CN105073807A - Curable resin composition, cured product, and optical article - Google Patents
Curable resin composition, cured product, and optical article Download PDFInfo
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- CN105073807A CN105073807A CN201480018087.3A CN201480018087A CN105073807A CN 105073807 A CN105073807 A CN 105073807A CN 201480018087 A CN201480018087 A CN 201480018087A CN 105073807 A CN105073807 A CN 105073807A
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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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/12—Polymers provided for in subclasses C08C or C08F
- C08F290/126—Polymers of unsaturated carboxylic acids or derivatives thereof
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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
- C08F220/00—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
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
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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
- C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
- G02B1/041—Lenses
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Abstract
The invention discloses a curable resin composition, a cured product, and an optical article. The curable resin composition exhibits superior optical properties, heat resistance, and accurate mold transferability, and is excellent as an optical lens or prism material. Also provided is a cured product of the same. The curable resin composition contains: 5.0-94wt% of a component (A), which is a polyfunctional copolymer having a plurality of reactive unsaturated groups, a Mw of 2,000-100,000, and solubility in a solvent such as toluene; 5.0-94wt% of a component (B), which is a (meth) acrylate including a bisphenolfluorene skeleton and at least one (meth) acryloyl group in a molecule; and 0.1-10wt% of a component (C), which is an initiator.
Description
Technical field
The present invention relates to curable resin composition, cured article and the optical article with excellent optical characteristics, thermotolerance and processibility.
Background technology
At present, in the optical field of camera lens etc., the thermoplastic resin of more cheap polycarbonate resin, methacrylic resin, ester ring type olefin polymer etc. can be used.But heat resisting temperature, the surface hardness of these thermoplastic resins are low, almost do not used in the sophisticated technology field of photoelectron material requiring the thermotolerance of height, surface hardness and microfabrication.
As the method for defect solving such thermoplastic polymer, in patent documentation 1, disclose one single-ethenyl aromatic compound and the copolymerization of di vinyl aromatic compounds of group are obtained, and at side chain, there is the soluble polyfunctional multipolymer of the structural unit containing the reaction-ity ethylene base being derived from di vinyl aromatic compounds of group.But, although the soluble polyfunctional multipolymer obtained by the technology disclosed in it has excellent thermotolerance relative to the thermal histories at high temperature, be difficult to have both the processibility needed for leading-edge field and high refractive index.
On the other hand, bisphenol fluorene derivative, owing to having multiple aromatic nucleus, therefore, has high refractive index, high heat resistance, and then, owing to forming the different face of ring structure, so, there is the speciality that low birefringence, low cure shrinkage are such.These specialities are very excellent in formation optical forming material, but insufficient in the precision of optical surface shape in optical lens purposes, intensity.Therefore, there is excellent optical characteristics, possesses the balance of properties that low water absorbable, plasticity, thermotolerance, surface hardness are such, the optical characteristics under the actual service conditions that this external wet heat condition is harsh like this and with the improved soluble polyfunctional multipolymer of transferability of the adaptation of inorganic materials and the precision of mold shape and use the curable resin composition of multipolymer not exist up to now.
Prior art document
Patent documentation
Patent documentation 1: JP 2008-247978 publication
Patent documentation 2: specially permit No. 4558643 publication
Patent documentation 3: JP 2009-109579 publication
Summary of the invention
Invent problem to be solved
The object of the invention is to, there is provided: there is the so excellent optical characteristics of high refractive index, high light line transmitance, thermotolerance and processibility, the optical characteristics under the actual service conditions that this external wet heat condition is harsh like this, low water absorbable and shaping time the mould transferability of good release property, scuff resistance, toughness, surface hardness and precision improved containing soluble polyfunctional multipolymer (A) with have the curable resin composition of reactivity (methyl) acrylate (B) of bisphenol fluorene skeleton, cured article and optical article.
For solving the means of problem
The present invention is curable resin composition, it is characterized in that, it contains (A) composition: there is multiple reactive unsaturated group, weight-average molecular weight is 2,000 ~ 100,000, and then dissolve in toluene, dimethylbenzene, tetrahydrofuran (THF), ethylene dichloride or chloroform, the monomer making to have 2 reactive unsaturated groups and the monomer copolymerization with 1 and the multi-functional copolymers that obtains;
(B) composition: (methyl) acrylate with fluorene skeleton shown in general formula (1); And
(C) composition: initiator,
Relative to the content of (A) composition of the total of (A) ~ (C) composition be 5.0 ~ 94wt%, the content of (B) composition be the content of 5.0 ~ 94wt% and (C) composition is 0.1 ~ 10wt%.
[chemical formula 1]
(in formula, R
1and R
2represent H or CH independently
3, R
3and R
4expression-CH independently
2o-,-CH
2cH
2o-,-CH
2cH (CH
3) O-,-CH
2cH
2cH
2o-,-CH
2cH (OH) CH
2o-or CH
2cH (OR
5) CH
2o-, R
5for (methyl) acryl, k and l represent the number of more than 0 or 1 independently, but k+l is the number of more than 1, m and n represents the number of 0 ~ 4 independently.)
In addition, the present invention is above-mentioned curable resin composition, it is characterized in that, (A) multi-functional copolymers of composition will be for will have aromatic nucleus, or the simple function of alicyclic structure (methyl) acrylate (a), 2 officials' energy (methyl) acrylate (b) of more than a kind, 2, the composition copolymerization of 4-phenylbenzene-4-methyl-1-pentene (c) and mercaptan compound (d) and the multipolymer that obtains, for having reactive (methyl) acrylic being derived from 2 officials' energy (methyl) acrylate (b) at side chain, have at end and be derived from 2, the multi-functional copolymers of the structural unit of 4-phenylbenzene-4-methyl-1-pentene (c) and mercaptan compound (d).
Also have, the present invention is above-mentioned curable resin composition, it is characterized in that, (A) multi-functional copolymers of composition is: single-ethenyl aromatic compound (e), di vinyl aromatic compounds of group (f) and the copolymerization of fragrant family ether compound are obtained, there is at side chain the reaction-ity ethylene base base being derived from di vinyl aromatic compounds of group (f), its end on average every 1 molecule has the multi-functional copolymers that more than 1 is derived from the structural unit of the fragrant family ether compound shown in following formula (2)
[chemical formula 2]
(in formula, R
6represent H or CH
3, R
7expression can contain the alkyl of the carbonatoms 1 ~ 18 of Sauerstoffatom or sulphur atom.)
And then, the present invention is above-mentioned curable resin composition, it is characterized in that, except above-mentioned (A), (B), (C) beyond composition, also containing (methyl) acrylate in the molecule with 1 ~ 8 (methyl) acryl as (D) composition, wherein, be equivalent to above-mentioned (A), (B) except the situation of composition, be 5.0 ~ 84wt% relative to the content of (A) composition of the total of (A) ~ (D) composition, (B) content of composition is 5.0 ~ 84wt%, and the content of (C) composition is 0.1 ~ 10wt%, (D) content of composition is 10 ~ 70wt%, and be 30 ~ 90wt% relative to the use level of (A) composition of total 100 weight part of (A) ~ (D) composition and the total of (B) composition.
In addition, the optical article that the present invention is resin cured matter and is formed by this resin cured matter, the feature of described resin cured matter is, above-mentioned curable resin composition solidification is obtained.As the optical article related to, there are optical lens, microlens array or camera head.
Invention effect
Curable resin composition of the present invention or the resin cured matter making it solidify and obtain have the excellent optical characteristics such as high refractive index, low birefringence, high transparent, thermotolerance and processibility, the optical characteristics under the actual service conditions that this external condition is repeatedly harsh like this, low water absorbable and shaping time the mould transferability of good release property, scuff resistance, toughness, surface hardness and precision improve.In addition, resin cured matter of the present invention is excellent as optical lens prism material.
