CN105102493B - Multifunctional (methyl) acrylate copolymer, hardening resin composition and its solidfied material - Google Patents
Multifunctional (methyl) acrylate copolymer, hardening resin composition and its solidfied material Download PDFInfo
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- CN105102493B CN105102493B CN201480019936.7A CN201480019936A CN105102493B CN 105102493 B CN105102493 B CN 105102493B CN 201480019936 A CN201480019936 A CN 201480019936A CN 105102493 B CN105102493 B CN 105102493B
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- 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
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/282—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing two or more oxygen atoms
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—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 an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/32—Monomers containing only one unsaturated aliphatic radical containing two or more rings
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- 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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- 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
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
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- 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
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
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- 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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Abstract
The present invention, which is provided, has excellent optical characteristics, adaptation with inorganic material under long-term wet heat condition is not also reduced, and can be maintained multifunctional (methyl) acrylate copolymer of the optical characteristics of height and be coordinated its hardening resin composition.Multifunctional (methyl) acrylate copolymer is that will contain simple function (methyl) acrylate (a), the CH generated by the alcohol of (methyl) acrylic acid and carbon number 9~302=CR CO O R2 O OC CR=CH2Shown 2 functions (methyl) acrylate (b) and 2, copolymer obtained from the monomer class copolymerization of the amylene (c) of 4 diphenyl, 4 methyl 1, its side chain has reactive (methyl) from (b) acrylate-based, end has the construction unit from (c), and dissolves in toluene equal solvent.
Description
Technical field
The present invention relates to optical isotropy, high light line transmitance so excellent optical characteristics, heat resistance and add
Work, the heat resistance under actual service conditions harsh as the wet heat condition and is obtained with the adaptation of inorganic material in addition
Improved hardening resin composition and its solidfied material.
Background technology
The monomer that many has the unsaturated bond that there is reactivity can cause chain by selecting unsaturated bond to disconnect
The catalyst of reaction and appropriate reaction condition and generate polymer.The species of the general monomer with unsaturated bond is extremely more
Sample, therefore, the species of obtained resin it is rich also notable.But, the molecule of commonly referred to as high-molecular compound can be obtained
The species of the monomer of the HMW body of amount more than 10,000 is less.It can such as enumerate:Ethene, substituted ethylene, propylene, substitution
Propylene, styrene, ring-alkylated styrenes, alkoxystyrene, ENB, various acrylate, butadiene, cyclopentadiene, two
Cyclopentadiene, isoprene, maleic anhydride, maleimide, fumarate, allyl compound etc. are used as representational list
Body.By making these monomer homopolymerizations or their copolymerization can be synthesized into diversified resin.
The purposes of these resins is limited primarily to the field of comparatively cheap civil equipment, hardly applied in photoelectron
Sophisticated technology field as the heat resistance, dimensional stability or microfabrication of height is required in Material Field.It is used as its reason
By it is thermoplasticity that can enumerate the polymer generally synthesize by above-mentioned monomer, in addition, in order to meet mechanical characteristic and needs shape
Into suitable polymer body, therefore, required characteristic is sacrificial in sophisticated technology field as heat resistance or microfabrication
Domestic animal.
On the other hand, heat cured resin combination is for example as mechanical part material, electrical and electronic parts material, vapour
Car component materials, civil construction material, moulding material etc. are useful, in addition, also being used as the material of coating or bonding agent.And then,
If combining to form mixing material with inorganic substrate, can not only reduce coefficient of thermal expansion, can also by combine inorganic substances and
The refractive index of resin controls the outward appearance of resin combination and its solidfied material, makes the presentation transparency, therefore, is used as electric and electronic
Material in component materials or optical applications is particularly useful.For example, digital camera module is arranged on the small-sized of mobile phone etc.
Change is developed, and also requires cost degradation.And then, it is used as new purposes, vehicle-mounted camera, the bar towards family dispatching personnel
The demand more and more higher of code reading machine etc..It is heat-resisting during solder reflow soldering when not requiring nothing more than manufacture when applied to these purposes
Property, and in actual use, it is contemplated that high temperature exposure of summer etc., it is desirable to the height of prolonged heat resistance, low water absorbable etc.
Reliability.
As the method for the shortcoming for solving such vinyl based thermoplastic polymer, have disclosed in patent document 1~3
A kind of side chain has the polymer of (methyl) acryloyl group or vinyl ether group.For example, have disclosed in patent document 1 it is a kind of by
(methyl) acryloyl obtained from making the different polymerizable monomer cationic polymerizations of acrylic acid -2- ethyleneoxies ethyl ester (VEA) etc.
The photosensitive composite that base side chain type polymer and Photoepolymerizationinitiater initiater are constituted.In addition, have disclosed in patent document 2 it is a kind of by
(methyl) acryloyl side chain type polymer, the compound of unsaturated carboxyl with photoreactivity and Photoepolymerizationinitiater initiater are constituted
Photosensitive composite.And then, it is inert light to have one kind to have at its own to cationic polymerization disclosed in patent document 3
In carboxylate solvent's compound of the unsaturated group of reactivity, make acrylic acid -2- ethylene oxies using cationic polymerization catalyst
Different the polymerizable monomer homopolymerizations or copolymerization of base ethyl ester (VEA) etc. and the manufacture method for obtaining polymer solution.
But, manufactured using according to the technology for having used the different polymerizable monomers disclosed in these patent documents
Reactive polymer in the case of, cannot have both the processability required in advanced optical applications field, heat resistance,
Balance of properties as high transparency and the optical characteristics under actual service conditions harsh as wet heat condition and with
Polymer and hardening resin composition that the adaptation of inorganic material is improved.
On the other hand, have a kind of by single-ethenyl aromatic compound and 2 functions (methyl) third disclosed in patent document 4
Have obtained from olefin(e) acid ester copolymerization, in side chain containing reactive (methyl) propylene from 2 functions (methyl) acrylate
The soluble polyfunctional vinyl aromatic copolymer of the construction unit of perester radical.But, obtained by technology disclosed herein
The soluble polyfunctional vinyl aromatic copolymer arrived also has excellent resistance to pyrolytic even for the thermal history of high temperature,
Have (methyl) of reactivity acrylate-based in side chain, excellent in workability has both solvent soluble, but with scattered in low color
It can not use the restriction in such actual use in the optical lens of purposes, and not obtained with the adaptation of inorganic material
Improved material.
And then, there is one kind in methyl methacrylate (MMA) is slurries as constituent disclosed in patent document 5
The weight % of two (methyl) acrylate 1~25 of the straight-chain aliphatic dihydroxy alcohol of the carbon number 4~8 contained composition.
