CN103172803A - Curable resin composition, cured article and optical artical - Google Patents
Curable resin composition, cured article and optical artical Download PDFInfo
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- CN103172803A CN103172803A CN2012105723328A CN201210572332A CN103172803A CN 103172803 A CN103172803 A CN 103172803A CN 2012105723328 A CN2012105723328 A CN 2012105723328A CN 201210572332 A CN201210572332 A CN 201210572332A CN 103172803 A CN103172803 A CN 103172803A
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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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
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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
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
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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 provides a curable resin composition and a cured article thereof, wherein excellent optical characteristic, heat resistance, precise metal mould transfer-printing performance are provided, and the curable resin composition is excellent material for preparing an optical lens and a prism. The curable resin composition contains 20 to 80 wt% of a component (A) which has a plurality of reactive unsaturated group, Mw is 2000 to 100000 and the toluene and so on can be dissolved in solvent soluble multi-functional co-polymers; 5.0 to 50 wt% of the (B) component the [R1SiO 3/2 ] n, wherein R1 is provided with methyl propylene acyl organic functional groups, n is 10 or 8 or 12 and the organic polymer silsesquioxane as main component of organic silicon resin; 5.0 to 75wt % of a component (C) is in the molecule have 1 to 6 methyl propylene acyl of methyl acrylic ester; and 0.1 to 10 wt% d of the ingredient (D) which is the initiator.
Description
Technical field
The curable resin composition, cured article and the optical article that the present invention relates to have specific refractory power, the good release property when optical characteristics, thermotolerance and the processibility of the excellence such as high light line transmitance and the optical characteristics under the such harsh actual service conditions of wet heat condition, low water absorbable and shaping, accurate metal die transfer printing and surface hardness are improved.
Background technology
All the time, use the thermoplastic resins such as comparatively cheap polycarbonate resin, methacrylic resin, ester ring type olefin polymer in the optical fields such as camera use lens (camera lens).But heat resisting temperature, the surface hardness of these thermoplastic resins are low, almost are not used in the sophisticated technology field of the light-electronic material of the thermotolerance, surface hardness and the microfabrication that require height.
Method as the shortcoming that solves this thermoplastic polymer, patent documentation 1 discloses a kind of soluble polyfunctional (methyl) acrylate copolymer, it obtains by can (methyl) acrylate with single-ethenyl aromatic compound and 2 officials carrying out copolymerization, side chain have contain can (methyl) acrylate from 2 officials the acrylate-based structural unit of reactivity (methyl).Yet, the soluble polyfunctional acrylate copolymer that obtains although utilize technology disclosed herein to the thermal process under high temperature also have excellent thermotolerance, excellent on the required processibility in leading-edge field, but do not reach the material of the hardness of height.
And then, disclose a kind of organosilicon resin composition in patent documentation 2 and 3, it is combined with the organic poly sesquisiloxane that has cagelike structure in the structural unit as the silicone resin of principal constituent and can forms with above-mentioned silicone resin the unsaturated compound of free-radical polymerized thing.And, the characteristic that the composition that utilizes this technology to obtain has kept the silicone resins such as optical characteristics, thermotolerance, weathering resistance such as the transparency to have, but the precision of the optical surface shape in the optical lens purposes, toughness aspect and insufficient.Therefore, also do not have so far excellent optical characteristics, possess the balance of properties such as low water absorbable, plasticity, thermotolerance, surface hardness and the optical characteristics under the such harsh actual service conditions of wet heat condition and with the adaptation of inorganic materials, and the soluble polyfunctional multipolymer that is improved of the transfer printing of the precision of metal die shape and the curable resin composition that has used this multipolymer.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2008-247978 communique
Patent documentation 2: No. the 4558643rd, Japanese Patent
Patent documentation 3: TOHKEMY 2009-109579 communique
Summary of the invention
The technical problem that invention will solve
the object of the present invention is to provide and have specific refractory power, the optical characteristics that high light line transmitance etc. are excellent, thermotolerance and processibility, and the optical characteristics under the such harsh actual service conditions of wet heat condition, good release property when low water absorbable and shaping, traumatic resistance, toughness, surface hardness and accurate metal die transfer printing are improved contains soluble polyfunctional multipolymer (A) and has the curable resin composition that the silicone resin (B) of acryl forms, cured article and optical article.
The means that are used for the technical solution problem
The present invention relates to a kind of curable resin composition, it contains following (A) ~ (D) composition, (A) content of composition be the use level of 20 ~ 80wt%, (B) composition be the use level of 5.0 ~ 50wt%, (C) composition be 5.0 ~ 75wt% and (D) use level of composition be 0.1 ~ 10wt%, and (A) composition is 20.0 ~ 96.0 weight parts with respect to the use level of total 100 weight parts of (A) ~ (D) composition.
(A) composition: have a plurality of reactive unsaturated groups, weight-average molecular weight and be 2000 ~ 100000 and in toluene, dimethylbenzene, tetrahydrofuran (THF), ethylene dichloride or chloroform soluble soluble polyfunctional multipolymer.
(B) composition: the silicone resin take the organic poly sesquisiloxane shown in general formula (1) as principal constituent.
[R
1SiO
3/2]
n (1)
(wherein, R
1For having the organo-functional group of (methyl) acryl, n is 8,10 or 12.)
(C) composition: (methyl) acrylate that has 1 ~ 6 (methyl) acryls in molecule.
(D) composition: initiator.
As (A) composition, can preferably enumerate following soluble polyfunctional multipolymer (A-1) or (A-2).
(A-1): by containing simple function (methyl) acrylate (a) with ester ring type structure, 2 officials' energy (methyl) acrylate (b) more than a kind, 2, the composition of 4-phenylbenzene-4-methyl-1-pentene (c) and mercaptan compound (d) carries out copolymerization and the multipolymer that obtains, its side chain have from 2 officials can (methyl) acrylate reactivity (methyl) acrylic of (b), have endways from 2, the structural unit of 4-phenylbenzene-4-methyl-1-pentene (c) and mercaptan compound (d), and be that weight-average molecular weight is 2000 ~ 60000, and at toluene, dimethylbenzene, tetrahydrofuran (THF), soluble soluble polyfunctional multipolymer in ethylene dichloride or chloroform.
(A-2): by with single-ethenyl aromatic compound (e), divinyl aromatics (f) and fragrant family ether compound carry out copolymerization and obtain, and has reaction-ity ethylene base from the divinyl aromatics at side chain, having average every 1 molecule at its end is the multipolymer from the structural unit of fragrant family ether compound shown in following formula (3) more than 1, and be that the weight-average molecular weight of this multipolymer is 2000 ~ 100000, molecular weight distribution (Mw/Mn) is below 50.0, and at toluene, dimethylbenzene, tetrahydrofuran (THF), soluble soluble polyfunctional multipolymer in ethylene dichloride or chloroform.