Embodiment
Below, curable resin composition of the present invention is described.First, to as must (A) ~ (C) composition of components matching be described.
(A) of the present invention composition can use has multiple reactive unsaturated link(age), and weight-average molecular weight is 2,000 ~ 100, and 000, and then the multi-functional copolymers dissolving in toluene, dimethylbenzene, tetrahydrofuran (THF), ethylene dichloride or chloroform.Below, be multipolymer by the multi-functional copolymers abbreviation as (A) composition sometimes.
(A) composition is the multi-functional copolymers of solubility, and so-called solubility refers to and dissolves in toluene, dimethylbenzene, tetrahydrofuran (THF), ethylene dichloride or chloroform.Preferably dissolve in the whole of above-mentioned solvent.The test of solubility is carried out under the condition shown in embodiment.
(A) composition multipolymer by by the monomer (monofunctional components) of the unsaturated group to have the polymerisation reactivities such as 1 monovinyl compound and have the polymerisation reactivities such as 2 divinyl compounds unsaturated group monomer (2 functional component) monomer component copolymerization and obtain expediently.2 functional component give branched structure or crosslinking structure, but the amount of the crosslinking structure related to is defined in the degree of display solubility.The end of branched structure contains the unreacted unsaturated group being derived from 2 functional component such as divinyl compound.Therefore, the multipolymer at side chain with the unsaturated group such as unreacted (methyl) acrylic or vinyl etc. being derived from 2 functional component is become.This unreacted unsaturated group is also referred to as side chain (methyl) acrylic or pendant vinyl base etc., and it is in order to show polymerizability, is polymerized by further aggregation processing, can provide the resin cured matter being insoluble to solvent.Unreacted unsaturated group needs average out to more than 2 in 1 molecule, but is preferably more than 3.In order to improve the ratio of unreacted unsaturated group, undertaken being polymerized etc. to carry out by usage quantity, the usage chain transfer agent increasing 2 functional component.
Preferred multipolymer has multipolymer (A-1), its be use simple function (methyl) acrylate (a) with aromatic nucleus or alicyclic structure as have 1 unsaturated group monomer, use 2 officials of more than a kind to be polymerized to obtain as having the monomer of 2 unsaturated groups and then use 2,4-phenylbenzene-4-methyl-1-pentene (c) and mercaptan compound (d) as minor component by (methyl) acrylate (b).
As monofunctional monomer (methyl) acrylate (a-1) with aromatic ring structure forming multipolymer (A-1), can enumerate: be selected from more than one simple functions (methyl) acrylate in the group be made up of the acrylate such as benzyl acrylate, phenyl acrylate, acrylate, 2-naphthyl acrylate, thiophenol acrylate, benzyl mercaptan acrylate and their methacrylic ester.As monofunctional monomer (methyl) acrylate (a-2) forming alicyclic structure, can enumerate: be selected from more than one simple functions (methyl) acrylate in the group be made up of the acrylate such as cyclohexyl acrylate, vinylformic acid bicyclopentyl ester, vinylformic acid dicyclopentenyl ester, isobornyl acrylate and their methacrylic ester.
As 2 officials' energy (methyl) acrylate (b) forming multipolymer (A-1), ethylene glycol bisthioglycolate (methyl) acrylate can be used, propylene glycol two (methyl) acrylate, 1, 4-butyleneglycol two (methyl) acrylate, 1, 6-hexylene glycol two (methyl) acrylate, Diethylene Glycol two (methyl) acrylate, cyclohexanedimethanol two (methyl) acrylate, dihydroxymethyl tristane two (methyl) acrylate, EO modified bisphenol A diacrylate, PO modified bisphenol A diacrylate, 2, 4-bis-(methyl) acryloxy naphthalene, 9, 2 officials' energy (methyl) acrylate of two [4-2 (-acryloyloxyethoxy) phenyl] fluorenes of 9-etc., but do not limit by these.At this, EO, PO refer to oxyethane, propylene oxide.
When the functions such as toughness, release property, reactivity will be given to multipolymer (A-1), at random can regulate according to (methyl) acrylate used.As the concrete example of (methyl) acrylate, from the viewpoint of cost, easness that polymerization controls and the thermotolerance of polymkeric substance that obtains, preferably can use (methyl) vinylformic acid bicyclopentyl ester, (methyl) isobornyl acrylate, cyclohexanedimethanol two (methyl) acrylate and dihydroxymethyl tristane two (methyl) acrylate with alicyclic structure.In addition, from the viewpoint of the shaping processability such as toughness, release property of cured article, preferably not there is n-butylacrylate, the just own ester of vinylformic acid, ethylene glycol bisthioglycolate (methyl) acrylate, propylene glycol two (methyl) acrylate, BDO two (methyl) acrylate, hexylene glycol two (methyl) acrylate, Diethylene Glycol two (methyl) acrylate of alicyclic structure.
2,4-phenylbenzene-4-methyl-1-pentene (c) and mercaptan compound (d) play a role as chain-transfer agent, control the molecular weight of multipolymer.The molecular weight of multipolymer of the present invention as weight-average molecular weight Mw (at this, Mw is the weight-average molecular weight using the polystyrene standard of gel permeation chromatography to convert) be 2,000 ~ 100, the scope of 000, is preferably 2,500 ~ 60,000, more preferably 3,000 ~ 50, the scope of 000.By using the multipolymer of this molecular weight ranges, can further improve plasticity and the release property of resin cured matter.
As mercaptan compound (d), as long as the known mercaptan compound played a role as chain-transfer agent, preferably tertiary lauryl mercaptan, n-dodecyl mercaptan, tert octyl mercaptan, n octylmercaptan, trimethylolpropane tris-3-mercaptopropionic acid ester, tetramethylolmethane four-3-mercaptopropionic acid ester, Dipentaerythritol six-3-mercaptopropionic acid ester and (three-[(3-mercaptopropionyl oxygen base)-ethyl]-isocyanuric acid esters) etc.Wherein, from the viewpoint of the toughness of being polymerized the easness of control, the multipolymer of generation, the monoalkyl mercaptan of the carbonatoms 5 ~ 30 of tertiary lauryl mercaptan, n-dodecyl mercaptan, tert octyl mercaptan, n octylmercaptan etc. can particularly preferably be used.
As other preferred multipolymer, have use single-ethenyl aromatic compound (e) as have 1 unsaturated group monomer, use di vinyl aromatic compounds of group (f) as the monomer with 2 unsaturated groups, and then, as minor component, use fragrant family ether compound and the multipolymer (A-2) obtained.
Multipolymer (A-2) is except the structural unit being derived from single-ethenyl aromatic compound (e) and the structural unit being derived from di vinyl aromatic compounds of group (f), also there is the structural unit (hereinafter also referred to as structural unit (g)) shown in above-mentioned formula (2) being derived from fragrant family ether compound.And, the terminal group shown in above-mentioned formula (2) is called end group (g).And preferably the polymeric chain (main chain and side chain) of general multipolymer is generated by di vinyl aromatic compounds of group and single-ethenyl aromatic compound, and a part for end is generated by fragrant family ether compound.
