CN107531831A - (methyl) acrylate and optical component - Google Patents
(methyl) acrylate and optical component Download PDFInfo
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- CN107531831A CN107531831A CN201680027788.2A CN201680027788A CN107531831A CN 107531831 A CN107531831 A CN 107531831A CN 201680027788 A CN201680027788 A CN 201680027788A CN 107531831 A CN107531831 A CN 107531831A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and 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 a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F20/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
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Abstract
Excellent (methyl) acrylate of the heat resistance, resistance to hygroscopicity, yellowing resistance of solidfied material is provided, contains its Photocurable composition and its solidfied material and the optical component for having used foregoing Photocurable composition.(methyl) acrylate, containing its Photocurable composition and its solidfied material and the optical component for having used foregoing Photocurable composition, (methyl) acrylate be characterised as using aromatic series 2-glycidyl ether compound (A), (methyl) acrylic acid (B) and methacrylic anhydride (C) as must reacted constituent reaction product.
Description
Technical field
The present invention relates to excellent (methyl) acrylate of the heat resistance of solidfied material, resistance to hygroscopicity, yellowing resistance, contain
There are its Photocurable composition and its solidfied material and optical component.
Background technology
The lens on chip (on-chip lens) on the imaging sensors such as CCD, CMOS are equipped on extensively using by heat
Plastic resin assigns dot pattern and carries out the fusion method of spherical lens shapes to it to manufacture using hot-fluid, but spherical lens
Because chromatic aberation is big, therefore fine high-sensitivity is limited.In addition, the hot melt is difficult to the lens figuration of slit.
As reduction chromatic aberation and the technology of the lens figuration of slit can be realized, it is proposed that utilize the mould of aspheric lens shape
The shape transfer method of figuration is carried out to light-cured resin.Because light-cured resin is by with light such as (methyl) acryloyl groups
The formation such as the resin of polymerizable group, monomer, and by the way that lowering viscousity can be realized containing more low molecular weight compositions, because
This is the material that can realize fine shape figuration.But when for lens application on chip, heat resistance, moisture-proof are insufficient,
Xanthochromia, deformation easily occurs.
The light-cured resin excellent as resistance to hygroscopicity etc., for example, it is known have make bisphenol A type epoxy resin and methyl-prop
Light-cured resin obtained from olefin(e) acid anhydride reactant (with reference to patent document 1).Although the high resin table of this aromatic rings containing ratio
Reveal higher heat resistance, but it is insufficient to be used for heat resistance and moisture-proof during lens application on chip, and xanthochromia easily occurs, becomes
Shape.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2008-038029 publications
The content of the invention
Problems to be solved by the invention
Therefore, the problem to be solved in the present invention is, there is provided the heat resistance of solidfied material, resistance to hygroscopicity, yellowing resistance are excellent
(methyl) acrylate, contain its Photocurable composition and its solidfied material and optical component.
The solution used to solve the problem
The present inventor etc. have made intensive studies to solve the above problems, and as a result find, aromatic series two is shunk sweet
Oily ether compound and the solidfied material of methacrylate resin obtained from (methyl) acrylic acid and methacrylic acid anhydride reactant
Heat resistance, resistance to hygroscopicity, yellowing resistance are excellent, so as to complete the present invention.
That is, the present invention relates to a kind of (methyl) acrylate, it is characterised in that is with aromatic series diglycidyl ether
The reaction product of compound (A), (methyl) acrylic acid (B) and methacrylic anhydride (C) as necessary reacted constituent.
The invention further relates to a kind of (methyl) acrylate, it is characterised in that has point shown in following formulas (1)
Minor structure, and at least one of Y present in resin is methylacryloyl.
[R in formula1For hydrogen atom or methyl, X is the structure position shown in any one in following formulas (2-1)~(2-8), Y
For hydrogen atom or methylacryloyl.
(in formula, R2It is each independently hydrogen atom, the alkyl of carbon number 1~4, the alkoxy of carbon number 1~4, benzene
Any of base, R3It is each independently appointing in the alkyl of carbon number 1~4, the alkoxy of carbon number 1~4, phenyl
Meaning person, n are 1~4 integer.)].
The invention further relates to a kind of Photocurable composition, and it contains foregoing (methyl) acrylate and photopolymerization is drawn
Send out agent.
The invention further relates to the solidfied material of said curing property composition.
The invention further relates to a kind of optical component, and it is formed using solidification compound.
The effect of invention
In accordance with the invention it is possible to provide the heat resistance of solidfied material, resistance to hygroscopicity, yellowing resistance excellent (methyl) acrylic acid
Ester resin, contain its Photocurable composition and its solidfied material and optical component.
