CN102471560A - Energy ray-curable epoxy resin composition having excellent curing properties in deep portions - Google Patents
Energy ray-curable epoxy resin composition having excellent curing properties in deep portions Download PDFInfo
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- CN102471560A CN102471560A CN2010800287779A CN201080028777A CN102471560A CN 102471560 A CN102471560 A CN 102471560A CN 2010800287779 A CN2010800287779 A CN 2010800287779A CN 201080028777 A CN201080028777 A CN 201080028777A CN 102471560 A CN102471560 A CN 102471560A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1525—Four-membered rings
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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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
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Abstract
Disclosed is an energy ray-curable epoxy resin composition wherein the problem of poor curing properties in deep portions has been solved, while maintaining high fixation accuracy. Specifically disclosed is an energy ray-curable epoxy resin composition containing an epoxy resin, a filler and a photoacid generator, wherein the difference between the refractive index of the filler and the refractive index of the energy ray-curable epoxy resin composition excluding the filler is within +-0.02.
Description
Technical field
The present invention relates to the energy ray-curable composition epoxy resin, relate in particular to and not only highly keep fixed precision, and have the energy ray-curable composition epoxy resin of fixedly usefulness of the optics of good deep solidified nature.
Background technology
In optical take-up apparatus, for photodetector is fixed to housing and uses light-cured type caking agent (patent documentation 1,2).For this caking agent, be asked to have high fixed precision and high deep solidified nature.
Fixed precision is meant, when photodetector is fixed to housing, and the precision that the display light detector can not move from the position of regulation.If fixed precision is low excessively, when making optical take-up apparatus or after the long duration test, photodetector can be moved from the position of regulation, can not carry out and light is detected.Therefore, require to have high fixed precision.
The deep solidified nature is meant, when carrying out rayed from top, shows the index that is cured to what kind of degree of depth, and this deep solidified nature is high more good more.
If consider fixed precision, then as the light-cured type caking agent, the cation-curable epoxy resin adhesive is better than light solidified acrylic resin caking agent.In addition, the cation-curable epoxy resin adhesive solidifies obstruction unlike acrylic resin caking agent that kind because of oxygen produces, and film hardening property also very good (non-patent literature 1).Yet there is the relatively poor problem of deep solidified nature in the cationic curing epoxy resin.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2002-251776 communique
Patent documentation 2: TOHKEMY 2007-35238 communique
Non-patent literature
Non-patent literature 1: " epoxy resin handbook (エ Port キ シ resin Ha Application De Block Star Network), 236 pages, clear and on December 25th, 62, first edition first impression distribution
Summary of the invention
The problem that invention will solve
Problem of the present invention is that it is the high energy ray-curable composition epoxy resin of fixed precision, when highly keeping fixed precision, has solved the relatively poor problem of deep curable.
Solve the means of problem
The present invention is a kind of composition epoxy resin; It is the energy ray-curable composition epoxy resin that contains epoxy resin, filler and light acid producing agent, and the difference of specific refractory power of the specific refractory power of this filler and the energy ray-curable composition epoxy resin that does not contain this filler is in ± 0.02.
Related with fixed precision; Low cure shrinkage; It is important that cure shrinkage when not solidifying because of the light-cured type caking agent moves the photodetector that has carried out the position adjustment; High elastic coefficient during high temperature, photodetector is not important because of the tension force of its deadweight or the incidental FPC of photodetector (polyimide distribution) moves during for high temperature, even the light-cured type caking agent is also softening and show harder character during high temperature.The inventor etc. are through various researchs, and the result finds: in order to obtain high fixed precision, need be below 3% with the cure shrinkage of composition epoxy resin and during high temperature the Young's modulus under (100 ℃ of the temperature of long duration test) be more than the 50MPa.
About deeply-curing property, the inventor etc. have carried out various analyses, and the result finds: the method (10 seconds of UV irradiation time) with regulation is measured, and preferably preferably has the above deep solidified nature of 2mm.