As the fragrant family ether compound providing structural unit (g) or terminal group (g), can preferably illustrate: (methyl) vinylformic acid 2-phenoxy ethyl, alkoxylate 2-Phenoxyethyl (methyl) acrylate.But, be not limited to these.From the viewpoint of the thermotolerance of reactive, cured article, the easness that obtains, more preferably (methyl) vinylformic acid 2-phenoxy ethyl.(methyl) vinylformic acid 2-phenoxy ethyl is owing to having polymerizable group, therefore, can with other monomer copolymerization, but in order to become end group (g), the reactivity of preferred polymeric group is low, major part unreacted and remaining, becomes the structure that the vinyl of di vinyl aromatic compounds of group (f) and its phenyl ring react.
In above-mentioned formula (2), R
6represent H or CH
3, but these are determined by the aromatic ether compound used.R
7expression can contain the alkyl of the carbonatoms 1 ~ 18 of Sauerstoffatom or sulphur atom between carbochain, but is preferably the alkyl of carbonatoms 1 ~ 6, is more preferably-CnH
2n-shown alkylidene group.At this, n more preferably 1 ~ 4 scope.
As single-ethenyl aromatic compound (e), can use containing more than more than 50 % by mole, preferably 70 % by mole, the preferred single-ethenyl aromatic compound being selected from the vinyl aromatic compounds of more than a kind in the group be made up of vinylbenzene, vinyl xylene, ethyl vinyl benzene, vinyl biphenyl and vinyl naphthalene of more than 85 % by mole further.
In addition, single-ethenyl aromatic compound (e) can contain single-ethenyl aromatic compound other than the above, preferably can a small amount of containing lower than 50 % by mole.As the example of these single-ethenyl aromatic compounds, there is core alkyl to replace single-ethenyl aromatic compound, alpha-alkyl replaces single-ethenyl aromatic compound, β-alkyl-substituted styrene, alkoxy substituted ethene etc.In order to prevent gelation, improvement solvability, the processibility in a solvent of multipolymer, particularly from the viewpoint of cost and the easness that obtains, optimization styrene, vinyl xylene, ethyl vinyl benzene (and isomer) to both, ethyl vinyl biphenyl (comprising Isomers).
As the example of di vinyl aromatic compounds of group (f), Vinylstyrene (and isomer) to both, divinyl naphthalene (comprising Isomers), divinyl biphenyls (comprising Isomers) etc. can be used, but be not limited to these.In addition, these can be used alone, and also may be combined with and use two or more.Particularly from the viewpoint of cost and the easness that obtains, preferably can use Vinylstyrene (and isomer) to both, but when requiring the thermotolerance of more height, divinyl naphthalene (comprising Isomers), divinyl biphenyls (comprising Isomers) preferably can be used.
The Mw of the multipolymer used in the present invention is 2,000 ~ 100, the scope of 000, is preferably 2,500 ~ 60,000, more preferably 3,000 ~ 50, the scope of 000.If Mw is lower than 2,000, then the viscosity of multipolymer becomes too low, and therefore, processibility reduces, and in addition, if Mw is more than 100,000, then easily generates gel, can not expect intermiscibility.The value of molecular weight distribution (Mw/Mn) is less than 50.0, is preferably less than 20.0, is more preferably 1.5 ~ 3.0.If Mw/Mn is more than 50.0, then the processing characteristics producing multipolymer worsens, produce the such problem of gel.
The multipolymer used in the present invention is acrylate-based owing to having (methyl) at side chain or end, therefore, can carry out well with the copolymerization of (methyl) acrylic compound, in addition, relative to (methyl) acrylic compound and resin, intermiscibility is very high.Therefore, when with (methyl) acrylic compound copolymerization and make it solidify, uniform curing property and the transparency are excellent.
The multipolymer of (A) composition used in the present invention can obtain according to method patent documentation 1, JP 2004-123873 publication, JP No. No. 2005-213443 publication, JP 2010-229263 publication etc. Suo Shi.
Then, (methyl) acrylate of (B) composition being used as curable resin composition of the present invention is described.
(B) composition for shown in above-mentioned general formula (1), (methyl) acrylate with fluorene skeleton.In general formula (1),
R
1and R
2be H or CH independently
3,
R
3and R
4be CH independently
2o, CH
2cH
2o, CH
2cH (CH
3) O, CH
2cH
2cH
2o, CH
2cH (OH) CH
2o or CH
2cH (OR
5) CH
2o.
R
5for (methyl) acryl, k and l is the number of more than 0 ~ 1 independently, but is 0 when both are different.Preferred k+l is 0 ~ 4.
M and n represents the number of 0 ~ 4 independently.
The characteristics such as high refractive index, intermiscibility, reactivity, R is had both well from the viewpoint of balance
3and R
4preferred CH
2cH
2o, CH
2cH (OH) CH
2o or CH
2cH (OR
5) CH
2o, m and n preferably 1 ~ 2.In addition, the number being somebody's turn to do (methyl) acryl that (methyl) acrylate has is preferably 1 ~ 4, is more preferably 2 ~ 4.
As (methyl) acrylate of B component, as concrete compound, such as, can enumerate: there is the diacrylate monomer of bisphenol fluorene skeleton, dimethacrylic monomers or there is the monomer of acrylic and methacrylic acid group.Specifically, can enumerate: two (4-(methyl) acryloxy phenyl) fluorenes of 9,9-, two (4-(methyl) acryloxy p-methoxy-phenyl) fluorenes of 9,9-, two (4-(2-(methyl) acryloyloxyethoxy) phenyl) fluorenes of 9,9-, two (4-(2-(methyl) acryloxy propoxy-) phenyl) fluorenes of 9,9-, two (4-(3-(methyl) acryloxy propoxy-) phenyl) fluorenes of 9,9-, two (4-(methyl) acryloxy Dimethoxyphenyl) fluorenes of 9,9-, two (4-(methyl) the acryloxy diethoxy phenyl) fluorenes of 9,9-, two (4-(methyl) the acryloxy dipropoxy phenyl) fluorenes of 9,9-, two (4-(methyl) acryloxy trimethoxyphenyl) fluorenes of 9,9-, two (4-(methyl) acryloxy triethoxy) fluorenes of 9,9-, two (4-(methyl) the acryloxy tripropoxy phenyl) fluorenes of 9,9-, two (4-(methyl) acryloxy-3-aminomethyl phenyl) fluorenes of 9,9-, two (4-(methyl) acryloyl-oxy ylmethoxy-3-aminomethyl phenyl) fluorenes of 9,9-, two (4-(2-(methyl) the acryloyloxyethoxy)-3-aminomethyl phenyl) fluorenes of 9,9-, two (4-(2-(methyl) acryloxy the propoxy-)-3-aminomethyl phenyl) fluorenes of 9,9-, two (4-(3-(methyl) acryloxy the propoxy-)-3-aminomethyl phenyl) fluorenes of 9,9-, two (4-(methyl) acryloxy dimethoxy-3-aminomethyl phenyl) fluorenes of 9,9-, two (4-(methyl) acryloxy diethoxy-3-aminomethyl phenyl) fluorenes of 9,9-, two (4-(methyl) acryloxy dipropoxy-3-aminomethyl phenyl) fluorenes of 9,9-, two (4-(methyl) acryloxy trimethoxy-3-aminomethyl phenyl) fluorenes of 9,9-, two (4-(methyl) acryloxy triethoxy-3-aminomethyl phenyl) fluorenes of 9,9-, two (4-(methyl) acryloxy tripropoxy-3-aminomethyl phenyl) fluorenes of 9,9-, two (4-(methyl) acryloxy-3-ethylphenyl) fluorenes of 9,9-, two (4-(methyl) acryloyl-oxy ylmethoxy-3-ethylphenyl) fluorenes of 9,9-, two (4-(2-(methyl) the acryloyloxyethoxy)-3-ethylphenyl) fluorenes of 9,9-, two (4-(2-(methyl) acryloxy the propoxy-)-3-ethylphenyl) fluorenes of 9,9-, two (4-(3-(methyl) acryloxy the propoxy-)-3-ethylphenyl) fluorenes of 9,9-, two (4-(methyl) acryloxy dimethoxy-3-ethylphenyl) fluorenes of 9,9-, two (4-(methyl) acryloxy diethoxy-3-ethylphenyl) fluorenes of 9,9-, two (4-(methyl) acryloxy dipropoxy-3-ethylphenyl) fluorenes of 9,9-, two (4-(methyl) acryloxy trimethoxy-3-ethylphenyl) fluorenes of 9,9-, two (4-(methyl) acryloxy triethoxy-3-ethylphenyl) fluorenes of 9,9-, two (4-(methyl) acryloxy tripropoxy-3-ethylphenyl) fluorenes of 9,9-, two (4-(methyl) acryloxy-3-propyl group phenyl) fluorenes of 9,9-, two (4-(methyl) acryloyl-oxy ylmethoxy-3-propyl group phenyl) fluorenes of 9,9-, two (4-(2-(methyl) the acryloyloxyethoxy)-3-propyl group phenyl) fluorenes of 9,9-, two (4-(2-(methyl) acryloxy the propoxy-)-3-propyl group phenyl) fluorenes of 9,9-, two (4-(3-(methyl) acryloxy the propoxy-)-3-propyl group phenyl) fluorenes of 9,9-, two (4-(methyl) acryloxy dimethoxy-3-propyl group phenyl) fluorenes of 9,9-, two (4-(methyl) acryloxy diethoxy-3-propyl group phenyl) fluorenes of 9,9-, two (4-(methyl) acryloxy dipropoxy-3-propyl group phenyl) fluorenes of 9,9-, two (4-(methyl) acryloxy trimethoxy-3-propyl group phenyl) fluorenes of 9,9-, two (4-(methyl) acryloxy triethoxy-3-propyl group phenyl) fluorenes of 9,9-, two (4-(methyl) acryloxy tripropoxy-3-propyl group phenyl) fluorenes of 9,9-, two (4-(methyl) acryloxy-(2-hydroxyl) propoxyphenyl) fluorenes of 9,9-, two (4-(methyl) acryloxy-(2-hydroxyl) propoxy--3-aminomethyl phenyl) fluorenes of 9,9-, two (4-(methyl) acryloxy-(2-hydroxyl) propoxy-ethoxyl phenenyl) fluorenes of 9,9-, the bisphenol fluorene dihydroxyl acrylate i.e. acrylic acid adduct (Nippon Steel's chemistry (strain) system) of the glycidyl ether of 9,9-two (4-hydroxy phenyl) fluorenes, bisphenol fluorene dimethacrylate (Nippon Steel's chemistry (strain) system), two phenoxyethyl alcohol fluorenes diacrylate (make by Osaka gas (strain), BPEF-A), two phenoxyethyl alcohol fluorenes dimethacrylate (make by Osaka gas (strain), BPEF-MA), two phenoxyethyl alcohol fluorenes diepoxy acrylate (make by Osaka gas (strain), BPEF-GA), bisphenol fluorene diepoxy acrylate (make by Osaka gas (strain), BPF-GA), two cresols fluorenes diepoxy acrylate (make by Osaka gas (strain), BCF-GA) etc.
As the initiator of (C) composition, there are Photoepolymerizationinitiater initiater or thermal polymerization.At this, as Photoepolymerizationinitiater initiater, the compounds such as methyl phenyl ketone system, bitter almond oil camphor system, benzophenone series, thioxanthone system, acylphosphine oxide system preferably can be used.Specifically; can illustrate: Trichloroacetophenon, diethoxy acetophenone, 1-phenyl-2-hydroxy-2-methyl propane-1-ketone, 1-hydroxycyclohexylphenylketone, 2-methyl isophthalic acid-(4-methylthiophenyi)-2-morpholinopropane-1-ketone, benzoin methylether, benzil dimethyl ketal, benzophenone, thioxanthone, 2; 4,6-trimethyl benzoyl diphenyl base phosphine oxide, methyl phenyl glyoxylate ester, camphorquinone, benzil, anthraquinone, Michler's keton etc.In addition, also can be used together and combine with Photoepolymerizationinitiater initiater and play light-initiated auxiliary agent or the sensitive agent of effect.These Photoepolymerizationinitiater initiaters can be used alone, and also can be mixed with two or more.
In addition, as thermal polymerization, the various organo-peroxides such as ketone peroxide system, ketal peroxide system, hydrogen peroxide system, dialkyl peroxide system, diacyl peroxide system, peroxy dicarbonate system, peroxyester system preferably can be used.Specifically, can illustrate: Cyclohexanone peroxides, 1, two (tertiary hexyl peroxidation) pimelinketone, hydrogen phosphide cumene, dicumyl peroxide, benzoyl peroxide, di-isopropyl superoxide, the peroxide-2-ethyl hexanoic acid tert-butyl etc. of 1-, but not by these any restrictions.In addition, these thermal polymerizations can be used alone, and also can be mixed with two or more.
Except above-mentioned (A) ~ (C) composition; can also coordinate as required as (D) composition there is 1 ~ 8 (methyl) acryl in the molecule (methyl) acrylate (wherein, corresponding to above-mentioned (A), (B) composition situation except).Now, for the content in curable resin composition, preferably relative to the content of (A) composition of the total of (A) ~ (D) composition be 5.0 ~ 84wt%, the content of (B) composition be the content of 5.0 ~ 84wt% and (C) composition is 0.1 ~ 10wt%, the content of (D) composition is 10 ~ 70wt%, and is 30 ~ 90wt% relative to the use level of (A) composition of total 100 weight part of (A) ~ (D) composition and the total of (B) composition.
As (D) composition, 1 ~ 8 official's energy (methyl) acrylate can be used.Wherein, (methyl) acrylate will in the molecule with more than 2 (methyl) acryls is called multifunctional (methyl) acrylate, preferably can use the one kind or two or more of multifunctional (methyl) acrylate.Advantageously, (D) composition can on average have 2 ~ 5 (methyl) acryls by every 1 molecule.At this; average (methyl) acryloyl radix of every 1 molecule is calculated by total (methyl) acryloyl radix/total molecule number; total molecule number calculates as the total with more than 1 (methyl) acrylate-based (methyl) acrylate, but (A) composition and (B) composition and (methyl) acryl contained in them are got rid of from calculating.
These polyfunctional acrylic esters being used as (D) composition, by with (A) composition and (B) composition and use, also improve the optical characteristics that low look disperses, high light line transmitance is so synergistically except thermotolerance and surface hardness except simultaneously.
As above-mentioned multifunctional (methyl) acrylate, can be advisable with (A) composition and the copolymerization of (B) composition, such as, can enumerate: BDO two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, polymer with bis phenol A oxyethyl group two (methyl) acrylate, polymer with bis phenol A propoxy-two (methyl) acrylate, Bisphenol F polyethoxye two (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, trimethylolpropane tris oxygen ethyl (methyl) acrylate, three (2-hydroxyethyl) isocyanuric acid ester three (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, three (acryloyl-oxyethyl) isocyanuric acid ester, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, tripentaerythritol six (methyl) acrylate, tripentaerythritol five (methyl) acrylate, hydroxypivalic acid neopentyl glycol two (methyl) acrylate, two (methyl) acrylate (such as Japanese chemical drug (strain) system of the 6-caprolactone affixture of hydroxypivalic acid neopentyl glycol, KAYARADHX-220, HX-620 etc.), trimethylolpropane tris (methyl) acrylate, TriMethylolPropane(TMP) polyethoxye three (methyl) acrylate, two TriMethylolPropane(TMP) four (methyl) acrylate, the monomer classes such as cyclohexanedimethanol two (methyl) acrylate and dihydroxymethyl tristane two (methyl) acrylate.From the viewpoint of surface hardness, can particularly preferably enumerate: tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, tripentaerythritol six (methyl) acrylate, tripentaerythritol five (methyl) acrylate, TriMethylolPropane(TMP) polyethoxye three (methyl) acrylate, two TriMethylolPropane(TMP) four (methyl) acrylate.