Brief description of the drawings
Fig. 1 is the GPC figures of (methyl) acrylate (1) obtained in embodiment 1.
Embodiment
Hereinafter, the present invention will be described in detail.
The present invention (methyl) acrylate be characterised by, be with aromatic series 2-glycidyl ether compound (A),
(methyl) acrylic acid (B) and methacrylic anhydride (C) are the reaction product of necessary reacted constituent.That is, the present invention is made by combination
(methyl) propylene of aromatic series 2-glycidyl ether compound (A) is used as by the use of (methyl) acrylic acid (B) and methacrylic anhydride (C)
Acid esters agent, so as to be successfully realized the heat resistance of solidfied material, resistance to moisture absorption compared with conventional so-called Epocryl
The excellent light-cured resin material of property, yellowing resistance.
The aromatic series 2-glycidyl ether compound (A) used in the present invention can for example include bisphenol-type epoxy resin,
Biphenyl type epoxy resin, phenylene ether type epoxy, naphthylene ether type epoxy, phenol aralkyl type epoxy resin, naphthalene
Phenol aralkyl-type epoxy resin, Dicycldpentadiene-phenol addition reaction-type epoxy resin etc., more specifically, can be included down
State compound shown in any one in structural formula (3-1)~(3-8) etc..
(in formula, R2It is each independently hydrogen atom, the alkyl of carbon number 1~4, the alkoxy of carbon number 1~4, benzene
Any of base, R3It is each independently appointing in the alkyl of carbon number 1~4, the alkoxy of carbon number 1~4, phenyl
Meaning person, G represent glycidyl.In addition, n is 1~4 integer.)
These can each be used alone, and two or more can also be applied in combination.Wherein, from can obtain the heat-resisting of solidfied material
Property, set out in terms of the excellent methacrylate resin of resistance to hygroscopicity, yellowing resistance, preferably shown in aforementioned structural formula (3-1)
Compound.
Foregoing (methyl) acrylic acid (B) can be any one in acrylic or methacrylic acid, can also be applied in combination two
Person.Wherein, from (methyl) the acrylate aspect for the excellent heat resistance for forming solidfied material, preferably metering system
Acid.In addition, from being not likely to produce gas aspect, preferably acrylic acid when being heated to solidfied material.
In the manufacture of (methyl) acrylate of the present invention, for aforementioned fragrance race 2-glycidyl ether compound
(A), the reaction ratio of (methyl) acrylic acid (B) and methacrylic anhydride (C), it is preferred that shunk relative to aromatic series two sweet
1 mole of epoxy radicals in oily ether compound (A), (methyl) acrylic acid (B) and first are used with total 0.9~1.1 mole scope
Base acrylic anhydride (C).
In addition, from the side for forming the excellent methacrylate resin of the heat resistance of solidfied material, resistance to hygroscopicity, yellowing resistance
Face is set out, and (methyl) acrylic acid (B) and the value of the mol ratio [(B)/(C)] of methacrylic anhydride (C) are preferably 1/9~6/4
Scope.
In the present invention, the manufacture method of (methyl) acrylate is not particularly limited, such as can include as follows
Method：Make aromatic series 2-glycidyl ether compound (A), (methyl) acrylic acid (B) and methacrylic anhydride (C) anti-in esterification
In the presence of answering catalyst and antioxidant, polymerization inhibitor, as needed using organic solvent, in 100~150 DEG C of temperature ranges
Interior reaction 5~12 hours or so.
(methyl) acrylate of the invention manufactured by this method can be for example included with following formulas
(1) at least one (methyl) acrylate for methylacryloyl of Y present in the molecular structure and resin shown in
Deng,
[R in formula1For hydrogen atom or methyl, X is the structure position shown in any one in following formulas (2-1)~(2-8), Y
For hydrogen atom or methylacryloyl.
(R in formula2It is each independently hydrogen atom, the alkyl of carbon number 1~4, the alkoxy of carbon number 1~4, benzene
Any of base, R3It is each independently appointing in the alkyl of carbon number 1~4, the alkoxy of carbon number 1~4, phenyl
Meaning person, n are 1~4 integer.)].
Resin component with the molecular structure shown in aforementioned formula (1) can specifically include following formulas (1-1)
Compound shown in any one in~(1-3).
[R in formula1For hydrogen atom or methyl, X is the structure position shown in any one in following formulas (2-1)~(2-8).
