CN102471560B - 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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- CN102471560B CN102471560B CN201080028777.9A CN201080028777A CN102471560B CN 102471560 B CN102471560 B CN 102471560B CN 201080028777 A CN201080028777 A CN 201080028777A CN 102471560 B CN102471560 B CN 102471560B
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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
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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
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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 energy ray-curable composition epoxy resin, relate in particular to and not only highly maintain fixed precision, and there is the energy ray-curable composition epoxy resin of the fixing use 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 required to have high fixed precision and high deep solidified nature.
Fixed precision refers to, in the time that photodetector is fixed to housing, and the precision that display light detector can not move from the position of regulation.If fixed precision is too low, in the time manufacturing optical take-up apparatus or after 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.
Deep solidified nature refers to, in the time carrying out rayed from top, shows the index that is cured to what kind of degree of depth, and this deep solidified nature is more high better.
If consideration fixed precision, as light-cured type caking agent, cation-curable epoxy resin adhesive is better than light solidified acrylic resin caking agent.In addition, cation-curable epoxy resin adhesive hinders because oxygen produces to solidify unlike acrylic resin caking agent, and also very good (non-patent literature 1) of film hardening.But there is the poor problem of deep solidified nature in cationic curing epoxy resin.
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 Trees fat 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 of Xie Decision is Yaoed in invention
Problem of the present invention is, it is the energy ray-curable composition epoxy resin that fixed precision is high, in highly maintaining fixed precision, and the poor problem of deep solidified nature of having separated Decision.
Solve the means of problem
The present invention is a kind of composition epoxy resin, it is for containing the energy ray-curable composition epoxy resin of epoxy resin, filler and light acid producing agent, the specific refractory power of this filler with not containing the specific refractivity of the energy ray-curable composition epoxy resin of this filler in ± 0.02.
Associated with fixed precision, low cure shrinkage, it is important that the photodetector that cure shrinkage when not solidifying because of light-cured type caking agent has made to carry out position adjustment moves, high elastic coefficient when high temperature, during for high temperature, photodetector is not important because the tension force of its deadweight or the incidental FPC of photodetector (polyimide distribution) moves, even light-cured type caking agent is also softening and show harder character when high temperature.The inventor etc. through various research, found that: in order to obtain high fixed precision, need to be below 3% by the cure shrinkage of composition epoxy resin and when high temperature the Young's modulus at (100 DEG C of the temperature of long duration test) be more than 50MPa.
About deeply-curing, the inventor etc. have carried out various analyses, found that: measure with the method (10 seconds of UV irradiation time) specifying, preferably preferably have deep solidified nature more than 2mm.
Invention effect
According to the present invention, not only can maintain 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 is containing epoxy resin, filler and light acid producing agent.
Be not particularly limited as epoxy resin, for example can illustrate 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 use separately, or combination more than two kinds is used.
As alicyclic epoxy resin, for example can enumerate vinyl cyclohexene list oxide compound 1, 2-epoxy-4-vinyl cyclohexane (CEL2000), 1, 2:8, 9 diepoxy limonene (CEL3000), 3, 4-oxirane ring hexenyl methyl-3 ', 4 '-oxirane ring hexene carboxylicesters (CEL2021P), 2, 1 of two (the hydroxymethyl)-n-butyl alcohols 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 be used singly or two or more kinds in combination.
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 be used singly, or two or more kinds of use.
As epoxy resin, (be for example preferably bisphenol A type epoxy resin, EPICLON850 or the EPICLON860 of DIC company system), bisphenol-A epoxy resin (for example, the YX8034 of jER company system), be particularly preferably the EPICLON860 of DIC company system.
In the present invention, as the phenol aldehyde type epoxy resin of bisphenol A type epoxy resin etc., also can use through refining material.In phenol aldehyde type epoxy resin, in the synthetic middle Epicholorohydrin using or epoxy group(ing), the halogen-containing intermediate of closed loop does not exist with impurity.These impurity are under the existence of cationic curing catalyzer, even if irradiation energy ray does not also solidify.Therefore,, by using the phenol aldehyde type epoxy resin after these impurity are removed, can reduce the uncured composition in the cured article after solidifying with energy-ray, and can obtain the energy ray-curable composition epoxy resin containing low halogen.