Moreover, the manufacture of MMA systems disclosed herein serosity combination is disclosed directly below:By MMA or MMA and can be with its copolymerization vinyl
Copolymer, chain-transferring agent are in the presence of polymerization initiator in non-active gas (such as N2Gas) in atmosphere, carry out normal temperature or
Heating polymerization.Moreover, as chain-transferring agent particular instantiation be only lauryl mercaptan, TGA octyl group ester, thiocresol,
The sulphur compound of thionaphthol, benzyl mercaptan etc., is not disclosed particularly for 2,4- diphenyl -4-methyl-1-pentene.Moreover
Do not instruct by the end group from 2,4- diphenyl -4-methyl-1-pentene and from simple function (methyl) acrylic acid yet
The generation of refractive index difference when the construction unit of ester is coexisted and synergistically can suppress damp and hot.Moreover, by being disclosed
Technology obtained from composition do not improve under actual service conditions harsh as wet heat condition with inorganic material
The adaptation of material.
In addition, having one kind disclosed in patent document 6 by vinyl monomer and two (methyl) acrylate compounds structures
Into polymerizable composition, polymerizable composition, although the use of 2,4- diphenyl -4-methyl-1-pentene also obtains disclosure, but its usage amount conduct
Common chain-transferring agent is decimal points % or so use, and solvent is not shown in the thing that product has been also cross-linked gel
It is soluble.
And then, there is a kind of colour filter hot curing resin composition disclosed in patent document 7, it includes self-curing
Copolymer and organic solvent, the self-curing copolymer contain by 1) containing epoxy radicals (methyl) acrylate, 2) hydroxyl (first
Base) acrylate, 3) (methyl) acrylic acid, 4) construction unit that constitutes of (methyl) acrylate containing aromatic group.And
And, the self-curing copolymer obtained by technology disclosed herein is in polymerization stage, in order to realize the model of desired molecular weight
Enclose, mercaptopropionic acid, mercaptopropionic acid ester, thio glycol, thioglycerin, DDM dodecyl mercaptan, α-methylstyrenedimer can be used
Deng known molecular weight regulator.However, in technology disclosed in these, having the disadvantage that:Due to not adding in polymerization
Plus vinyl compounds more than 2 functions with multiple vinyl, therefore it is only capable of in polymer chain importing the source of less than 1
From the end group of molecular weight regulator, it is impossible to fully carry out the function from end group and assign.And then, also there is following lack
Point:Thermosetting resin group is formed in the resin combination with epoxy resin by self-curing copolymer obtained from the technology
Compound, but do not cause between acrylate curing reaction, therefore cause the intensity, heat-resisting of the resin combination of cooperation
The reduction of property.
In order to solve these problems, there is a kind of soluble polyfunctional with ester ring type structure disclosed in patent document 8
(methyl) acrylate copolymer.However, in technology disclosed herein, having the disadvantage that:Under high temperature, high humidity
In long-term reliability experiment, reduced with the adaptation of inorganic material.
Therefore, so far and in the absence of with optical isotropy, high light line transmitance so excellent optical characteristics,
Possess workability, balance of properties as heat resistance, and in long-term wet heat condition so harsh actual service conditions
Under optical characteristics and the hardening resin composition that is improved with the adaptation of inorganic material.
Prior art literature
Patent document
Patent document 1:Examined patent publication 49-13212 publications
Patent document 2:Examined patent publication 51-34433 publications
Patent document 3:Examined patent publication 54-27394 publications
Patent document 4:JP 2008-247978 publications
Patent document 5:JP 57-167340 publications
Patent document 6:JP 2002-121228 publications
Patent document 7:JP 2009-1770 publications
Patent document 8:JP 2011-127008 publications
The content of the invention
Invent problem to be solved
It is an object of the invention to provide with optical isotropy, high light line transmitance so excellent optical characteristics,
In advanced technology field as workability, heat resistance, the various balance of properties required by optical material are excellent, and i.e.
The adaptation with inorganic material under long-term wet heat condition so harsh actual service conditions is not also reduced, remain high
The optical characteristics of degree, and have both new multifunctional (methyl) acrylate of the molecular weight distribution controlled and solvent soluble
Copolymer and its hardening resin composition of cooperation.
Means for solving the problems
The present invention is multifunctional (methyl) acrylate copolymer, and it makes containing the simple function (first shown in following formulas (1)
Base) acrylate (a), 2 functions (methyl) acrylate (b) shown in following formulas (2) and 2,4- diphenyl -4- methyl isophthalic acids -
The monomer class copolymerization of amylene (c) and obtain,
CH2=CR-COOR1 (1)
(in formula, R1 is that can contain aerobic original in the carbon number more than 9 and less than 30 alkyl of straight chain or side chain, alkyl
Son, sulphur atom or nitrogen-containing group.R is H or methyl.)
CH2=CR-COO-R2-OOC-CR=CH2 (2)
(in formula, R2 is carbon number more than 2 and less than 30 alkyl, containing oxygen atom, sulphur atom or can be contained in alkyl
Nitrogen groups.R is H or methyl.)
Multifunctional (methyl) acrylate copolymer is that side chain has from 2 functions (methyl) acrylate (b)
(methyl) of reactivity is acrylate-based, and end has the construction unit from 2,4- diphenyl -4-methyl-1-pentene (c)
Copolymer, weight average molecular weight is 10,000~1,000,000, the unit from (b) composition in total acrylic ester unit
Mole fraction Mb is by the unit from simple function (methyl) acrylate (a) and from 2 functions (methyl) acrylate (b)
When the import volume (mole) of unit is set to a and b, 0.01~0.5 is calculated as with b/ (a+b), and then, dissolve in toluene, diformazan
Benzene, propylene glycol monomethyl ether, tetrahydrofuran, dichloroethanes or chloroform.
In addition, the present invention is above-mentioned multifunctional (methyl) acrylate copolymer, it is characterised in that meet formula (1)
In, R1 is carbon number more than 9 and less than 30 straight-chain or aliphatic chain or glycol chain or formula with branched structure
(2) in, R2 is more than carbon number more than 2 and the aliphatic chain of less than 30 straight-chain or any of glycol chain.
In addition, the present invention is above-mentioned multifunctional (methyl) acrylate copolymer, it is characterised in that 2 will be derived from by meeting
, should when the import volume (mole) containing reactive (methyl) acrylate-based unit of function (methyl) acrylate (b) is set to b1
The mole fraction Mb1 of unit is calculated as 0.02~0.5 with b1/ (a+b) or will be derived from 2,4- diphenyl -4-methyl-1-pentene (c)
The import volume (mole) of unit when being set to c, the mole fraction Mc of the unit is calculated as 0.005~0.3 any with c/ (a+b+c)
More than kind.