(in formula, R2It is each independently hydrogen atom, the alkyl of carbon number 1~4, the alkoxy of carbon number 1~4, benzene
Any of base, R3It is each independently appointing in the alkyl of carbon number 1~4, the alkoxy of carbon number 1~4, phenyl
Meaning person, n are 1~4 integer.)].
For the methacrylate resin of the present invention, heat resistance, resistance to hygroscopicity from solidfied material, yellowing resistance are excellent
Aspect is set out, it is preferred that (methyl) the acryloyl group equivalent calculated by the input amount of raw material is the model of 160~230g/ equivalents
Enclose.
The Photocurable composition of the present invention contains foregoing methacrylate resin and Photoepolymerizationinitiater initiater.
Photoepolymerizationinitiater initiater used herein can for example include diethoxy acetophenone, 2- hydroxy-2-methyl -1- phenyl
Propane -1- ketone, benzil dimethyl ketal, 1- (4- isopropyl phenyls) -2- hydroxy-2-methyl propane -1- ketone, 4- (2- hydroxyls
Ethyoxyl) phenyl-(2- hydroxyl -2- propyl group) ketone, 1- hydroxycyclohexyl-phenylketones, 2- methyl -2- morpholino (4- sulphomethyls
Phenyl) propane -1- ketone, the acetophenones of 2- benzyl -2- dimethylaminos -1- (4- morphlinophenyls)-butanone etc；Benzene is even
The benzoin class of relation by marriage, benzoin methylether, benzoin iso-propylether etc；2,4,6- trimethylbenzene acyloin diphenyl phosphine oxides etc
Acylphosphine oxide class；Benzil, methyl benzoylformate equimolecular internal key cracking type Photoepolymerizationinitiater initiater, benzophenone, adjacent benzene
Acyl radical methyl benzoate -4- phenyl benzophenones, 4,4 '-dichloro benzophenone, dihydroxy benaophenonel, 4- benzoyls -4 ' -
Methyl-diphenyl sulfide, acrylated benzophenone, 3,3 ', 4,4 '-four (tert-butyl hydroperoxide carbonyl) benzophenone, 3,3 '-two
The benzophenone of methyl -4- methoxy benzophenones etc；ITX, 2,4- dimethyl thioxanthones, 2,4- bis-
The thioxanthene ketone class of ethyl thioxanthones, the clopenthixal ketones of 2,4- bis- etc；Michaelis ketone, 4,4 '-diethylamino benzophenone etc
Aminobenzophenone class；10- butyl -2- chloro-acridines ketone, 2- EAQs, 9,10- phenanthrenequione, hydrogen-abstraction light in camphorquinone equimolecular
Polymerization initiator.These can each be used alone, and two or more can also be applied in combination.
The commercially available product of these Photoepolymerizationinitiater initiaters can for example include " IRGACURE-184 ", " IRGACURE-149 ",
“IRGACURE-261”、“IRGACURE-369”、“IRGACURE-500”、“IRGACURE-651”、“IRGACURE-754”、
“IRGACURE-784”、“IRGACURE-819”、“IRGACURE-907”、“IRGACURE-1116”、“IRGACURE-1664”、
“IRGACURE-1700”、“IRGACURE-1800”、“IRGACURE-1850”、“IRGACURE-2959”、“IRGACURE-
4043 ", " DAROCUR-1173 " (Ciba Specialty Chemicals Inc. systems), " Lucirin TPO " (BASF AG
System), " KAYACURE-DETX ", " KAYACURE-MBP ", " KAYACURE-DMBI ", " KAYACURE-EPA ", " KAYACURE-
OA " (Nippon Kayaku K. K's system), " VICURE-10 ", " VICURE-55 " (Stauffer Chemical Company systems),
" TRIGONAL P1 " (Akzo Co. Ltd. systems), " SANDORAY 1000 " (SANDOZ Co., Ltd. system), " DEAP "
(APJOHN Co. Ltd. systems), " QUANTACURE-PDO ", " QUANTACURE-ITX ", " QUANTACURE-EPD " (WARD
BLENKINSOP Co., Ltd. system) etc..
For the addition of foregoing photo-polymerization initiator, for example, relative to the mass parts of Photocurable composition 100 be 1~
Used in the range of 20 mass parts.
The Photocurable composition of the present invention can additionally include other in addition to foregoing methacrylate resin
(methyl) acrylate compounds, sensitising agent, curing accelerator, organic solvent, non-reacted resin, filler, inorganic filler,
It is organic filler, coupling agent, tackifier, defoamer, levelling agent, closely sealed auxiliary agent, releasing agent, lubricant, ultra-violet absorber, anti-
The additive components such as oxidant, heat stabilizer, plasticizer, fire retardant, pigment, dyestuff.