On the other hand, from the viewpoint of the form accuracy of optical surface, can preferably enumerate: cyclohexanedimethanol two (methyl) acrylate, dihydroxymethyl tristane two (methyl) acrylate.
In addition; as (D) composition; also simple function (methyl) acrylate of more than a kind in the molecule with 1 (methyl) acryl can be used; these simple functions (methyl) acrylate by with (A) composition, (B) composition and multifunctional (methyl) use; mobility can be improved synergistically while improving the optical characteristics that low look disperses, high optical transmittance is such, can plasticity be improved thus.As above-mentioned simple function (methyl) acrylate, preferably can use simple function (methyl) acrylate (a) with ester ring type structure for the manufacture of the multipolymer as (A) composition, in addition, such as can enumerate: acryloyl morpholine, (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 4-hydroxybutyl, polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate, hexanaphthene-Isosorbide-5-Nitrae-dimethanol list (methyl) acrylate, (methyl) tetrahydrofurfuryl acrylate, (methyl) acrylate, (methyl) phenylethyl polyethoxye ester, (methyl) vinylformic acid 2-hydroxyl-3-phenoxy-propyl, orthoxenol polyethoxye (methyl) acrylate, to cumylphenoxy ethyl (methyl) acrylate, (methyl) isobornyl acrylate, tribromophenoxy ethyl (methyl) acrylate, (methyl) vinylformic acid bicyclopentyl ester, (methyl) vinylformic acid dicyclopentenyl ester, (methyl) vinylformic acid dicyclopentenyl oxygen base ethyl ester etc.
Described in the preferred cooperation of curable resin composition of the present invention is composed as follows.(A) use level of composition is 5.0 ~ 80wt%, be preferably 5.0 ~ 60wt%, the use level of (B) composition is 5.0 ~ 80wt%, is preferably 10 ~ 60wt%, and the use level of (C) composition is 0.1 ~ 10wt%, be preferably 0.1 ~ 5wt%.When coordinating (D) composition, with the cooperation gauge of above-mentioned (A) ~ (C) composition, (D) composition is 10 ~ 70wt%, is preferably 20 ~ 60wt%.And the content of (A) composition+(B) composition is 30 ~ 90wt%, be preferably 40 ~ 80wt%.
If (A) use level of composition is lower than 5.0wt%, then the precision of the optical surface shape of molding reduces, therefore not preferred, in addition, if the use level of (A) composition is too much, then with the rising of viscosity, plasticity, operability significantly reduce, therefore not preferred.On the other hand, if the use level of (B) composition is lower than 5.0wt%, then the specific refractory power of cured article reduces, therefore not preferred, if too much, then cured article low elasticity, the thermotolerance of molding reduces, therefore not preferred.In addition, in curable resin composition containing organic solvent and filler, above-mentioned content calculates except it.
In addition, in curable resin composition of the present invention, also can add stopper, antioxidant, releasing agent, photosensitizers, organic solvent, silane coupling agent, flow agent, defoamer, antistatic agent and UV light absorber, photostabilizer, inorganic, organic various filler, mould inhibitor, antiseptic-germicide etc. as required in curable resin composition of the present invention, that gives separately as object is functional.
Curable resin composition of the present invention is by with random order mixing above-mentioned (A) composition, (B) composition and (C) composition and (D) composition as required, other composition and obtaining.Curable resin composition of the present invention through time stable.
Curable resin composition of the present invention solidifies by heating or rayed.When being shaped by heating, its forming temperature can be selected from room temperature according to the selection of thermal polymerization to the wide scope of about 200 DEG C.
When shaping by rayed, obtain cured article by irradiation ultraviolet radiation isoreactivity energy line.At this, as the concrete example of the light source used when irradiating active energy ray and being cured, such as, can enumerate the electron beam etc. of xenon lamp, carbon arc lamp, germicidal lamp, ultraviolet luminescent lamp, duplicating high pressure mercury vapour lamp, middle medium pressure mercury lamp, high pressure mercury vapour lamp, extra-high-pressure mercury vapour lamp, Non-polarized lamp, metal halide lamp or sweep type, the generation of curtain electron-beam accelerator.In addition, when being cured by curable resin composition of the present invention by irradiation ultraviolet radiation, the ultraviolet irradiation amount needed for solidification is 300 ~ 20,000mJ/cm
2left and right.It should be noted that, by solidifying in the non-active gas atmosphere such as nitrogen, more efficiently can make resin composition.
Curable resin composition of the present invention can be used for the injection article as plastic lens etc. and so on.As the making method of plastic lens employing resin combination of the present invention, there is following method etc.: make the two panels glass mould of gasket by being made up of polyvinyl chloride, vinyl-vinyl acetate copolymer etc. and intended shape and the mould manufactured, after injecting resin combination of the present invention wherein, cured article, by resin composition, is peeled off from mould by irradiation ultraviolet radiation isoreactivity energy line.
In addition, as the method be coated on film-like substrate as prismatic lens resin combination by curable resin composition of the present invention, the known various method of industry can be used.As concrete grammar, such as can enumerate following method: coated by resin combination and have on the mould of prism shape on surface, the layer of resin combination is set, this resin composition layer crimps water white film-like substrate (such as polyvinyl chloride in the mode not entering bubble, polystyrene, polycarbonate, poly-(methyl) acrylate, polyester, polyethylene terephthalate etc.), then use high pressure mercury vapour lamp irradiation ultraviolet radiation that resin composition layer is solidified in this condition from film-like substrate side, then the film-like substrate of the resin layer defining prism-like is peeled off from mould.
Curable resin composition of the present invention is formed, solidify and the resin cured matter that obtains as optical material or optical article excellent.Especially the optical plastic lens material as prismatic lens, lenticular lens, eyeglass lens, non-spherical lens etc. is useful.And such lens can be advantageously used in camera.In addition, curable resin composition or resin cured matter also may be used for the purposes, printing-ink, coating, clear-coated agent, satin light varnish etc. of the opto-electronic device towards CD, optical fiber, light-guide wave path etc. in addition.
Embodiment
Then, by embodiment, the present invention will be described, but the present invention is not limited to these embodiments.In addition, the part in each example unless otherwise specified, is then weight part.In addition, the mensuration of the softening temperature in embodiment etc. carries out sample preparation and mensuration by method shown below.
(physical property measurement of multipolymer and cured article thereof)
1) molecular weight of polymkeric substance and molecular weight distribution
Use GPC (eastern Cao HLC-8120GPC), at solvent: tetrahydrofuran (THF) (THF), flow: 1.0ml/min, column temperature: the molecular weight and the molecular weight distribution determination that carry out soluble polyfunctional multipolymer in 40 DEG C.The molecular weight of multipolymer uses the typical curve according to monodisperse polystyrene, measures as polystyrene conversion molecular weight.
2) structure of polymkeric substance
Use NEC JNM-LA600 type nucleus magnetic resonance light-dividing device, pass through
13c-NMR and
1h-NMR analyzes and determines.Use chloroform-d1 as solvent, the resonance line of tetramethylsilane is used as internal standard.