And then, the present invention for a kind of hardening resin composition and by the hardening resin composition solidification, shaping and
Obtained optical article, the hardening resin composition is characterised by, contains above-mentioned multifunctional (methyl) acrylate
Copolymer, monomer and initiator with more than 1 functional group with unsaturated double-bond.
Invention effect
In accordance with the invention it is possible to provide with optical isotropy, high light line transmitance so excellent optical characteristics,
In low water absorbable, processability, advanced technology field as heat resistance, the engineering part such as optical lens prism, adhesives
Optical characteristics under the excellent and long-term wet heat condition of required various balance of properties so harsh actual service conditions
The hardening resin composition improved with the adaptation with inorganic material.
Embodiment
Multifunctional (methyl) acrylate copolymer and hardening resin composition of the present invention are described in detail.
Multifunctional (methyl) acrylate copolymer (hereinafter sometimes referred to simply as copolymer) of the present invention is to make containing single official
The monomer and 2,4- diphenyl -4-methyl-1-pentene of energy (methyl) acrylate (a) and 2 functions (methyl) acrylate (b)
(c) copolymer obtained from existing and carrying out copolymerization, is to have the reaction from 2 functions (methyl) acrylate (b) in side chain
Property (methyl) it is acrylate-based, and then end have from 2,4- diphenyl -4-methyl-1-pentene (c) construction unit
Soluble polyfunctional (methyl) acrylate copolymer.Here, so-called solubility refers in toluene, dimethylbenzene, propane diols list
It is solvable in methyl ether acetate (PGMEA), tetrahydrofuran, dichloroethanes or chloroform.Soluble experiment is in the bar shown in embodiment
Part is carried out.In addition, simple function (methyl) acrylate (a) also is referred to as into (a) composition, by 2 functions (methyl) acrylate (b)
Referred to as (b) composition and 2,4- diphenyl -4-methyl-1-pentene (c) is referred to as (c) composition or DMP.
Above-mentioned copolymer be by obtained from simple function (methyl) acrylate and 2 functions (methyl) acrylic ester copolymer,
Therefore, with branched structure or cross-linked structure, but it is related to the degree that the amount of structure is limited to display solubility.So, turn into
There is the construction unit containing unreacted (methyl) acrylic from 2 functions (methyl) acrylate (b) in side chain
(b1) copolymer.Unreacted (methyl) acrylic is also referred to as side chain (methyl) acrylic, and it is polymerize due to display
Property, therefore can be polymerize by further polymerization processing, produce the insoluble resin cured matter of solvent.
In addition, copolymer has the construction unit from (c) composition in end.By importing the knot in the end of copolymer
Structure unit, can obtain the solidfied material that the shaping processabilities such as release property are improved.
Copolymer has the construction unit (a) from (a) composition, the unit (b) from (b) composition and from (c) composition
Construction unit (c).Here, in the construction unit (b) from (b) composition, it is contained during 2 (methyl) are acrylate-based to gather
Both of conjunction property double bond (be referred to as vinyl) exist and participate in polymerization and form branched structure or the construction unit (b2) of cross-linked structure
With the knot for unreacted (methyl) acrylic for not reacting and remaining containing only 1 vinyl participation polymerization, other vinyl
Structure unit (b1).Played a role as the DMP of (c) composition as chain-transferring agent, prevent the increase of molecular weight, at the end of copolymer
End is present.Pass through to polymeric end import above range the construction unit from (c) composition, it is possible to increase release property and
Low water absorbable.(c) composition is together contained in monomer class with (a)~(b) compositions.
By the import volume (mole) of said structure unit (a), (b), (c), (b1) and (b2) in the copolymer respectively with a,
B, c, b1 and b2 are represented, their mole fraction is represented with Ma, Mb, Mc, Mb1 and Mb2 respectively.
As import volume from (c) composition to copolymer, as the mole fraction Mc shown in following formula (4) be 0.005~
0.3, preferably 0.01~0.25, particularly preferably 0.03~0.15.
Mc=c/ (a+b+c) (4)
Simple function (methyl) acrylate (a) is for improving solvent soluble, low water absorbable, heat resistance, the light of copolymer
It is important to learn characteristic and processability, is important especially for the adaptation in long-term damp heat test.It is used as such simple function (first
Base) acrylate (a), the compound shown in formula (1) can be used.It is that R1 is carbon number more than 9 and less than 30 hydrocarbon in formula
There may be the structure of the xenogenesis such as oxygen atom or nitrogen-containing group, sulphur atom atom or group in base, and alkyl.It is former there is xenogenesis
In the case of the structure of son or group, it is advantageous that there is these xenogenesis atoms or base between the carbon-carbon bond of the alkyl is constituted
The structure of group.Such as oxygen atom or sulphur atom are the structure existed in the form of ehter bond or thioether bond.In addition, being used as nitrogenous base
, there are amide groups or imide in group.
It is preferably the fat of carbon number more than 9 and less than 30 straight-chain or structure with element branches as R1
(methyl) acrylate of chain or glycol chain.Preferably CnH2nShown alkylidene chain, (C2H4O)nShown oxirane
Chain (n is more than 1 number) or the alkylidene chain and the structure of ethylene oxide chain bonding.Now, it is bonded with H in single end.Pass through
Carbon number is more than 9, and the modulus of elasticity of copolymer is reduced, and alkyl becomes many relative to the ratio of polar group, therefore, as resistance to
Aqueous excellent copolymer.And then, by the way that for straight-chain, the structure of element branches, the adaptation of low elastic modulus is further
Improve.In addition, by importing glycol chain, flexibility is improved, therefore it is preferred that.Specifically, it can enumerate:2- ethylhexyls EO changes
Property (n ≒ 2) (methyl) acrylate, (methyl) lauryl acrylate, (methyl) stearyl acrylate ester, methoxy poly (ethylene glycol) #
400 acrylate (Xin Zhong villages chemical industry (strain) company system), methoxy poly (ethylene glycol) #550 acrylate (Xin Zhong villages chemistry work
Industry (strain) company system) etc. as preferred example, among these, particularly preferred 2- ethylhexyls EO is modified (n ≒ 2) (methyl) third
The example for having aliphatic chain and glycol chain concurrently representated by olefin(e) acid ester.
