WO2003076544A1 - Uv-curable epoxy resin composition comprising lactone monomer - Google Patents
Uv-curable epoxy resin composition comprising lactone monomer Download PDFInfo
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- WO2003076544A1 WO2003076544A1 PCT/KR2002/002096 KR0202096W WO03076544A1 WO 2003076544 A1 WO2003076544 A1 WO 2003076544A1 KR 0202096 W KR0202096 W KR 0202096W WO 03076544 A1 WO03076544 A1 WO 03076544A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
Definitions
- the present invention relates to a UV-curable epoxy resin composition
- a UV-curable epoxy resin composition comprising a photopolymerizable epoxy oligomer, a photopolymerizable epoxy monomer, a photoimtiator and a lactone monomer, which is useful as an optical adhesive having improved moisture and heat resistance and adhesive properties.
- a photocurable adhesive is preferred over a thermosetting adhesive in such application because it can be set quickly at a low temperature using simple equipment and facilities, and, therefore, many UV-curable adhesives have been used in optoelectronic industries.
- photocurable adhesives for assembling optical devices comprise an acrylate, epoxy, vinyl, or other resin as a main component, together with an epoxy oligomer, an epoxy monomer, a filler and additives.
- Most of optical adhesives made of photocurable epoxides deteriorate under a humid condition, e.g., when the temperature is cycled between -40°C and 75°C or -40°C and 85 °C under a relative humidity of 90%, due to moisture penetration at the adhesion interface, with consequential peeling and delamination.
- a primary object of the present invention to provide a UV-curable epoxy resin composition having improved performance characteristics including high moisture and heat resistance, adhesive strength and reduced shrinkage.
- UV-curable epoxy resin composition comprising an epoxy oligomer, an epoxy monomer, a cationic initiator and a lactone monomer.
- an optical article manufactured using said UV-curable epoxy resin composition.
- the UV-curable epoxy resin composition of the present invention characteristically contains a lactone monomer, which is polymerized during UV curing by the action of a cationic initiator, as illustrated below:
- the lactone monomer used in the present invention functions to impart improved optical and adhesive properties, low shrinkage, high moisture resistance and thermal stability to the cured composition.
- Specific examples of the lactone monomer include ⁇ -caprolactone, ⁇ -caprolactone, ⁇ -caprolactone, ⁇ -butyrolactone, ⁇ -propiolactone, ⁇ -dodecanolactone, 4-dodecanolide, 2,3-o-isopropylidene-D-erythronolactone, ( ⁇ )- ⁇ -valerolactone, (+)-corey lactone, (+)- ⁇ -decalactone, pantolactone, 5-tetradecanolide, ⁇ -butyrolactone, ⁇ -jasmolactone, and ⁇ -methylene- ⁇ -butyrolactone monomer.
- These monomers may be used alone or in combination with others, preferably in an amount ranging from 1 to 80% by weight, more preferably, from 1 to 60% by weight based on the amount of the composition
- the epoxy oligomer used in the epoxy resin composition of the present invention comprises at least one epoxy group in its chemical structure; and examples thereof include end-capped poly(bisphenol A-co-epichlorohydrin) glycidyl having a molecular weight of 348, 355, 374, 377, 480, 1075, 1750, 4000 or 6100, poly[(o-cresyl glycidyl ether)-co-formaldehyde] having a molecular weight of 540, 870, 1080 or 1270, tetraphenyloethane glycidyl ether, brominated bisphenol A diglycidyl ether, bisphenol A propoxylate (IPO/phenol) diglycidyl ether, bis(4-glycidyloxyphenyl)methane, and a mixture thereof.
- the epoxy oligomer may be employed preferably in an amount ranging from 5 to 80% by weight based on the amount of the composition.
- the epoxy monomer used in the epoxy resin composition of the present invention comprises at least one epoxy group in its chemical structure; and examples thereof include 3,4-epoxycyclohexylmethyl-3,4- epoxycyclohexanecarboxylate, bis(3,4-epoxycyclohexylmethyl)adipate,
- Examples of a suitable cationic initiator which may be used in the epoxy resin composition of the present invention include triaryl sulfonium hexafluoroantimonate, triaryl sulfonium hexafluorophosphate, diaryl iodonium hexafluoroantimonate, iodonium butyltriphenylborate, tetrakis(pentafluorophenyl)borate, S-phenyl thianthrenium hexafluorophosphate, triphenyl sulfonium hexafluorophosphate, diphenyl sulfide, p-hydroxy benzylphosphonium hexafluoroantimonate, and a mixture thereof.