Foregoing other (methyl) acrylate compounds can for example include：(methyl) n-butyl acrylate, (methyl) third
Olefin(e) acid isobutyl ester, (methyl) tert-butyl acrylate, (methyl) acrylic acid n-pentyl ester, (methyl) the just own ester of acrylic acid, (methyl) third
Olefin(e) acid n-octyl, (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid-2-ethyl caproite, (methyl) glycidyl acrylate,
(methyl) acrylic acid morpholine ester, (methyl) 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate, (methyl) propylene
Acid -4- hydroxybutyls, (methyl) acrylic acid -2- methoxy acrylates, (methyl) acrylic acid -2- butoxyethyls, (methyl) propylene
Acid -2- ethoxy ethyl esters, 2- (2- ethoxy ethoxies) ethyl (methyl) acrylate, 4- Nonylphenoxies ethylene glycol (methyl)
Acrylate, (methyl) tetrahydrofurfuryl acrylate, caprolactone modification (methyl) tetrahydrofurfuryl acrylate, (methyl) acrylate
Ester, (methyl) acrylate base methyl esters, (methyl) acrylate base ethyl ester, (methyl) isobornyl acrylate, (methyl)
The ring pentyl ester of acrylic acid two, the cyclopentyloxy ethyl ester of (methyl) acrylic acid two, (methyl) acrylic acid dicyclopentenyl ester, (methyl) acrylic acid
Dicyclopentenyl epoxide ethyl ester, (methyl) phenyl acrylate, (methyl) benzyl acrylate, (methyl) acrylate, (first
Base) acrylic acid phenoxy group 2- Methylethyls, (methyl) acrylic acid phenoxy ethyl, (methyl) acrylic acid is to cumyl benzene oxygen
Base ethyl ester, (methyl) acrylic acid phenoxy group benzyl ester, (methyl) acrylic acid -2- hydroxyl -3- phenoxy-propyls, (methyl) acrylic acid benzene
Base benzyl ester, phenylethyl phenoxy ethyl, 2- acryloyl-oxyethyl hexahydro-phthalic acids ester, following formulas (4) or
(5) single (methyl) acrylate compounds such as list (methyl) acrylate compounds containing fluorene skeleton shown in；
[in formula, X is hydrogen atom or hydroxyl, R1And R4It is each independently the alkyl of hydrogen atom or carbon number 1~3, R2
For hydrogen atom or methyl, R3For Direct Bonding or methylene, m is 0 or 1.]
[in formula, 2 X are each independently hydrogen atom or hydroxyl, 2 R1It is each independently hydrogen atom or carbon number 1
~3 alkyl, R2For hydrogen atom or methyl, m and n are each independently 0 or 1.]
Ethylene glycol two (methyl) acrylate, propane diols two (methyl) acrylate, butanediol two (methyl) acrylate,
1,4- butanediols two (methyl) acrylate, 1,6-HD two (methyl) acrylate, 1,9- nonanediols two (methyl) propylene
Acid esters, neopentyl glycol two (methyl) acrylate, bisphenol-A two (methyl) acrylate, Bisphenol F two (methyl) acrylate, two
Cyclopenta two (methyl) acrylate, glycerine two (methyl) acrylate, neopentyl glycol 3-hydroxypivalic acid ester two (methyl) propylene
Acid esters, caprolactone modification 3-hydroxypivalic acid neopentyl glycol two (methyl) acrylate, tetrabromobisphenol A two (methyl) acrylate,
Hydrogenate special valeral be modified trimethylolpropane two (methyl) acrylate, 1,4 cyclohexane dimethanol two (methyl) acrylate,
Double [(methyl) acryloyl methyl] biphenyl, following formulas (6) or two (methyl) acroleic acid esterifications containing fluorene skeleton shown in (7)
Compound etc. two (methyl) acrylate compounds；
[in formula, X is each independently hydrogen atom or hydroxyl, R1It is each independently hydrogen atom or carbon number 1~3
Alkyl, R2It is each independently hydrogen atom or methyl, R3Direct Bonding or methylene are each independently, m and n are independently of one another
For 0 or 1.]
[in formula, 2 X are each independently hydrogen atom or hydroxyl, 2 R1It is each independently hydrogen atom or carbon number 1
~3 alkyl, 2 R2Hydrogen atom or methyl are each independently, m and n are each independently 0 or 1.]
Trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, glycerine three (methyl) third
Olefin(e) acid ester, two (trimethylolpropane) four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol
(methyl) acrylate compounds more than 3 functions such as six (methyl) acrylate；
Make butane -1,4- diisocyanate, hexamethylene diisocyanate, the isocyanic acid of 2,2,4- tri-methyl hexamethylenes two
Ester, 2,4,4- trimethyl hexamethylene diisocyanates, xylylene diisocyanate, an isocyanic acid of durol dimethyl two
Ester, hexamethylene -1,4- diisocyanate, IPDI, lysine diisocyanate, dicyclohexyl methyl hydride -4,
Double (isocyanatomethyl) hexamethylenes of 4 '-diisocyanate, 1,3-, methylcyclohexane diisocyanate, 1,5- naphthylenes two are different
Cyanate, 4,4 '-methyl diphenylene diisocyanate, 2,2 '-bis- (to phenyl isocyanate) propane, 4,4 '-dibenzyl two are different
Cyanate, dialkyl group methyl diphenylene diisocyanate, tetraalkyl methyl diphenylene diisocyanate, the isocyanide of 1,3- phenylenes two
The diisocyanate cpds such as acid esters, 1,4- phenylene vulcabonds, toluene di-isocyanate(TDI) or their urea acid esters are modified
Thing and 2-Hydroxy ethyl acrylate, 2-hydroxypropyl acrylate, acrylic acid -4- hydroxybutyls, glycerol diacrylate, three hydroxyls
(methyl) third of the hydroxyls such as diacrylate, pentaerythritol triacrylate, Dipentaerythritol Pentaacrylate
Carbamate (methyl) acrylate etc. obtained from enoic acid ester compounds reaction.These other (methyl) acrylate chemical combination
Thing can each be used alone, and two or more can also be applied in combination.
The Photocurable composition of the present invention shows extra high heat resistance, moisture-proof and color inhibition due to its solidfied material
Property, therefore can be used for the various uses such as electronic unit, formed products purposes, coating applications.It is excellent especially to produce yellowing resistance
Feature, optical component purposes can be suitable for.As optical component, such as eyeglass lens, CCD, CMOS etc. can be included
The imaging sensor plastic lens such as lens on chip, Fresnel lens, prismatic lens, optics outer paint, hard paint, antireflection
Film, optical fiber, fiber waveguide, hologram, prismatic lens, LED encapsulants, coating material used for solar batteries etc..
Foregoing lens on chip, prismatic lens for example can be by using moulds or resin die formed with lens pattern
Manufactured Deng the shape transfer method of figuration mould.Specifically, following method can be included：Photocuring is coated with figuration mould
Property composition, make transparent base overlapping with composition surface, from the transparent base side irradiate active energy beam, make its solidify
Method.Transparent base used herein can be included by acrylic resin, polycarbonate resin, polyester resin, polystyrene
Resin, fluororesin, the plastic basis material of polyimide resin formation, glass etc..
The lens manufactured by this method can be used with being attached at the state of transparent base, can also peel off transparent base
Material and used with the single state of lens.In the case of being attached at the state use of transparent base, in order to improve lens with thoroughly
The cementability of bright base material, it is preferred that implement the processing that primary coat processing etc. improves cementability to transparent substrate surface in advance.It is another
Aspect, peel off transparent base and in the case of use, preferably with organosilicon, fluorine system remover to the surface of transparent base at
Reason, so that the transparent base can be easily peeled off.
In the case that the Photocurable composition of the present invention is used for into this figuration lens use, it is generally desirable to, by the present invention
Methacrylate resin be applied in combination with foregoing other (methyl) acrylate compounds, by the viscous of Photocurable composition
Degree (25 DEG C) is adjusted to 100mPas~800mPas scope.Other (methyl) acrylate compounds used are according to the phase
The performance of prestige suitably selects, such as is preferably adjusted in a manner of the refractive index of solidfied material turns into more than 1.5560.
Embodiment
Hereinafter, with embodiment and comparative example, the present invention will be described in more detail.
The manufacture of embodiment 1 (methyl) acrylate (1)
In the flask for possessing thermometer, agitator and reflux condenser, bisphenol A type epoxy resin (DIC strain formula meetings are put into
Society's system " EPICLON 850-S " epoxide equivalent 187g/ equivalents) 374 mass parts, add the butylated hydroxy-a as antioxidant
The mass parts of benzene 0.6, as the mass parts of MEHQ 0.2 of hot polymerization inhibitor after, addition methacrylic acid 86 mass parts, methyl
The mass parts of acrylic anhydride 154, the mass parts of triphenylphosphine 1.8, esterification 10 hours is carried out at 110 DEG C when being blown into air,
Obtain (methyl) acrylate (1).(methyl) third calculated by the input amount of raw material of (methyl) acrylate (1)
Enoyl- equivalent is 205g/ equivalents.It should be noted that the mol ratio of methacrylic acid (B) and methacrylic anhydride (C)
[(B)/(C)] is 5/5.