As refining of phenol aldehyde type epoxy resin, for example can enumerate refining, refining, refining etc. to what be hydrolyzed with the halogen of covalent bonding in the such alkali aqueous solution of aqueous sodium hydroxide solution based on what use that silica gel or aluminum oxide isochromatic spectrum carry out based on distillation.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), global environment, halogen quantity is preferably below 500ppm.As epoxy resin, if use EXA-8067,, except the effect of the invention described above, also can reach low halogen.
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 be used singly or two or more kinds in combination.Preferred filler is, 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 the epoxy resin of 45 weight parts, 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 specific refractory power of filler with not containing the specific refractivity of the energy ray-curable composition epoxy resin of filler in ± 0.02, preferably in ± 0.01.Herein, do not refer to containing the energy ray-curable composition epoxy resin of filler, from the composition epoxy resin containing having removed filler the energy ray-curable composition epoxy resin of the present invention of epoxy resin, filler and light acid producing agent and composition as required.By selecting filler, or select aptly epoxy resin, other the additive that can general layout need to contain described later, the specific refractory power of filler and the specific refractivity containing the energy ray-curable composition epoxy resin of filler not can be established within the limits prescribed.
As light acid producing agent, as long as for the compound of the irradiation generation Lewis acid by energy-ray or bronsted acid does not just limit, can enumerate sulfonium salt, salt compounded of iodine.With respect to the epoxy resin of 45 weight parts, 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-butyrolactone etc. adds.
As sulfonium salt, for example can enumerate triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoro antimonate, triphenylsulfonium four (pentafluorophenyl group) borate, 4, the two hexafluorophosphates of 4 '-bis-(phenylbenzene sulfonium base) diphenyl sulfide, 4, the two hexafluoro antimonates of 4 '-bis-(two (beta-hydroxy oxyethyl group) phenyl sulfonium base) diphenyl sulfide, 4, the two hexafluorophosphates of 4 '-bis-(two (beta-hydroxy oxyethyl group) phenyl sulfonium base) diphenyl sulfide, 7-(two (to toluyl) sulfonium base)-ITX hexafluoro antimonate, 7-(two (to toluyl) sulfonium base)-ITX four (pentafluorophenyl group) borate, 4-phenylcarbonyl group-4 '-phenylbenzene sulfonium base-diphenyl sulfide hexafluorophosphate, 4-(to tert-butyl-phenyl carbonyl)-4 '-phenylbenzene sulfonium base-diphenyl sulfide hexafluoro antimonate, 4-(to tert-butyl-phenyl carbonyl)-4 '-bis-(to toluyl) sulfonium base-diphenyl sulfide four (pentafluorophenyl group) borate, the rising sun electrification SP-170 processed of company, SP-172, SP-150, SP-152, the CPI-210S processed of SAN-APRO company etc.Be preferably the rising sun electrification SP-170 processed of company, SP-172 or the CPI-210S processed of SAN-APRO company as sulfonium salt.These salt can be distinguished use separately, or combination more than two kinds is used.
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, the PI2074 processed of Rodia company etc.Be preferably the PI2074 processed of Rodia company as salt compounded of iodine.These salt can be used singly or two or more kinds in combination.
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 coating operability, taking lowering viscousity, low-shrinkage as object add 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)), the two trimethylene oxide (OXT-121 (XDO)) of xylylene, two (3-ethyl-3-trimethylene oxide ylmethyl) ether (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 parantheses, it is the goods number of East Asia Synesis Company.With respect to the epoxy resin of 45 weight parts, the addition of oxetane compound is preferably 5～100 weight parts, more preferably 10～50 weight parts.Each oxetane compound can be used alone, or combination more than two kinds is used.