- Such an initiator may be used in combination with a solvent such as propylene carbonate.
- the cationic initiator may be employed preferably in an amount ranging from 1 to 10% by weight based on the amount of the composition.
- the epoxy resin composition of the present invention may further comprise other additives such as an adhesion promoter, heat stabilizer and a silicone compound.
- additives such as an adhesion promoter, heat stabilizer and a silicone compound.
- Said additives may be employed preferably in an amount ranging from 0.01 to 10% by weight based on the amount of the composition.
- the UV-curable epoxy resin composition in accordance with the present invention may be prepared in a conventional manner by using the above-mentioned components.
- a solid epoxy oligomer it is dissolved in a liquid epoxy monomer, and then, mixed with other components at a temperature of 40 to 120°C.
- the UV-curable epoxy resin composition of the present invention containing a lactone monomer exhibits high adhesive strength, low shrinkage, and superior moisture resistance at a relatively high temperature, superior to conventional epoxy-type optical adhesives. Further, the use of the composition of the present invention makes it possible to produce optical devices possessed with satisfactory and highly reliable optical properties.
- Example 1 The procedure of Example 1 was repeated except that a ring-opened ⁇ -caprolactone polyol having a molecular weight of 530(TONE ® 0201, Union Carbide Corp.) was used instead of ⁇ -caprolactone, to obtain an optical adhesive composition.
- a ring-opened ⁇ -caprolactone polyol having a molecular weight of 530(TONE ® 0201, Union Carbide Corp.) was used instead of ⁇ -caprolactone, to obtain an optical adhesive composition.
- Example 2 The procedure of Example 1 was repeated except that lOg of ⁇ -caprolactone and 30g of poly[( ⁇ -cresyl glycidyl ether)-co-formaldehyde] having a molecular weight of 540 were used instead of ⁇ -caprolactone and end-capped poly(bisphenol A-c ⁇ -epichlorohydrin) glycidyl, respectively, to obtain an optical adhesive composition.
- Example 2 The procedure of Example 2 was repeated except that a ring-opened ⁇ -caprolactone polyol having a molecular weight of 830(PLACCEL 208, Daiccel Chemical Industries) was used instead of ⁇ -caprolactone, to obtain an optical adhesive composition.
- Example 3 The procedure of Example 3 was repeated except that a ring-opened ⁇ -caprolactone polyol having a molecular weight of 1000(CAPA ® 210, Solvay Corp.) was used instead of ⁇ -caprolactone, to obtain an optical adhesive composition.
- a ring-opened ⁇ -caprolactone polyol having a molecular weight of 1000(CAPA ® 210, Solvay Corp.) was used instead of ⁇ -caprolactone, to obtain an optical adhesive composition.
- Example 3 The procedure of Example 3 was repeated except that 35g of end-capped poly(bisphenol A-co-epichlorohydrin) glycidyl having a molecular weight of 4000 and 40g of ⁇ -caprolactone were used in place of end-capped poly(bisphenol A-c ⁇ -epichlorohydrin) glycidyl and ⁇ -caprolactone, respectively, to obtain an optical adhesive composition.
- Example 4 The procedure of Example 4 was repeated except that a ring-opened ⁇ -caprolactone polyol having a molecular weight of 530(CAPA 200, Solvay Corp.) was used instead of ⁇ -caprolactone, to obtain an optical adhesive composition.
- a ring-opened ⁇ -caprolactone polyol having a molecular weight of 530(CAPA 200, Solvay Corp.) was used instead of ⁇ -caprolactone, to obtain an optical adhesive composition.
- Example 3 The procedure of Example 3 was repeated except that 20g of poly[(o-cresyl glycidyl ether)-cc-formaldehyde] having a molecular weight of
- Example 5 The procedure of Example 5 was repeated except that a ring-opened ⁇ -caprolactone polyol having a molecular weight of 830(PLACCEL ® 212, Daicel Chemical Industries) was used instead of ⁇ -caprolactone, to obtain an optical adhesive composition.
- a ring-opened ⁇ -caprolactone polyol having a molecular weight of 830(PLACCEL ® 212, Daicel Chemical Industries) was used instead of ⁇ -caprolactone, to obtain an optical adhesive composition.