(wherein, R
2That the carbonatoms that can contain Sauerstoffatom or sulphur atom is 1 ~ 18 alkyl, R
3Expression hydrogen or methyl.)
As (B) composition; can preferably enumerate following silicone resin: it is to issue the unboiled water solution and react and make its part condensation, make the further silicone resin that obtains of condensation again under non-polar solvent and basic catalyst existence of the hydrolysate that obtains by the silicon compound shown in following general formula (4) is existed at polar solvent and basic catalyst, and in molecule, the Siliciumatom number equates with (methyl) acryloyl radix and has a cagelike structure.
R
1SiX
3 (4)
(wherein, R
1Identical with the implication in general formula (1), X represents hydrolization group.)
In addition, the invention still further relates to above-mentioned curable resin composition is solidified and obtain as the resin cured matter of feature and the optical article that is formed by this resin cured matter.As described optical article, optical lens, microlens array and camera head are arranged.
The invention effect
Curable resin composition of the present invention or make its curing and the resin cured matter that obtains has excellent optical characteristics, thermotolerance and processibility, and good release property, traumatic resistance, toughness, surface hardness and accurate metal die transfer printing when the optical characteristics under the such harsh actual service conditions of Reflow Soldering (reflow) condition, low water absorbable and shaping 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.At first, to describing as (A) ~ (D) composition that must components matching.
(A) of the present invention composition use have a plurality of reactive unsaturated link(age)s, weight-average molecular weight be 2000 ~ 100000 and in toluene, dimethylbenzene, tetrahydrofuran (THF), ethylene dichloride or chloroform soluble soluble polyfunctional multipolymer.Below, sometimes will be as the soluble polyfunctional multipolymer of (A) composition referred to as multipolymer.
As above-mentioned multipolymer, preferably use multipolymer (A-1) or (A-2).
multipolymer (A-1) is simple function (methyl) acrylate (a) that has the ester ring type structure by containing, 2 officials' energy (methyl) acrylate (b) more than a kind, 2, the composition of 4-phenylbenzene-4-methyl-1-pentene (c) and mercaptan compound (d) carries out copolymerization and the multipolymer that obtains, its side chain have from 2 officials can (methyl) acrylate reactivity (methyl) acrylic of (b), have endways from 2, the structural unit of 4-phenylbenzene-4-methyl-1-pentene (c) and mercaptan compound (d), and be that weight-average molecular weight is 2000 ~ 100000, and at toluene, dimethylbenzene, tetrahydrofuran (THF), soluble soluble polyfunctional multipolymer in ethylene dichloride or chloroform.
multipolymer (A-2) is by with single-ethenyl aromatic compound (e), divinyl aromatics (f) and fragrant family ether compound carry out copolymerization and obtain, has reaction-ity ethylene base from the divinyl aromatics at side chain, having average every 1 molecule at its end is the multipolymer from the structural unit of fragrant family ether compound shown in above-mentioned formula (3) more than 1, and be that the weight-average molecular weight of this multipolymer is 2000 ~ 100000, molecular weight distribution (Mw/Mn) is below 50.0, and at toluene, dimethylbenzene, tetrahydrofuran (THF), soluble soluble polyfunctional multipolymer in ethylene dichloride or chloroform.
(A) composition is the soluble polyfunctional multipolymer, and solubility refers in toluene, dimethylbenzene, tetrahydrofuran (THF), ethylene dichloride or chloroform solvable.Preferably all solvable in above-mentioned whole solvents.The test of solubility is carried out under the condition shown in embodiment.
About the multipolymer of (A) composition, carry out copolymerization by mainly containing the monomer component that 2 officials such as the simple function composition such as mono-vinyl compound and divinyl compound can compositions, can advantageously obtain.2 officials can compositions give branched structure or crosslinking structure, but the amount of this crosslinking structure is subject to showing the restriction of the degree of solubility.The end of branched structure contains the unreacted unsaturated group from 2 officials' energy compositions such as divinyl compounds.Therefore, formed side chain have can compositions from 2 officials unreacted (methyl) acrylic or the multipolymer of the unsaturated group such as vinyl.This unreacted unsaturated group because it shows polymerizability, therefore carries out polymerization by further aggregation processing also referred to as hanging (methyl) acrylic or hanging vinyl etc., can form the resin cured matter that is insoluble to solvent.Unreacted unsaturated group on average needs to be preferably more than 3 more than 2 in every 1 molecule.In order to improve the ratio of unreacted unsaturated group, can be by increasing by usage quantity that 2 officials can compositions, realizing with chain-transfer agent etc.
The synthetic middle simple function with ester ring type structure (methyl) acrylate (a) that uses as multipolymer (A-1), can enumerate and be selected from isobornyl methacrylate, isobornyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, vinylformic acid two cyclopentenes esters, vinylformic acid two cyclopentenes oxygen base ethyl esters, vinylformic acid two cyclopentyl esters, methacrylic acid two cyclopentenes oxygen base ethyl esters, reach the simple function with ester ring type structure (methyl) acrylate more than a kind in methacrylic acid two cyclopentyl esters, but be not limited to these.
as 2 officials' energy (methyl) acrylate (b), can use cyclohexane dimethanol diacrylate, dihydroxymethyl tristane diacrylate, the cyclohexanedimethanol dimethacrylate, dihydroxymethyl tristane dimethacrylate, glycol diacrylate, propylene glycol diacrylate, 1, the 4-butylene glycol diacrylate, hexanediyl ester, diethylene glycol diacrylate, 1, the 4-butylene glycol dimethacrylate, hexanediol dimethacrylate, 2 officials' energy (methyl) acrylate such as Diethylene Glycol dimethacrylate, but be not limited to these.
Preferred object lesson as 2 officials' energy (methyl) acrylate (b), consider preferred cyclohexanedimethanol two (methyl) acrylate and dihydroxymethyl tristane two (methyl) acrylate with alicyclic structure that use from the easiness of cost, polymerization control and the stable on heating aspect of resulting polymkeric substance.In addition, consider from the aspect of the shaping processabilities such as the toughness of cured article, release property, preferred use does not have 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) are controlled the molecular weight of multipolymer as chain-transfer agent performance function.The molecular weight of multipolymer of the present invention is counted 2000 ~ 100000 scope, is preferably 2500 ~ 60000, more preferably 3000 ~ 50000 scope with weight-average molecular weight Mw (Mw is the weight-average molecular weight of using the polystyrene standard of gel permeation chromatography to convert here).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), so long as the known mercaptan compound that plays the chain-transfer agent effect gets final product, but be preferably uncle's lauryl mercaptan, n-dodecyl mercaptan, tert octyl mercaptan, n-octyl mercaptan, trimethylolpropane tris-3-mercaptopropionic acid ester, tetramethylolmethane four-3-mercaptopropionic acid ester, Dipentaerythritol six-3-mercaptopropionic acid ester and (3-[(3-sulfydryl propionyloxy)-ethyl]-isocyanuric acid ester) etc.Wherein, the viewpoint of the toughness of the easiness of controlling from polymerization, the multipolymer that generates, what particularly preferably use is that the carbonatomss such as uncle's lauryl mercaptan, n-dodecyl mercaptan, tert octyl mercaptan, n-octyl mercaptan are 5 ~ 30 monoalkyl mercaptan.
