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CN103429632B - Multi-functional epoxy compound - Google Patents

Multi-functional epoxy compound Download PDF

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Publication number
CN103429632B
CN103429632B CN201280013358.7A CN201280013358A CN103429632B CN 103429632 B CN103429632 B CN 103429632B CN 201280013358 A CN201280013358 A CN 201280013358A CN 103429632 B CN103429632 B CN 103429632B
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valency
epoxide
carbon number
integer
formula
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CN103429632A (en
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远藤勇树
武山敏明
柳泽佐代子
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Nissan Chemical Corp
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Nissan Chemical Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Epoxy Resins (AREA)
  • Epoxy Compounds (AREA)

Abstract

It is an object of the invention to provide low viscosity, not only Thermocurable but also the high composition epoxy resin of cation-curable.The invention provides the epoxide represented by following formula (1), in formula (1), A represents that the unsaturated alkyl of the carbon number 2～10 of (n4) valency, the cyclic hydrocarbon group of carbon number 4～20 of (n4) valency, (n4) valency are containing azo-cycle base, the chain alkyl of the carbon number 3～10 of (n4) valency or their (n4) valency groups of combining, R1And R2Separately represent the alkyl of hydrogen atom or carbon number 1～10, R3Representing (n3+1) valency alkyl, n1 represents that integer 2, n2 represents that integer 1, n3 represents integer 2～5, and n4 represents integer 2～8, and n5 represents integer 0 or 1, and n6 represents integer 0 or 1.Additionally provide the solidification compound containing described epoxide and acid agent or firming agent.Acid agent is photoacid generator or thermal acid generator, and firming agent is anhydride or amine.

Description

Multi-functional epoxy compound
Technical field
The present invention relates to light or heat-curable epoxy resin composition.More particularly, it relates to can obtain that there is the high close attachment of opposing substrate, high transparent (transparency of relative visible ray), the light being firmly coated with the solidfied material of the excellent specific properties such as (hardcoating) property, high-fire resistance or heat-curable epoxy resin composition (electronic material is used and resin composition for optical material) and its solidfied material (composite solid compound).
Background technology
All the time, epoxy resin, it is widely used in field of electronic materials in combination as composition epoxy resin with firming agent.In such field of electronic materials, in the purposes of the high refractive index layer of such as antireflection film (antireflection film etc. of liquid crystal display), optical thin film (reflecting plate etc.), electronic component-use encapsulant, printed circuit board, layer insulation membrane material (lamination (buildup) printed base plate layer insulation membrane material etc.) etc., moulding material is required the performance such as high transparent of the high close attachment of relative base material, firmly painting property, thermostability, relative visible ray.
On the other hand, the composition epoxy resin that epoxide and light and heat acid agent combine, it is possible to do not use solvent and make epoxide individually solidify, so having carried out big quantity research in recent years.In particular with the light cationic curing that ultraviolet carries out, it is not necessary to large-scale solidification baking oven, very excellent in Energy input amount is few.
Alicyclic structure only has the cycloaliphatic epoxy of epoxy radicals, owing to being widely used making to use up in the cationic curing carried out reactive high, owing to its structure is hard, so solidfied material has tendency hardening, that become fragile.
Then, it is proposed that use composition epoxy resin and their manufacture method (with reference to patent documentation 1) of lactone-modified polyfunctional cycloaliphatic epoxy and this epoxide.
On the other hand, the epoxide of glycidyl ester type is low to the reactivity of acid agent, and reaction expends time in, so it has been generally acknowledged that and being not suitable for cationic curing.
As the multi-functional epoxy compound with glycidyl ester group, it has been proposed that use the composition epoxy resin (with reference to patent documentation 2,3) of cyclobutanetetracarboxylic four glycidyl group ester, cyclopentane four glycidyl group ester, hexamethylene tricarboxylic acid triglycidyl group ester.
Further it is proposed that use the epoxy alkyl ester resin (with reference to patent documentation 4) containing carboxyl as cross-linked compound of the cyclohexane cyclohexanedimethanodibasic with epoxy radicals.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 4-069360 publication
Patent documentation 2: Japanese Laid-Open Patent Publication 50-010893 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2006-274190 publication
Patent documentation 4: No. 3565922 description of U.S. Patent No.
Summary of the invention
The problem that invention to solve
Present inventor has performed further investigation, found that, structure is that parent has various skeleton, organic group as this skeleton has multi-functional epoxy compound that multiple side chain and its side chain have multiple epoxy radicals via alkyl, that have this epoxy radicals multiple in 1 molecule, not only has Thermocurable but also has cation-curable.
By so, the present invention to provide described epoxy composite and use aqueous, not only Thermocurable but also the high solidification compound of cation-curable of described epoxide.The solidfied material obtained by this solidification compound has high transparent, high-fire resistance.
Solve the means of problem
The viewpoint 1 of the present invention is the epoxide represented by following formula (1),
In formula (1), A represents that the unsaturated alkyl of the carbon number 2～10 of (n4) valency, the cyclic hydrocarbon group of carbon number 4～20 of (n4) valency, (n4) valency are containing azo-cycle base, the chain alkyl of the carbon number 3～10 of (n4) valency or their (n4) valency groups of combining, R1And R2Separately represent the alkyl of hydrogen atom or carbon number 1～10, R3Representing (n3+1) valency alkyl, n1 represents that integer 2, n2 represents that integer 1, n3 represents integer 2～5, and n4 represents integer 2～8, and n5 represents integer 0 or 1, and n6 represents integer 0 or 1.
Viewpoint 2 is the epoxide as described in viewpoint 1, and above-mentioned formula (1) represents with formula (1-1), formula (1-2) or formula (1-3),
In formula (1-1) and formula (1-3), A represents that the unsaturated alkyl of the carbon number 2～10 of (n4) valency, the cyclic hydrocarbon group of carbon number 4～20 of (n4) valency, (n4) valency are containing azo-cycle base, the chain alkyl of the carbon number 3～10 of (n4) valency or their (n4) valency groups of combining, in formula (1-2), A ' represents that (n4) valency is containing azo-cycle base
R1And R2Separately represent the alkyl of hydrogen atom or carbon number 1～10, R3Representing (n3+1) valency alkyl, n1 represents that integer 2, n2 represents that integer 1, n3 represents integer 2～5, and n4 represents integer 2～8.
Viewpoint 3 is the epoxide as described in viewpoint 1 or 2, described A remove (n4) individual hydrogen atom from ethylene, propylene or norborene after (n4) valency unsaturated alkyl.
Viewpoint 4 is the epoxide as described in viewpoint 1 or 2, described A from Tetramethylene., Pentamethylene., hexamethylene, 7-oxa-bicyclo[4.1.0, removed (n4) valency cyclic hydrocarbon group after (n4) individual hydrogen atom by alkyl substituted 7-oxa-bicyclo[4.1.0, double-heptene, bicyclooctene or diamantane (obsolete).
Viewpoint 5 is the epoxide as described in viewpoint 1 or 2, described A remove (n4) individual hydrogen atom from trialkyl isocyanuric acid ester after (n4) valency containing azo-cycle base, described A ' remove (n4) individual hydrogen atom from isocyanuric acid, cyanurate, hydantoin or barbiturates after (n4) valency containing azo-cycle base.
Viewpoint 6 is the epoxide as described in viewpoint 1 or 2, described A remove (n4) individual hydrogen atom from propane, butane, pentane or hexane after (n4) valency chain alkyl.