In addition, as simple function (methyl) acrylate, in addition to the acrylate of above-mentioned chain, can also and with other
Simple function (methyl) acrylate (d) composition.Thus, other physical property be can adjust.Particularly have (methyl) of ring structure
Acrylate can adjust heat resistance, modulus of elasticity, dissolubility, refractive index etc. according to purposes, therefore it is preferred that.As with ring structure
Simple function (methyl) acrylate, specifically, can be enumerated:(methyl) isobornyl acrylate, the ring of (methyl) acrylic acid two
Amylene ester, (methyl) acrylic acid bicyclopentyl ester, (methyl) acrylic acid dicyclopentenyl epoxide ethyl ester and the ring of (methyl) acrylic acid two
Amyl group epoxide ethyl ester, phenoxy group polyethylene glycol acrylate, ethoxylation o-phenyl phenol acrylate, nonyl phenol EO additions
Thing acrylate.
In addition it is also possible to and simple function (methyl) acrylate with carbon number below 8, be used as these (methyl) propylene
Acid esters, can be enumerated:The positive fourth of methyl methacrylate, EMA, methyl acrylate, ethyl acrylate, acrylic acid
Ester, the own ester of acrylic acid 2- methyl, 2-EHA, 2-ethyl hexyl acrylate etc..Alternatively, it is also possible to use (methyl) acrylic acid
2- hydroxy propyl esters, (methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 3- hydroxy propyl esters, (methyl) acrylic acid 4- hydroxyl fourths
(methyl) propylene of ester, (methyl) acrylic acid 5- hydroxyls pentyl ester, the own ester of (methyl) acrylic acid 6- hydroxyls and part ethoxylation
Sour 2- hydroxy esters etc., preferably methyl methacrylate, n-butyl acrylate and 2-hydroxyethyl methacrylate.These low point
(methyl) acrylic ester monomer of son amount can be used alone, and can also use two or more.
These other construction units from monofunctional components (d) are relative to the construction unit from monofunctional components
Total amount is 60 moles of below %, in the scope for being particularly preferably located at 50 moles of below %.
Secondly, 2 functions (methyl) acrylate (b) is as making copolymer branched or being crosslinked, while producing side chain second
Alkenyl, to the copolymer assign curability, solidification when present heat resistance crosslinking component play an important role.
As 2 functions (methyl) acrylate (b), the compound shown in formula (2) can be used.It is R2 former for carbon in formula
The alkyl of subnumber more than 2 and less than 30, preferred carbon number 9~30, and there may be oxygen atom in a part for alkyl or contain
The structure of the xenogenesis such as nitrogen groups, sulphur atom atom or group.On these xenogenesis atoms or group or structure that they are replaced,
It is same with above-mentioned R1 in addition to the group of divalent that R2 carbon number is 2~30.
As 2 functions (methyl) acrylate (b) shown in formula (2), for example, it can use cyclohexanedimethanol dipropyl
Olefin(e) acid ester, dihydroxymethyl tristane diacrylate, cyclohexanedimethanol dimethylacrylate, dihydroxymethyl tristane
Dimethylacrylate, glycol diacrylate, propylene glycol diacrylate, 1,4 butanediol diacrylate, hexylene glycol
Diacrylate, diethylene glycol diacrylate, glycol diacrylate, propylene glycol diacrylate, 1,4- butanediols two
The function of methacrylate, hexanediol dimethacrylate, dimethacrylate etc. 2 (methyl) acrylic acid
Ester, but it is not limited to these.From the aspect of reactivity, dissolubility and heat resistance, particularly preferred carbon number more than 9 and
The aliphatic chain of less than 30 straight-chain or (methyl) acrylate of glycol chain.Specifically, it can enumerate:1,9- nonyls two
Alcohol two (methyl) acrylate, 2- methyl isophthalic acids, 8- ethohexadiols two (methyl) acrylate, triethylene glycol two (methyl) acrylic acid
Ester, tetraethylene glycol two (methyl) acrylate, tetradecane ethylene glycol two (methyl) acrylate, 2- butyl -2- ethyls -1,3- third
(methyl) acrylate of glycol two is used as preferred example.In addition, in addition to the acrylate of above-mentioned chain, by and with have
2 functions (methyl) acrylate of ring structure, can adjust heat resistance, modulus of elasticity, dissolubility, refractive index etc. according to purposes.Make
For 2 functions (methyl) acrylate with ring structure, specifically, it can enumerate:Dihydroxymethyl tristane two (methyl)
Acrylate, bisphenol-A EO additions two (methyl) acrylate, bisphenol-ap O additions (methyl) diacrylate etc..
Construction unit from 2 functions (methyl) acrylate (b) can include construction unit (b1) and the structure beyond it
Unit, comprising the construction unit (b) all from 2 functions (methyl) acrylate (b) including these by formula (5) calculate
Mole fraction Mb is 0.01~0.5, preferably 0.15~0.45.
Mb=b/ (a+b) (5)
Copolymer has containing reactive (methyl) acrylic acid from 2 functions (methyl) acrylate (b) in side chain
The construction unit (b1) of ester group, the mole fraction Mb1 of the construction unit (b1) shown in formula (3) is 0.02~0.5, is preferably
0.1~0.3.
Mb1=b1/ (a+b) (3)
By meeting above-mentioned mole fraction, can obtain light, heat under curability it is rich, solidification after heat resistance and machinery
The formed products of excellent.
In addition, considering from other viewpoints, copolymer contains 5~70 moles of % of construction unit from (a) composition, is derived from
(b) construction unit of composition 5~50 moles of %, preferably 7~45 moles % of %, more preferably 10~40 moles and from (c) composition
Construction unit 0.5~30 mole of %, preferably 1~25 mole %, particularly preferred 3~15 moles of %.If from (a) composition
Construction unit less than 5 moles of %, then the adaptation under moisture-proof is not enough, and it is not preferable.If from 2 functions (methyl) acrylate
(b) less than 5 moles % of construction unit, then the heat resistance of solidfied material is not enough, and it is not preferable, if in addition, the construction unit exceedes
50 moles of %, then modulus of elasticity rises, while shaping processability is reduced, the intensity of molding is significantly reduced, and it is not preferable.Separately
Outside, other total amounts of the construction unit relative to the construction unit from monofunctional components for being derived from monofunctional components (d) composition
In scope for 60 moles of below %.
Be not particularly limited as the manufacture method of copolymer, can be adjusted by way of with as defined content DMP,
Monofunctional acrylate compound and 2 functions (methyl) acrylate, use radical polymerization initiator and solvent as needed
Manufacture its polymerization in 20~200 DEG C of temperature, such as can by vaporizing extract process, with the precipitation of poor solvent it is usually used
Method is reclaimed.