Though be not particularly limited 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 such benzoin derivatives of alpha, alpha-dimethyl oxygen base-α-phenyl methyl phenyl ketone; Benzophenone, 2,4-dichloro benzophenone, the such benzophenone derivates of o-benzoyl M-nitro benzoic acid methyl esters, 4,4 '-bis-(diethylamino) benzophenone; 2,4-diethyl thioxanthone, CTX, the such thioxanthone derivates of ITX; 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 be used alone, or two kinds are used in combination above.Preferred photosensitizer is 2,4-diethyl thioxanthone (Japanese chemical drug DETX-S processed).With respect to the epoxy resin of 45 weight parts, the addition of photosensitizer is 0.001～1 weight part, is preferably 0.005～0.1 weight part.Be PI2074 during as light acid producing agent using salt compounded of iodine, preferably use photosensitizer DETX-S, its addition, with respect to the epoxy resin of 45 weight parts, is preferably 0.001～0.1 weight part, is particularly preferably 0.01 weight part.During as light acid producing agent, might not need photosensitizer at the CPI-210S that uses sulfonium salt system, even if do not add, solidified nature is also good.
Taking give cohesiveness as object add silane coupling agent.As silane coupling agent, for example can exemplify the tetraalkoxysilane classes such as tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilan, four butoxy silanes, dimethoxy diethoxy silane, dimethoxy diisopropoxy silane, diethoxy diisopropoxy silane, diethoxy dibutoxy silane; The trialkoxysilanes such as methyltrimethoxy silane, Union carbide A-162, methyl three isopropoxy silane, ethyl triethoxysilane, ethyl three butoxy silanes, cyclohexyltriethyloxysilane, phenyl three isopropoxy silane; The dialkoxy silicane classes such as dimethyldimethoxysil,ne, dimethyldiethoxysilane, diethyl diethoxy silane, diethyl dibutoxy silane, phenylethyl diethoxy silane.These silane coupling agents can be used alone, also can 2 kinds to be used in combination.The addition of silane coupling agent, with respect to the epoxy resin of 45 weight parts, 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, due to can high fixed precision, promptly fixed L D (laser diode), photodetector (PD: photodetector), lens, prism etc. optics or be equipped with the optical module etc. of the opticses such as lens, very useful as the caking agent of Optical devices assembling use.As Optical devices, for example, at patent documentation 1,2, or in the optical take-up apparatus of recording in the paragraph 0023 of TOHKEMY 2007-311006 communique, for fixing after the obliquity with helical screw (Skew-Screw) adjustment solenoid coil (actuator).In addition, also can be used in fixing or messenger wire fixing of other the optics such as mirror.
Embodiment
The present invention will be described by the following examples.It should be noted that, use level represents with weight part.
[embodiment 1 and comparative example 1～2]
The proportioning of recording based on table 1 is dissolved light acid producing agent PI2074 in 4-butyrolactone, is added in EPICLON 850 and CEL3000, is stirred to transparently, has prepared the energy ray-curable composition epoxy resin of comparative example 1.
Based on the proportioning shown in table 1, in the composition epoxy resin of comparative example 1, add GS350T or GS310T, till being stirred to homogeneous, prepare the energy ray-curable composition epoxy resin of embodiment 1 or comparative example 2.