Viewpoint 7 is a kind of solidification compound, the epoxide described in any one containing viewpoint 1～6 and firming agent.
Viewpoint 8 is the solidification compound as described in viewpoint 7, and described firming agent is anhydride, amine, phenolic resin, polyamide, imidazoles or multi-thiol.
Viewpoint 9 is the solidification compound as described in viewpoint 7 or 8, relative to epoxy radicals 1 equivalent of described epoxide, contains described firming agent with the ratio of 0.5～1.5 equivalent.
Viewpoint 10 is a kind of solidification compound, the epoxide described in any one containing viewpoint 1～6 and acid agent.
Viewpoint 11 is the solidification compound as described in viewpoint 10, and described acid agent is photoacid generator or thermal acid generator.
Viewpoint 12 is the solidification compound as described in viewpoint 11, and described acid agent isSalt.
Viewpoint 13 is the solidification compound as described in viewpoint 11, and described acid agent is sulfonium salt compound or iodineSalt compound.
Viewpoint 14 is the solidification compound as described in any one such as viewpoint 10～13, relative to the quality of described epoxide, contains described acid agent with the ratio of 0.1～20 mass %.
Invention effect
Having at the epoxide as the multiple epoxide rings combined via alkyl on the organic group of skeleton, owing to this alkyl is more long, then the degree of freedom of this epoxide ring is more big, reactivity is more high, so epoxy radicals all participates in reaction, in addition, by having multiple epoxide ring, cation-curable uprises.
If additionally, make at least to contain the solidification compound photocuring of above-mentioned epoxide and photoacid generator, it becomes possible to expect the solidfied material or the cured coating film that form the mechanical property realizing excellence and excellent optical characteristics simultaneously.Particularly, alkyl is more long, it becomes possible to expect that the toughness of this solidfied material and cured coating film is more high.
From the epoxide of the present invention that such viewpoint is found out, its structure is, parent has various skeleton, the organic group becoming its skeleton has multiple side chain, and its side chain has multiple epoxy radicals via alkyl, by having this epoxy radicals multiple in 1 molecule, it is possible to play characteristic effect, not only there is Thermocurable, but also there is cation-curable.
The solidification compound of the present invention contains the epoxide represented by above-mentioned formula (1) and firming agent (such as amine, anhydride), according to circumstances can also contain auxiliary curing agent.
Additionally, in the present invention, use photoacid generator or thermal acid generator to carry out photocuring or heat cure the epoxide represented by above-mentioned formula (1).Therefore, by using photoacid generator or thermal acid generator, can not use typically by epoxy firming agent (such as amine, anhydride) even if or to use them be also that their content is considerably less, so the storage stability of the solidification compound of the present invention is good.
The solidification compound of the present invention, it is possible to irradiate by UV and carry out photocuring and solidify, so being suitable for heat labile material (base material).
Additionally, due to the epoxide used in the present invention is aqueous, so using the solidification compound fillibility of its present invention good.
And then, the solidification compound of epoxide containing the present invention there is the feature such as low viscosity, rapid-drying properties, it is possible to electronic unit, optics, precision mechanism parts coating and bonding middle use.
Detailed description of the invention
The present invention is the epoxide represented by above-mentioned formula (1).In above-mentioned formula (1), A represents that the unsaturated alkyl of the carbon number 2～10 of (n4) valency, the cyclic hydrocarbon group of carbon number 4～20 of (n4) valency, (n4) valency are containing azo-cycle base, the chain alkyl of the carbon number 3～10 of (n4) valency or their (n4) valency groups of combining, R1And R2Separately represent the alkyl of hydrogen atom or carbon number 1～10, R3Representing (n3+1) valency alkyl, n1 represents that integer 2, n2 represents that integer 1, n3 represents integer 2～5, and n4 represents integer 2～8, and n5 represents integer 0 or 1, and n6 represents integer 0 or 1.
Above-mentioned formula (1) comprises the epoxide represented by above-mentioned formula (1-1), formula (1-2) or formula (1-3).In formula (1-1) and formula (1-3), A represents that the unsaturated alkyl of the carbon number 2～10 of (n4) valency, the cyclic hydrocarbon group of carbon number 4～20 of (n4) valency, (n4) valency are containing azo-cycle base, the chain alkyl of the carbon number 3～10 of (n4) valency or their (n4) valency groups of combining, in formula (1-2), A ' represent (n4) valency containing azo-cycle base, R1And R2Separately represent the alkyl of hydrogen atom or carbon number 1～10, R3Representing (n3+1) valency alkyl, n1 represents that integer 2, n2 represents that integer 1, n3 represents integer 2～5, and n4 represents integer 2～8.
The situation of the unsaturated alkyl that A is (n4) valency in formula (1), formula (1-1) and formula (1-3), can list such as A, remove (n4) the valency unsaturated alkyl after (n4) individual hydrogen atom from ethylene, propylene or norborene.
The situation of the cyclic hydrocarbon group that A is (n4) valency in formula (1), formula (1-1) and formula (1-3), can list such as A, from Tetramethylene., Pentamethylene., hexamethylene, 7-oxa-bicyclo[4.1.0, removed (n4) the valency cyclic hydrocarbon group after (n4) individual hydrogen atom by alkyl substituted 7-oxa-bicyclo[4.1.0, double-heptene, bicyclooctene or diamantane (obsolete).
A and A ' in formula (1), formula (1-1), formula (1-2) and formula (1-3) is (n4) valency situation containing azo-cycle base, A can list such as, (n4) valency after removing (n4) individual hydrogen atom from trialkyl isocyanuric acid ester is containing azo-cycle base, as A ', it is possible to (n4) valency after such as removing (n4) individual hydrogen atom from isocyanuric acid, cyanurate, hydantoin or barbiturates that lists is containing azo-cycle base.
The situation that A is (n4) valency chain alkyl in formula (1), formula (1-1) and formula (1-3), can list (n4) valency chain alkyl after such as removing (n4) individual hydrogen atom from propane, butane, pentane or hexane as A.
R1And R2Separately represent hydrogen atom or the alkyl of carbon number 1～10.