The weight average molecular weight Mw of the copolymer is 10,000~1,000,000.If less than 10,000, then receipts of polymer
Rate is reduced, if more than 1,000,000, then reactivity reduction.And then, answered from high response, highly dissoluble, low viscosity, contraction
From the viewpoint of power, Mw can enumerate 20,000~500,000 as preferred scope.
The copolymer is the solubility that more than 1g is dissolved relative to above-mentioned solvent 100g.It is preferred that at 25 DEG C relative to above-mentioned
Solvent 100g dissolving more than 5g.
The hardening resin composition of the present invention contains above-mentioned multifunctional (methyl) acrylate copolymer (A), with 1
There is the monomer (B) and initiator (C) of the functional group of unsaturated double-bond above.
As the monomer (B) of the functional group with more than 1 with unsaturated double-bond, oligomer can be contained, but with it is above-mentioned
Multifunctional (methyl) acrylate copolymer (A) is different, under identical circumstances, is used as multifunctional (methyl) acrylic ester copolymer
Thing (A) is calculated.Moreover, oligomer can be homopolymer, or copolymer, molecular weight (Mw) can be less than 10000
The polymer of low molecule amount, preferably less than 6000, more preferably less than 5000, more preferably less than 1000.In addition, should
Monomer (B) can be the compound without molecular weight distribution, at this point it is possible to use multiple compounds.Preferably molecular weight is
Less than 1000 monomer.In the case where monomer is oligomer, above-mentioned molecular weight refers to Mw.In addition, with soluble polyfunctional
, can be than it in the molecular weight Mw and the Mw of copolymer (A) of monomer relation in the relation of (methyl) acrylate copolymer
It is low, it is preferably low by more than 1000.
Above-mentioned monomer (B) be with more than 1 with polymerism unsaturated double-bond functional group monomer, as with
, there are vinyl, (methyl) acryloyl group etc. in the functional group of the unsaturated double-bond of polymerism.
With more than 1, the monomer of the functional group with unsaturated double-bond is preferably (methyl) acrylate monomer.(first
Base) acrylate monomer has more than 1 (methyl) acryloyl group in the molecule, can be used one kind or two or more.These (first
Base) acrylate, by being used in combination with copolymer, can adjust the viscosity of composition in the case where not reducing curability, and it is mutually auxiliary
Ground is in addition to heat resistance, and low color is scattered, optical characteristics as high light line transmitance is improved simultaneously.In addition, can also improve solidification
Physical property as the hardness and flexibility of thing.
(methyl) acrylate monomer be molecular weight for less than 6000, preferably less than 5000, particularly less than 1000 list
Body.It is (oligomeric alternatively, it is also possible to the monomer with molecular weight distribution as polyethylene glycol two (methyl) acrylate
Thing), Mw now is less than 6000, preferably less than 5000, more preferably less than 2000, specifically for less than 1000.Have
Profit is the monomer or its mixture being made up of the compound without molecular weight distribution.
As above-mentioned (methyl) acrylate monomer, for example can preferably have ester ring type knot with copolymer (A) copolymerization
(methyl) acrylate of (methyl) acrylate of structure, more preferably simple function, 2 functions or 3 functions, more preferably single official
(methyl) acrylate of energy.In addition, the aliphatic acrylate of preferred C4~20 of (methyl) acrylate monomer is somebody's turn to do, with 1
(methyl) acrylate monomer of~3 unsaturated bonds from acrylate.Aliphatic (methyl) acrylate due to
Intermiscibility with copolymer is excellent, therefore, improves in order to mutually auxiliary with copolymer as the overall low water absorbable of composition, low bullet
Property, optical characteristics and processability are effective.In addition, urethane is modified (methyl) esters of acrylic acid or ethylene-oxide-modified (methyl)
Esters of acrylic acid is effective for the flexibility for improving solidfied material.And then, in order to improve the hardness of solidfied material, effectively 3
(methyl) acrylate monomer more than function.
As (methyl) acrylate monomer, it can enumerate:Acryloyl morpholine, (methyl) acrylic acid 2- hydroxy methacrylates, (first
Base) acrylic acid 2- hydroxy propyl esters, (methyl) acrylic acid 4- hydroxybutyls, polyethyleneglycol (methyl) acrylate, polypropylene glycol
Single (methyl) acrylate, hexamethylene -1,4- dimethanols list (methyl) acrylate, (methyl) tetrahydrofurfuryl acrylate, (first
Base) acrylate, phenyl polyethoxy (methyl) acrylate, 2- hydroxyl -3- phenoxy propyls (methyl) propylene
Acid esters, o-phenyl phenol monosubstituted ethoxy (methyl) acrylate, o-phenyl phenol polyethoxy (methyl) acrylate, to cumyl
Phenoxyethyl (methyl) acrylate, (methyl) isobornyl acrylate, tribromophenoxy ethyl (methyl) acrylate,
(methyl) acrylic acid bicyclopentyl ester, (methyl) acrylic acid dicyclopentenyl ester, (methyl) acrylic acid dicyclopentenyl epoxide ethyl ester, 1,
4- butanediols two (methyl) acrylate, 1,6-HD two (methyl) acrylate, 1,9- nonanediols two (methyl) acrylic acid
(such as SARTOMER is public for ester, Tricyclodecane Dimethanol (methyl) acrylate, bisphenol-A polyethoxy two (methyl) acrylate
The system of department, SR-349, SR-348 etc.), polymer with bis phenol A propoxyl group two (methyl) acrylate, Bisphenol F polyethoxy two (methyl) propylene
Acid esters, ethylene glycol two (methyl) acrylate, trimethylolpropane tris epoxide ethyl (methyl) acrylate, three (2- hydroxyl second
Base) isocyanuric acid ester three (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylic acid
Ester, polyethylene glycol two (methyl) acrylate (such as SARTOMER company systems, SR-344, SR-268), three (acryloxies
Ethyl) isocyanuric acid ester, pentaerythrite four (methyl) acrylate, dipentaerythritol six (methyl) acrylate, two seasons penta 4
Alcohol five (methyl) acrylate, tripentaerythritol six (methyl) acrylate, tripentaerythritol five (methyl) acrylate, hydroxyl
Two (methyl) third of pivalic acid neopentyl glycol two (methyl) acrylate, the 6-caprolactone addition product of 3-hydroxypivalic acid neopentyl glycol
Olefin(e) acid ester (such as Japanese chemical drug (strain) system, KAYARAD HX-220, HX-620), trimethylolpropane tris (methyl) acrylic acid
Ester, trimethylolpropane polyethoxy three (methyl) acrylate, two (trimethylolpropane) four (methyl) acrylate, urethane
The monomer classes such as modified (methyl) acrylate (such as Daicel-Cytec (strain) systems, EBACRYL8405, EBACRYL8402 etc.).