Multipolymer (A-2) also has from the structural unit shown in the above-mentioned formula (3) of fragrant family ether compound (following also referred to as structural unit (g)) except having from the structural unit of single-ethenyl aromatic compound (e) and the structural unit from divinyl aromatics (f).And, the end group shown in above-mentioned formula (3) is called end group (g).And, the polymeric chain of multipolymer on preferred general (main chain and side chain) by divinyl aromatics and single-ethenyl aromatic compound produce, the part of end produces by fragrant family ether compound.
As the fragrant family ether compound of giving structural unit (g) or end group (g), can (methyl) vinylformic acid 2-phenoxy ethyl, (methyl) vinylformic acid alcoxyl base 2-phenoxy ethyl be shown preference.But, be not limited to these.From reactive, the thermotolerance of cured article, the viewpoint of acquisition easiness, further preferred (methyl) vinylformic acid 2-phenoxy ethyl.(methyl) vinylformic acid 2-phenoxy ethyl etc. is given the compound of end group (g) owing to having polymerizable group, therefore can with other monomer copolymerization, but in order to form end group (g), preferably: polymerizable group reactive low, most residual with unreacted state, the structure of reaction has occured in the vinyl that formation divinyl aromatics (f) etc. has and its phenyl ring.
In above-mentioned formula (3), R
2Be that the carbonatoms that can contain Sauerstoffatom and sulphur atom is 1 ~ 18 alkyl, preferred carbonatoms is 1 ~ 4 alkyl.R
3Be hydrogen or methyl, but they are decided by the fragrant family ether compound that uses.Preferred R
2For-C
nH
2n-shown in group.Here, n is preferably 1 ~ 6 scope.
As single-ethenyl aromatic compound (e), use contain 50mol% above, be preferably that 70mol% is above, the above single-ethenyl aromatic compound that is selected from the vinyl aromatic compounds more than a kind in vinylbenzene, vinyl xylene, ethyl vinyl benzene, vinyl biphenyl and vinyl naphthalene of 85mol% more preferably.
In addition, single-ethenyl aromatic compound (e) can also contain the single-ethenyl aromatic compound except above-mentioned, preferably can contain a small amount of lower than 50mol.As the example of these single-ethenyl aromatic compounds, there is the core alkyl to replace single-ethenyl aromatic compound, alpha-alkyl replacement single-ethenyl aromatic compound, β-alkyl-substituted styrene, alkoxy substituted ethene etc.For gelation, solvability, the processibility of improvement in solvent that prevents multipolymer, from cost and obtain the viewpoint of easiness, vinylbenzene, vinyl xylene, ethyl vinyl benzene (meta-and p-both isomer), ethyl vinyl biphenyl (comprising each isomer) are particularly suitable for.
Example as divinyl aromatics (f), can use Vinylstyrene (meta-and p-both isomer), divinyl naphthalene (comprising each isomer), divinyl biphenyl (comprising each isomer) etc., but be not limited to these.In addition, they can be used singly or in combination more than 2 kinds.Particularly from cost and obtain the viewpoint of easiness, the preferred Vinylstyrene (meta-and p-both isomer) that uses, when requiring higher thermotolerance, preferably use divinyl naphthalene (comprising each isomer), divinyl biphenyl (comprising each isomer).
The Mw of the multipolymer that uses in the present invention is 2000 ~ 100000 scope, is preferably 2500 ~ 60000, more preferably 3000 ~ 50000 scope.Lower than 2000 the time, because the viscosity of multipolymer is too low, so processibility can reduce, and when Mw surpasses 100000, easily generates gel as Mw, and consistency is undesirable.The value of molecular weight distribution (Mw/Mn) is below 50.0, be preferably below 20.0, more preferably 1.5 ~ 3.0.When Mw/Mn surpassed 50.0, the processing characteristics that can produce multipolymer was deteriorated, the problem such as gel occurs.
Therefore the multipolymer that uses in the present invention can carry out copolymerization with (methyl) acrylic compound because end is acrylate modified by (methyl), very high with the consistency of (methyl) acrylic compound and resin.Therefore, when making itself and (methyl) acrylate carry out copolymerization and it is solidified, evenly solidified nature and the transparency are excellent.
The multipolymer of (A) composition that uses in the present invention can obtain according to the method shown in patent documentation 1, TOHKEMY 2004-123873 communique, No. 2005-213443, TOHKEMY, TOHKEMY 2010-229263 communique etc.
Then, the silicone resin that (B) composition as curable resin composition of the present invention is used describes.
(B) composition is the silicone resin that is made of the organic poly sesquisiloxane shown in above-mentioned general formula (1).In general formula (1), R
1For organo-functional group, the n with (methyl) acryl is that 8,10 or 12 composition is principal constituent.Here, more than principal constituent refers to account for 50wt%, consider from the aspect of viscosity, degree of crosslinking, more than being preferably 70wt%.As the composition except above-mentioned, be that n is the composition of the even number more than 14.Silicone resin preferably has cagelike structure, should have cagelike structure more than above, the preferred 70wt% of 50wt%.
As R
1, can enumerate the group shown in following general formula (5) as preferred example.
(in formula, m is 1 ~ 3 integer, R
5Be hydrogen atom or methyl.)
The silicone resin that the silicone resin that is made of the organic poly sesquisiloxane shown in above-mentioned general formula (1) preferably obtains by following method: make the silicon compound shown in above-mentioned general formula (4) issue the reaction of unboiled water solution at polar solvent and basic catalyst existence, make simultaneously its part condensation, make the further condensation again under non-polar solvent and basic catalyst existence of resulting hydrolysate; And described silicone resin is the silicone resin that in molecule, Siliciumatom number and (methyl) acryloyl radix equate and have cagelike structure.In general formula (4), R
1Identical with the implication in general formula (1), be the organo-functional group with (methyl) acryl.X represents hydrolization group.