The manufacture of embodiment 2 (methyl) acrylate (2)
In the flask for possessing thermometer, agitator and reflux condenser, bisphenol A type epoxy resin (DIC strain formula meetings are put into
Society's system " EPICLON 850-S " epoxide equivalent 187g/ equivalents) 374 mass parts, add the butylated hydroxy-a as antioxidant
The mass parts of benzene 0.6, as the mass parts of MEHQ 0.2 of hot polymerization inhibitor after, addition methacrylic acid 52 mass parts, methyl
The mass parts of acrylic anhydride 216, the mass parts of triphenylphosphine 1.8, esterification 10 hours is carried out at 110 DEG C when being blown into air,
Obtain (methyl) acrylate (2).(methyl) third calculated by the input amount of raw material of (methyl) acrylate (2)
Enoyl- equivalent is 188g/ equivalents.It should be noted that the mol ratio of methacrylic acid (B) and methacrylic anhydride (C)
[(B)/(C)] is 3/7.
The manufacture of embodiment 3 (methyl) acrylate (3)
In the flask for possessing thermometer, agitator and reflux condenser, bisphenol A type epoxy resin (DIC strain formula meetings are put into
Society's system " EPICLON 850-S " epoxide equivalent 187g/ equivalents) 374 mass parts, add the butylated hydroxy-a as antioxidant
The mass parts of benzene 0.7, as the mass parts of MEHQ 0.2 of hot polymerization inhibitor after, addition methacrylic acid 17 mass parts, methyl
The mass parts of acrylic anhydride 278, the mass parts of triphenylphosphine 2.0, esterification 10 hours is carried out at 110 DEG C when being blown into air,
Obtain (methyl) acrylate (3).(methyl) third calculated by the input amount of raw material of (methyl) acrylate (3)
Enoyl- equivalent is 176g/ equivalents.It should be noted that the mol ratio of methacrylic acid (B) and methacrylic anhydride (C)
[(B)/(C)] is 1/9.
The manufacture of embodiment 4 (methyl) acrylate (4)
In the flask for possessing thermometer, agitator and reflux condenser, bisphenol A type epoxy resin (DIC strain formula meetings are put into
Society's system " EPICLON 850-S " epoxide equivalent 187g/ equivalents) 374 mass parts, add the butylated hydroxy-a as antioxidant
The mass parts of benzene 0.6, as the mass parts of MEHQ 0.2 of hot polymerization inhibitor after, addition acrylic acid 72 mass parts, metering system
The mass parts of acid anhydrides 154, the mass parts of triphenylphosphine 1.8, esterification 10 hours is carried out at 110 DEG C when being blown into air, is obtained
(methyl) acrylate (4).(methyl) acryloyl calculated by the input amount of raw material of (methyl) acrylate (4)
Base equivalent is 200g/ equivalents.It should be noted that the mol ratio [(B)/(C)] of acrylic acid (B) and methacrylic anhydride (C) is
5/5。
The manufacture of embodiment 5 (methyl) acrylate (5)
In the flask for possessing thermometer, agitator and reflux condenser, bisphenol A type epoxy resin (DIC strain formula meetings are put into
Society's system " EPICLON 850-S " epoxide equivalent 187g/ equivalents) 374 mass parts, add the butylated hydroxy-a as antioxidant
The mass parts of benzene 0.6, as the mass parts of MEHQ 0.2 of hot polymerization inhibitor after, addition acrylic acid 43 mass parts, metering system
The mass parts of acid anhydrides 216, the mass parts of triphenylphosphine 1.8, esterification 10 hours is carried out at 110 DEG C when being blown into air, is obtained
(methyl) acrylate (5).(methyl) acryloyl calculated by the input amount of raw material of (methyl) acrylate (5)
Base equivalent is 186g/ equivalents.It should be noted that the mol ratio [(B)/(C)] of acrylic acid (B) and methacrylic anhydride (C) is
3/7。
The manufacture of embodiment 6 (methyl) acrylate (6)
In the flask for possessing thermometer, agitator and reflux condenser, bisphenol A type epoxy resin (DIC strain formula meetings are put into
Society's system " EPICLON 850-S " epoxide equivalent 187g/ equivalents) 374 mass parts, add the butylated hydroxy-a as antioxidant
The mass parts of benzene 0.7, as the mass parts of MEHQ 0.2 of hot polymerization inhibitor after, addition acrylic acid 14 mass parts, metering system
The mass parts of acid anhydrides 278, the mass parts of triphenylphosphine 2.0, esterification 10 hours is carried out at 110 DEG C when being blown into air, is obtained
(methyl) acrylate (6).(methyl) acryloyl calculated by the input amount of raw material of (methyl) acrylate (6)