- Example 3 The procedure of Example 3 was repeated except that 40g of poly[( ⁇ -cresyl glycidyl ether)-c ⁇ -formaldehyde] having a molecular weight of
- Example 6 The procedure of Example 6 was repeated except that a ring-opened ⁇ -caprolactone polyol having a molecular weight of 530(TONE 0301, Union Carbide Corp.) was used instead of ⁇ -caprolactone, to obtain an optical adhesive composition.
- a ring-opened ⁇ -caprolactone polyol having a molecular weight of 530(TONE 0301, Union Carbide Corp.) was used instead of ⁇ -caprolactone, to obtain an optical adhesive composition.
- Each of the epoxy resin compositions was used to bind the longitudinal terminals of two quartz plates having a size of 35n ⁇ mx25mmx5mm by overlapping 3mm x 20mm, and cured using a mercury vacuum lamp(more than lOmW) for 5 to 10 minutes at room temperature, and post-cured under the condition of 60 to 85 °C for 4 to 10 hours.
- the specimen was tested using a conventional tension tester at 1 to lOmm/min in accordance with ASTM D-1144 to evaluate the shear adhesive strength. The results are shown in Table 1.
- each of the UV-curable epoxy resin compositions comprising a lactone monomer according to the present invention has a shear adhesive strength comparable or superior to that of a conventional composition containing a ring-opened ⁇ -caprolactone polyol.
- Table 2 shows that each of the UV-curable epoxy resin compositions comprising a lactone monomer according to the present invention exhibits markedly smaller shrinkage than that of a conventional composition containing a ring-opened ⁇ -caprolactone polyol.
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Abstract
A UV-curable epoxy resin composition comprising an epoxy oligomer, an epoxy monomer, a photoinitiator and a lactone monomer has improved moisture and heat resistance, high adhesive strength and low shrinkage, and is useful as an optical adhesive.
Description
UV-CURABLE EPOXY RESIN COMPOSITION COMPRISING LACTONE MONOMER
FIELD OF THE INVENTION
The present invention relates to a UV-curable epoxy resin composition comprising a photopolymerizable epoxy oligomer, a photopolymerizable epoxy monomer, a photoimtiator and a lactone monomer, which is useful as an optical adhesive having improved moisture and heat resistance and adhesive properties.
BACKGROUND OF THE INVENTION
Required of adhesives used in assembling optoelectronic devices are high reliability, accuracy, and high productivity. A photocurable adhesive is preferred over a thermosetting adhesive in such application because it can be set quickly at a low temperature using simple equipment and facilities, and, therefore, many UV-curable adhesives have been used in optoelectronic industries.
Conventionally, photocurable adhesives for assembling optical devices comprise an acrylate, epoxy, vinyl, or other resin as a main component, together with an epoxy oligomer, an epoxy monomer, a filler and additives. Most of optical adhesives made of photocurable epoxides deteriorate under a humid condition, e.g., when the temperature is cycled between -40°C and 75°C or -40°C and 85 °C under a relative humidity of 90%, due to moisture penetration at the adhesion interface, with consequential peeling and delamination. In order to solve such problems, there has been suggested a process of adding a ring-opened caprolactone polyol having a molecular weight of 200 to 3000 to a mixture of an epoxy oligomer, an epoxy monomer, a cationic initiator and other additives. However, adhesives manufactured by said process still exhibit unsatisfactory performance properties in a high temperature and humid environment (see J. Adhesion, 1991, Vol. 35, p.251-267; J. Adhesion Sci.
Techol., No. 10, p.1343-1355 (1995); and Electrical Technology, March 1997, p.139-146).
SUMMARY OF THE INVENTION
Accordingly, it is a primary object of the present invention to provide a UV-curable epoxy resin composition having improved performance characteristics including high moisture and heat resistance, adhesive strength and reduced shrinkage. In accordance with one aspect of the present invention, there is provided a
UV-curable epoxy resin composition comprising an epoxy oligomer, an epoxy monomer, a cationic initiator and a lactone monomer.
In accordance with another aspect of the present invention, there is provided an optical article manufactured using said UV-curable epoxy resin composition.
DETAILED DESCRIPTION OF THE INVENTION
The UV-curable epoxy resin composition of the present invention characteristically contains a lactone monomer, which is polymerized during UV curing by the action of a cationic initiator, as illustrated below:
The lactone monomer used in the present invention functions to impart improved optical and adhesive properties, low shrinkage, high moisture resistance and thermal stability to the cured composition. Specific examples of the lactone monomer include ε-caprolactone, γ-caprolactone, δ-caprolactone, β-butyrolactone, β-propiolactone, δ-dodecanolactone, 4-dodecanolide,
2,3-o-isopropylidene-D-erythronolactone, (±)-γ-valerolactone, (+)-corey lactone, (+)-γ-decalactone, pantolactone, 5-tetradecanolide, γ-butyrolactone, γ-jasmolactone, and γ-methylene-γ-butyrolactone monomer. These monomers may be used alone or in combination with others, preferably in an amount ranging from 1 to 80% by weight, more preferably, from 1 to 60% by weight based on the amount of the composition.