(B) silicone resin of composition (B) on the contrary by making the low siloxane backbone part of the outside that reactive functional groups extend out to cage and the consistency of organic compound be incorporated into inboard to cage, therefore thereby form doubtful micellar structure, can mix with ratio arbitrarily with unsaturated compounds such as Acrylic Acid Monomer, oligopolymer.
Has reactive functional groups on the Siliciumatom of cage modle organic poly sesquisiloxane in molecule shown in general formula (1).Be the concrete structure of 8,10,12 cage modle organic poly sesquisiloxane as the n in general formula (1), can enumerate the cagelike structure body shown in following structural formula (6), (7) and (8).In addition, the R in following formula represent with general formula (1) in R
1Identical group.
(B) silicone resin of composition can obtain according to the method shown in TOHKEMY 2004-143449 communique etc.In addition, as silicone resin, so long as the organic poly sesquisiloxane shown in general formula (1) gets final product, can be the ladder type organic poly sesquisiloxane except the cage modle organic poly sesquisiloxane.In addition, be above-mentioned extraneous other silicone resin although can contain n in general formula (1), in n was organic poly sesquisiloxane 8 or more, n was that above-mentioned extraneous other silicone resin is below 50wt%, is preferably below 30wt%.Usually, because the silicone resin of the large high molecular of n is difficult to generate, so in general formula (1), n is that composition 20 below should account for the major part more than 90wt%.
(C) composition uses 1 ~ 6 official's energy (methyl) acrylate.Wherein, (methyl) acrylate that has (methyl) acryl more than 2 in molecule is called multifunctional (methyl) acrylate, preferably uses one kind or two or more multifunctional (methyl) acrylate.Advantageously (C) composition should on average have 2 ~ 5 (methyl) acryls in every 1 molecule.Here; the number of (methyl) acryl that every 1 molecule is average calculates with total (methyl) acryloyl radix/total molecule number; total molecule number is calculated with the total with (methyl) more than 1 acrylate-based (methyl) acrylate, but (A) composition and (B) composition and their contained (methyl) acryls are got rid of from calculate.
These polyfunctional acrylic esters that use as (C) compositions by with (A) composition and (B) composition and use, not only improve synergistically thermotolerance and surface hardness, and the optical characteristics such as low dispersion, high light line transmitance improve simultaneously also.
as above-mentioned multifunctional (methyl) acrylate, be preferably and can reach (B) multifunctional (methyl) acrylate of composition copolymerization with (A) composition, for example 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, ethoxylated trimethylolpropane three (methyl) acrylate (trimethylol propane ethoxy tri (meth) 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 (acryloxy ethyl) isocyanuric acid ester, Dipentaerythritol five (methyl) acrylate, tripentaerythritol six (methyl) acrylate, tripentaerythritol five (methyl) acrylate, hydroxypivalic acid neopentyl glycol two (methyl) acrylate, two (methyl) acrylate of the 6-caprolactone affixture of hydroxypivalic acid neopentyl glycol (Nippon Kayaku K. K's system for example, KAYARAD HX-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, particularly preferably can 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, preferably can enumerate cyclohexanedimethanol two (methyl) acrylate, dihydroxymethyl tristane two (methyl) acrylate.
In addition; as (C) composition; also can use the simple function more than a kind (methyl) acrylate that has 1 (methyl) acryl in molecule; these simple functions (methyl) acrylate is by also using with (A) composition, (B) composition and multifunctional (methyl) acrylate; high dispersion or the optical characteristics such as low dispersion, high light line transmitance are improved simultaneously, also can improve plasticity by improving mobility.as the simple function that can be used as above-mentioned copolymer composition (C) (methyl) acrylate, the preferred simple function with ester ring type structure (methyl) acrylate (a) that uses for the manufacture of the multipolymer of conduct (A) composition for example also can be enumerated acryloyl morpholine in addition, (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 4-hydroxyl butyl ester, polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate, hexanaphthene-Isosorbide-5-Nitrae-dimethanol list (methyl) acrylate, (methyl) vinylformic acid tetrahydro furfuryl ester, (methyl) vinylformic acid phenoxy ethyl, phenyl polyethoxye (methyl) acrylate, 2-hydroxyl-3-phenyl oxygen base propyl group (methyl) acrylate, orthoxenol monosubstituted ethoxy (methyl) acrylate, orthoxenol polyethoxye (methyl) acrylate, to cumyl phenoxy group ethyl (methyl) acrylate, (methyl) isobornyl acrylate, tribromo phenyl oxygen base ethyl (methyl) acrylate, (methyl) vinylformic acid two cyclopentyl esters, (methyl) vinylformic acid two cyclopentenes esters, (methyl) vinylformic acid two cyclopentenes oxygen base ethyl esters etc.
Be polymerization starter as (D) composition, as long as use Photoepolymerizationinitiater initiater or thermal polymerization.Here, as Photoepolymerizationinitiater initiater, can preferably use the compounds such as methyl phenyl ketone system, bitter almond oil camphor system, benzophenone series, thioxanthone system, acylphosphine oxide system.Particularly; can Trichloroacetophenon, diethoxy acetophenone, 1-phenyl-2-hydroxy-2-methyl propane-1-ketone, 1-hydroxycyclohexylphenylketone, 2-methyl isophthalic acid-(4-methyl thio-phenyl)-2-morpholino propane-1-ketone, benzoin methylether, benzyl dimethyl ketal, benzophenone, thioxanthone, 2 be shown example; 4,6-trimethylbenzoyl diphenyl phosphine oxide, methyl benzoylformate, camphorphorone, benzil, anthraquinone, tetramethyldiaminobenzophenone etc.In addition, also can and use light-initiated auxiliary agent or the sensitizing agent of bringing into play effect with the Photoepolymerizationinitiater initiater combination.These Photoepolymerizationinitiater initiaters can use separately, also can be mixed with two or more.
In addition; as the thermal polymerization that uses for above-mentioned purpose, can preferably use 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.Particularly, can cyclohexanone peroxide, 1 be shown example, two (the tertiary butyl six peroxidation) pimelinketone of 1-, cumene hydroperoxide, dicumyl peroxide, benzoyl peroxide, di-isopropyl superoxide, tert-butyl hydroperoxide-2-ethylhexanoate etc., but be not limited to this.In addition, these thermal polymerizations can use separately, also can be mixed with two or more.
About curable resin composition of the present invention, (A) content of composition is that the use level of 20 ~ 80wt%, (B) composition is that the use level of 5.0 ~ 50wt%, (C) composition is that 5.0 ~ 75wt%, (D) composition are 0.1 ~ 10wt%, and (A) use level of composition, (B) composition, (C) composition, (D) composition need to satisfy the weight ratio of formula (2).The weight ratio of preferred formula (2) is 0.3 ~ 0.5 scope.