The invention effect
According to the present invention, not only can keep high fixed precision, and can significantly improve the deep solidified nature of resin combination.
Embodiment
Energy ray-curable composition epoxy resin of the present invention contains epoxy resin, filler and light acid producing agent.
Do not have special qualification as epoxy resin; But illustration for example, bisphenol A type epoxy resin, bisphenol f type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, phenol novolak type epoxy resin, cresols phenolic resin varnish type epoxy resin, bisphenol-A epoxy resin, A Hydrogenated Bisphenol A F type epoxy resin, polyhutadiene type epoxy resin, polyisobutylene type epoxy resin, alicyclic epoxy resin, fatty family epoxy resin etc.These resins can be distinguished independent use, or make up more than two kinds and use.
As alicyclic epoxy resin, for example can enumerate VCH list oxide compound 1,2-epoxy-4-vinyl cyclohexane (CEL2000), 1; 2:8; 9 diepoxy PC 560s (CEL3000), 3,4-oxirane ring hexenyl methyl-3 ', 4 '-oxirane ring hexene carboxylicesters (CEL2021P), 2; 1 of two (the hydroxymethyl)-1-butanols of 2-; 2-epoxy-4-(2-epoxy ethyl) hexanaphthene affixture (EHPE3150), 3,4-oxirane ring hexenyl methyl-3 ', 4 '-oxirane ring hexene carboxylicesters, hydrogenation biphenyl type alicyclic epoxy resin etc.Can distinguish independent use, or combination is used more than two kinds.
As aliphatic epoxy resin; For example can enumerate ethylene glycol diglycidylether, Diethylene Glycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, neopentylglycol diglycidyl ether, 1; 4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, TriMethylolPropane(TMP) diglycidylether, polyethyleneglycol diglycidylether etc.Can distinguish independent use, or form more than two kinds and use.
As epoxy resin, be preferably bisphenol A type epoxy resin (for example, the EPICLON850 of DIC corporate system or EPICLON860), bisphenol-A epoxy resin (for example, the YX8034 of jER corporate system), be preferably the EPICLON860 of DIC corporate system especially.
In the present invention, the phenol aldehyde type epoxy resin as bisphenol A type epoxy resin etc. also can use through the purified material.In the phenol aldehyde type epoxy resin, in Epicholorohydrin that uses in synthetic or the epoxy group(ing) not the halogen-containing midbody of closed loop exist with impurity.These impurity are in the presence of the cationic curing catalyzer, even the irradiation energy ray does not solidify yet.Therefore,, the uncured composition in the cured article after solidifying with energy-ray can be reduced, and the energy ray-curable composition epoxy resin of low halogen can be obtained containing through using the phenol aldehyde type epoxy resin after these impurity are removed.
As making with extra care of phenol aldehyde type epoxy resin; For example can enumerate, refining based on distillatory, based on use that silica gel or aluminum oxide isochromatic spectrum carry out refining, in the such alkali aqueous solution of aqueous sodium hydroxide solution to the halogen with covalent bonding be hydrolyzed refining etc.As the highly finished product of the epoxy resin of bisphenol A-type, can obtain EXA-8067 from DIC company.
In energy ray-curable composition epoxy resin of the present invention, from the viewpoint of the problem of the problem of electrocorrosion (galvanic corrosion property), global environment, halogen quantity is preferably below the 500ppm.As epoxy resin,, then except the effect of the invention described above, also can reach low halogenization if use EXA-8067.
As filler, can enumerate acrylic acid series filler, polystyrene filler, vinylformic acid/styrene copolymerized is filler, fluorine resin filler, polyethylene-based filler, polypropylene-based filler, silicone-based filler, silica-based filler, mica, talcum etc.Can distinguish independent use, or combination is used more than two kinds.Preferred filler does, vinylformic acid/styrene copolymerized is filler, polyethylene-based filler, polypropylene-based filler, glass filler, and preferred filler is that vinylformic acid/styrene copolymerized is filler.With respect to 45 parts by weight of epoxy resin, the addition of filler is preferably 5～100 weight parts, more preferably 15～60 weight parts.