Measure the deep solidified nature of the composition epoxy resin of embodiment 1, comparative example 1 and 2.Deep solidified nature is measured with as described below: opening
in the clarinet in hole, the embodiment 1 that packing height is 5mm respectively and the energy ray-curable composition epoxy resin of comparative example 1,2, with Hamamatsu Photonics UV irradiating machine processed from top with 500mW/cm
2(365nm) irradiate after 10 seconds kinds, from clarinet, take out cured article, remove uncured portion, measure the thickness of cured portion with milscale.Result is shown in 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 |
| 4-butyrolactone | 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 | ||
| Do not contain the specific refractory power of 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 company system)
CEL3000:1,2:8,9 diepoxy limonene (DAICEL CHEMICAL company system)
CPI-210S: sulfonium is light acid producing agent (SAN-APRO company system)
4-butyrolactone: solvent (with Guang Chun medicine company system)
Art Pearl GS-350T: vinylformic acid/styrol copolymer filler: specific refractory power 1.55 (Gen Shang industrial system)
Art Pearl GS-310T: vinylformic acid/styrol copolymer filler: specific refractory power 1.51 (Gen Shang industrial system)
*: be not following composition containing the resin combination of filler: about comparative example 1 for the identical composition of proportioning of the comparative example of table 1; About embodiment 1 for remove the composition of the proportioning of Art Pearl GS350T from the proportioning of the embodiment 1 of table 1; About comparative example 2 for remove the composition of the proportioning of Art Pearl GS310T from the proportioning of the comparative example 2 of table 1.
[embodiment 2 and comparative example 3,4]
The proportioning of recording based on table 2, has prepared the composition epoxy resin of embodiment 2, comparative example 3 and 4.Measure the deep solidified nature of each composition epoxy resin.Result is shown in 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 | |
| Do not contain the specific refractory power of 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 company 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 company system)
DETX-S:2,4-diethyl thioxanthone (sensitizing agent: Japanese chemical drug company system)
CPI-210S: sulfonium is light acid producing agent (SAN-APRO company system)
Art Pearl GS-350T: vinylformic acid/styrol copolymer filler: specific refractory power 1.55 (Gen Shang industrial system)
TALC P-2: talcum specific refractory power 1.58 (Japanese TALC company system)
[embodiment 3 and comparative example 5]
The proportioning of recording based on table 3, has prepared the composition epoxy resin of embodiment 3 and comparative example 5.Measure the deep solidified nature of each composition epoxy resin.Result is shown in 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 | |
| Do not contain the specific refractory power of 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 (SAN-APRO company system)
Art Pearl GS-310T: vinylformic acid/styrol copolymer filler: specific refractory power 1.51 (Gen Shang industrial system)
Art Pearl GS-350T: vinylformic acid/styrol copolymer filler: specific refractory power 1.55 (Gen Shang industrial 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.The CUP method that cure shrinkage is recorded according to JIS K 6833 is measured.Young's modulus uses the EXSTAR6000 processed of SII company, measures with plate tension method.Result is shown in table 4.
[table 4]
| Embodiment 2 | Embodiment 3 | Comparative example 3 | |
| Cure shrinkage (%) | 1.5 | 2.0 | 1.4 |
| 25 DEG C of Young's modulus (MPa) | 3000 | 2580 | 4040 |
| 100 DEG C of Young's modulus (MPa) | 120 | 65 | 250 |
[embodiment 4 and 5]
Based on the proportioning shown in table 5, prepare the matrix (not containing the composition epoxy resin of 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 composition | 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), Art Pearl GS-330T (specific refractory power 1.53) and each 45 weight parts of Art Pearl GS-350T (specific refractory power 1.55), prepared 8 kinds of energy ray-curable composition epoxy resins.
[test example 2]
For 8 kinds of energy ray-curable composition epoxy resins of preparation in embodiment 4 and 5, (wherein, UV irradiation time was changed to for 20 seconds from 10 seconds) similarly to Example 1, measure deep solidified nature.Its result is shown in table 6.
[table 6]
[embodiment 6～8]
Based on the proportioning shown in table 7, prepare the energy ray-curable composition epoxy resin of embodiment 6～8.
[table 7]
EXA-8067: bisphenol A type epoxy resin (DIC company system: through the highly finished product of distillation)
1-651:2,2-dimethoxy-1,2-diphenylethane (Chiba company sensitizing agent processed)
[test example 3]
Test respectively the LED solidified nature of the energy ray-curable composition epoxy resin of embodiment 6 and 7.LED solidified nature is as described below carries out: the energy ray-curable composition epoxy resin that drips on aluminium sheet, and used the LED irradiating machine of wavelength 365nm with 500mW/cm
2illumination (luxmeter Hamamatsu Photonics C6080-13 processed) irradiate 10 seconds be cured, solid state with refer to touch confirm.The benchmark of LED solidified nature is, zero: solidify (solid) × mark: uncured (liquid state).Test-results is shown in table 8.