nullAlkyl as carbon number 1～10，Methyl can be listed、Ethyl、N-pro-pyl、Isopropyl、Cyclopropyl、Normal-butyl、Isobutyl group、Sec-butyl、The tert-butyl group、Cyclobutyl、1-methyl-cyclopropyl、2-methyl-cyclopropyl、N-pentyl、1-methyl-normal-butyl、2-methyl-normal-butyl、3-methyl-normal-butyl、1,1-dimethyl-n-propyl、1,2-dimethyl-n-propyl、2-methyl-2-ethyl-n-pro-pyl、2-methyl-2-methyl-n-propyl、2,2-dimethyl-n-propyl、1-ethyl-n-pro-pyl、Cyclopenta、1-methyl-cyclobutyl、2-methyl-cyclobutyl、3-methyl-cyclobutyl、1,2-Dimethyl-cyclopropyl、2,3-Dimethyl-cyclopropyl、1-ethyl-cyclopropyl base、2-ethyl-cyclopropyl base、N-hexyl、1-methyl-n-pentyl、2-methyl-n-pentyl、3-methyl-n-pentyl、4-methyl-n-pentyl、1,1-dimethyl-normal-butyl、1,2-dimethyl-normal-butyl、1,3-dimethyl-normal-butyl、2,2-dimethyl-normal-butyl、2,3-dimethyl-normal-butyl、3,3-dimethyl-normal-butyl、1-ethyl-normal-butyl、2-ethyl-normal-butyl、1,1,2-trimethyl-n-propyl、1,2,2-trimethyl-n-propyl、1-ethyl-1-methyl-n-propyl、1-Ethyl-2-Methyl-n-pro-pyl、Cyclohexyl、1-methyl-cyclopentyl、2-methyl-cyclopentyl、3-methyl-cyclopentyl、1-ethyl-cyclobutyl、2-ethyl-cyclobutyl、3-ethyl-cyclobutyl、1,2-dimethyl-cyclobutyl、1,3-dimethyl-cyclobutyl、2,2-dimethyl-cyclobutyl、2,3-dimethyl-cyclobutyl、2,4-dimethyl-cyclobutyl、3,3-dimethyl-cyclobutyl、1-n-pro-pyl-cyclopropyl、2-n-pro-pyl-cyclopropyl、1-isopropyl-cyclopropyl、2-isopropyl-cyclopropyl、1,2,2-trimethyl-cyclopropyl、1,2,3-trimethyl-cyclopropyl、2,2,3-trimethyl-cyclopropyl、1-Ethyl-2-Methyl-cyclopropyl、2-ethyl-1-methyl-cyclopropyl、2-Ethyl-2-Methyl-cyclopropyl and 2-ethyl-3-methyl-cyclopropyl etc..
R3Represent (n3+1) valency alkyl, as alkyl, it is possible to list (n3+1) the valency alkyl after such as removing (n3+1) individual hydrogen atom from abovementioned alkyl.
As the B replaced on above-mentioned parent, it is possible to list and exemplified below there is the alkyl ester group of epoxy radicals, alkyl and alkoxyl.Following middle A represents parent.
In formula (2-1)～formula (2-4), n5 represent 0 or 1 expression integer, n6 represents 0 or 1 integer.?
Additionally, parent A and A ' can illustrate following.Following middle B represents above-mentioned multi-functional epoxy's base.
Represent the situation of the unsaturated alkyl of the carbon number 2～10 of (n4) valency at A, A can illustrate following alkyl.
Represent the situation of the cyclic hydrocarbon group of the carbon number 4～20 of (n4) valency at A, A can illustrate following cyclic hydrocarbon group.
At A and A ' represent (n4) valency situation containing azo-cycle base, A and A ' can illustrate following containing azo-cycle base.
［ (in formula (5-1), R represents hydrogen atom or the alkyl of carbon number 1～10.?
Represent the situation of the chain alkyl of the carbon number 3～10 of (n4) valency at A, A can illustrate following chain alkyl.
The compound represented by formula (1) of the present invention, is made up of the combination of above-mentioned parent A and above-mentioned substituent B.
Epoxide represented by above-mentioned formula (1-1), can pass through such as, make the carboxylic acid derivates with carboxylic acid or the carboxylic acid anhydrides etc. of the structure of above-mentioned A and enol react, then make the compound (intermediate) with unsaturated bond obtained and peroxide reactions manufacture.In addition, this intermediate, it is possible to manufacture by any means, however it is not limited to the reaction of carboxylic acid or carboxylic acid anhydrides and enol, the intermediate with this unsaturated bond and peroxide is made to react, it becomes possible to manufacture the epoxide represented by above-mentioned formula (1-1).
With corresponding for B (there is the alkyl ester group of the multi-functional epoxy's base) enol replaced on above-mentioned parent A, it is possible to illustrate following enol.
There is carboxylic acid or the carboxylic acid anhydrides of the structure of parent A, it is possible to below illustrating.
Carboxylic acid when representing the unsaturated alkyl of carbon number 2～10 of (n4) valency as A or carboxylic acid anhydrides, it is possible to illustrate following.
Carboxylic acid when representing the cyclic hydrocarbon group of carbon number 4～20 of (n4) valency as A or carboxylic acid anhydrides, it is possible to illustrate following.
Carboxylic acid when representing (n4) valency containing azo-cycle base as A, it is possible to list tricarboxylic alkyl isocyanide urea acid esters (but as alkyl, to be carbon number be, and 1～5, preferably carbon number are the alkyl of 1～3), it is possible to illustrate following.
［ in formula (5-1-1), R represents hydrogen atom or the alkyl of carbon number 1～10.?
Carboxylic acid when representing the chain alkyl of carbon number 3～10 of (n4) valency as A or carboxylic acid anhydrides, it is possible to illustrate following.
As the compound (intermediate) with unsaturated bond that there is the carboxylic acid of structure of above-mentioned A or carboxylic acid anhydrides and enol reacts and obtains, it is possible to illustrate formula (1-1-1).
［ in formula (1-1-1), A represents that the unsaturated alkyl of the carbon number 2～10 of (n4) valency, the cyclic hydrocarbon group of carbon number 4～20 of (n4) valency, (n4) valency are containing azo-cycle base, the chain alkyl of the carbon number 3～10 of (n4) valency or their (n4) valency groups of combining, R1And R2Separately represent the alkyl of hydrogen atom or carbon number 1～10, R3Representing (n3+1) valency alkyl, n1 represents that integer 2, n2 represents that integer 1, n3 represents integer 2～5, and n4 represents integer 2～8.?
Namely, the epoxide represented by formula (1-1) used in the present invention, if for the epoxide represented by the formula (1-1) that formula (4-3) and formula (2-1) combine, it is possible to obtain by following method.
Carboxylic acid anhydrides and enol is made to react, synthetic intermediate (alkene).This reaction, is the use catalyst such as p-methyl benzenesulfonic acid, sulphuric acid in toluene equal solvent, and the temperature room temperature (such as 20 DEG C)～110 DEG C carries out 0～100 hour.Then with peroxide, this unsaturated compound is aoxidized, it becomes possible to obtain epoxide.As peroxide here, it is possible to use such as, metachloroperbenzoic acid, peracetic acid, hydrogen peroxide-wolframic acid etc..This reaction, be in chloroform equal solvent, 0～60 DEG C carry out 1～200 hour.Above-mentioned reaction, it is possible to use dicarboxylic acid compound replaces anhydride to carry out as raw material.In addition, in the situation of carboxylic acid being difficult in toluene equal solvent to dissolve, by being esterified with alcohol such as methanol, then the method carrying out ester exchange reaction with enol, or, utilize method that the condensing agents such as carbodiimide make carboxylic acid and enol react or, make carboxylic acid become acyl chlorides compound with thionyl chloride etc., then the method reacted with enol, it is also possible to synthesize above-mentioned intermediate (alkene).
Epoxide represented by above-mentioned formula (1-2), it is possible to by make to have the structure of A ' containing azo-cycle compound, (this compound has NH base.) and there is the enol that can slough base or allyl halide reacts, then make the compound (intermediate) with unsaturated bond obtained and peroxide react and manufacture.
Additionally, the epoxide represented by above-mentioned formula (1-2), it is possible to by making to have the nitrogen-containing compound of the structure of A ', (this compound has NH base.) and there is the epoxide of unsaturated bond react, then by the alcoholic compound obtained and have the enol that can slough base or allyl halide reacts, then the compound (intermediate) with unsaturated bond obtained and peroxide is made to react and manufacture.