In energy ray-curable composition epoxy resin of the present invention, the difference of specific refractory power of the specific refractory power of filler and the energy ray-curable composition epoxy resin that does not contain filler is in ± 0.02, preferably in ± 0.01.Here; The energy ray-curable composition epoxy resin that does not contain filler is meant, from the energy ray-curable composition epoxy resin of the present invention that contains epoxy resin, filler and light acid producing agent and composition as required, has removed the composition epoxy resin of filler.Through selecting filler, but perhaps select aptly epoxy resin, after the general layout stated other the additive that need contain, can the difference of the specific refractory power of filler with the specific refractory power of the energy ray-curable composition epoxy resin that does not contain filler be located in the scope of regulation.
As light acid producing agent,, can enumerate sulfonium salt, salt compounded of iodine as long as to produce the compound of Lewis acid or bronsted acid just unqualified for the irradiation through energy-ray.With respect to 45 parts by weight of epoxy resin, the scope of the usage quantity of light acid producing agent is preferably 0.5～10 weight part, more preferably 1～4 weight part.Light acid producing agent also solubilized or be dispersed in the solvent of 4-GBL etc. adds.
As sulfonium salt; For example can enumerate triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoro antimonate, triphenylsulfonium four (pentafluorophenyl group) borate, 4; The two hexafluorophosphates, 4 of 4 '-two (phenylbenzene sulfonium base) diphenyl sulfide; The two hexafluoro antimonates, 4 of 4 '-two (two (beta-hydroxy oxyethyl group) phenyl sulfonium base) diphenyl sulfide; The two hexafluorophosphates of 4 '-two (two (beta-hydroxy oxyethyl group) phenyl sulfonium base) diphenyl sulfide, 7-(two (to toluyl) sulfonium base)-2-isopropyl thioxanthone hexafluoro antimonate, 7-(two (to toluyl) sulfonium base)-2-isopropyl thioxanthone four (pentafluorophenyl group) borate, 4-phenylcarbonyl group-4 '-phenylbenzene sulfonium base-diphenyl sulfide hexafluorophosphate, 4-(to the tert-butyl-phenyl carbonyl)-4 '-phenylbenzene sulfonium base-diphenyl sulfide hexafluoro antimonate; 4-(to the tert-butyl-phenyl carbonyl)-4 '-two (to toluyl) sulfonium base-diphenyl sulfide four (pentafluorophenyl group) borate, rising sun electrification corporate system SP-170; SP-172; SP-150, SP-152, SAN-APRO corporate system CPI-210S etc.Be preferably the rising sun electrification corporate system SP-170, SP-172 or SAN-APRO corporate system CPI-210S as sulfonium salt.These salt can be distinguished independent use, or make up more than two kinds and use.
As salt compounded of iodine, for example can enumerate phenylbenzene iodine four (pentafluorophenyl group) borate, diphenyl iodine hexafluorophosphate, phenylbenzene iodine hexafluoro antimonate, two (4-nonyl phenyl) iodine hexafluorophosphate, Rodia corporate system PI2074 etc.Be preferably Rodia corporate system PI2074 as salt compounded of iodine.These salt can be distinguished independent use, or combination is used more than two kinds.
Energy ray-curable composition epoxy resin of the present invention can contain other additive of oxetane compound, photosensitizer, silane coupling agent etc.