Base equivalent is 175g/ equivalents.It should be noted that the mol ratio [(B)/(C)] of acrylic acid (B) and methacrylic anhydride (C) is
1/9。
Compare the manufacture of (methyl) acrylate of Production Example 1 (1 ')
In the flask for possessing thermometer, agitator and reflux condenser, bisphenol A type epoxy resin (DIC strain formula meetings are put into
Society's system " EPICLON 850-S " epoxide equivalent 187g/ equivalents) 374 mass parts, add the butylated hydroxy-a as antioxidant
The mass parts of benzene 0.5, as the mass parts of MEHQ 0.2 of hot polymerization inhibitor after, addition methacrylic acid 172 mass parts, three
The mass parts of Phenylphosphine 1.6, esterification 10 hours is carried out at 110 DEG C when being blown into air, obtains (methyl) acrylate tree
Fat (1 ').(methyl) the acryloyl group equivalent calculated by the input amount of raw material of (methyl) acrylate (1 ') is 273g/
Equivalent.
Compare the manufacture of (methyl) acrylate of Production Example 2 (2 ')
In the flask for possessing thermometer, agitator and reflux condenser, bisphenol A type epoxy resin (DIC strain formula meetings are put into
Society's system " EPICLON 850-S " epoxide equivalent 187g/ equivalents) 374 mass parts, add the butylated hydroxy-a as antioxidant
The mass parts of benzene 0.5, as the mass parts of MEHQ 0.2 of hot polymerization inhibitor after, addition acrylic acid 144 mass parts, triphenyl
The mass parts of phosphine 1.6, esterification 10 hours is carried out at 110 DEG C when being blown into air, obtains (methyl) acrylate
(2’).(methyl) the acryloyl group equivalent calculated by the input amount of raw material of (methyl) acrylate (2 ') is worked as 259g/
Amount.
Embodiment 7~12, comparative example 1,2
Using embodiment 1~6 and compare (methyl) acrylate obtained in Production Example 1,2, according to following main points
Solidification compound and solidfied material are prepared, carries out various evaluation tests.Show the result in table 1.
The preparation of solidification compound
Photoepolymerizationinitiater initiater (BASF AG's system " IRGACURE184D ") is added in (methyl) acrylate 100g
1g, prepare solidification compound.
The measure of glass transition temperature
The solidification compound previously obtained is coated on acrylic board in a manner of thickness turns into 100 μm, uses high pressure
Hg lamp irradiation 2000mJ/cm2Ultraviolet, obtain solidfied material.
6mm × 25mm test film is cut out from obtained solidfied material, with determination of viscoelasticity device (DMA：Rheometric is public
Department's solid determination of viscoelasticity device " RSA-G2 " processed, pulling method：3 DEG C/min of frequency 1Hz, programming rate), by springform quantitative change
The temperature that change becomes maximum (tan δ rates of change are maximum) is evaluated as glass transition temperature.
The measure of water absorption rate
The same solidfied material of the solidfied material that is used from the measure with glass transition temperature cuts out 6mm × 25mm experiment
Piece, it is set to be impregnated 24 hours in 23 DEG C of water.The weight rate for impregnating front and rear is evaluated as water absorption rate.
The evaluation of yellowing resistance
The solidification compound previously obtained is coated with a glass in a manner of thickness turns into 100 μm, uses high-pressure mercury
Light irradiation 2000mJ/cm2Ultraviolet, obtain laminate film.
Obtained laminate film is heated 3 minutes in 265 DEG C of baking oven.420nm is determined to heating front and rear test film
The transmitance (%) of light, is evaluated with the difference of two values.
Evaluated caused by gas
The solidification compound previously obtained is coated with a glass in a manner of thickness turns into 100 μm, uses high-pressure mercury
Light irradiation 1000mJ/cm2Or 2000mJ/cm2Ultraviolet, obtain laminate film.
Obtained laminate film is heated 3 minutes on 265 DEG C of hot plate.Visually whether observation now produces gas to enter
Row evaluation.Gas is not produced：0th, produce gas and have foaming：×
[table 1]
Table 1
Claims (6)
1. a kind of (methyl) acrylate, it is characterised in that be with aromatic series 2-glycidyl ether compound (A), (first
Base) reaction product of acrylic acid (B) and methacrylic anhydride (C) as necessary reacted constituent.