Can particularly preferably it enumerate:1,6-HD two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, three hydroxyl first
Base propane three epoxide ethyl (methyl) acrylate, pentaerythrite three (methyl) acrylate, dipentaerythritol six (methyl) third
Olefin(e) acid ester, urethane are modified (methyl) acrylate, bisphenol-A polyethoxy two (methyl) acrylate, ethylene glycol two (methyl) third
Olefin(e) acid ester.
The hardening resin composition of the present invention contains polymerization initiator, preferably Photoepolymerizationinitiater initiater.The solidification of the present invention
Property resin combination even if for thermal polymerization also it is formable, solidification, but will the optical materials such as lens shaping, solidification in the case of,
Advantageously the photocuring of shape can be closely controlled, it would thus be advantageous to add Photoepolymerizationinitiater initiater.
As Photoepolymerizationinitiater initiater, for example, it can enumerate:Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin
The benzoin class such as propyl ether, benzoin isobutyl ether;Acetophenone, 2,2- diethoxy -2- phenyl acetophenones, 2,2- diethoxies
Base -2- phenyl acetophenones, 1,1- dichloroacetophenones, 2- hydroxy-2-methyls-phenyl-propane -1- ketone, diethoxy acetophenone, 1-
The acetophenones such as hydroxycyclohexylphenylketone, 2- methyl isophthalic acids-[4- (methyl mercapto) phenyl] -2- morpholino propane -1- ketone;2- ethyls
The Anthraquinones such as anthraquinone, 2- tert-butyl groups anthraquinone, 2- chloroanthraquinones, 2- amyl anthraquinones;2,4- diethyl thioxanthones, 2- isopropylthioxanthones
The thioxanthene ketone class such as ketone, CTX;The ketal class such as acetophenone dimethyl ketal, benzyl dimethyl ketal;Benzophenone, 4- benzene
The benzophenones such as the double methylamino benzophenone of formoxyl -4'- dimethyl diphenyl sulfides, 4,4'-;2,4,6- trimethylbenzene first
Phosphinoxides such as acyl group diphenyl phosphine oxide, double (2,4,6- trimethylbenzoyls)-phenyl phosphine oxides etc..
These can be used individually or in the form of mixture of more than two kinds, and then can be with triethanolamine, methyl diethyl
The tertiary amines such as hydramine, N, N- dimethyl amino benzoates, N, the benzoic acid derivative such as N- dimethylaminobenzoic acid isopentyl ester
It is applied in combination Deng accelerator etc..
The hardening resin composition of the present invention contains above-mentioned copolymer, has the official of unsaturated double-bond with more than 1
The monomer and initiator that can be rolled into a ball are as required composition, and its content ratio is as described below.The use level of monomer relative to copolymer and
Total 100 parts by weight of the use level of monomer are 90~30 parts by weight, preferably 80~30 parts by weight, more preferably 60~
45 parts by weight.And then, total 100 parts by weight of use level of the use level relative to copolymer and monomer of initiator are 0.1~
10 parts by weight, preferably 1.0~5 parts by weight.
By compounding ratio in above-mentioned scope, it can synergistically improve formability seen by release property or curability and resistance to
Hot and optical characteristics balance of properties.If in addition, initiator is very few, easily producing solidification deficiency, heat resistance and light resistance
Reduction, if excessively, mechanical strength reduction, or heat resistance reduction.In addition, containing organic solvent in hardening resin composition
And in the case of filler, above-mentioned content is calculated in addition to them.
In addition, in the hardening resin composition of the present invention, can also be as needed in the curable resin of the present invention
In composition add polymerization inhibitor, antioxidant, releasing agent, sensitising agent, organic solvent, silane coupler, levelling agent, defoamer,
Antistatic agent and ultra-violet absorber, light stabilizer, inorganic, organic various fillers, mould inhibitor, antiseptic etc., are assigned respective
Target functionality.
The hardening resin composition of the present invention can by with random order mix above-mentioned copolymer, monomer and initiator with
And as needed other compositions and obtain.The hardening resin composition of the present invention through when it is stable.
The hardening resin composition of the present invention can obtain solidfied material by irradiation ultraviolet radiation isoreactivity energy line.
This, as the concrete example of light source used in irradiation active energy ray in the case of being solidified, for example, can enumerate xenon
Lamp, carbon arc lamp, bactericidal lamp, ultraviolet fluorescent lamp, duplicating high-pressure mercury-vapor lamp, middle medium pressure mercury lamp, high-pressure mercury-vapor lamp, super-pressure
Electron beam that mercury vapor lamp, Non-polarized lamp, metal halide lamp or sweep type, curtain electron-beam accelerator are produced etc..In addition,
In the case that by irradiation ultraviolet radiation, the hardening resin composition of the present invention is solidified, the ultraviolet irradiation needed for solidification
Measure as 300~20000mJ/cm2Left and right.In addition, in order to which resin combination is cured sufficiently, preferably in non-live such as nitrogen
Irradiation ultraviolet radiation isoreactivity energy line in property gas atmosphere.
Resin cured matter obtained from the hardening resin composition of the present invention is formed, solidify is used as prism, saturating
The optical materials such as mirror are excellent.It is especially used as that adhesive linkage is very useful, shows that the mutual bonding of optical material under resistance to wet environment is excellent
Effect.In addition, also serving as the optical plastic lens material such as prismatic lens, Fresnel Lenses, biconvex lens.
During using hardening resin composition laminating polarizing coating of the invention and protection board, receptor 1 activity energy line is not passed through
Property excellent alkali-free glass system or quartz glass etc. protection board limitation, even if being the big acrylic panel of ultraviolet radiation absorption, poly-
The protection board of carbonic ester etc., also due to the good reaction curability of said composition and use may.
The hardening resin composition of the present invention is using applying devices such as roll coater, spin coater, silk screen print methods to be bonded
Agent thickness is coated on the base materials such as polarizing coating and protection board of fitting for 1~100 μm of mode, by ultraviolet from the top of protection board
Irradiation is solidified, and thus can be bonded it.
Embodiment
Secondly, by embodiment, the present invention will be described, but the present invention is not limited to these embodiments.In addition, each
Part in example is parts by weight.In addition, the measure of softening temperature in embodiment etc. passes through method progress sample as shown below
Prepare and determine.
