The reaction percentage for the resin mold is estimated by calculation of decrease ratio of the intensity of the peak at 810 cm−1 by the light irradiation of a coating film of a composition for a resin mold or resin to which a pattern of the resin mold is transferred from the resin mold on the bases of the intensity of a peak at 1,700 cm−1, which is assigned to C═O stretching and remains unchanged even by photoirradiation of the coating film. Concretely, the reaction rate is calculated by the following equation:





Percentage of Reaction (%)=(1−(A1UV/A2UV)/(A10/A20))×100

    • wherein: A10, A20, A1UV and A2UV are an area of the peak at C═O stretching of the coating film, an area of the peak at C═CH bending vibration of the coating film, an area of the peak at C═O stretching of the resin mold and an area of the peak at C═CH bending vibration of the resin mold.


Reaction percentage for the separated mold is estimated in manner similar to the above method.


FT-IR Spectroscopy Measurement of Resin Mold

A non-alkali glass subjected to a treatment for improving mold releasability with a treatment agent containing a fluorocompound (OPTOOL HD-1101Z, Daikin Industries, Ltd) is prepared. The thickness and area of the non-alkali glass are 1.1 mm and 100 mm2, respectively. A composition for formation of resin mold is deposited on the non-alkali glass. Further a non-alkali glass of which thickness and area are 1.1 mm and 100 mm2, respectively, is disposed on the coating film of the composition such that the thickness of the coating film becomes approximately 1 mm. The coating film is irradiated under nitrogen atmosphere with a light from UV-LED lamp of which wavelength and intensity are 365 nm and 50 mW/cm2, respectively, for 10 seconds. The resin mold formed by the light irradiation is separated from the non-alkali glass. FT-IR measurement of the resin mold is used by attenuated total reflection (ATR) method.


FT-IR Spectroscopy Measurement of Patterned Resin

A non-alkali glass subjected to a treatment for improving mold releasability with a treatment agent containing a fluorocompound (OPTOOL HD-1101Z, Daikin Industries, Ltd) is prepared. The thickness and area of the non-alkali glass are 1.1 mm and 100 mm2, respectively. A composition for formation of resin to which a pattern of the resin mold is transferred from the resin mold is deposited on the non-alkali glass. Further a non-alkali glass of which thickness and area are 1.1 mm and 100 mm2, respectively, is disposed on the coating film of the composition such that the thickness of the coating film becomes approximately 3 mm. The coating film is irradiated under nitrogen atmosphere with a light from UV-LED lamp of which wavelength and intensity are 365 nm and 20 mW/cm2, respectively, for 10 seconds. The resin formed by the light irradiation is separated from the non-alkali glass. FT-IR measurement of the resin is used by attenuated total reflection (ATR) method.

Claims
  • 1. A method of manufacturing a component, the method comprising: providing a first composition;providing a resin mold with a pattern;curing the first composition to form a film to which the pattern is transferred from the resin mold; andseparating the film from the resin mold, wherein: when the Shore hardness of the resin mold ranges from 1 to 50, the Shore hardness of the film ranges from 1 to 100.
  • 2. The method of claim 1, wherein a size of the pattern is greater than or equal to 50 μm.
  • 3. The method of claim 1, wherein a size of the pattern is greater than or equal to 100 μm.
  • 4. The method of claim 1, wherein a size of the pattern is greater than or equal to 200 μm.
  • 5. The method of claim 1, wherein a size of the pattern is greater than or equal to 600 μm.
  • 6. A method of manufacturing a component, the method comprising: providing a first composition;providing a resin mold with a pattern;curing the first composition to form a film to which the pattern is transferred from the resin mold; andseparating the film from the resin mold, wherein: when the Shore hardness of the resin mold ranges from 51 to 60, the Shore hardness of the film ranges from 1 to 60.
  • 7. The method of claim 6, wherein a size of the pattern is greater than or equal to 50 μm.
  • 8. The method of claim 6, wherein a size of the pattern is greater than or equal to 100 μm.
  • 9. The method of claim 6, wherein a size of the pattern is greater than or equal to 200 μm.
  • 10. The method of claim 6, wherein a size of the pattern is greater than or equal to 600 μm.
  • 11. A method of manufacturing a component, the method comprising: curing a first composition to form a film to which a pattern is transferred from a resin mold having the pattern; andseparating the film from the resin mold, wherein: when the resin mold's Shore hardness is from 1 to 50, the film's Shore hardness is between 1 to 100, andwherein: when the resin mold's Shore hardness is from 51 to 60, the film's Shore hardness is between 1 to 60.
  • 12. The method according to claim 11, wherein the pattern's size is at least 50 μm.
  • 13. The method according to claim 11, wherein the pattern's size is at least 100 μm.
  • 14. The method according to claim 11, wherein the pattern's size is at least 200 μm
  • 15. The method according to claim 11, wherein the pattern's size is at least 600 μm.
  • 16. The method according to claim 11, wherein the component is selected from the group consisting of a lens, a waveguide, and a diffuser.
CROSS-REFERENCE TO RELATED APPLICATION

This application claims the benefit under 35 U.S.C. §119(e) of U.S. Provisional Patent Application Ser. No. 62/217,621 filed on Sep. 11, 2015, the disclosure of which is hereby incorporated herein in its entirety by these references.

Provisional Applications (1)
Number Date Country
62217621 Sep 2015 US