0.2≤[(A)]/[(A)+(B)+(C)+(D)]≤0.96 (2)
When the use level of (A) composition during lower than 20wt%, because the precision of the optical surface shape of molding reduces and not preferred, when the use level of (A) composition surpassed 80wt%, along with the rising of viscosity, plasticity significantly reduced, thereby not preferred.On the other hand, not preferred because the surface hardness of cured article reduces when the use level of (B) composition during lower than 5.0wt%, when surpassing 50wt% and use, the toughness drop of cured article produces the crackle, the disappearance that are shaped, thereby not preferred.And then during lower than 5.0wt%, along with the rising of viscosity, plasticity significantly reduces, thereby not preferred when the use level of (C) composition, and is when surpassing 50wt% and use, not preferred because the form accuracy of lens reduces.In addition, when containing organic solvent and weighting material in curable resin composition, after being got rid of, it calculates above-mentioned content.
In addition, for curable resin composition of the present invention, also can add as required stopper, antioxidant, releasing agent, light sensitizer, organic solvent, silane coupling agent, flow agent, defoamer, antistatic agent and UV light absorber, photostabilizer, inorganic or organic various weighting material, mould inhibitor, antiseptic-germicide etc. in curable resin composition of the present invention, thereby give respectively the functional of target.
Curable resin composition of the present invention can by with above-mentioned (A) composition, (B) composition, (C) composition, (D) composition and as required other composition of use mix in any order to obtain.Curable resin composition of the present invention through the time stable.
Curable resin composition of the present invention can make its curing by heating or rayed.When being shaped by heating, its forming temperature can be according to the selection of thermal polymerization and is selected in the wider range of room temperature to 200 ℃ left and right.
When it is shaped, can obtain cured article by irradiation ultraviolet radiation isoreactivity energy-ray.Here, the object lesson of the light source that uses when being cured as the irradiation active energy beam, such as can enumerate xenon lamp, carbon arc, germicidal lamp, ultraviolet ray with luminescent lamp, duplicate with high voltage mercury lamp, medium pressure mercury lamp, high voltage mercury lamp, ultrahigh pressure mercury lamp, electrodeless lamp, metal halide lamp or utilize the electron rays etc. on sweep type, the acceleration of curtain type electron rays road.In addition, when by uviolizing, curable resin composition of the present invention being solidified, solidify required ultraviolet irradiation amount and be preferably 300 ~ 20000mJ/cm
2The left and right.In addition, in order fully resin combination to be solidified, preferably make its curing in the inertness gas atmospheres such as nitrogen.
Curable resin composition of the present invention can be used in the casting forming spares such as plastic lens.Making method as the plastic lens that has used resin combination of the present invention, following method etc. is arranged: utilize the gasket seal that consisted of by polyvinyl chloride, ethylene vinyl acetate copolymer etc. and 2 ribbons of desired shape to make moulds, after injecting wherein resin combination of the present invention, irradiation ultraviolet radiation isoreactivity energy-ray solidifies resin combination, and cured article is peeled off from mould.
In addition, as curable resin composition of the present invention is coated the method for membranaceous base material with resin combination as the prismatic lens sheet material, can use the whole bag of tricks well known in the art.as concrete method, for example can enumerate following method: resin combination is coated on the metal die of shape that the surface has prismatic lens, the layer of resin combination is set, on this resin combination layer with the water white membranaceous base material of the mode crimping that does not enter bubble (polyvinyl chloride for example, polystyrene, polycarbonate, poly-(methyl) acrylate, polyester, polyethylene terephthalate etc.), then after the layer that uses the high voltage mercury lamp radiation ultraviolet ray with resin combination under this state from membranaceous base material side solidifies, the membranaceous base material that has formed the resin layer of prismatic lens shape is peeled off from metal die.
The resin cured matter that curable resin composition of the present invention is formed, solidifies and obtains is excellent as optical material or optical article.Particularly useful with material as optical plastic lenss such as prismatic lens sheet material, Fresnel lens, biconvex lens, eyeglass lens, non-spherical lenses.And such lens can advantageously be applied to camera head.In addition, curable resin composition or resin cured matter also can be used for CD, optical fiber, optical waveguides etc. in addition in optoelectronic purposes, printing-ink, coating, transparent coating agent, glazing varnish etc.
Embodiment
Then, by embodiment, the present invention is described, but the present invention is not limited to these.In addition, the part in each example is weight part unless otherwise specified.In addition, about the mensuration of the softening temperature in embodiment etc., carry out the sample preparation and measure by method shown below.
(physical property measurement of multipolymer and cured article thereof)
1) molecular weight of polymkeric substance and molecular weight distribution
About molecular weight and the molecular weight distribution determination of soluble polyfunctional multipolymer, use GPC (eastern Cao's system, HLC-8120GPC), (THF), flow are measured as 1.0ml/min, column temperature as 40 ℃ take solvent as tetrahydrofuran (THF).About the molecular weight of multipolymer, use the calibration curve that utilizes monodisperse polystyrene, measure as the polystyrene conversion molecular weight.
2) structure of polymkeric substance
Use NEC JNM-LA600 type processed nucleus magnetic resonance light-dividing device, by
13C-NMR reaches
1H-NMR analyzes to identify.Use chloroform-dl as solvent, use the resonance line of tetramethylsilane as interior mark.
3) mensuration of the mensuration of solvent resistance and solvent solubility
Mensuration about solvent resistance, will be under 200 ℃ to multipolymer carry out that 1 hour vacuum pressed is shaped and the sample board that obtains at room temperature impregnated in toluene in 10 minutes, the variation of the sample after the Visual Confirmation dipping, by being categorized as zero: unchanged, △: swelling, *: distortion, expansion are arranged, solvent resistance is estimated.
About the mensuration of solvent solubility, multipolymer 5g is joined in the solvent of 100ml, observe the dissolving situation after stirring 10 minutes under 25 ℃.The situation of dissolving equably and have no the existence of insolubles and gel is judged as 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, wide for 50mm, long be to reserve the gap that thickness is 1.0mm between 2 sheet glass of 1.0mm for 50mm, thickness, with Kapton Tape, periphery is wound around and is fixed, inject composition in the glass mold that obtains thus, by 1) utilize the above-mentioned high voltage mercury lamp radiation ultraviolet ray several seconds from the single face of this glass mold; Perhaps 2) replace this glass mold and use SUS metal sheet processed to make same test film die for manufacturing, be placed in the rare gas element baking oven under stream of nitrogen gas, heating is 1 hour under 180 ℃, thereby makes its curing.With the resin board after solidifying from glass mold or the metal die demoulding, as sample.Specific refractory power and Abbe number with Abbe refractometer (ATAGO Co., Ltd. system) working sample.