The epoxy oligomer used in the epoxy resin composition of the present invention comprises at least one epoxy group in its chemical structure; and examples thereof include end-capped poly(bisphenol A-co-epichlorohydrin) glycidyl having a molecular weight of 348, 355, 374, 377, 480, 1075, 1750, 4000 or 6100, poly[(o-cresyl glycidyl ether)-co-formaldehyde] having a molecular weight of 540, 870, 1080 or 1270, tetraphenyloethane glycidyl ether, brominated bisphenol A diglycidyl ether, bisphenol A propoxylate (IPO/phenol) diglycidyl ether, bis(4-glycidyloxyphenyl)methane, and a mixture thereof. The epoxy oligomer may be employed preferably in an amount ranging from 5 to 80% by weight based on the amount of the composition.
The epoxy monomer used in the epoxy resin composition of the present invention comprises at least one epoxy group in its chemical structure; and examples thereof include 3,4-epoxycyclohexylmethyl-3,4- epoxycyclohexanecarboxylate, bis(3,4-epoxycyclohexylmethyl)adipate,
1 ,2-epoxy-4-vinylcyclohexane, 1 ,2-epoxytetradecane, 1 ,2-epoxydodecane, 1,2-epoxydecane, l,2-epoxy-9-decene, l,2-epoxy-3-phenoxypropane,
4-vinyl-l-cyclohexene diepoxide, 4-vinyl-l-cyclohexene 1,2-epoxide, 1,4-cyclohexanedimethanol diglycidyl ether, 4-tert-butylpheyl glycidyl ether, 1,2-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, dodecanediol diglycidyl ether, pentaerythritol polyglycidyl ether, trimethylpropane polyglycidyl ether, phenyl glycidyl ether, resorcinol diglycidyl ether, nonyl phenyl glycidyl ether, allyl glycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, tetrafluoropropyl glycidyl ether, octafluoropropyl glycidyl ether, dodecafluorooctyl diglycidyl ether, styrene oxide, limonene monoxide, and
a mixture thereof. The epoxy monomer may be employed preferably in an amount ranging from 5 to 80% by weight based on the amount of the composition.
Examples of a suitable cationic initiator which may be used in the epoxy resin composition of the present invention include triaryl sulfonium hexafluoroantimonate, triaryl sulfonium hexafluorophosphate, diaryl iodonium hexafluoroantimonate, iodonium butyltriphenylborate, tetrakis(pentafluorophenyl)borate, S-phenyl thianthrenium hexafluorophosphate, triphenyl sulfonium hexafluorophosphate, diphenyl sulfide, p-hydroxy benzylphosphonium hexafluoroantimonate, and a mixture thereof. Such an initiator may be used in combination with a solvent such as propylene carbonate. The cationic initiator may be employed preferably in an amount ranging from 1 to 10% by weight based on the amount of the composition.
In addition, the epoxy resin composition of the present invention may further comprise other additives such as an adhesion promoter, heat stabilizer and a silicone compound. Examples of such additives include
2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, (3-glycidoxypropyl)- trimethoxysilane, (3-glycidoxypropyl)bis(trimethylsiloxy)methylsilane,
(3-glycidoxypropyl)dimethylethoxysilane, (3-glycidoxypropyl)methyldiethoxy- silane, (3-glycidoxy-propyl)methyldimethoxysilane, and
2,6-di-tert-butyl-4-methylphenol. Said additives may be employed preferably in an amount ranging from 0.01 to 10% by weight based on the amount of the composition.
The UV-curable epoxy resin composition in accordance with the present invention may be prepared in a conventional manner by using the above-mentioned components. For example, in case of using a solid epoxy oligomer, it is dissolved in a liquid epoxy monomer, and then, mixed with other components at a temperature of 40 to 120°C.
The UV-curable epoxy resin composition of the present invention containing a lactone monomer exhibits high adhesive strength, low shrinkage, and superior moisture resistance at a relatively high temperature, superior to
conventional epoxy-type optical adhesives. Further, the use of the composition of the present invention makes it possible to produce optical devices possessed with satisfactory and highly reliable optical properties.