As the enol with B corresponding the sloughed base that replace upper with parent A ', allyl halide, can use such as, by making above-mentioned formula (2-1-1), formula (2-2-1), formula (2-3-1), (2-4-1) compound represented by and methylsulfonyl halogen, trifluoromethanesulfanhydride anhydride, tosyl halogen, nitrobenzene sulphonyl halogen, acetyl halide, acetic anhydride, trifluoroacetic anhydride, phosphorus oxychloride, tribromo oxygen phosphorus, halogenation sulfoxide, halogenation sulfonyl, hydrogen chloride, hydrogen bromide, hydrogen iodides etc. react and obtained following formula (2-1-2), formula (2-2-2), formula (2-3-2), with the compound represented by formula (2-4-2).
［ (in formula (2-1-2), formula (2-2-2), formula (2-3-2) and formula (2-4-2), X represents mesyloxy, trifluoro-methanesulfonyl oxy, tosyloxy, nitrobenzenesulfonyloxy, acetoxyl group, trifluoroacetyl oxygen base, chlorine atom, bromine atoms or atomic iodine.?
As have parent A ' structure containing azo-cycle compound, (this compound has NH base.), it is possible to illustrate following containing azo-cycle compound.
Have A ' structure containing azo-cycle compound, (this compound has NH base.) and there is the enol that can slough base or the compound (intermediate) with unsaturated bond that allyl halide reacts and obtains, it is possible to exemplify formula (1-2-1).
(in formula (1-2-1), A ' represent (n4) valency containing azo-cycle base, R1And R2Separately represent the alkyl of hydrogen atom or carbon number 1～10, R3Representing (n3+1) valency alkyl, n1 represents that integer 2, n2 represents that integer 1, n3 represents integer 2～5, and n4 represents integer 2～8.?
Namely, the epoxide represented by formula (1-2) used in the present invention, if for the epoxide represented by the formula (1-2) that formula (5-6) and formula (2-1) combine, it is possible to obtain by following method.
Make containing azo-cycle compound that (this compound has NH base.) and there is the enol that can slough base react synthetic intermediate (alkene).This reaction is to use the alkali such as sodium hydride, potassium carbonate, potassium tert-butoxide, triethylamine in DMF equal solvent, be carried out below 0～100 hour in the boiling temperature of room temperature (such as 20 DEG C) above solvent.Then the oxidation of this unsaturated compound is made to obtain epoxide with peroxide.As peroxide here, it is possible to use such as, metachloroperbenzoic acid, peracetic acid, hydrogen peroxide-wolframic acid etc..This reaction is to carry out 1～200 hour in chloroform equal solvent, at 0～60 DEG C.
And then, epoxide represented by above-mentioned formula (1-3), can pass through such as make the alcohol with the structure of above-mentioned A and there is the enol that can slough base or allyl halide reacts to the compound (intermediate) with unsaturated bond and peroxide react and manufacture.
Enol or allyl halide as corresponding for the B base sloughed having and replace on parent A, can use such as, by making above-mentioned formula (2-1-1), formula (2-2-1), formula (2-3-1), (2-4-1) compound represented by and methylsulfonyl halogen, trifluoromethanesulfanhydride anhydride, tosyl halogen, nitrobenzene sulphonyl halogen, acetyl halide, acetic anhydride, trifluoroacetic anhydride, phosphorus oxychloride, tribromo oxygen phosphorus, halogenation sulfoxide, halogenation sulfonyl, hydrogen chloride, hydrogen bromide, the above-mentioned formula (2-1-2) that hydrogen iodide etc. react and obtain, formula (2-2-2), formula (2-3-2), with the compound represented by formula (2-4-2).
There is the alcohol of the structure of parent A, it is possible to illustrate following alcohol.
The alcohol during unsaturated alkyl of carbon number 2～10 of (n4) valency is represented, it is possible to illustrate following alcohol as A.
The alcohol during cyclic hydrocarbon group of carbon number 4～20 of (n4) valency is represented, it is possible to illustrate following alcohol as A.
Alcohol when representing (n4) valency containing azo-cycle base as A, it is possible to illustrate following alcohol.
In formula (5-1-3), R represent hydrogen atom or the alkyl of carbon number 1～10.?
The alcohol during chain alkyl of carbon number 3～10 of (n4) valency is represented, it is possible to illustrate following as A.
There is the alcohol of the structure of above-mentioned A and there is the enol that can slough base or the compound (intermediate) with unsaturated bond that allyl halide reacts and obtains, it is possible to exemplifying formula (1-3-1).
［ in formula (1-3-1), A represents that the unsaturated alkyl of the carbon number 2～10 of (n4) valency, the cyclic hydrocarbon group of carbon number 4～20 of (n4) valency, (n4) valency are containing azo-cycle base, the chain alkyl of the carbon number 3～10 of (n4) valency or their (n4) valency groups of combining, R1And R2Separately represent the alkyl of hydrogen atom or carbon number 1～10, R3Representing (n3+1) valency alkyl, n1 represents that integer 2, n2 represents that integer 1, n3 represents integer 2～5, and n4 represents integer 2～8.?
Namely, in the present invention use formula (1-3) represented by epoxide, if for the epoxide represented by the formula (1-3) that formula (4-4) and formula (2-1) combine, it is possible to obtain by following method.
Make alcohol and there is the enol that can slough base react synthetic intermediate (alkene).This reaction, be in ether, amide equal solvent, use the alkali such as sodium hydroxide, potassium carbonate, potassium tert-butoxide, triethylamine, more than room temperature (such as 20 DEG C), the boiling temperature of solvent be carried out below 0～100 hour.Then with peroxide, the oxidation of this unsaturated compound is obtained epoxide.Can use such as peroxide here, metachloroperbenzoic acid, peracetic acid, hydrogen peroxide-wolframic acid etc..This reaction is to carry out 1～200 hour in chloroform equal solvent, at 0～60 DEG C.
Epoxide represented by above-mentioned formula (1-3), can pass through such as, the allyl alcohol making tricyanogen chloride represented with formula (2-1-1), formula (2-2-1), formula (2-3-1) and formula (2-4-1) etc. reacts, then with making the compound (intermediate) with unsaturated bond obtained and peroxide react and manufacture as before.
Additionally, the present invention is the solidification compound containing the epoxide represented by above-mentioned formula (1) and firming agent.
And then, the present invention be the solidification compound containing the epoxide represented by above-mentioned formula (1) and acid agent.
The solidification compound of the present invention can also contain solvent, other epoxide, firming agent, surfactant and close attachment accelerator etc. as required.
The ratio of the solid constituent in the solidification compound of the present invention can be 1～100 mass % or 5～100 mass % or 50～100 mass % or 80～100 mass %.
Solid constituent refers to the ratio of remaining composition after removing solvent from solidification compound.Owing to the present invention using aqueous epoxide, it is possible to be mixed into firming agent or acid agent wherein, so substantially without using solvent, but solvent can also be added as required.Such as, acid agent be solid, make acid agent be dissolved in propylene carbonate equal solvent, then mix with aqueous epoxide and produce curable compound.Additionally, in the situation making acid agent be dissolved in aqueous epoxide, in order to regulate the viscosity of obtained solidification compound, it is also possible to add common solvent.
The content of the epoxide represented by above-mentioned formula (1) in the solidification compound of the present invention, content based on the solid constituent of this solidification compound calculates, it is possible to be 8～99.9 mass %, preferably 40～99 mass % and then preferred 70～99 mass %.
Additionally, the content of the acid agent in the solidification compound of the present invention, the content based on the solid constituent of this solidification compound calculates, it is possible to be 0.1～20 mass % or 0.1～10 mass %.