2. a kind of (methyl) acrylate, it is characterised in that there is the molecular structure shown in following formulas (1), and resin
Present at least one of Y be methylacryloyl,
In formula (1), R1For hydrogen atom or methyl, X is the structure position shown in any one in following formulas (2-1)~(2-8), and Y is
Hydrogen atom or methylacryloyl,
In formula (2-1)~(2-8), R2It is each independently hydrogen atom, the alkyl of carbon number 1~4, the alkane of carbon number 1~4
Any of epoxide, phenyl, R3It is each independently the alkyl of carbon number 1~4, the alkoxy of carbon number 1~4, benzene
Any of base, n are 1~4 integer.
3. (methyl) acrylate according to claim 1 or 2, wherein, (methyl) acryloyl group equivalent is 160~
The scope of 230g/ equivalents.
4. a kind of solidification compound, it contains (methyl) acrylate and the light any one of claim 2~3
Polymerization initiator.
5. the solidfied material of the solidification compound described in claim 4.
6. a kind of optical component, it is that usage right requires that the solidification compound described in 4 forms.
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| JP2015-098216 | 2015-05-13 | ||
| JP2015098216 | 2015-05-13 | ||
| PCT/JP2016/062613 WO2016181784A1 (en) | 2015-05-13 | 2016-04-21 | (meth)acrylate resin and optical member |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111712764A (en) * | 2018-02-20 | 2020-09-25 | 汉高股份有限及两合公司 | Heat-and UV-curable adhesive compositions |
| CN111954848A (en) * | 2018-04-10 | 2020-11-17 | Dic株式会社 | Photosensitive resin composition, cured product, insulating material, resin material for solder resist, and resist member |
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| US6339113B1 (en) * | 2000-07-05 | 2002-01-15 | Dentkist Co., Ltd. | Photopolymerizable composite resin compositions for dental restoration |
| JP2008170767A (en) * | 2007-01-12 | 2008-07-24 | Ricoh Co Ltd | Electrophotographic photoreceptor, image forming method and apparatus using the same, and process cartridge for image forming apparatus |
| JP2009069241A (en) * | 2007-09-11 | 2009-04-02 | Ricoh Co Ltd | Electrophotographic device and process cartridge |
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| JP4687004B2 (en) * | 2003-04-30 | 2011-05-25 | Ｄｉｃ株式会社 | Curable resin composition, molding material and fuel cell separator |
| KR100995942B1 (en) * | 2003-04-30 | 2010-11-22 | 디아이씨 가부시끼가이샤 | Curable resin composition |
| EP2565935A4 (en) | 2011-06-01 | 2014-07-02 | Raon Tech Co Ltd | Solar cell module support assembly |
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- 2016-04-21 WO PCT/JP2016/062613 patent/WO2016181784A1/en active Application Filing
- 2016-04-21 JP JP2016560023A patent/JP6168241B2/en active Active
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| JPS551204B2 (en) * | 1975-02-08 | 1980-01-12 | ||
| US6339113B1 (en) * | 2000-07-05 | 2002-01-15 | Dentkist Co., Ltd. | Photopolymerizable composite resin compositions for dental restoration |
| JP2008170767A (en) * | 2007-01-12 | 2008-07-24 | Ricoh Co Ltd | Electrophotographic photoreceptor, image forming method and apparatus using the same, and process cartridge for image forming apparatus |
| JP2009069241A (en) * | 2007-09-11 | 2009-04-02 | Ricoh Co Ltd | Electrophotographic device and process cartridge |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111712764A (en) * | 2018-02-20 | 2020-09-25 | 汉高股份有限及两合公司 | Heat-and UV-curable adhesive compositions |
| CN111954848A (en) * | 2018-04-10 | 2020-11-17 | Dic株式会社 | Photosensitive resin composition, cured product, insulating material, resin material for solder resist, and resist member |
| CN111954848B (en) * | 2018-04-10 | 2024-05-03 | Dic株式会社 | Photosensitive resin composition, cured product, insulating material, resin material for solder resist, and resist member |
Also Published As
| Publication number | Publication date |
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| WO2016181784A1 (en) | 2016-11-17 |
| TW201706319A (en) | 2017-02-16 |
| JP6168241B2 (en) | 2017-07-26 |
| JPWO2016181784A1 (en) | 2017-05-25 |
| TWI688581B (en) | 2020-03-21 |
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