(2) tone
With color colour-difference meter (commodity be called " MODELTC-8600 ", Tokyo electricity look Co., Ltd. system) to thickness be 1.0mm, wide for 40mm, longly measure for the flat board of 40mm, its YI value is shown.
(3) mist degree (turbidity) and total light penetration
It is 1.0mm, wide test film for 40mm, long flat board for 40mm that making is solidified into thickness, uses integrating sphere type light penetration determinator (Japanese electric look company system, SZ-Σ 90) to measure its mist degree (turbidity) and total light penetration.
(4) release property
To be solidified into thickness be that 1.0mm, wide resin for 40mm, long flat board for the 40mm difficulty during from the metal die demoulding is estimated by making.
Zero: good from the release property of metal die
△: the demoulding is slightly had any problem
*: the demoulding is difficult or have mould residual
(5) mould circulation ratio
Be that 0.6mm, diameter are that surface shape and the resin of resin layer of the spherical lens shape of 3.0mm estimated to the leakage in the gap of metal die by being solidified into thickness.
Zero: circulation ratio is good
*: circulation ratio is bad
(6) overlap, leakage
By to be solidified into thickness be that 0.6mm, diameter are that size and the resin of the overlap that produces beyond the goods part during from the metal die demoulding of the resin of spherical lens shape of 3.0mm estimated to the leak degree in the gap of metal die making.
Zero: the growing amount of overlap is less than 0.05mm, resin to the leakage in metal die gap less than 1.0mm
△: the growing amount of overlap is that 0.05mm is above and less than 0.2mm, resin is more than 1.0mm and less than 3.0mm to the leakage in metal die gap
*: the growing amount of overlap is more than 0.02mm, and resin is more than 3.0mm to the leakage in metal die gap
(7) bubble
By to be solidified into thickness be that 0.6mm, diameter are that the resin of spherical lens shape of 3.0mm partly has the degree of bubble-free generation and Air Bubble Size to estimate at molding during from the metal die demoulding making.
Zero: do not observe the generation of bubble
△: the size of generation, bubble of observing bubble with respect to the volume of molding less than 2%
*: the size of observing generation, the bubble of bubble is more than 2% with respect to the volume of molding
(8) crackle
By make be solidified into thickness be 0.6mm, diameter be the resin of spherical lens shape of 3.0mm during from the metal die demoulding goods at molding partly have the degree of flawless generation and crackle size to estimate.
Zero: do not observe the generation of crackle
△: although observe the generation of crackle, only the bight Partial Observation at the peripheral part of molding arrives
*: observe the generation of crackle, also observe beyond the bight part of the peripheral part of molding
(9) Reflow Soldering thermotolerance
With thickness be 1.0mm, wide for 40mm, long flat board for 40mm as test film, using spectral photometric colour measuring meter CM-3700d (KONICA MINOLTA company system) mensuration wavelength is the spectrophotometric transmittance of 400nm.Mensuration is before the oven test of having carried out after 200 ℃ of lower after fixing of 60 minutes and in air oven after 250 ℃ of lower oven tests of 7 minutes opportunity.The spectrophotometric transmittance that will obtain by these mensuration changes the results are shown in following table 3.
(10) water-intake rate
To be that the weight of 1.0mm, wide test film for 40mm, long flat board for 40mm is as W at the thickness of 60 ℃ of lower vacuum-dryings after 24 hours
0, with the scale that can measure to ± 0.1mg, it is carried out weighing, be that 85 ℃, relative humidity are 1 week of humidification in 85% constant temperature and humidity cabinet in temperature.After humidification, wipe the moisture that is attached to test sample, with the scale that can measure to ± 0.1mg, sample is carried out weighing, as W.Calculate water-intake rate with following formula (1).Prepare 3 identical test samples, similarly test.
W
0/ W * 100=water-intake rate
(11) pencil hardness
According to JISK5400, use pencil scraping experiment machine, measure and be solidified into the pencil hardness that thickness is 1.0mm, wide test film for 40mm, long flat board for 40mm.With the angles of 45 degree by on apply 1kg load with the pencil 5mm left and right of swiping, confirm degree of injury.Carry out 5 times and measure, the pencil hardness under 1 grade of visible damage more than 2 times in 5 times is put down in writing as the pencil hardness test result.
Synthesis example 1
With dihydroxymethyl tristane diacrylate 1.6mol (463.2ml), methacrylic acid two cyclopentyl ester 1.2mol (254.2ml), 1,4-butylene glycol diacrylate 1.2mol (226.3ml), 2, (0.4mol (95.5ml), uncle's lauryl mercaptan 2.4mol (564.8ml), toluene 600ml put in the reactor of 3.0L 4-phenylbenzene-4-methyl-1-pentene, add tert-butyl hydroperoxide-2-ethylhexanoate of 40mmol (11.5g) under 90 ℃, make its reaction 2 hours 45 minutes.By cooling polyreaction is stopped after, at room temperature reaction mixture is put in a large amount of hexanes, multipolymer is separated out.The multipolymer that obtains is washed with hexane, filter, dry, weighing, obtain the 691.0g copolymer A.
The Mw of the copolymer A that obtains is 34200, Mn is 5620, Mw/Mn is 6.1.By carrying out
13C-NMR,
1H-NMR analyzes and ultimate analysis, copolymer A contains the structural unit from 1,4 butanediol diacrylate (3) of the structural unit from dihydroxymethyl tristane diacrylate (1) that adds up to 39.6mol%, the structural unit from methacrylic acid two cyclopentyl esters (2) that adds up to 31.1mol%, 29.3mol%.In addition, there is 1.8mol% from the end group (4) of the structure of 2,4-phenylbenzene-4-methyl-1-pentene (α MSD) with respect to structural unit (1), (2) and (3) and end group (4) and from the total (hereinafter referred to as the total amount of whole Component units) of the end group (5) of the structure of uncle's lauryl mercaptan (TDM).
On the other hand, there is 7.2mol% in end group (5) with respect to the total amount of whole Component units.Copolymer A is solvable in toluene, dimethylbenzene, THF, ethylene dichloride, methylene dichloride, chloroform, has no the generation of gel.
Synthesis example 2
with dihydroxymethyl tristane diacrylate 2.64mol (764.3ml), vinylformic acid two cyclopentyl ester 0.24mol (47.2ml), 1,4-butylene glycol diacrylate 0.96mol (181.0ml), vinylformic acid 2-hydroxy propyl ester 0.96mol (118.5ml), 2,4-phenylbenzene-4-methyl-1-pentene 0.48mol (114.6ml), uncle's lauryl mercaptan 3.12mol (734.3ml), toluene 720ml puts in the reactor of 3.0L, add tert-butyl hydroperoxide-2-ethylhexanoate of 62mmol (13.9g) under 90 ℃, make its reaction 2 hours 30 minutes.By cooling polyreaction is stopped after, at room temperature reaction mixture is put in a large amount of hexanes, multipolymer is separated out.The multipolymer that obtains is washed with hexane, filter, dry, weighing, obtain 782.2g multipolymer B.