The solidification compound of the present invention is, relative to the quality of the epoxide represented by above-mentioned formula (1), contains acid agent with the ratio of 0.1～20 mass % or 0.1～10 mass %.
In the present invention, it is possible to and with the epoxide represented by above-mentioned formula (1) and the epoxide except it.Epoxide represented by above-mentioned formula (1) and the epoxide except it can use in the scope of 1:0.1～1:10 with the mol ratio of epoxy radicals.
As the epoxide beyond the epoxide represented by above-mentioned formula (1), it is possible to exemplify following.
Three (2,3-glycidyl) isocyanuric acid ester (formula (7-1), trade name テ ピ ッ Network, Nissan Chemical Industries (strain) are made) as solid epoxidic compound.
Trade name エ ピ U ト 828 (formula (7-2), ジ ャ パ Application エ Port キ シ レ ジ Application (strain) make) as aqueous epoxide.
Trade name YX8000 (formula (7-3), ジ ャ パ Application エ Port キ シ レ ジ Application (strain) make) as aqueous epoxide.
Trade name DME100 (formula (7-4), new Japan Chemical (strain) are made) as aqueous epoxide.
Trade name CE-2021P (formula (7-5), ダ イ セ Le Co., Ltd. system) as aqueous epoxide.
In addition, in the present invention, as aqueous epoxide, following three (3 can be used, 4-epoxybutyl) isocyanuric acid ester (formula (7-6)), three (4,5-epoxypentyl) isocyanuric acid ester (formula (7-7)), three (5,6-epoxyhexyl) isocyanuric acid ester (formula (7-8)), three (glycidyl oxygen ethyl) isocyanuric acid ester (formula (7-9)).
The aqueous epoxide (formula (7-10), Nissan Chemical Industries (strain) system, trade name: テ ピ ッ Network パ ス B22) adding propionic andydride 0.8 mole in three (2,3-glycidyl) isocyanuric acid ester 1 mole and modifiied can also be used.The ratio that formula (7-10) is about 35%:45%:17%:3% with mol ratio contains (7-10-1): (7-10-2): (7-10-3): (7-10-4).
The aqueous epoxide (formula (7-11), Nissan Chemical Industries (strain) system, trade name テ ピ ッ Network パ ス B26) adding propionic andydride 0.4 mole in three (2,3-glycidyl) isocyanuric acid ester 1 mole and modifiied can also be used.The ratio that formula (7-11) is about 60%:32%:8% with mol ratio contains (7-11-1): (7-11-2): (7-11-3).
As cation-curable monomer in the present invention, except epoxide, it is also possible to use vinyl ether compound, oxetane compound etc..
As the compound (vinyl ether compound etc.) containing vinyl, as long as have the compound of vinyl, just it is not particularly limited, it is possible to list such as, 2-hydroxyethyl vinyl ether (HEVE), diethylene glycol monovinyl base ether (DEGV), 2-hydroxybutyl vinyl ether (HBVE), triethyleneglycol divinylether.Further, it is also possible to be used in the vinyl compound on α and/or β position with the substituent group such as alkyl, pi-allyl.In addition it is possible to use the vinyl ether compound containing the cyclic ether group such as epoxy radicals and/or oxetanyl, it is possible to list such as, aoxidize norborene divinyl ether, 3,3-dimethanol oxetanes divinyl ethers.Further, it is also possible to use the mixed compounds with vinyl and (methyl) acryloyl group, it is possible to list such as, (methyl) acrylic acid 2-(2-vinyloxyethoxy) ethyl ester (VEEA, VEEM) etc..They can be used alone, or two kinds of combination of the above use.
As the compound (oxetane compound) containing oxetanyl, as long as have the compound of oxetanyl, just it is not particularly limited, 3-ethyl-3-(phenoxymethyl) oxetanes (POX) can be listed, two ［ 1-ethyl (3-oxetanyl) ］ methyl ether (DOX), 3-ethyl-3-(2-Ethylhexoxymethyl) oxetanes (EHOX), 3-ethyl-3-{ ［ 3-(triethoxysilyl) propoxyl group ］ methyl } oxetanes (TESOX), oxetanyl silsesquioxane (OX-SQ), phenol novolacs oxetanes (PNOX-1009) etc..Further, it is also possible to use the mixed compounds ((methyl) acrylic acid 1-ethyl-3-oxetanyl methyl ester) with oxetanyl and (methyl) acrylic.These oxetanes based compounds can be used alone, or two kinds of combination of the above use.
The present invention can obtain the solidification compound containing the epoxide represented by above-mentioned formula (1) and firming agent.
As firming agent, it is possible to use anhydride, amine, phenolic resin, polyamide, imidazoles or multi-thiol.Among those, particularly preferably anhydride and amine.These firming agent, even solid, it is also possible to use in a solvent by dissolving.But, due to the evaporation because of solvent the decrease in density of solidfied material, because of the generation of pore, intensity reduces, resistance to water reduces, it is advantageous to firming agent from being aqueous under room temperature, normal pressure.
Firming agent, with epoxy radicals 1 equivalent relative to epoxide be 0.5～1.5 equivalent, preferably the ratio of 0.8～1.2 equivalent contain.Firming agent relative to the equivalent of epoxide, with the curable group of firming agent relative to epoxy radicals equivalent proportion represent.
As phenolic resin, it is possible to list such as, phenol resol resins, cresol novolac resin etc..
As amine, such as piperidines, N can be listed, N-lupetazin, triethylene diamine, 2,4,6-tri-(dimethylaminomethyl) phenol, benzyldimethylamine, 2,4,2-(dimethylaminomethyl) phenol, diethylenetriamine, triethylene tetramine, TEPA, diethyl amino propylamine, N-aminoethyl piperazine, two (1-methyl-2-amino cyclohexyl) methane,Alkane diamidogen, isophorone diamine, diamino-dicyclohexyl methane, 1,3-bis aminomethyl hexamethylene, dimethylphenylene diamine, m-diaminobenzene., diaminodiphenyl-methane, diamino diphenyl sulfone etc..Among those, it is preferred to use aqueous diethylenetriamine, triethylene tetramine, TEPA, diethyl amino propylamine, N-aminoethyl piperazine, two (1-methyl-2-amino cyclohexyl) methane,Alkane diamidogen, isophorone diamine and diamino-dicyclohexyl methane etc..
Polyamide, is daiamid that generated by the condensation of dimer acids and polyamine, that have primary amine and secondary amine in molecule.
As imidazoles, it is possible to list 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyano ethyl-2-undecyl imidazole trimellitic acid salt and epoxy imidazole adducts etc..
Multi-thiol, be such as the end of polypropylene glycol chain there is mercapto or at the end of polyglycol chain, there is mercapto, it is preferable that aqueous.
As anhydride, it is preferable that a part has the anhydride of the compound of multiple carboxyl.Anhydride as them, phthalic anhydride can be listed, trimellitic anhydride, pyromellitic acid anhydride, benzophenone tetracarboxylic dianhydride, ethylene glycol bis trimellitic acid ester, glycerol three trimellitic acid ester, maleic anhydride, tetrabydrophthalic anhydride, methyl tetrahydrophthalic anhydride, Nadic anhydride, methylendomethylenetetrahydrophthalic tetrabydrophthalic anhydride, methyl butene base tetrabydrophthalic anhydride, dodecenylsuccinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydrides, methylcyclohexene dicarboxylic acid anhydride, chlorendic anhydride etc..