The present invention is further described and illustrated in Examples, which are, however, not intended to limit the scope of the present invention.
Formulation of epoxy optical adhesive composition
Example 1
25g of ε-caprolactone, 25g of end-capped poly(bisphenol A-co-epichlorohydrin) glycidyl having a molecular weight of 348, lOg of 4-vinyl-l-cyclohexene diepoxide, lOg of resorcinol diglycidyl ether, 5g of 1,2-butyl glycidyl ether, a mixture of 2g of triaryl sulfonium hexafluoroantimonate and 2g of propylene carbonate, and lg of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane were mixed to obtain an optical adhesive composition.
Comparative Example 1
The procedure of Example 1 was repeated except that a ring-opened ε-caprolactone polyol having a molecular weight of 530(TONE® 0201, Union Carbide Corp.) was used instead of ε-caprolactone, to obtain an optical adhesive composition.
Example 2
The procedure of Example 1 was repeated except that lOg of δ-caprolactone and 30g of poly[(ø-cresyl glycidyl ether)-co-formaldehyde] having a molecular weight of 540 were used instead of ε-caprolactone and
end-capped poly(bisphenol A-cø-epichlorohydrin) glycidyl, respectively, to obtain an optical adhesive composition.
Comparative Example 2
The procedure of Example 2 was repeated except that a ring-opened ε-caprolactone polyol having a molecular weight of 830(PLACCEL 208, Daiccel Chemical Industries) was used instead of δ-caprolactone, to obtain an optical adhesive composition.
Example 3
15g of end-capped poly(bisphenol A-cø-epichlorohydrin) glycidyl having a molecular weight of 1075, lOg of 4-vinyl-l-cyclohexene diepoxide, lOg of resorcinol diglycidyl ether and 5g of 1,2-butyl glycidyl ether were stirred for 1 hour at 80°C, and cooled to room temperature. 30g of γ-caprolactone, a mixture of 2g of triaryl sulfonium hexafluoroantimonate and 2g of propylene carbonate, and lg of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane were added to the mixture, and stirred to obtain an optical adhesive composition.
Comparative Example 3
The procedure of Example 3 was repeated except that a ring-opened ε-caprolactone polyol having a molecular weight of 1000(CAPA® 210, Solvay Corp.) was used instead of γ-caprolactone, to obtain an optical adhesive composition.
Example 4
The procedure of Example 3 was repeated except that 35g of end-capped poly(bisphenol A-co-epichlorohydrin) glycidyl having a molecular weight of
4000 and 40g of ε-caprolactone were used in place of end-capped poly(bisphenol A-cø-epichlorohydrin) glycidyl and γ-caprolactone, respectively, to obtain an optical adhesive composition.
Comparative Example 4
The procedure of Example 4 was repeated except that a ring-opened ε-caprolactone polyol having a molecular weight of 530(CAPA 200, Solvay Corp.) was used instead of ε-caprolactone, to obtain an optical adhesive composition.
Example 5
The procedure of Example 3 was repeated except that 20g of poly[(o-cresyl glycidyl ether)-cc-formaldehyde] having a molecular weight of
1270 and 50g of ε-caprolactone were used in place of end-capped poly(bisphenol A-cø-epichlorohydrin) glycidyl and γ-caprolactone, respectively, to obtain an optical adhesive composition.
Comparative Example 5
The procedure of Example 5 was repeated except that a ring-opened ε-caprolactone polyol having a molecular weight of 830(PLACCEL® 212, Daicel Chemical Industries) was used instead of ε-caprolactone, to obtain an optical adhesive composition.
Example 6
The procedure of Example 3 was repeated except that 40g of poly[(ø-cresyl glycidyl ether)-cø-formaldehyde] having a molecular weight of
1270 and 60g of ε-caprolactone were used in place of end-capped
poly(bisphenol A-cø-epichlorohydrin) glycidyl and γ-caprolactone, respectively, to obtain an optical adhesive composition.
Comparative Example 6
The procedure of Example 6 was repeated except that a ring-opened ε-caprolactone polyol having a molecular weight of 530(TONE 0301, Union Carbide Corp.) was used instead of ε-caprolactone, to obtain an optical adhesive composition.
Performance Test
The performances of the UV-curable epoxy resin compositions prepared in Examples 1 to 6 and Comparative Examples 1 to 6 were evaluated as follows.