Similarly multipolymer B is tested with copolymer A, and result is recorded in table 1.
Synthesis example 3
With dihydroxymethyl tristane diacrylate 0.8mol (231.5ml), methacrylic acid two cyclopentyl ester 2.0mol (393.4ml), 1,4-butylene glycol diacrylate 1.2mol (226.3ml), 2,4-phenylbenzene-4-methyl-1-pentene 0.4mol (95.5ml), uncle's lauryl mercaptan 1.6mol (376.45ml), toluene 600ml put in the reactor of 3.0L, add tert-butyl hydroperoxide-2-ethylhexanoate of 40mmol (11.5g) under 90 ℃, make its reaction 2 hours 45 minutes.By cooling polyreaction is stopped after, at room temperature reaction mixture is put in a large amount of hexanes, multipolymer is separated out.The multipolymer that obtains is washed with hexane, filter, dry, weighing, obtain 598.5g multipolymer C.
Similarly multipolymer C is tested with copolymer A, and result is recorded in table 1.
Synthesis example 4
Vinylstyrene 0.66mol (94.0mL), vinyl xylene, ethyl vinyl benzene 0.0275mol (3.9mL), 4-vinyl biphenyl 1.56mol (281.1g), methacrylic acid 2-phenoxy ethyl 0.88mol (167.1mL), toluene 610ml are put in the reactor of 3.0L, add the etherate of the boron trifluoride of 50mmol under 50 ℃, make its reaction 4 hours 30 minutes.After with sodium bicarbonate aqueous solution, polyreaction being stopped,, at room temperature reaction mixture being put in a large amount of methyl alcohol oil reservoir washing 5 times with pure water, polymkeric substance is separated out.After the polymkeric substance that obtains is dissolved, carry out redeposition with methyl alcohol in toluene, after repeating this operation 3 times, pulverous solid polymer is washed with methyl alcohol, filter, dry, weighing, obtain 258.3g multipolymer D.
Similarly multipolymer D is tested with copolymer A, and result is recorded in table 1.
Synthesis example 5
Vinylstyrene 0.44mol (62.7mL), vinyl xylene, ethyl vinyl benzene 0.0183mol (2.6mL), 4-vinyl biphenyl 1.76mol (317.2g), methacrylic acid 2-phenoxy ethyl 0.66mol (125.3mL), toluene 610ml are put in the reactor of 3.0L, add the etherate of the boron trifluoride of 50mmol under 50 ℃, make its reaction 4 hours 30 minutes.After with sodium bicarbonate aqueous solution, polyreaction being stopped,, at room temperature reaction mixture being put in a large amount of methyl alcohol oil reservoir washing 5 times with pure water, polymkeric substance is separated out.After the polymkeric substance that obtains is dissolved, carry out redeposition with methyl alcohol in toluene, after repeating this operation 3 times, pulverous solid polymer is washed with methyl alcohol, filter, dry, weighing, obtain 250.6g multipolymer E.
Similarly multipolymer E is tested with copolymer A, and result is recorded in table 1.
Synthesis example 6
Vinylstyrene 0.27mol (38.5mL), vinyl xylene, ethyl vinyl benzene 0.063mol (9.0mL), 2-vinyl naphthalene 0.567mol (87.4g), methacrylic acid 2-phenoxy ethyl 0.36mol (68.4mL), toluene 250ml are put in the reactor of 1.0L, add the etherate of the boron trifluoride of 18mmol under 50 ℃, make its reaction 4 hours.After with sodium bicarbonate aqueous solution, polyreaction being stopped,, at room temperature reaction mixture being put in a large amount of methyl alcohol oil reservoir washing 5 times with pure water, polymkeric substance is separated out.After the polymkeric substance that obtains is dissolved, carry out redeposition with methyl alcohol in toluene, after repeating this operation 3 times, pulverous solid polymer is washed with methyl alcohol, filter, dry, weighing, obtain 85.3g multipolymer F.
Similarly multipolymer F is tested with copolymer A, and result is recorded in table 1.
Synthesis example 7
Pack in the reaction vessel that possesses agitator, dropping funnel, thermometer as 2-propyl alcohol (IPA) 40ml of solvent with as 5% tetramethylammonium hydroxide aqueous solution (the TMAH aqueous solution) of basic catalyst.Add in dropping funnel IPA and the 12.69g of 15ml the 3-methacryloxypropyl trimethoxy silane (MTMS: the eastern beautiful DOW CORNING organosilicon SZ-6300 processed of Co., Ltd.), on one side the stirring reaction container on one side at room temperature with the IPA solution of 30 minutes dropping MTMS.MTMS did not stir 2 hours after dripping and finishing heatedly.Stir after 2 hours, under reduced pressure desolventizing, 50ml dissolves with toluene.Reaction soln is washed until after reaching neutrality, dewater with anhydrous magnesium sulfate with saturated aqueous common salt.Anhydrous magnesium sulfate is filtered, by the concentrated 8.6g hydrolysate (silicone resin A) that obtains.This silsesquioxane is soluble colorless viscous liquid in various organic solvents.Reactant after condensation reaction has again been carried out mass spectroscopy after liquid chromatography is separated, confirm the molion of having ammonium ion on the molecular structure of said structure formula (6), (7) and (8), composition is T8:T10:T12: other is about 2:4:1:3, can confirm as the silicone resin (cage-type silsesquioxane A) take cagelike structure as principal constituent.In addition, T8, T10 and T12 correspond respectively to formula (6), (7) and (8).In addition, about other, be that n is 14,16 etc. high molecular body in general formula 1, be below 5% but n surpasses 20 composition.
Embodiment 1 ~ 7 and comparative example 1 ~ 4
With each components matching (numeral is weight part), the ADK STAB AO-60 of Asahi Denka Co., Ltd.'s system of interpolation 0.1 weight part obtains curable resin composition as stablizer in the ratio shown in table 2.Then, this curable resin composition is cured by above-mentioned various test methods, carries out performance evaluation.Evaluation results is shown in table 3.
The abbreviation that uses in table below is shown.