[table 8]
LED solidified nature
| Embodiment 6 | Embodiment 7 | |
| LED solidified nature | ○ | ○ |
[test example 4]
Measure respectively the halogen quantity of the energy ray-curable composition epoxy resin of embodiment 6 and 8 by EN14582 combustion ion chromatography.Measurement result is shown in table 9.
[table 9]
Full halogen quantity
[test example 5]
Measure respectively the deep solidified nature of the energy ray-curable composition epoxy resin of embodiment 6 and 8.For the deep solidified nature of being undertaken by UV-lamp, to internal diameter
the clarinet of length 5mm in fill energy ray-curable composition epoxy resin, utilize ultraviolet irradiation machine (LC5 processed of Hamamatsu Photonics company) from top with illumination 500mW/cm
2(365nm) (luxmeter: Hamamatsu Photonics C6080-13 processed) irradiates ultraviolet ray in 10 seconds, and measures the length of the energy ray-curable composition epoxy resin having solidified.For the deep solidified nature of utilizing LED to carry out: to internal diameter
the clarinet of length 5mm in fill energy ray-curable composition epoxy resin, the LED irradiating machine that utilizes wavelength 365nm from top with illumination 500mW/cm
2(luxmeter: Hamamatsu Photonics C6080-13 processed) irradiated for 10 seconds, measured the length of the energy ray-curable composition epoxy resin after solidifying.Measurement result is shown in table 10.
[table 10]
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 are measured respectively.The sclerometer that hardness (D) is recorded by JIS K 7215 is measured.The CUP method that cure shrinkage is recorded according to JIS K 6833 is measured.Tan δ and energy storage Young's modulus use the EXSTAR6000 processed of SII company to measure with plate tension method.
[table 11]
| Embodiment 6 | Embodiment 8 | ||
| Hardness (D) | D type | 84 | 84 |
| Cure shrinkage | 1.6％ | 1.5％ | |
| Tanδ | 90℃ | 90℃ | |
| Energy storage Young's modulus | 25℃ | 4270MPa | 3000MPa |
| Energy storage Young's modulus | 100℃ | 180MPa | 120MPa |
In industry, utilize possibility
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 the opticses such as lens can be fixed with good deep solidified nature to high fixed precision, very useful as the caking agent of Optical devices assembling use.
Claims (9)
1. an epoxy resin adhesive, it is the energy ray-curable epoxy resin adhesive containing epoxy resin, filler and light acid producing agent,
Filler is the multipolymer of acrylic resin and styrene resin,
The specific refractory power of this filler with not containing the specific refractivity of the energy ray-curable epoxy resin adhesive of this filler in ± 0.02,
With respect to the epoxy resin of 45 weight parts, the filler that contains 32.5～60 weight parts, the light acid producing agent that contains 1～4 weight part.
2. epoxy resin adhesive according to claim 1, is characterized in that, the specific refractory power of filler with not containing the specific refractivity of the energy ray-curable epoxy resin adhesive of this filler in ± 0.01.
3. epoxy resin adhesive according to claim 1 and 2, is characterized in that, with respect to the epoxy resin of 45 weight parts, further contains the oxetane compound of 10～50 weight parts.
4. epoxy resin adhesive according to claim 1 and 2, is characterized in that, is the caking agent of Optical devices assembling use.
5. epoxy resin adhesive according to claim 3, is characterized in that, is the caking agent of Optical devices assembling use.
6. epoxy resin adhesive according to claim 1 and 2, is characterized in that, is the caking agent of optical take-up apparatus assembling use.
7. epoxy resin adhesive according to claim 3, is characterized in that, is the caking agent of optical take-up apparatus assembling use.