3) solvent resistance and dissolve deliquescent mensuration
For the mensuration of solvent resistance, multipolymer is made sample board 200 DEG C of vacuum presses one hour, by sample board in toluene in room temperature immersion 10 minutes, by the visual change confirming the sample after dipping, carry out the evaluation of solvent resistance by classifying as follows: zero: not change, △: swelling, ×: there are distortion, expansion.
For the mensuration of solvent solubility, multipolymer 5g is joined in the solvent of 100ml, observe the dissolving situation after stirring 10 minutes at 25 DEG C.The situation of uniform dissolution, the existence to non-solute and gel unconfirmed is judged to be solubility.
(physical property measurement of composition and cured article thereof)
(1) mensuration of specific refractory power
In order to measure the specific refractory power of resin combination, open between two glass sheets of width 50mm, length 50mm, thickness 1.0mm 1.0mm gap and by periphery to inject solidification compound in Kapton Tape winding, fixing glass mold, 1) above-mentioned high pressure mercury vapour lamp irradiation ultraviolet radiation a few second is passed through from the one side of this glass mold, or 2) use the metal sheet of SUS to replace this glass mold to make same test film die for manufacturing, put into the inactive gas stove under stream of nitrogen gas, 180 DEG C of heating 1 hour, it is made to solidify thus.From the resin board demoulding that glass mold or mould will have cured, as sample.With specific refractory power and the Abbe number of Abbe refractomecer (Atago (strain) system) working sample.
(2) form and aspect
Utilize color evaluating (trade(brand)name " MODELTC_8600 ", Tokyo electricity look (strain) system) to measure the flat board of thickness 1.0mm, width 40mm, length 40mm, its YI value is shown.
(3) Haze (mist degree) and total light penetration
Make the test film of flat board being cured as thickness 1.0mm, width 40mm, length 40mm, use integrating sphere type optical transmittance determinator (Japanese electricity Se Inc. SZ-Σ 90) to measure the Haze (mist degree) of this test film and total light penetration.
(4) release property
By making to be cured as thickness 1.0mm, width 40mm, the resin of flat board of length 40mm evaluates from difficulty during mold releasability.
Zero is good from the release property of mould.
The △ demoulding is slightly difficult.
× demoulding difficulty or mould remain
(5) mould reproducibility
Evaluate to the leakage in the gap of mould by being cured as thickness 0.6mm, the surface shape of resin layer of spherical lens shapes of diameter 3.0mm and resin.
Zero reproducibility is good
× reproducibility is bad
(6) burr, seepage
By making to be cured as thickness 0.6mm, the resin of spherical lens shapes of diameter 3.0mm evaluates from the size of the burr produced beyond product part during mold releasability and resin to the degree of the leakage in the gap of mould.
The growing amount of zero burr lower than 0.05mm, resin to the leakage in the gap of mould lower than 1.0mm.
The growing amount of △ burr is more than 0.05mm and lower than 0.2mm.Resin is more than 1.0mm and lower than 3.0mm to the leakage in the gap of mould.
The growing amount of × burr is more than 0.2mm, and resin is more than 3.0mm to the leakage in the gap of mould.
(7) bubble
By making to be cured as thickness 0.6mm, the resin of spherical lens shapes of diameter 3.0mm evaluates from the degree of the size that has that it's too late of the bubble produced in molding part during mold releasability.
Zero generation not observing bubble.
△ observes the generation of bubble, the size of bubble relative to the volume of molding lower than 2%.
× observe the generation of bubble, the size of bubble is more than 2% relative to the volume of molding.
(8) crackle
By making to be cured as thickness 0.6mm, the resin of spherical lens shapes of diameter 3.0mm evaluates from the degree of the size that has that it's too late of the crackle produced at the product part of molding during mold releasability.
Zero generation not observing crackle.
Although △ observes the generation of crackle, only observe the generation of crackle in the corner portion of molding peripheral part.
× observe the generation of crackle, beyond the corner portion of molding peripheral part, also observe the generation of crackle.
(9) thermotolerance repeatedly
Using the flat board of thickness 1.0mm, width 40mm, length 40mm as test specimen, spectral photometric colour measuring meter CM-3700d (Konicaminolta Inc.) is used to measure wavelength: the spectrophotometric transmittance of 400nm.Before minute is set to the oven test of having carried out 200 DEG C of after fixing of 60 minutes and in air oven, after the oven test of 250 DEG C, 7 minutes.The result being measured the spectrophotometric transmittance change obtained by these is shown in following table 3.
(10) water-intake rate
The weight of the test film of the flat board at 60 DEG C of the thickness 1.0mm of 24 hours, width 40mm, length 40mm in vacuum-drying is set to Wo, the scale that can measure to ± 0.1mg is used to weigh, in temperature: 85 DEG C, relative humidity: in the constant temperature and humidity cabinet of 85%, carry out one week humidification.After humidification, wipe attached aqueous vapor on the test specimen, the sample scale that can measure to ± 0.1mg is weighed, is set to W.Water-intake rate is calculated by following formula (3).Prepare 3 identical test samples, similarly test.
Wo/W × 100=water-intake rate (%) (3)
(11) pencil hardness
According to JISK5400, use pencil test machine to measure to be cured as the pencil hardness of test film of flat board of thickness 1.0mm, width 40mm, length 40mm.By pencil with the angle of 45 degree, apply the load of 1kg from top and draw stroke an about 5mm, confirming the degree of wound.Carry out 5 times measure, by found in 5 times more than 2 times wound generation 1 grade under pencil hardness be recited as pencil hardness test result.
Synthesis example 1
By dihydroxymethyl tristane diacrylate 1.6 moles (463.2mL), methacrylic acid bicyclopentyl ester 1.2 moles (254.2mL), 1,4-butylene glycol diacrylate 1.2 moles (226.3mL), 2,4-phenylbenzene-4-methyl-1-pentene 0.4 mole (95.5mL), tertiary lauryl mercaptan 2.4 moles (564.8mL), toluene 600mL put in the reactor of 3.0L, add the tert-butyl hydroperoxide-2-ethylhexanoate of 40mmol (11.5g) at 90 DEG C, make it react 2 hours 45 minutes.After polyreaction being stopped by cooling, in room temperature, reaction mixture is put in a large amount of hexanes, multipolymer is separated out.The multipolymer hexane obtained is cleaned, filters, dry, weigh, obtain copolymer A 691.0g.
The Mw of the copolymer A obtained is 34,200, Mn is 5,620, Mw/Mn is 6.1.When total acrylate amount is set to 100 % by mole, copolymer A contains the structural unit (3) 29.3 % by mole that the structural unit (1) being derived from dihydroxymethyl tristane diacrylate adds up to 39.6 % by mole, is derived from the structural unit (2) of dicyclopentylmethyl acrylate total 31.1 % by mole, is derived from 1,4 butanediol diacrylate.In addition, the end group (4) being derived from the structure of 2,4-phenylbenzene-4-methyl-1-pentene (α MSD) exists 1.8 % by mole relative to the total (total amount hereinafter referred to as total Component units) of end group (5) of structural unit (1), (2) and (3), end group (4) and the structure that is derived from tertiary lauryl mercaptan (TDM).
On the other hand, end group (5) exists 7.2 % by mole relative to the total amount of total Component units.
In addition, for copolymer A, carry out testing relative to the solvent solubility of toluene, dimethylbenzene, THF, ethylene dichloride, methylene dichloride or chloroform, result does not all find the generation of insolubles or gel when arbitrary dissolving.