In order to improve the coating operability, with lowering viscousity, low-shrinkageization is that purpose is added oxetane compound.As oxetane compound; Can enumerate 3-ethyl-3-hydroxymethyl trimethylene oxide (OXA), 1, two ({ (3-ethyl-3-oxetanyl) methoxyl group } methyl) benzene (XDO) of 4-, 3-ethyl-3-(phenoxymethyl) trimethylene oxide (OXT-211 (POX)), 2-ethylhexyl trimethylene oxide (OXT-212 (EHOX)), xylylene dioxygen heterocycle butane (OXT-121 (XDO)), two (3-ethyl-3-trimethylene oxide ylmethyl) ethers (OXT-221 (DOX)), oxetanyl silicon ester OXT-191,3-ethyl-({ (3-triethoxysilyl propoxy-) methyl) trimethylene oxide, oxetanyl silsesquioxane, phenol phenolic varnish trimethylene oxide etc.In the parantheses is the goods number of East Asia Synesis Company.With respect to 45 parts by weight of epoxy resin, the addition of oxetane compound is preferably 5～100 weight parts, more preferably 10～50 weight parts.Each oxetane compound can use separately, or makes up more than two kinds and use.
Though do not have special the qualification as photosensitizer, for example can enumerate, carbonyl compound, organosulfur compound, persulfide, redox based compound, azo and diazonium compound, halogen compounds, light is unit's property pigment etc. also.As photosensitizer, specifically can enumerate benzoin methyl ether, bitter almond oil camphor isopropyl ether, α, the alpha, alpha-dimethyl oxygen base-α-such benzoin derivatives of phenyl methyl phenyl ketone; UVNUL MS-40,2,4-dichloro benzophenone, o-benzoyl TRIMETHOXY BENZOIC ACID (FOR MANUFACTURING OF T.M. methyl esters, 4, the 4 '-such benzophenone derivates of two (diethylamino) benzophenone; 2,4-diethyl thioxanthone, 2-clopenthixal ketone, the such thioxanthone derivates of 2-isopropyl thioxanthone; 2-chloroanthraquinone, the such anthraquinone derivative of 2-methylanthraquinone; N-methylacridine ketone, the such acridone derivatives of N-butyl dihydroketoacridine; Other, α, α-diethoxy acetophenone, benzil, Fluorenone, xanthone, uranyl compound etc.These photosensitizers can use separately, or combination is used more than two kinds.Preferred photosensitizer is 2,4-diethyl thioxanthone (Japanese chemical drug system DETX-S).With respect to 45 parts by weight of epoxy resin, the addition of photosensitizer is 0.001～1 weight part, is preferably 0.005～0.1 weight part.Using salt compounded of iodine is PI2074 during as light acid producing agent, preferably uses photosensitizer DETX-S, and its addition with respect to 45 parts by weight of epoxy resin, is preferably 0.001～0.1 weight part, is preferably 0.01 weight part especially.During as light acid producing agent, might not need photosensitizer at the CPI-210S that uses sulfonium salt system, even do not add, solidified nature is also good.
To give the purpose interpolation silane coupling agent that cohesiveness is.As silane coupling agent; But example for example goes out, tetraalkoxysilane classes such as tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilan, four butoxy silanes, dimethoxy diethoxy silane, dimethoxy diisopropoxy silane, diethoxy diisopropoxy silane, diethoxy dibutoxy silane; Trialkoxysilanes such as methyltrimethoxy silane, Union carbide A-162, methyl three isopropoxy silane, ethyl triethoxysilane, ethyl three butoxy silanes, cyclohexyl triethoxyl silane, phenyl three isopropoxy silane; Dialkoxy silicane classes such as dimethyldimethoxysil,ne, dimethyldiethoxysilane, diethylammonium diethoxy silane, diethylammonium dibutoxy silane, phenylethyl diethoxy silane.These silane coupling agents can use separately, also can 2 kinds use with combination.The addition of silane coupling agent with respect to 45 parts by weight of epoxy resin, is preferably 0.1～10 weight part, more preferably 0.5～5 weight part.
Energy ray-curable composition epoxy resin of the present invention; For example; Because can high fixed precision, fixed L D (laser diode), photodetector (PD: photodetector), the optics of lens, prism etc. or be equipped with the optical module etc. of optics such as lens, very useful promptly as the caking agent of Optical devices assembling usefulness.As Optical devices, for example,, or in the optical take-up apparatus of record in the paragraph 0023 of TOHKEMY 2007-311006 communique, be used for fixing after the obliquity of helical screw (Skew-Screw) adjustment solenoid coil (actuator) at patent documentation 1,2.In addition, also can be used in other fixing of opticses such as mirror or fixing of messenger wire.