8. Optical devices, its right to use requires the epoxy resin adhesive described in 4 or 5 to assemble.
9. an optical take-up apparatus, its right to use requires the epoxy resin adhesive described in 6 or 7 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 |
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| CN102471560B true CN102471560B (en) | 2014-11-26 |
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| Country | Link |
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| JP (1) | JP5634993B2 (en) |
| KR (1) | KR101555738B1 (en) |
| CN (1) | CN102471560B (en) |
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| US20140107295A1 (en) * | 2011-05-30 | 2014-04-17 | Mitsubishi Rayon Co., Ltd. | Epoxy resin composition, cured object and optical semiconductor sealing material |
| CN103666320B (en) * | 2012-09-20 | 2016-07-06 | 广东恒大新材料科技有限公司 | A kind of bonding agent composition for add-on type silica gel and application thereof |
| JP6163043B2 (en) * | 2013-08-08 | 2017-07-12 | 株式会社Adeka | Energy ray sensitive composition |
| TWI519560B (en) | 2014-11-24 | 2016-02-01 | 財團法人工業技術研究院 | Resin containing oxetane and epoxy groups and resin composition including the same |
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| CN101355142A (en) * | 2007-07-27 | 2009-01-28 | 东进世美肯株式会社 | Sealing method for display element |
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| JPH0625386A (en) * | 1991-04-26 | 1994-02-01 | Sumitomo Bakelite Co Ltd | Epoxy resin composition for photo-coupler |
| JPH05315652A (en) * | 1992-04-02 | 1993-11-26 | Nec Corp | Optical semiconductor device |
| JPH09243870A (en) * | 1996-03-14 | 1997-09-19 | Hitachi Ltd | Production of optical module |
| JPH11289161A (en) * | 1998-04-03 | 1999-10-19 | Ngk Spark Plug Co Ltd | Through-hole filling paste and manufacture of printed wiring board using the paste |
| JP2000348360A (en) * | 1999-06-08 | 2000-12-15 | Sankyo Seiki Mfg Co Ltd | Manufacture of optical pickup device |
| JP2002185021A (en) * | 2000-12-15 | 2002-06-28 | Matsushita Electric Ind Co Ltd | Optical semiconductor device |
| JP2004126159A (en) * | 2002-10-01 | 2004-04-22 | Ngk Spark Plug Co Ltd | Photosensitive resin composition and printed wiring board using the same |
| JP2004168869A (en) * | 2002-11-19 | 2004-06-17 | Mitsubishi Rayon Co Ltd | Active energy ray-curable resin composition for sheet-like optical article and the resulting sheet-like optical article |
| JP2006063194A (en) * | 2004-08-27 | 2006-03-09 | Toagosei Co Ltd | Curable composition |
| 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 |
| JP4845602B2 (en) * | 2005-06-20 | 2011-12-28 | 三洋電機株式会社 | Optical pickup device |
| CN100468540C (en) * | 2005-06-20 | 2009-03-11 | 三洋电机株式会社 | Optical pickup unit |
| JP2007207350A (en) * | 2006-02-02 | 2007-08-16 | Sharp Corp | Method for manufacturing optical pickup device |
| JP5480469B2 (en) * | 2006-10-31 | 2014-04-23 | 株式会社日本触媒 | Resin composition, optical material, and control method of optical material |
| JP2008214555A (en) * | 2007-03-07 | 2008-09-18 | Mitsui Chemicals Inc | Resin composition and resin cured product |
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| KR101555738B1 (en) | 2015-09-25 |
| JPWO2011001912A1 (en) | 2012-12-13 |
| TW201116605A (en) | 2011-05-16 |
| JP5634993B2 (en) | 2014-12-03 |
| CN102471560A (en) | 2012-05-23 |
| TWI479002B (en) | 2015-04-01 |
| WO2011001912A1 (en) | 2011-01-06 |
| KR20120103433A (en) | 2012-09-19 |
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