Synthesis example 2
By dihydroxymethyl tristane diacrylate 2.64 moles (764.3mL), vinylformic acid bicyclopentyl ester 0.24 mole (47.2mL), 1, 4-butylene glycol diacrylate 0.96 mole (118.0mL), vinylformic acid 2-hydroxy propyl ester 0.96 mole (118.5mL), 2, 4-phenylbenzene-4-methyl-1-pentene 0.48 mole (114.6mL), tertiary lauryl mercaptan 3.12 moles (734.3mL), toluene 720mL puts in the reactor of 3.0L, tert-butyl hydroperoxide-the 2-ethylhexanoate of 62mmol (13.9g) is added at 90 DEG C, it is made to react 2 hours 30 minutes.After polyreaction being stopped by cooling, in room temperature, reaction mixture is put in a large amount of hexanes, polymkeric substance is separated out.The polymkeric substance hexane obtained is cleaned, filters, dry, weigh, obtain multipolymer B782.2g.
Carry out the test of multipolymer B in the same manner as copolymer A, result is recorded in table 1.
Synthesis example 3
By dihydroxymethyl tristane diacrylate 0.8 mole (231.5mL), methacrylic acid bicyclopentyl ester 2.0 moles (393.4ml), 1,4-butylene glycol diacrylate 1.2 moles (226.3mL), 2,4-phenylbenzene-4-methyl-1-pentene 0.4 mole (95.5mL), tertiary lauryl mercaptan 1.6 moles (376.45mL), toluene 600mL put in the reactor of 3.0L, add the tert-butyl hydroperoxide-2-ethylhexanoate of 40mmol (11.5g) at 90 DEG C, make it react 2 hours 45 minutes.After polyreaction being stopped by cooling, in room temperature, reaction mixture is put in a large amount of hexanes, multipolymer is separated out.The multipolymer hexane obtained is cleaned, filters, dry, weigh, obtain multipolymer C536.4g (productive rate: 73.2wt%).
Carry out the test of multipolymer C in the same manner as copolymer A, result is recorded in table 1.
Synthesis example 4
Vinylstyrene 0.66 mole (94.0mL), vinyl xylene, ethyl vinyl benzene 0.0275 mole (3.9mL), 4-vinyl biphenyl 1.56 moles (281.1g), methacrylic acid 2-phenoxy ethyl 0.88 mole (167.1mL), toluene 610mL are dropped in the reactor of 3.0L, add the Anaesthetie Ether complex compound of the boron trifluoride of 50mmol at 50 DEG C, make it react 4 hours 30 minutes.After polyreaction being stopped with sodium bicarbonate aqueous solution, clean 5 oil reservoirs with pure water, in room temperature, reaction mixture is devoted in a large amount of methyl alcohol, polymer is separated out.Make the polymer dissolution obtained after toluene, carry out redeposition with methyl alcohol, after repeating 3 these operations, by granular solid polymer washed with methanol, filter, dry, weigh, obtain multipolymer D258.3g.
Carry out the test of multipolymer D in the same manner as copolymer A, result is recorded in table 1.
Synthesis example 5
Vinylstyrene 0.44 mole (62.7mL), vinyl xylene, ethyl vinyl benzene 0.0183 mole (2.6mL), 4-vinyl biphenyl 1.76 moles (317.2g), methacrylic acid 2-phenoxy ethyl 0.66 mole (125.3mL), toluene 610mL are dropped in the reactor of 3.0L, add the Anaesthetie Ether complex compound of the boron trifluoride of 50mmol at 50 DEG C, make it react 4 hours 30 minutes.After polyreaction being stopped with sodium bicarbonate aqueous solution, clean 5 oil reservoirs with pure water, in room temperature, reaction mixture is devoted in a large amount of methyl alcohol, polymer is separated out.Make the polymer dissolution obtained after toluene, carry out redeposition with methyl alcohol, after repeating 3 these operations, by granular solid polymer washed with methanol, filter, dry, weigh, obtain multipolymer E250.6g.
Carry out the test of multipolymer E in the same manner as copolymer A, result is recorded in table 1.
Synthesis example 6
Vinylstyrene 0.27 mole (38.5mL), vinyl xylene, ethyl vinyl benzene 0.063 mole (9.0mL), 2-vinyl naphthalene 0.567 mole (87.4g), methacrylic acid 2-phenoxy ethyl 0.36 mole (68.4mL), toluene 250mL are dropped in the reactor of 1.0L, add the Anaesthetie Ether complex compound of the boron trifluoride of 18mmol at 50 DEG C, make it react 4 hours 00 minute.After polyreaction being stopped with sodium bicarbonate aqueous solution, clean 5 oil reservoirs with pure water, in room temperature, reaction mixture is devoted in a large amount of methyl alcohol, polymer is separated out.Make the polymer dissolution obtained after toluene, carry out redeposition with methyl alcohol, after repeating 3 these operations, by granular solid polymer washed with methanol, filter, dry, weigh, obtain multipolymer F85.3g.
Carry out the test of multipolymer F in the same manner as copolymer A, result is recorded in table 1.
Embodiment 1 ~ 7 and comparative example 1 ~ 4
Coordinate each composition (numeral is for weight part) with the ratio shown in table 2, add the AdekastabAO-600.1 weight part as Co., Ltd. Adeka of stablizer and obtain curable resin composition.Then, by above-mentioned various test methods, this curable resin composition solidified and carry out performance evaluation.Evaluation results is shown in table 3.
The abbreviation used in table is shown in following.
BZ: benzyl methacrylate (simple function)
Two [4-2 (-acryloyloxyethoxy) phenyl] fluorenes of BPEF:9,9-(2 officials' energy)
Two [4-3 (-acryloxy propoxy--2-hydroxyl) phenyl] fluorenes of BPFEA:9,9-(2 officials' energy)
BPA:BPA-2EO-dimethacrylate
19NDA:1,9-nonanediol diacrylate (2 officials' energy)
TMP: trimethylolpropane trimethacrylate (3 officials' energy)
DPHA: dipentaerythritol acrylate (6 officials' energy)
PerbutylO: tert-butyl hydroperoxide-2-ethylhexanoate (NOF Corp's system)
IRGACURE184:1-hydroxy-cyclohexyl-phenyl-one (BASF AG's system)
[table 1]
[table 2]
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| (A) composition | ||||||||||
| Copolymer A | 20 | 90 | ||||||||
| Multipolymer B | 10 | |||||||||
| Multipolymer C | 20 | |||||||||
| Multipolymer D | 30 | 40 | 10 | |||||||
| Multipolymer E | 20 | |||||||||
| Multipolymer F | 30 | |||||||||
| (B) composition | ||||||||||
| BPEF | 60 | 40 | 60 | 10 | 60 | 30 | 5 | 15 | 50 | 5 |
| BPFEA | 20 | 10 | ||||||||
| (D) composition | ||||||||||
| BZ | 10 | 20 | 5 | 20 | 15 | 10 | 30 | 25 | 20 | 5 |
| BPA | 10 | 10 | 10 | 20 | 10 | 20 | 50 | 30 | ||
| 19NDA | 5 | |||||||||
| TMP | 10 | 5 | 5 | 5 | ||||||
| DPHA | 5 | 10 | ||||||||
| Add up to | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| (C) composition | ||||||||||
| Perbutyl O | 1 | 1 | 1 | 1 | 1 | 1 | 1 | |||
| IRGACURE 184 | 1 | 1 | 1 | 1 |
[table 3]
※ comparative example 3, owing to being high viscosity, therefore cannot be shaped.