It is preferably aqueous methyl tetrahydrophthalic anhydride, methyl-5-norborene-2 among those under room temperature, normal pressure, 3-dicarboxylic acid anhydride (methylnadic anhydride, methyl humic acids acid anhydride), hydrogenating methyl carbic anhydride, methyl butene base tetrabydrophthalic anhydride, dodecenylsuccinic anhydride, methylhexahydrophthalic anhydride, or the mixture of methylhexahydrophthalic anhydride and hexahydrophthalic anhydride.At about 10mPas～1000mPas when the viscosity of these aqueous anhydride measures at 25 DEG C.For anhydride group, 1 anhydride group be can be regarded as 1 equivalent.
Additionally, when being obtained solidfied material by the solidification compound of the present invention, it is also possible to suitably and use auxiliary curing agent.
As auxiliary curing agent, it is possible to list the organic phosphorus compound of triphenylphosphine, tributylphosphine etc., ethyltriphenyl phosphonium bromide, the tetrabutylThe seasons such as two sulfur band diethyl phosphatesSalt, 1,8-diazabicyclo ［ 5,4,0 ］ 11-7-alkene, 1,8-diazabicyclo ［ 5,4,0 ］ 11 quaternary ammonium salt such as-7-alkene and sad salt, zinc octoate, tetrabutyl ammonium bromide.These auxiliary curing agents, it is possible to be 0.001～0.1 mass parts relative to firming agent 1 mass parts ratio use.
In the present invention, by making epoxide represented by above-mentioned formula (1) and above-mentioned firming agent and the auxiliary curing agent mixing added according to hope, it is possible to obtain solidification compound.Their mixing, if can Homogeneous phase mixing, be just not particularly limited, it is possible to use such as reaction flask and agitator or mixer etc. carry out.
Mixing, will consider viscosity, carry out under heating as required, carry out 0.5～1 hour at the temperature of 10 DEG C～100 DEG C.
The solidification compound obtained, has the suitable viscosity used as aqueous encapsulant.The solidification compound of the present invention, owing to arbitrary viscosity can be adjusted, by utilizing the tape casting, embedding method, point gum machine method, print process etc. to use as the transparent sealant of LED etc., it is possible to by partially sealed for its any part.Utilize said method that with aqueous, solidification compound is administered directly to LED etc. so that it is dry, solidification, just obtain epoxy resin cured product.
The solidfied material obtained by solidification compound, by this solidification compound is applied on base material, or be injected into be coated with releasing agent be cast as on template, at the temperature of 100～120 DEG C, then carry out precuring, then solidify after carrying out at the temperature of 120～200 DEG C, thus obtain.
Heat time heating time is 1～12 hour, preferred 2～5 hours.
The thickness of the film obtained by the solidification compound of the present invention, it is possible to select in the scope of 0.01 μm～about 10mm according to the purposes of solidfied material.
Above-mentioned solidification compound can contain solvent as required.
nullAs solvent，Can list such as、The ethers of oxolane etc.、Ethylene glycol monomethyl ether、The glycol ethers such as ethylene glycol monomethyl ether、Methylcellosolve acetate、The ethylene glycol alkyl ether acetate esters of ethyl cellosolve acetate etc.、Diethylene glycol monomethyl ether、TC、Diethylene glycol dimethyl ether、Diethylene glycol diethyl ether、The diethylene glycol class of diethylene glycol ethyl methyl ether etc.、Propylene glycol monomethyl ether、Propylene glycol monoethyl、Propylene glycol monopropyl ether、The propylene-glycol monoalky lether class of glycol monobutyl ether etc.、Methyl proxitol acetate、Propylene glycol ethyl ether acetas、Propylene glycol propyl ether acetas、The propylene glycol alkyl ether acetic acid esters of propylene glycol butyl ether acetas etc.、Methyl proxitol propionic ester、Propylene glycol ethyl ether propionic ester、Propylene glycol propyl ether propionic ester、The propylene glycol alkyl ether acetic acid esters of propylene glycol butyl ether propionic ester etc.、Toluene、Dimethylbenzene etc. aromatic hydrocarbon based、Methyl ethyl ketone、Ketohexamethylene、The ketones such as 4-hydroxy-4-methyl-2-pentanone、And methyl acetate、Ethyl acetate、Propyl acetate、Butyl acetate、2 hydroxy propanoic acid ethyl ester、2-hydroxy-2-methyl methyl propionate、2-hydroxy-2-methyl ethyl propionate、Hydroxy methyl acetate、Hydroxyl ethyl acetate、Butyl Glycolate、Methyl lactate、Ethyl lactate、Propyl lactate、Butyl lactate、3-hydroxy methyl propionate、3-hydroxypropionate、3-hydracrylic acid propyl ester、3-hydracrylic acid butyl ester、2-hydroxy-3-methyl methyl butyrate、Methoxy menthyl acetate、Ethyl methoxyacetate、Methoxy propyl acetate、2-Methoxyacetic acid butyl ester、Ethoxy acetate、Ethoxy ethyl acetate、Ethoxyacetic acid propyl ester、Ethoxyacetic acid butyl ester、Propoxyl group methyl acetate、Propoxyl group ethyl acetate、Propoxyl group propyl acetate、Propoxyl group butyl acetate、Butoxy acetic acid methyl ester、Butoxy acetic acid ethyl ester、Butoxy acetic acid propyl ester、Butoxy acetic acid butyl ester、2-methoxy methyl propionate、2-methoxypropionate、2-methoxy propyl propyl propionate、2-methoxy propyl acid butyl ester、2-ethoxypropanoate、2-ethoxyl ethyl propionate、2-ethoxy-c propyl propionate、2-ethoxy-c acid butyl ester、2-butoxy methyl propionate、2-butoxy ethyl propionate、2-butoxy propyl propionate、2-butoxy butyl propionate、3-methoxy methyl propionate、3-methoxypropionate、3-methoxy propyl propyl propionate、3-methoxy propyl acid butyl ester、3-ethoxypropanoate、3-ethoxyl ethyl propionate、3-ethoxy-c propyl propionate、3-ethoxy-c acid butyl ester、3-propoxyl group methyl propionate、3-propoxyl group ethyl propionate、3-propoxyl group propyl propionate、3-propoxyl group butyl propionate、3-butoxy methyl propionate、3-butoxy ethyl propionate、3-butoxy propyl propionate、The esters of 3-butoxy butyl propionate etc..
The present invention can obtain the solidification compound containing the epoxide represented by above-mentioned formula (1) and acid agent.Acid agent can use photoacid generator or thermal acid generator.
Photoacid generator or thermal acid generator, directly or indirectly produced acid as long as can be irradiated by light or heat, be just not particularly limited.
Concrete example as photoacid generator, it is possible to list triazine based compound, acetophenone derivs compound, disulfone based compound, Azimethylene. based compound, sulfonic acid compound, iodineSalt, sulfonium salt,Salt, seleniumSalt etc.Salt, metallocene complex, iron arene complexes etc.