Embodiment
Below the present invention will be described through embodiment.Need to prove that use level is represented with weight part.
[embodiment 1 and comparative example 1～2]
The proportioning of putting down in writing based on table 1, dissolving light acid producing agent PI2074 adds it among EPICLON 850 and the CEL3000 in the 4-GBL, is stirred to transparently, has prepared the energy ray-curable composition epoxy resin of comparative example 1.
Based on the proportioning shown in the table 1, in the composition epoxy resin of comparative example 1, add GS350T or GS310T, be stirred to till the homogeneous, prepared the energy ray-curable composition epoxy resin of embodiment 1 or comparative example 2.
Measured the deep solidified nature of the composition epoxy resin of embodiment 1, comparative example 1 and 2.The deep solidified nature is measured to be described below: opening
In the clarinet in hole, packing height is the embodiment 1 of 5mm and the energy ray-curable composition epoxy resin of comparative example 1,2 respectively, with Hamamatsu Photonics system UV irradiating machine from top with 500mW/cm
2(365nm) after 10 seconds kinds of irradiation, from clarinet, take out cured article, remove uncured portion, measure the thickness of cured portion with milscale.The result is shown in the table 1.
[table 1]
| Goods number | Comparative example 1 | Embodiment 1 | Comparative example 2 |
| EPICLON?850 | 40.9 | 40.9 | 40.9 |
| CEL3000 | 4.1 | 4.1 | 4.1 |
| CPI-210S | 1.2 | 1.2 | 1.2 |
| The 4-GBL | 0.6 | 0.6 | 0.6 |
| Art Pearl GS350T (specific refractory power 1.55) | 40.9 | ||
| Art Pearl GS310T (specific refractory power 1.51) | 40.9 | ||
| The specific refractory power that does not contain the resin combination * of filler | 1.56 | 1.56 | 1.56 |
| 500mW/cm 2Deep solidified nature after * 10 seconds | 1.7mm | 2.8mm | 2.1mm |
EPICLON 850: bisphenol A type epoxy resin (DIC corporate system)
CEL3000:1,2:8,9 diepoxy PC 560s (DAICEL CHEMICAL corporate system)
CPI-210S: sulfonium is light acid producing agent (a SAN-APRO corporate system)
4-GBL: solvent (with the pure medicine corporate system of light)
Art Pearl GS-350T: vinylformic acid/styrol copolymer filler: specific refractory power 1.55 (root is attend industrial's system)
Art Pearl GS-310T: vinylformic acid/styrol copolymer filler: specific refractory power 1.51 (root is attend industrial's system)
*: the resin combination that does not contain filler is following compsn: about comparative example 1 for the identical compsn of proportioning of the comparative example of table 1; About embodiment 1 for from the proportioning of the embodiment 1 of table 1, removing the compsn of the proportioning of Art Pearl GS350T; About comparative example 2 for from the proportioning of the comparative example 2 of table 1, removing the compsn of the proportioning of Art Pearl GS310T.
[embodiment 2 and comparative example 3,4]
Based on the proportioning that table 2 is put down in writing, prepared the composition epoxy resin of embodiment 2, comparative example 3 and 4.Measured the deep solidified nature of each composition epoxy resin.The result is shown in the table 2.