(1) Shear adhesive strength
Each of the epoxy resin compositions was used to bind the longitudinal terminals of two quartz plates having a size of 35nτmx25mmx5mm by overlapping 3mm x 20mm, and cured using a mercury vacuum lamp(more than lOmW) for 5 to 10 minutes at room temperature, and post-cured under the condition of 60 to 85 °C for 4 to 10 hours. The specimen was tested using a conventional tension tester at 1 to lOmm/min in accordance with ASTM D-1144 to evaluate the shear adhesive strength. The results are shown in Table 1.
Table 1
As shown in Table 1, each of the UV-curable epoxy resin compositions comprising a lactone monomer according to the present invention has a shear adhesive strength comparable or superior to that of a conventional composition containing a ring-opened ε-caprolactone polyol.
(2) Shrinkage
Shrinkage during curing was calculated from the specific gravity of above examples, which were measured before and after curing according to ASTM D-792. UV and post-curing condition for preparing specimens is the same as the shear adhesive strength test. The results are shown in Table 2.
Table 2
Table 2 shows that each of the UV-curable epoxy resin compositions comprising a lactone monomer according to the present invention exhibits markedly smaller shrinkage than that of a conventional composition containing a ring-opened ε-caprolactone polyol.
(3) Moisture and heat resistance
The moisture and heat resistance was determined using the same specimen as used in the shear adhesive strength. After the specimen was subjected to a pressure cooker test(PCT) under the condition of 121 °C, 2atm, and 100% relative humidity, shear adhesive strength was evaluated with a UTM(Instron) at 25 °C and a shear speed of 5mm/min. The results are shown in Table 3.
Table 3
De denotes delamination.
The results in Table 3 demonstrate that the moisture and heat resistance of the inventive UV-curable epoxy resin composition is greatly enhanced owing to the presence of a lactone monomer.
While the invention has been described with respect to the above specific embodiments, it should be recognized that various modifications and changes may be made to the invention by those skilled in the art which also fall within the scope of the invention as defined by the appended claims.
Claims
1. A UV-curable epoxy resin composition comprising an epoxy oligomer, an epoxy monomer, a cationic initiator and a lactone monomer.
2. The UV-curable epoxy resin composition of claim 1, wherein the contents of the epoxy oligomer, epoxy monomer, cationic initiator and lactone monomer are 5 to 80% by weight, 5 to 80% by weight, 1 to 10% by weight and 1 to 80% by weight, respectively, based on the total weight of the composition.
3. The UV-curable epoxy resin composition of claim 1, wherein the lactone monomer is selected from the group consisting of ε-caprolactone, y-caprolactone, δ-caprolactone, β-butyrolactone, β-propiolactone, δ-dodecanolactone, 4-dodecanolide, 2,3-o-isopropylidene-D-erythronolactone, (±)-γ-valerolactone, (- )-corey lactone, (-f)-γ-decalactone, pantolactone, 5-tetradecanolide, γ-butyrolactone, γ-jasmolactone,
Y-methylene-γ-butyrolactone, and a mixture thereof.
4. The UV-curable epoxy resin composition of claim 1, wherein the epoxy oligomer is selected from the group consisting of end-capped poly(bisphenol A-cø-epichlorohydrin) glycidyl, poly[(ø-cresyl glycidyl ether)-cø-formaldehyde], tetraphenyloethane glycidyl ether, brominated bisphenol A diglycidyl ether, bisphenol A propoxylate diglycidyl ether, bis(4-glycidyloxyphenyl)methane, and a mixture thereof.
5. The UV-curable epoxy resin composition of claim 1, wherein the epoxy monomer is selected from the group consisting of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis(3 ,4-epoxycyclohexylmethyl) adipate, 1 ,2-epoxy-4-vinylcyclohexane, 1,2-epoxytetradecane, 1,2-epoxydodecane, 1,2-epoxydecane, l,2-epoxy-9-decene, l,2-epoxy-3-phenoxypropane, 4-vinyl-l-cyclohexene diepoxide, 4-vinyl-l-cyclohexene 1,2-epoxide, 1,4-cyclohexanedimethanol diglycidyl ether, 4-tert-butylpheyl glycidyl ether, 1,2-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, dodecanediol diglycidyl ether, pentaerythritol polyglycidyl ether, trimethylpropane polyglycidyl ether, phenyl glycidyl ether, resorcinol diglycidyl ether, nonyl phenyl glycidyl ether, allyl glycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, tetrafluoropropyl glycidyl ether, octafluoropropyl glycidyl ether, dodecafluorooctyl diglycidyl ether, styrene oxide, limonene monoxide, and a mixture thereof.