19NDA:1,9-nonanediol diacrylate (2 officials' energy)
BZ: benzyl methacrylate
DPHA: dipentaerythritol acrylate (6 officials' energy)
TMPTA: Viscoat 295 (3 officials' energy)
TMP: trimethylolpropane trimethacrylate (3 officials' energy)
DMTCD: dihydroxymethyl tristane diacrylate (2 officials' energy)
BPEF:(9, two [4-2 (acryloyl-oxy base oxethyl) phenyl] fluorenes of 9-) (2 officials' energy)
PERBUTYL O: tert-butyl hydroperoxide-2-ethylhexanoate (NOF Corp's system)
Irgacure 184:1-hydroxyl-cyclohexyl-phenyl-ketone
Claims (7)
1. curable resin composition, it is characterized in that, contain following (A) ~ (D) composition, (A) content of composition be the use level of 20 ~ 80wt%, (B) composition be the use level of 5.0 ~ 50wt%, (C) composition be 5.0 ~ 75wt% and (D) composition be 0.1 ~ 10wt%, and (A) use level (weight ratio) of composition, (B) composition, (C) composition, (D) composition satisfies formula (2)
0.2≤[(A)]/[(A)+(B)+(C)+(D)]≤0.96 (2)
(A) composition: have a plurality of reactive unsaturated groups, weight-average molecular weight and be 2000 ~ 100000 and in toluene, dimethylbenzene, tetrahydrofuran (THF), ethylene dichloride or chloroform soluble soluble polyfunctional multipolymer;
(B) composition: the silicone resin take the organic poly sesquisiloxane shown in general formula (1) as principal constituent,
[R
1SiO
3/2]
n (1)
Wherein, R
1For having the organo-functional group of (methyl) acryl, n is 8 ~ 12 even number;
(C) composition: (methyl) acrylate that has 1 ~ 6 (methyl) acryls in molecule;
(D) composition: initiator.
2. curable resin composition according to claim 1, it is characterized in that, (A) the soluble polyfunctional multipolymer of composition is following soluble polyfunctional multipolymer: it is simple function (methyl) acrylate (a) that has the ester ring type structure by containing, 2 officials' energy (methyl) acrylate (b) more than a kind, 2, the composition of 4-phenylbenzene-4-methyl-1-pentene (c) and mercaptan compound (d) carries out copolymerization and the multipolymer that obtains, and side chain have from 2 officials can (methyl) acrylate reactivity (methyl) acrylic of (b), have endways from 2, 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) the soluble polyfunctional multipolymer of composition is following soluble polyfunctional multipolymer: it passes through single-ethenyl aromatic compound (e), divinyl aromatics (f) and fragrant family ether compound carry out copolymerization and obtain, and has reaction-ity ethylene base from divinyl aromatics (f) at side chain, having average every 1 molecule at its end is the structural unit from fragrant family ether compound shown in following formula (3) more than 1
Wherein, R
2That the carbonatoms that can contain Sauerstoffatom or sulphur atom is 1 ~ 18 alkyl, R
3Expression hydrogen or methyl.
4. curable resin composition according to claim 1, it is characterized in that, (B) silicone resin of composition is to issue the unboiled water solution and react and make its part condensation by the silicon compound shown in following general formula (4) is existed at polar solvent and basic catalyst, make the hydrolysate that obtains further condensation and the silicone resin that obtains again under non-polar solvent and basic catalyst exist, and be that in molecule, the Siliciumatom number equates with (methyl) acryloyl radix, and the silicone resin with cagelike structure
R
1SiX
3 (4)
Wherein, R
1For having the organo-functional group of (methyl) acryl, X represents hydrolization group.
5. a resin cured matter, is characterized in that, it is cured the described curable resin composition of claim 1 ~ 4 any one and obtain.
6. an optical article, is characterized in that, it is formed by curable resin cured article claimed in claim 5.
7. optical article according to claim 6, wherein, optical article is optical lens.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011283454A JP5841835B2 (en) | 2011-12-26 | 2011-12-26 | Curable resin composition, cured product and optical article |
| JP2011-283454 | 2011-12-26 |
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| JP (1) | JP5841835B2 (en) |
| KR (1) | KR101996087B1 (en) |
| CN (1) | CN103172803B (en) |
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| WO2019024254A1 (en) | 2017-08-04 | 2019-02-07 | 广东生益科技股份有限公司 | Thermosetting resin composition, and prepreg and metal foil clad laminate prepared from same |
| WO2019024255A1 (en) | 2017-08-04 | 2019-02-07 | 广东生益科技股份有限公司 | Thermosetting resin composition, and prepreg and metal foil clad laminate made therefrom |
| WO2019024253A1 (en) | 2017-08-04 | 2019-02-07 | 广东生益科技股份有限公司 | Thermosetting resin composition and prepreg and metal foil-covered laminate made using same |
| CN110651016A (en) * | 2017-05-17 | 2020-01-03 | 株式会社大赛璐 | Adhesive composition, cured product, laminate, and device |
| US12091588B2 (en) | 2017-05-17 | 2024-09-17 | Daicel Corporation | Curable composition for adhesive agents, adhesive sheet, cured article, laminate, and device |
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| JP2008038117A (en) * | 2006-08-10 | 2008-02-21 | Denki Kagaku Kogyo Kk | Resin composition and photocurable casting method |
| JP2010229263A (en) * | 2009-03-26 | 2010-10-14 | Nippon Steel Chem Co Ltd | Terminal end-modified soluble multifunctional vinyl aromatic copolymer, curable resin composition, and cured product |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110651016A (en) * | 2017-05-17 | 2020-01-03 | 株式会社大赛璐 | Adhesive composition, cured product, laminate, and device |
| CN110651016B (en) * | 2017-05-17 | 2022-06-24 | 株式会社大赛璐 | Adhesive composition, cured product, laminate, and device |
| US12091588B2 (en) | 2017-05-17 | 2024-09-17 | Daicel Corporation | Curable composition for adhesive agents, adhesive sheet, cured article, laminate, and device |
| WO2019024254A1 (en) | 2017-08-04 | 2019-02-07 | 广东生益科技股份有限公司 | Thermosetting resin composition, and prepreg and metal foil clad laminate prepared from same |
| WO2019024255A1 (en) | 2017-08-04 | 2019-02-07 | 广东生益科技股份有限公司 | Thermosetting resin composition, and prepreg and metal foil clad laminate made therefrom |
| WO2019024253A1 (en) | 2017-08-04 | 2019-02-07 | 广东生益科技股份有限公司 | Thermosetting resin composition and prepreg and metal foil-covered laminate made using same |
| US11390735B2 (en) | 2017-08-04 | 2022-07-19 | Shengyi Technology Co., Ltd. | Thermosetting resin composition and prepreg and metal foil-covered laminate made using same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103172803B (en) | 2017-10-13 |
| KR101996087B1 (en) | 2019-07-03 |
| JP5841835B2 (en) | 2016-01-13 |
| JP2013133375A (en) | 2013-07-08 |
| KR20130074760A (en) | 2013-07-04 |
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