Use as above-mentioned photoacid generatorSalt, iodineSalt can list such as chlorinated diphenyl base iodineDiphenyl iodineFluoroform sulphonate, diphenyl iodineMesylate, diphenyl iodineToluene fulfonate, brominated diphenyl base iodineDiphenyl iodineTetrafluoroborate, diphenyl iodineHexafluoro antimonate, diphenyl iodineHexafluoro arsenate, double; two (to tert-butyl-phenyl) iodineHexafluorophosphate, double; two (to tert-butyl-phenyl) iodineMesylate, double; two (to tert-butyl-phenyl) iodineToluene fulfonate, double; two (to tert-butyl-phenyl) iodineFluoroform sulphonate, double; two (to tert-butyl-phenyl) iodineTetrafluoroborate, double; two (to the tert-butyl-phenyl) iodine of chlorination, double; two (rubigan) iodine of chlorination, double; two (rubigan) iodineTetrafluoroborate.And then double; two (4-tert-butyl-phenyl) iodine can also be listedDouble; two (alkyl phenyl) iodine such as hexafluorophosphateSalt, Alkoxycarbonylalkoxy-trialkyl aryl iodideSalt (such as, 4-［ (1-ethoxy carbonyl-ethyoxyl) phenyl ］-(2,4,6-trimethylphenyl)-iodineHexafluorophosphate etc.), double; two (alkoxy aryl) iodineSalt (such as, (4-methoxyphenyl) phenyl-iodideDouble; two (alkoxyl phenyl) iodine of hexafluoro antimonate etc.Salt).
As above-mentioned sulfonium salt, chlorinated triphenyl base sulfonium can be listed, triphenylsulphonium bromide, three (p-methoxyphenyl) sulfonium tetrafluoroborate, three (p-methoxyphenyl) sulfonium hexafluorophosphonate, three (to ethoxyl phenenyl) sulfonium tetrafluoroborate, triphenylsulfonium triflate sulfonate, triphenylsulfonium hexafluoro antimonate, the triphenyl sulfonium salts such as triphenylsulfonium hexafluorophosphate, (4-phenyl sulfur phenenyl) diphenyl sulfonium hexafluoro antimonate, (4-phenyl sulfur phenenyl) diphenyl sulfonium hexafluorophosphate, double, two ［ 4-(diphenyl sulfonium base) phenyl ］ thioether-bis--hexafluoro antimonate, double, two ［ 4-(diphenyl sulfonium base) phenyl ］ sulfide-pairs-hexafluorophosphate, (4-methoxyphenyl) diphenyl sulfonium hexafluoro antimonate) etc. sulfonium salt.
As above-mentionedSalt, it is possible to list chlorinated triphenyl base, bromination triphenyl, three (p-methoxyphenyls)Tetrafluoroborate, three (p-methoxyphenyls)Hexafluorophosphonate, three (to ethoxyl phenenyls)Tetrafluoroborate, 4-chlorobenzene diazoniumHexafluorophosphate, benzyltriphenyl phosphoniumHexafluoro antimonate etc.Salt.
As above-mentioned seleniumSalt, has triphenyl seleniumThe selenium such as hexafluorophosphateSalt, additionally, as above-mentioned metallocene complex, it is possible to list the metallocene complexes such as (η 5 or η 6-cumene) (η 5-cyclopentadienyl group) ferrum (II) hexafluorophosphate.
Additionally, as photoacid generator, it is also possible to use following compound.
As photoacid generator, it is preferable that sulfonium salt compound and iodineSalt compound.Anion base as them, it is possible to list CF3SO3 -、C4F9SO3 -、C8F17SO3 -, camphorsulfonic acid anion, toluenesulfonate anion, BF4 -、PF6 -、AsF6 -And SbF6 -Deng.Particularly preferably show the anion bases such as highly acid phosphorus hexafluoride and antimony hexafluoride.
As photoacid generator, preference is above-mentioned formula (8-1), (8-2), (8-3), (8-8), (8-9) and (8-10) such as, it is preferable that formula (8-1) and (8-2) especially.
These photoacid generators can be used alone, or two or more combination uses.
As thermal acid generator, it is possible to list sulfonium salt andSalt, it is preferred to use sulfonium salt.
Additionally, as thermal acid generator, it is possible to list following compound.
R ' separately represents the alkyl of carbon number 1～12, carbon number 6～20 aryl, it is particularly preferred to the alkyl of carbon number 1～12.
These thermal acid generator can be used alone, or two or more combination uses.
Above-mentioned composition, can also contain usual additive as required.As these additives, it is possible to list such as pigment, coloring agent, viscosifier, sensitizer, defoamer, levelling agent, coating modifying agent, lubricant, stabilizer (antioxidant, heat stabilizer, resistance to light stabilizer etc.), plasticiser, surfactant, dissolution accelerator, filler, antistatic agent, firming agent etc..These additives can be used alone, or two or more combination.
In the present invention, by the solidification compound containing the epoxide represented by above-mentioned formula (1) and photoacid generator is applied on substrate and carries out light irradiation, it is possible to solidify.Additionally, can be heated in the front and back that light irradiates.
Additionally, in the present invention, it is possible to solidify by making the solidification compound containing the epoxide represented by above-mentioned formula (1) and thermal acid generator be applied on substrate and to heat.
And then, can pass through make the solidification compound containing the epoxide represented by above-mentioned formula (1) and thermal acid generator and photoacid generator be applied on substrate and heat, then carry out light irradiation and solidify.
Above-mentioned solidification compound can contain solvent.Solvent can use above-mentioned solvent.
As the method solidification compound of the present invention being applied on substrate, it is possible to list such as, flow coat method, spin-coating method, spraying process, silk screen print method, the tape casting, stick coating method, heavy curtain rubbing method, roller rubbing method, gravure coating process, infusion process, bar stitch etc..
The thickness of the film formed by the solidification compound of the present invention, scope at 0.01 μm～about 10mm can select according to the purposes of solidfied material, such as, in the situation for photoresist, it can be 0.05～10 μm (particularly 0.1～5 μm) left and right, in the situation for printed circuit board, it can be 10 μm～5mm (particularly 100 μm～1mm) left and right, in the situation for optical thin film, it is possible to be 0.1～100 μm (particularly 0.3～50 μm) left and right.
As irradiation when using photoacid generator or exposure light, it is possible to list such as, gamma-rays, X ray, ultraviolet, visible ray etc., it is common to use visible ray or ultraviolet, more especially with ultraviolet situation.
The wavelength of light is such as 150～800nm, preferably 150～600nm and then preferably 200～400nm, special about 300～400nm.
Irradiate light quantity different according to the thickness of film, it is possible to for such as 2～20000mJ/cm2, preferred 5～5000mJ/cm2Left and right.
As light source, it is possible to select according to the kind of exposure light line, for instance, in ultraviolet situation, it is possible to use low pressure mercury lamp, high voltage mercury lamp, ultrahigh pressure mercury lamp, deuterium lamp, halogen lamp, laser (He-Cd laser, excimer laser etc.) etc..The curing reaction of described compositions can be undertaken by the irradiation of these light.
In the situation using thermal acid generator, or using photoacid generator, after carrying out light irradiation, carrying out the situation of the heating of film as required, for instance carrying out about room temperature～250 DEG C.Heat time heating time can select from the scope of more than 3 seconds (such as 3 seconds～5 hours), for such as 5 seconds～2 hours.
And then, in the situation (such as, in the situation making printed circuit board etc.) forming pattern, image, it is also possible to the film formed on base material is carried out pattern exposure.This pattern exposure both can be undertaken by the scanning of laser light, it is also possible to is undertaken by carrying out light irradiation across photomask.By non-irradiated region (unexposed portion) developing liquid developing (or dissolving) that will generate through such pattern exposure, it becomes possible to form pattern or image.