Claims (7)
1. a curable resin composition, is characterized in that, it contains:
(A) composition: there is multiple reactive unsaturated group, weight-average molecular weight is 2,000 ~ 100,000, and then dissolve in toluene, dimethylbenzene, tetrahydrofuran (THF), ethylene dichloride or chloroform, the monomer making to have 2 reactive unsaturated groups and the monomer copolymerization with 1 reactive unsaturated group and the multi-functional copolymers that obtains;
(B) composition: (methyl) acrylate with fluorene skeleton shown in general formula (1);
And (C) composition: initiator,
Relative to the content of (A) composition of the total of (A) ~ (C) composition be 5.0 ~ 94wt%, the content of (B) composition be the content of 5.0 ~ 94wt% and (C) composition is 0.1 ~ 10wt%,
In formula, R
1and R
2represent H or CH independently
3-, R
3and R
4expression-CH independently
2o-,-CH
2cH
2o-,-CH
2cH (CH
3) O-,-CH
2cH
2cH
2o-,-CH
2cH (OH) CH
2o-or CH
2cH (OR
5) CH
2o-, R
5for (methyl) acryl, k and l represent the number of more than 0 or 1 independently, but k+l is the number of more than 1, m and n represents the number of 0 ~ 4 independently.
2. curable resin composition according to claim 1, it is characterized in that, (A) multi-functional copolymers of composition is will containing having aromatic nucleus, or the simple function of alicyclic structure (methyl) acrylate (a), 2 officials' energy (methyl) acrylate (b) of more than a kind, 2, the composition copolymerization of 4-phenylbenzene-4-methyl-1-pentene (c) and mercaptan compound (d) and the multipolymer that obtains, for having reactive (methyl) acrylic being derived from 2 officials' energy (methyl) acrylate (b) at side chain, have at end and be derived from 2, the multi-functional copolymers of the structural unit of 4-phenylbenzene-4-methyl-1-pentene (c) and mercaptan compound (d).
3. curable resin composition according to claim 1, it is characterized in that, (A) multi-functional copolymers of composition is: single-ethenyl aromatic compound (e), di vinyl aromatic compounds of group (f) and the copolymerization of fragrant family ether compound are obtained, there is at side chain the reaction-ity ethylene base being derived from di vinyl aromatic compounds of group (f), its end on average every 1 molecule has the multi-functional copolymers being derived from the structural unit of fragrant family ether compound shown in more than 1 following formula (2)
In formula, R
6represent H or CH
3, R
7expression can contain the alkyl of the carbonatoms 1 ~ 18 of Sauerstoffatom or sulphur atom.
4. curable resin composition according to claims 1 to 3, it is characterized in that, except above-mentioned (A), (B), (C) beyond composition, also containing (methyl) acrylate in the molecule with 1 ~ 8 (methyl) acryl as (D) composition, wherein, be equivalent to above-mentioned (A), (B) except the situation of composition, be 5.0 ~ 84wt% relative to the content of (A) composition of the total of (A) ~ (D) composition, (B) content of composition is 5.0 ~ 84wt%, and the content of (C) composition is 0.1 ~ 10wt%, (D) content of composition is 10 ~ 70wt%, and be 30 ~ 90wt% relative to the use level of (A) composition of total 100 weight part of (A) ~ (D) composition and the total of (B) composition.
5. a resin cured matter, is characterized in that, the curable resin composition solidification according to any one of Claims 1 to 4 is obtained.
6. an optical article, is characterized in that, is formed with resin cured matter according to claim 5.
7. optical article according to claim 6, is characterized in that, optical article is optical lens.
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| KR (1) | KR20150134398A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108690166A (en) * | 2017-04-05 | 2018-10-23 | 宁波激智科技股份有限公司 | A kind of flexible diffusion particle of high refractive index and preparation method thereof and a kind of optical thin film |
| TWI706963B (en) * | 2015-12-28 | 2020-10-11 | 日商日鐵化學材料股份有限公司 | Soluble polyfunctional vinyl aromatic copolymer, its production method, hardenable composition and its application |
| CN112745463A (en) * | 2019-10-31 | 2021-05-04 | 威斯坦(厦门)实业有限公司 | Light-cured resin and preparation method thereof |
| TWI782688B (en) * | 2021-09-02 | 2022-11-01 | 財團法人工業技術研究院 | Polymer, polymer composition, and solar cell module |
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| JP6582413B2 (en) * | 2014-01-16 | 2019-10-02 | 三菱ケミカル株式会社 | Curable resin composition, cured product, optical member and optical device |
| CN106660953B (en) * | 2014-07-22 | 2020-07-28 | 沙特基础工业全球技术有限公司 | High heat resistant monomers and methods of use thereof |
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| JP2008094987A (en) * | 2006-10-13 | 2008-04-24 | Nippon Kayaku Co Ltd | Resin composition with high refractive index for optical material and its cured article |
| CN101965373A (en) * | 2008-03-04 | 2011-02-02 | 新日铁化学株式会社 | Polyfunctional vinyl aromatic copolymer, process for producing the same, and resin composition |
| CN102822217A (en) * | 2010-02-26 | 2012-12-12 | 新日铁化学株式会社 | Curable resin composition, cured article thereof, and optical material |
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| JP2000136220A (en) * | 1998-10-30 | 2000-05-16 | Kureha Chem Ind Co Ltd | Optical material made from synthetic resin and its production |
| CN100564349C (en) * | 2003-10-01 | 2009-12-02 | 大阪瓦斯株式会社 | Multifunctional (methyl) acrylate and preparation method thereof |
| JP2011039165A (en) * | 2009-08-07 | 2011-02-24 | Hitachi Chem Co Ltd | Alkali-soluble photocurable composition, cured coating film using the composition and transparent member |
| JP5760522B2 (en) * | 2011-03-07 | 2015-08-12 | 帝人株式会社 | PHOTOCURABLE RESIN COMPOSITION, ARTICLE HAVING CURED CURTAIN THEREOF, AND PRODUCTION METHOD THEREFOR |
| JP6158084B2 (en) * | 2011-08-11 | 2017-07-05 | 大阪ガスケミカル株式会社 | Multifunctional (meth) acrylate having fluorene skeleton and curable composition thereof |
| JP5898551B2 (en) * | 2012-03-29 | 2016-04-06 | 富士フイルム株式会社 | Semi-cured product, cured product and production method thereof, optical component, cured resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008094987A (en) * | 2006-10-13 | 2008-04-24 | Nippon Kayaku Co Ltd | Resin composition with high refractive index for optical material and its cured article |
| CN101965373A (en) * | 2008-03-04 | 2011-02-02 | 新日铁化学株式会社 | Polyfunctional vinyl aromatic copolymer, process for producing the same, and resin composition |
| CN102822217A (en) * | 2010-02-26 | 2012-12-12 | 新日铁化学株式会社 | Curable resin composition, cured article thereof, and optical material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| TWI706963B (en) * | 2015-12-28 | 2020-10-11 | 日商日鐵化學材料股份有限公司 | Soluble polyfunctional vinyl aromatic copolymer, its production method, hardenable composition and its application |
| CN108690166A (en) * | 2017-04-05 | 2018-10-23 | 宁波激智科技股份有限公司 | A kind of flexible diffusion particle of high refractive index and preparation method thereof and a kind of optical thin film |
| CN112745463A (en) * | 2019-10-31 | 2021-05-04 | 威斯坦(厦门)实业有限公司 | Light-cured resin and preparation method thereof |
| CN112745463B (en) * | 2019-10-31 | 2023-11-03 | 威斯坦(厦门)实业有限公司 | Photo-curing resin and preparation method thereof |
| TWI782688B (en) * | 2021-09-02 | 2022-11-01 | 財團法人工業技術研究院 | Polymer, polymer composition, and solar cell module |
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| JP6525867B2 (en) | 2019-06-05 |
| JPWO2014157131A1 (en) | 2017-02-16 |
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