[table 2]
| Goods number | Embodiment 2 | Comparative example 3 | Comparative example 4 |
| EPICL0N?860 | 45 | 45 | 45 |
| OXT-211 | 15 | 15 | 15 |
| OXT-121 | 5 | 5 | 5 |
| OXT-191 | 5 | 5 | 5 |
| PI2074 | 3 | 3 | 3 |
| DETX-S | 0.01 | 0.01 | 0.01 |
| CPI-210S | |||
| Art Pearl GS-350T (specific refractory power 1.55) | 45 | ||
| TALC P-2 (specific refractory power 1.58) | 20 | 45 | |
| The specific refractory power that does not contain the resin combination of filler | 1.55 | 155 | 1.55 |
| Deep solidified nature 500mW/cm 2×10s | 2.7mm | 1.9mm | 1.4mm |
EPICLON 860: bisphenol A type epoxy resin (DIC corporate system)
OXT-211:3-ethyl-3-(phenoxymethyl) trimethylene oxide (East Asia Synesis Company system)
OXT-121:1, two [[(3-ethyl-3-oxetanyl) methoxyl group] methyl] benzene (East Asia Synesis Company system) of 4-
OXT-191: oxetanyl silicon ester (East Asia Synesis Company system)
PI2074: iodine is light acid producing agent (Rodia corporate system)
DETX-S:2,4-diethyl thioxanthone (sensitizing agent: Japanese chemical drug corporate system)
CPI-210S: sulfonium is light acid producing agent (a SAN-APRO corporate system)
Art Pearl GS-350T: vinylformic acid/styrol copolymer filler: specific refractory power 1.55 (root is attend industrial's system)
TALC P-2: talcum specific refractory power 1.58 (Japanese TALC corporate system)
[embodiment 3 and comparative example 5]
Based on the proportioning that table 3 is put down in writing, prepared the composition epoxy resin of embodiment 3 and comparative example 5.Measured the deep solidified nature of each composition epoxy resin.The result is shown in the table 3.
[table 3]
| Embodiment 3 | Comparative example 5 | |
| YX8034 | 45 | 45 |
| OXT-211 | 30 | 30 |
| OXT-191 | 5 | 5 |
| CPI-210S | 2 | 2 |
| Art Pearl GS-310T (specific refractory power 1.51) | 32.5 | |
| Art Pearl GS-350T (specific refractory power 1.55) | 325 | |
| The specific refractory power that does not contain the resin combination of filler | 1.51 | 1.51 |
| Deep hardening 500mW/cm 2×10s | 3.3mm | 1.7mm |
YX8034: bisphenol-A epoxy resin: jER company (Japan Epoxy Resins)
OXT-211:3-ethyl-3-(phenoxymethyl) trimethylene oxide (East Asia Synesis Company system)
OXT-191: oxetanyl silicon ester (East Asia Synesis Company system)
CPI-210S: sulfonium is light acid producing agent (a SAN-APRO corporate system)
Art Pearl GS-310T: vinylformic acid/styrol copolymer filler: specific refractory power 1.51 (root is attend industrial's system)
Art Pearl GS-350T: vinylformic acid/styrol copolymer filler: specific refractory power 1.55 (root is attend industrial's system)
[Test Example 1]
Respectively to embodiment 2 and 3 and the composition epoxy resin of comparative example 3 measured cure shrinkage and Young's modulus.Cure shrinkage is measured according to the CUP method of JIS K 6833 records.Young's modulus uses SII corporate system EXSTAR6000, measures with the plate tension method.The result is shown in the table 4.
[table 4]
| Embodiment 2 | Embodiment 3 | Comparative example 3 | |
| Cure shrinkage (%) | ?1.5 | ?2.0 | ?1.4 |
| 25 ℃ of Young's modulus (MPa) | ?3000 | ?2580 | ?4040 |
| 100 ℃ of Young's modulus (MPa) | ?120 | ?65 | ?250 |
[embodiment 4 and 5]
Based on the proportioning shown in the table 5, prepared the matrix (composition epoxy resin that does not contain filler) of the energy ray-curable composition epoxy resin of embodiment 4 and 5.
[table 5]
| Goods number | The matrix of embodiment 4 | The matrix of embodiment 5 |
| EPICLON?860 | 45 | |
| YX8034 | 45 | |
| OXT-211 | 15 | 35 |
| OXT-121 | 5 | |
| CPI-210S | 2 | 2 |
| The specific refractory power of matrix resin compsn | 1.55 | 1.50 |
Respectively in the matrix of embodiment 4 and 5; Add Art Pearl GS-310T (specific refractory power 1.51); Art Pearl GS-320T (specific refractory power 1.52); Each 45 weight part of Art Pearl GS-330T (specific refractory power 1.53) and Art Pearl GS-350T (specific refractory power 1.55) have prepared 8 kinds of energy ray-curable composition epoxy resins.