6. The UV-curable epoxy resin composition of claim 1, wherein the cationic initiator is selected from the group consisting of triaryl sulfonium hexafluoroantimonate, triaryl sulfonium hexafluorophosphate, diaryl iodonium hexafluoroantimonate, iodonium butyltriphenylborate, tetrakis(pentafluorophenyl)borate, S-phenyl thianthrenium hexafluorophosphate, triphenyl sulfonium hexafluorophosphate, diphenyl sulfide, p-hydroxy benzylphosphonium hexafluoroantimonate, and a mixture thereof.
7. The UV-curable epoxy resin composition of claim 6, wherein the cationic initiator is used in combination with a solvent.
8. The UV-curable epoxy resin composition of claim 7, wherein the solvent is propylene carbonate.
9 . The UV-curable epoxy resin composition of claim 1, which further comprises at least one additive selected from the group consisting of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, (3-glycidoxypropyl)trimethoxy -silane, (3-glycidoxypropyl)bis(trimethylsiloxy)methylsilane, (3-glycidoxypropyl) -dimethylethoxysilane, (3-glycidoxypropyl)methyldiethoxysilane, (3-glycidoxy -propyl)methyldimethoxysilane, and 2,6-di-tert-butyl-4-methylphenol.
10. The UV-curable epoxy resin composition of claim 9, wherein the content of the additive ranges from 0.01 to 10% by weight based on the total weight of the composition.
11. An optical article manufactured using the UV-curable epoxy resin composition according to any one of claims 1 to 10 as an adhesive.
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| Application Number | Priority Date | Filing Date | Title |
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| AU2002353593A AU2002353593A1 (en) | 2002-03-08 | 2002-11-11 | Uv-curable epoxy resin composition comprising lactone monomer |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2002-0012350A KR100502993B1 (en) | 2002-03-08 | 2002-03-08 | Optical adhesives for optical transmission parts |
| KR2002/12350 | 2002-03-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2003076544A1 true WO2003076544A1 (en) | 2003-09-18 |
Family
ID=27800656
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/KR2002/002096 WO2003076544A1 (en) | 2002-03-08 | 2002-11-11 | Uv-curable epoxy resin composition comprising lactone monomer |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR100502993B1 (en) |
| AU (1) | AU2002353593A1 (en) |
| WO (1) | WO2003076544A1 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007111606A1 (en) * | 2006-03-29 | 2007-10-04 | National Starch And Chemical Investment Holding Corporation | Radiation-or thermally-curable barrier sealants |
| WO2007135094A1 (en) * | 2006-05-22 | 2007-11-29 | Henkel Ag & Co. Kgaa | Low shrinkage epoxy-cationic curable compositions |
| US8067481B2 (en) * | 2004-05-26 | 2011-11-29 | Dentsply International, Inc. | Low shrinkage dental material and method |
| CN102985459A (en) * | 2010-06-28 | 2013-03-20 | 陶氏环球技术有限责任公司 | Curable resin compositions |
| CN103772649A (en) * | 2006-03-29 | 2014-05-07 | 汉高股份两合公司 | Radiative or heat-curable anti-seepage sealant |
| CN107236502A (en) * | 2017-05-02 | 2017-10-10 | 湖北绿色家园材料技术股份有限公司 | A kind of low cost, fast solidification, the Stone back mesh glue of high intensity and preparation method thereof |
| WO2021042013A1 (en) * | 2019-08-30 | 2021-03-04 | Dsm Ip Assets B.V. | Liquid, hybrid uv/vis radiation curable resin compositions for additive fabrication |
| CN113948481A (en) * | 2020-07-17 | 2022-01-18 | 华为技术有限公司 | Semiconductor device, epoxy resin, preparation method of epoxy resin, packaging material and terminal |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5742724A (en) * | 1980-08-29 | 1982-03-10 | Toagosei Chem Ind Co Ltd | Curable composition |
| JPS5943072A (en) * | 1982-09-02 | 1984-03-09 | Toyo Ink Mfg Co Ltd | Energetic ray-curable coating composition |