1) molecular weight and molecular weight distribution of polymer
Using GPC (eastern Cao HLC-8120GPC), in solvent:Tetrahydrofuran (THF), flow:1.0ml/min, column temperature:
The molecular weight and molecular weight distribution determination of multifunctional (methyl) acrylate copolymer of 40 DEG C of progress.The molecular weight of copolymer is used
Standard curve by the use of monodisperse polystyrene, it is measured as polystyrene conversion molecular weight.
2) structure of polymer
Using JEOL JNM-LA600 type nuclear magnetic resonance light-dividing devices, pass through13C-NMR and1H-NMR analyses are carried out
It is determined that.Using chloroform-d1 as solvent, the resonance line of tetramethylsilane is used as internal standard.
3) solvent soluble and the measure of gel generation
The deliquescent measure of polyfunctional vinyl aromatic copolymer makes sample 2g be dissolved in various solvents (toluene, two
Toluene, propylene glycol monomethyl ether, tetrahydrofuran, dichloroethanes or chloroform) 10g and the visual sample after observation dissolving
The transparency, by being categorized as zero:Transparent, △:Translucent, ×:It is opaque or undissolved carry out deliquescent evaluation.Separately
Outside, while also visually confirming the generation of gel, evaluation whether there is gel.
4) sample determined is prepared and determined
Multifunctional (methyl) acrylate copolymer is dissolved in PGMEA and coordinated and is used as thermal polymerization
Perbutyl O (Japanese grease system), by the varnish coating using hardening resin composition on the glass substrate, in nitrogen stream
Under make after it dries, under nitrogen flowing with 200 DEG C/1h to be solidified, make the thick measure of 200um and try with 100 DEG C/10min
Sample.It is positioned in DMA (dynamic viscoelastic analytical equipment) to determine in device, under nitrogen flowing with 10 DEG C/min of programming rate
It is scanned, is thus measured from 20 DEG C to 150 DEG C, the modulus of elasticity of sample is obtained by the value for the E ' for reading 30 DEG C.
5) thermogravimetric amount decrement and the measure of resistance to thermochromism
Sample is arranged at by the heat decomposition temperature of multifunctional (methyl) acrylate copolymer and the measure of resistance to thermochromism
TGA (thermobalance) is determined in device, and under stream of nitrogen gas, with programming rate, 10 DEG C/min from 30 DEG C to 320 DEG C are scanned,
Thus it is measured, obtains 300 DEG C of weight decrement, while visually confirming the change colo(u)r specification of the sample after determining, passes through classification
For ◎:There is no thermo-color, zero:Faint yellow, △:Dark brown, ×:Black carries out the evaluation of resistance to thermochromism.
6) measure of refractive index
Multifunctional (methyl) acrylate copolymer is dissolved in toluene, added thereto relative to soluble polyfunctional
The parts by weight of (methyl) acrylate copolymer 100 are used as initiator for the Perbutyl O of 1.0 parts by weight.By the polymer solution
Casting sheet material is made, the casting sheet material is crushed, is granulated, is filled in pressing mold, it is solidified with pressure forming machine at 170 DEG C
1 hour.Using the obtained parallel flat that have cured as test specimen, d rays are determined with KPR-200 (Shimadzu Calnew company systems)
The refractive index of (587.6nm).Be set to during tester just shaping after (initial stage), 85 DEG C × 85RH wet heat condition it is hot and humid
Put into device after 1 time-of-week (after damp and hot).
7) moisture absorption fitness test
The varnish for being diluted copolymer with PGMEA is coated with the glass substrate, its drying 10 minutes is made at 100 DEG C, so
200 DEG C, 1 hour are carried out in inert gas baking oven (inert oven), under stream of nitrogen gas afterwards to solidify.Then, according to JIS K
5400 will be placed with the glass substrate of the film that copolymer have cured forms longitudinal and transverse 11 on the surface of film with 1mm interval
Joint-cutting, makes 100 gridiron patterns.After the closely sealed cellophane tape in its surface, counted when peeling without a break and do not peel off and remain
The number (initial stage) of grid.And then, wiped after the glass substrate for being placed with film is impregnated into the stipulated time in 85 DEG C of hot water
The water on surface, again in the closely sealed cellophane tape in surface, counts the number (leaching for the grid do not peeled off and remained after peeling without a break
After stain).
The abbreviation of the raw material used is shown in following.
DMTCD:Dihydroxymethyl tristane diacrylate
NDDA:1,9- nonanediol diacrylates
BDDA:1,4 butanediol diacrylate
HOP:Acrylic acid 2- hydroxy propyl esters
HO:2-hydroxyethyl methacrylate
EHDGA:2- ethylhexyls EO (n ≒ 2) modification acrylate
LA:Lauryl acrylate
LM:Lauryl methacrylate
nBA:N-butyl acrylate
DCPA:Acrylic acid bicyclopentyl ester
αMSD:2,4- diphenyl -4-methyl-1-pentene
DDME:N-dodecyl mercaptan
Embodiment 1
By NDDA252.35g, DCPA309.42g, EHDGA544.76g, HOP65.07g, α MSD222.32g, toluene
In 700ml inputs 3.0L reactor, 65.60mmol benzoyl peroxide is added at 85 DEG C, it is reacted 2 hours.Pass through
Cooling makes after polymerisation stopping, being put into reaction mixture in substantial amounts of methanol in room temperature, separates out polymer.It will obtain
Polymer cleaned with methanol, filter, dry, weigh, obtain copolymer A 431.1g (yields:31wt%).
The Mw of obtained copolymer A is that 117,234, Mn is that 20,874, Mw/Mn is 5.6.By carrying out13C-NMR、1H-
NMR is analyzed and elementary analysis, and copolymer A contains the construction unit from NDDA and adds up to 11.8 moles of %, structures from DCPA
Unit adds up to 30.1 moles of %, 49.7 moles of % of construction unit from EHDGA, 9.4 moles of % of construction unit from HOP.
In addition, there are 2.7 moles of % in the end group of the structure from α MSD.In addition, construction unit from esters of acrylic acid rubs
Construction unit from total esters of acrylic acid is set to 100 and calculated by your point rate, and α MSD etc. mole fraction is total for that will be derived from
Esters of acrylic acid+α MSD etc. construction unit be set to 100 calculated obtained from value.Mb1 is mole of pendent acrylate
Divide rate, the construction unit from total esters of acrylic acid is set to 100 and calculated.
Copolymer A dissolves in toluene, dimethylbenzene, THF, dichloroethanes, dichloromethane, chloroform, and the generation of gel is not found.
In addition, the cast membrane of copolymer A is without muddy transparent film.