[Test Example 2]
8 kinds of energy ray-curable composition epoxy resins for preparation in embodiment 4 and 5 likewise (wherein, change to the UV irradiation time 20 seconds from 10 seconds) with embodiment 1, have measured the deep solidified nature.Its result is shown in the table 6.
[table 6]
[embodiment 6～8]
Based on the proportioning shown in the table 7, prepared the energy ray-curable composition epoxy resin of embodiment 6～8.
[table 7]
EXA-8067: bisphenol A type epoxy resin (DIC corporate system :) through the distillatory highly finished product
1-651:2,2-dimethoxy-1,2-diphenylethane (Chiba corporate system sensitizing agent)
[Test Example 3]
Tested the LED solidified nature of the energy ray-curable composition epoxy resin of embodiment 6 and 7 respectively.The LED solidified nature is described below and carries out: the energy ray-curable composition epoxy resin that on aluminium sheet, drips, with its with the LED irradiating machine of wavelength 365nm with 500mW/cm
2Illumination (luxmeter Hamamatsu Photonics makes C6080-13) irradiation be cured for 10 seconds, solid state is confirmed to refer to touch.The benchmark of LED solidified nature is zero: solidify (solid) * mark: uncured (liquid state).Test-results is shown in the table 8.
[table 8]
The LED solidified nature
| Embodiment 6 | Embodiment 7 | |
| The LED solidified nature | ?○ | ?○ |
[Test Example 4]
Measure the halogen quantity of the energy ray-curable composition epoxy resin of embodiment 6 and 8 respectively through EN14582 combustion ion chromatography.Measure the result shown in the table 9.
[table 9]
Full halogen quantity
[Test Example 5]
Measured the deep solidified nature of the energy ray-curable composition epoxy resin of embodiment 6 and 8 respectively.For the deep solidified nature of being undertaken, to internal diameter by UV-lamp
The clarinet of length 5mm in fill the energy ray-curable composition epoxy resin, utilize uviolizing machine (Hamamatsu Photonics corporate system LC5) from top with illumination 500mW/cm
2(365nm) (luxmeter: Hamamatsu Photonics makes C6080-13) irradiation 10 seconds ultraviolet ray, and measure the length of the energy ray-curable composition epoxy resin that has solidified.For the deep solidified nature of utilizing LED to carry out: to internal diameter
The clarinet of length 5mm in fill the energy ray-curable composition epoxy resin, the LED irradiating machine that utilizes wavelength 365nm from top with illumination 500mW/cm
2(luxmeter: Hamamatsu Photonics makes C6080-13) shone for 10 seconds, measured the length of the energy ray-curable composition epoxy resin after solidifying.Measure the result shown in the table 10.
[table 10]
The deep solidified nature
[Test Example 6]
Hardness, cure shrinkage, the Young's modulus of the energy ray-curable composition epoxy resin of embodiment 6 and 8 have been measured respectively.Hardness (D) is measured through the sclerometer of JIS K 7215 records.Cure shrinkage is measured according to the CUP method of JIS K 6833 records.Tan δ and energy storage Young's modulus use SII corporate system EXSTAR6000 to measure with the plate tension method.
[table 11]
| Embodiment 6 | Embodiment 8 | ||
| Hardness (D) | The D type | 84 | 84 |
| Cure shrinkage | 1.6％ | 1.5％ | |
| Tanδ | 90℃ | 90℃ | |
| The energy storage Young's modulus | 25℃ | 4270MPa | 3000MPa |
| The energy storage Young's modulus | 100℃ | 180MPa | 120MPa |
Utilize possibility on the industry
According to energy ray-curable composition epoxy resin of the present invention; For example; Because the optics of LD, photodetector, lens, prism etc. or the optical module etc. that is equipped with optics such as lens can be fixed with good deep solidified nature on high fixed precision ground, and be very useful as the caking agent of Optical devices assembling usefulness.