| JPH01103655A (en) * | 1987-09-09 | 1989-04-20 | Daicel Chem Ind Ltd | Polycaprolactone resin composition |
| JPH06136016A (en) * | 1992-10-23 | 1994-05-17 | Nippon Kayaku Co Ltd | Energy ray-curable composition and its cured product |
| JPH11181391A (en) * | 1997-12-22 | 1999-07-06 | Nippon Kayaku Co Ltd | Adhesive composition, adhered body, adhering method, and production of optical disk |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS596211A (en) * | 1982-07-02 | 1984-01-13 | Toyo Ink Mfg Co Ltd | Ultraviolet ray-curable composition |
| JPS5920371A (en) * | 1982-07-27 | 1984-02-02 | Toyo Ink Mfg Co Ltd | Conductive adhesive |
| JPS60217279A (en) * | 1984-04-11 | 1985-10-30 | Kyocera Corp | Adhesive |
-
2002
- 2002-03-08 KR KR10-2002-0012350A patent/KR100502993B1/en active IP Right Grant
- 2002-11-11 AU AU2002353593A patent/AU2002353593A1/en not_active Abandoned
- 2002-11-11 WO PCT/KR2002/002096 patent/WO2003076544A1/en not_active Application Discontinuation
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5742724A (en) * | 1980-08-29 | 1982-03-10 | Toagosei Chem Ind Co Ltd | Curable composition |
| JPS5943072A (en) * | 1982-09-02 | 1984-03-09 | Toyo Ink Mfg Co Ltd | Energetic ray-curable coating composition |
| JPH01103655A (en) * | 1987-09-09 | 1989-04-20 | Daicel Chem Ind Ltd | Polycaprolactone resin composition |
| JPH06136016A (en) * | 1992-10-23 | 1994-05-17 | Nippon Kayaku Co Ltd | Energy ray-curable composition and its cured product |
| JPH11181391A (en) * | 1997-12-22 | 1999-07-06 | Nippon Kayaku Co Ltd | Adhesive composition, adhered body, adhering method, and production of optical disk |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8067481B2 (en) * | 2004-05-26 | 2011-11-29 | Dentsply International, Inc. | Low shrinkage dental material and method |
| TWI408152B (en) * | 2006-03-29 | 2013-09-11 | Henkel Ag & Co Kgaa | Radiation- or heat-curable barrier sealant |
| US8278401B2 (en) * | 2006-03-29 | 2012-10-02 | Henkel Ag & Co. Kgaa | Radiation or thermally curable barrier sealants |
| CN103772649A (en) * | 2006-03-29 | 2014-05-07 | 汉高股份两合公司 | Radiative or heat-curable anti-seepage sealant |
| WO2007111606A1 (en) * | 2006-03-29 | 2007-10-04 | National Starch And Chemical Investment Holding Corporation | Radiation-or thermally-curable barrier sealants |
| WO2007135094A1 (en) * | 2006-05-22 | 2007-11-29 | Henkel Ag & Co. Kgaa | Low shrinkage epoxy-cationic curable compositions |
| US7740734B2 (en) | 2006-05-22 | 2010-06-22 | Henkel Ag & Co. Kgaa | Low shrinkage epoxy-cationic curable compositions |
| US20130090407A1 (en) * | 2010-06-28 | 2013-04-11 | James Wells Carter | Curable resin compositions |
| CN102985459A (en) * | 2010-06-28 | 2013-03-20 | 陶氏环球技术有限责任公司 | Curable resin compositions |
| CN107236502A (en) * | 2017-05-02 | 2017-10-10 | 湖北绿色家园材料技术股份有限公司 | A kind of low cost, fast solidification, the Stone back mesh glue of high intensity and preparation method thereof |
| WO2021042013A1 (en) * | 2019-08-30 | 2021-03-04 | Dsm Ip Assets B.V. | Liquid, hybrid uv/vis radiation curable resin compositions for additive fabrication |
| CN114341732A (en) * | 2019-08-30 | 2022-04-12 | 科思创(荷兰)有限公司 | Liquid hybrid uv/vis radiation curable resin compositions for additive manufacturing |
| US11866526B2 (en) | 2019-08-30 | 2024-01-09 | Stratasys, Inc. | Liquid, hybrid UV/vis radiation curable resin compositions for additive fabrication |
| CN113948481A (en) * | 2020-07-17 | 2022-01-18 | 华为技术有限公司 | Semiconductor device, epoxy resin, preparation method of epoxy resin, packaging material and terminal |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2002353593A1 (en) | 2003-09-22 |
| KR20030073005A (en) | 2003-09-19 |
| KR100502993B1 (en) | 2005-07-25 |
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