Embodiment 2,3 and comparative example 1,2
Using 2 various functional acrylic esters, simple function (methyl) esters of acrylic acid with shown in table 1 raw material composition with
Embodiment 1 is similarly polymerize.
The usage amount of the raw material used in reaction is shown in table 1, the result of the test of copolymer and its solidfied material is shown in table
2.Unless otherwise specified, then other reaction conditions and condition determination are same as Example 1.In table 1, raw material usage amount with
Mole and weight (g) represent that the form of record is set to mol/g.
[table 1]
Usage amount mol/g | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 |
DMTCD | 0.75/228.3 | 1.6/487.0 | 1.8/547.9 | ||
NDDA | 1.0/252.4 | 0.75/189.3 | 0.3/75.7 | ||
BDDA | 0.3/59.5 | 1.2/237.9 | 0.3/59.5 | ||
HOP | 0.5/65.1 | 0.3/39.0 | |||
HO | 0.6/69.7 | ||||
EHDGA | 2.0/544.8 | ||||
LA | 2.0/480.8 | ||||
LM | 2.4/610.6 | ||||
nBA | 2.4/307.6 | ||||
DCPA | 1.5/309.4 | 1.5/309.4 | 1.2/247.5 | 0.6/123.8 | |
αMSD | 1.0/222.3 | 0.06/13.9 | 0.6/133.4 | 2.8/622.5 | 1.0/202.4 |
DDME | 0.44/88.6 | 1.0/222.3 |
[table 2]
Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | |
Mw | 117,234 | 25,500 | 92,000 | 21,190 | 12,500 |
Mn | 20,874 | 8,526 | 26,000 | 5,752 | 3,640 |
Mw/Mn | 5.6 | 3.0 | 3.5 | 3.7 | 3.43 |
DMTCD ratios | 15.3% | 40.1% | 78.2% | ||
NDDA ratios | 20.8% | 15.1% | 5.2% | 2.1% | |
BDDA ratios | 5.4% | 30.0% | |||
EHDGA ratios | 39.7% | ||||
LA ratios | 39.6% | ||||
LM ratios | 39.8% | ||||
HOP ratios | 9.4% | 9.8% | |||
HO ratios | 9.7% | ||||
NBA ratios | 39.9% | ||||
DCPA ratios | 30.1% | 30.0% | 29.9% | 9.9% | |
α MSD ratios | 2.7% | 0.5% | 1.2% | 7.8% | 5.3% |
DDME ratios | 3.1% | 4.7% | |||
Mb1 | 14.5% | 15.9% | 10.1% | 32.2% | 31.6% |
Physical property | |||||
Solvent soluble | ○ | ○ | ○ | ○ | ○ |
Gel is generated | Nothing | Nothing | Nothing | Nothing | Nothing |
Weight reduction rates | 0.04% | 0.05% | 0.05% | 0.06% | 0.05% |
Resistance to thermo-color | ◎ | ◎ | ◎ | ○ | ◎ |
Modulus of elasticity | 0.13GPa | 0.45GPa | 0.05GPa | 2.0GPa | 2.2GPa |
Refractive index | |||||
Initial stage | 1.510 | 1.511 | 1.510 | 1.512 | 1.512 |
After damp and hot | 1.508 | 1.508 | 1.509 | 1.509 | 1.509 |
Abbe number | 52.5 | 52.3 | 52.8 | 52.5 | 52.5 |
Fitness test | |||||
Initial stage | 100/100 | 100/100 | 100/100 | 100/100 | 100/100 |
After dipping | 100/100 | 100/100 | 100/100 | 0/100 | 20/100 |
Claims (7)
1. a kind of multifunctional (methyl) acrylate copolymer, it makes containing the simple function (methyl) third shown in following formulas (1)
2 functions (methyl) acrylate (b) and 2,4- diphenyl -4-methyl-1-pentene shown in olefin(e) acid ester (a), following formulas (2)
(c) monomer class copolymerization and obtain,
CH2=CR-CO-OR1 (1)
In formula, R1 is the carbon number more than 9 and less than 30 alkyl of straight or branched, can contain oxygen atom, sulphur in alkyl
Atom or nitrogen-containing group, R be H or methyl,
CH2=CR-CO-O-R2-O-OC-CR=CH2 (2)
In formula, R2 is carbon number more than 2 and less than 30 alkyl, can contain oxygen atom, sulphur atom or nitrogenous base in alkyl
Group, R be H or methyl,
Multifunctional (methyl) acrylate copolymer is that side chain has the reaction from 2 functions (methyl) acrylate (b)
Property (methyl) acrylate-based, end has the copolymerization of the construction unit from 2,4- diphenyl -4-methyl-1-pentene (c)
Thing, weight average molecular weight is 10,000~1,000,000, the unit from (b) composition in total acrylic ester unit mole point
Rate Mb will be derived from the unit of simple function (methyl) acrylate (a) and unit from 2 functions (methyl) acrylate (b)
When import volume (mole) is set to a and b, 0.01~0.5 is calculated as with b/ (a+b), and then, dissolve in toluene, dimethylbenzene, the third two
Alcohol monomethyl ether acetate, tetrahydrofuran, dichloroethanes or chloroform.
2. multifunctional (methyl) acrylate copolymer according to claim 1, it is characterised in that in formula (1), R1 is
Carbon number more than 9 and less than 30 straight-chain or aliphatic chain or glycol chain with branched structure.
3. multifunctional (methyl) acrylate copolymer according to claim 1 or 2, it is characterised in that in formula (2),
R2 is carbon number more than 2 and the aliphatic chain or glycol chain of less than 30 straight-chain.
4. multifunctional (methyl) acrylate copolymer according to claim 1 or 2, it is characterised in that 2 officials will be derived from
When the import volume (mole) containing reactive (methyl) acrylate-based unit of energy (methyl) acrylate (b) is set to b1, the list
The mole fraction Mb1 of member is calculated as 0.02~0.5 with b1/ (a+b).
5. multifunctional (methyl) acrylate copolymer according to claim 1 or 2, it is characterised in that 2 will be derived from,
When the import volume (mole) of the unit of 4- diphenyl -4-methyl-1-pentene (c) is set to c, the mole fraction Mc of the unit is with c/ (a
+ b+c) it is calculated as 0.005~0.3.
6. a kind of hardening resin composition, it is characterised in that contain multifunctional (first according to any one of claims 1 to 5
Base) acrylate copolymer, with more than 1 have unsaturated double-bond functional group monomer and initiator.
7. a kind of optical article, the hardening resin composition described in claim 6 is solidified, shapes and obtain by it.
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