Claims (8)
1. composition epoxy resin; It is the energy ray-curable composition epoxy resin that contains epoxy resin, filler and light acid producing agent, and the difference of specific refractory power of the specific refractory power of this filler and the energy ray-curable composition epoxy resin that does not contain this filler is in ± 0.02.
2. composition epoxy resin according to claim 1 is characterized in that, the difference of specific refractory power of the specific refractory power of filler and the energy ray-curable composition epoxy resin that does not contain this filler is in ± 0.01.
3. composition epoxy resin according to claim 1 and 2 is characterized in that, filler is the multipolymer of vinyl resin and styron.
4. according to each described composition epoxy resin in the claim 1～3, it is characterized in that, further contain oxetane compound.
5. according to each described composition epoxy resin in the claim 1～4, it is characterized in that, be the caking agent of Optical devices assembling usefulness.
6. according to each described composition epoxy resin in the claim 1～4, it is characterized in that, be the caking agent of optical take-up apparatus assembling usefulness.
7. Optical devices, it uses the described composition epoxy resin of claim 5 to assemble.
8. optical take-up apparatus, it uses the described composition epoxy resin of claim 6 to assemble.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009156854 | 2009-07-01 | ||
| JP2009-156854 | 2009-07-01 | ||
| PCT/JP2010/060833 WO2011001912A1 (en) | 2009-07-01 | 2010-06-25 | Energy ray-curable epoxy resin composition having excellent curing properties in deep portions |
Publications (2)
| Publication Number | Publication Date |
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| CN102471560A true CN102471560A (en) | 2012-05-23 |
| CN102471560B CN102471560B (en) | 2014-11-26 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201080028777.9A Active CN102471560B (en) | 2009-07-01 | 2010-06-25 | Energy ray-curable epoxy resin composition having excellent curing properties in deep portions |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP5634993B2 (en) |
| KR (1) | KR101555738B1 (en) |
| CN (1) | CN102471560B (en) |
| TW (1) | TWI479002B (en) |
| WO (1) | WO2011001912A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103666320A (en) * | 2012-09-20 | 2014-03-26 | 广东恒大新材料科技有限公司 | Tackifier composition for addition type silica gel and application thereof |
| US10059803B2 (en) | 2014-11-24 | 2018-08-28 | Industrial Technology Research Institute | Resin containing oxetane and epoxy groups and resin composition including the same |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101560075B1 (en) * | 2011-05-30 | 2015-10-13 | 미쯔비시 레이온 가부시끼가이샤 | Epoxy resin composition, cured product, and optical semiconductor encapsulation material |
| JP6163043B2 (en) * | 2013-08-08 | 2017-07-12 | 株式会社Adeka | Energy ray sensitive composition |
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- 2010-06-25 KR KR1020117031478A patent/KR101555738B1/en active IP Right Grant
- 2010-06-25 CN CN201080028777.9A patent/CN102471560B/en active Active
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| JPH09243870A (en) * | 1996-03-14 | 1997-09-19 | Hitachi Ltd | Production of optical module |
| JP2006233129A (en) * | 2005-02-28 | 2006-09-07 | Nitto Denko Corp | Resin sheet, liquid crystal cell substrate, substrate for electroluminescent display, substrate for solar battery and liquid crystal display device, electro luminescent display device and sollar battery |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN102471560B (en) | 2014-11-26 |
| TW201116605A (en) | 2011-05-16 |
| TWI479002B (en) | 2015-04-01 |
| KR20120103433A (en) | 2012-09-19 |
| KR101555738B1 (en) | 2015-09-25 |
| JP5634993B2 (en) | 2014-12-03 |
| WO2011001912A1 (en) | 2011-01-06 |
| JPWO2011001912A1 (en) | 2012-12-13 |
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