As developer solution, it is possible to use alkaline aqueous solution or organic solvent.
As alkaline aqueous solution, it is possible to list the amine aqueous solution of the aqueous solution of the quaternary ammonium hydroxides such as the aqueous solution of the alkali metal hydroxide of potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate etc., tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, choline, ethanolamine, propylamine, ethylenediamine etc..
Described alkaline-based developer is usually the aqueous solution of below 10 mass %, but the aqueous solution etc. of 0.1～3.0 mass % is preferably used.And then use alcohols, surfactant can also be added in above-mentioned developer solution, their addition is preferably respectively, is 0.05～10 mass parts relative to developer solution 100 mass parts.Wherein it is possible to use the aqueous solution of the tetramethyl ammonium hydroxide of 0.1～2.38 mass %.
In addition, organic solvent as developer solution, common organic solvent can be used, it is possible to list such as acetone, acetonitrile, toluene, dimethylformamide, methanol, ethanol, isopropanol, propylene glycol monomethyl ether, propylene glycol monoethyl, propylene glycol monopropyl ether, glycol monobutyl ether, methyl proxitol acetate, propylene glycol ethyl ether acetas, propylene glycol propyl ether acetas, propylene glycol butyl ether acetas, ethyl lactate, Ketohexamethylene etc..They can be used alone, or uses as mixture of more than two kinds.Particularly preferably use methyl proxitol, methyl proxitol acetate, ethyl lactate etc..
The solidification compound of the present invention, in order to improve coating, it is also possible to adds surfactant.Such surfactant can list fluorine system surfactant, silicone type surface active agent, nonionic system surfactant etc., but is not particularly limited to these.Described surfactant, it is possible to be used alone, or two or more combination use.
In these surfactants, the preferred fluorine system surfactant owing to coating improves that effect is high.nullThe concrete example of fluorine system surfactant can list，Trade name: エ Off ト ッ プ ［ registered trade mark ］ EF301、EF303、EF352 (Rhizoma Sparganii マ テ リ ア Le electronics chemical conversion (strain) ((strain) ト ケ system プ ロ ダ Network Star) system)、Trade name: メ ガ Off ァ ッ Network ［ registered trade mark ］ F171、F173、R-30、R-08、R-90、BL-20、F-482 (DIC (strain) (big Japan イ Application キ chemical industry (strain)) system)、Trade name: Off ロ ラ De FC430、FC431 (Sumitomo ス リ エ system (strain) system)、Trade name: ア サ ヒ ガ De ［ registered trade mark ］ AG710、サ Off ロ Application ［ registered trade mark ］ S-382、SC101、SC102、SC103、SC104、SC105、SC106 (Asahi Glass (strain) system) etc.，But it is not limited to these.
The addition of the surfactant in the solidification compound of the present invention, the cubage based on the solid constituent of this solidification compound is 0.0008～4.5 mass %, preferably 0.0008～2.7 mass %, more preferably 0.0008～1.8 mass %.
The solidification compound of the present invention, in order to improve with development after the close attachment of substrate, it is possible to add close attachment accelerator.nullAs these close attachment accelerator，Trim,ethylchlorosilane can be listed、Dimethyl vinyl chlorosilane、Methyldiphenyl base chlorosilane、The chlorosilane such as CMDMCS chloromethyl dimethyl chlorosilane、Trimethylmethoxysilane、Dimethyldiethoxysilane、Methyl dimethoxysilane、Vinyldimethylethoxysilane、Dimethoxydiphenylsilane、The alkoxyl silicone alkanes such as phenyl triethoxysilane、Hexamethyldisiloxane、N,N '-bis-(trimethyl silyl) urea、Dimethyl trimethyl silyl amine、The silazane classes such as trimethyl-silyl-imidazole、Vinyl trichlorosilane、γ-r-chloropropyl trimethoxyl silane、γ aminopropyltriethoxy silane、γ-methacryloxypropyl trimethoxy silane、γ-(glycidoxy) propyl trimethoxy silicane、The silanes such as γ-(N-piperidyl) propyl trimethoxy silicane、Benzotriazole、Benzimidazole、Indazole、Imidazoles、2-mercaptobenzimidazole、2-mercaptobenzothiazole、2-sulfydryl benzoThe carbamide such as the assorted cyclic compound such as azoles, urazole, deracil, mercaptoimidazole, mercaptopyrimidine, 1,1-dimethyl urea, 1,3-dimethyl urea or, thiourea compound.Described close attachment accelerator, it is possible to be used alone, or two or more combination use.
The addition of the close attachment accelerator in the solidification compound of the present invention, based on the cubage of the solid constituent of this solidification compound, is generally below 18 mass %, is preferably 0.0008～9 mass %, is more preferably 0.04～9 mass %.
The solidification compound of the present invention, it is also possible to containing sensitizer.As the sensitizer that can use, it is possible to list anthracene, phenothiazine, thiaxanthone, benzophenone thiaxanthone etc..And then, as sensitizing dyestuff, it is possible to list thia pyransSalt based dye, merocyanine based dye, quinoline based dye, styryl quinoline based dye, coumarin ketone based dye, thioxanthene based dye,Ton based dye, Oxonol class cyanines based dye, cyanine based dye, rhodamine based dye, pyransSalt based dye etc..It particularly preferably is the sensitizer of anthracene system, by with cationic cure catalyst (radiosensitivity cationic polymerization initiators) using, so can tremendous raising sensitivity, and there is radical polymerization and cause function, the present invention like that by Cationic curing systems and radically curing system and mix type, it is possible to make catalyst become simple.As the compound of concrete anthracene, dibutoxy anthracene, dipropoxy anthraquinone etc. are effective.
The addition of the sensitizer in the solidification compound of the present invention, based on the cubage of the solid constituent of this solidification compound, is 0.01～20 mass %, preferably 0.01～10 mass %.
Embodiment
Each mensuration uses following machine respectively.
NMR: Jeol Ltd. FT-NMR (ECX300)
LC-MS: Co., Ltd. ウ ォ タ ズ liquid chromatography mass instrument (Alliance-ZQ-LC-MS)
GC-MS: Shimadzu Scisakusho Ltd's gas chromatography mass spectrometer (GC-MSQP5050A)
TOF-MS (MALDI): Block Le カ ダ Le ト ニ Network ス Co., Ltd.'s MALDI-TOF mass spectrometric apparatus (autoflexIII)
Viscosimetric analysis: Co., Ltd. ト キ メ ッ Network E type viscometer (VISCONICED type)
Absorbance measures: Shimadzu Scisakusho Ltd's UV, visible light near infrared spectrometer (UV-3600)
Bend test: Shimadzu Scisakusho Ltd's precision universal testing machine (AGS-X series)
Linear expansivity, glass transition temperature measure: Co., Ltd. テ ィ エ イ イ Application ス Star Le メ Application ト heats machinery determinator (TMAQ400)
Prepare following epoxide.
(preparation of epoxide)
Synthesis example 1
The synthesis of 4,5-7-oxa-bicyclo[4.1.0-1,2-dioctyl phthalate double; two (double; two (2,3-glycidyl oxy methyl) butyl of 2,2-) ester
To with Dean-Stark (Dean-Stark) device, condenser reactor in add cis 4-cyclohexene-1,2-dicarboxylic acid anhydride 10g, p-methyl benzenesulfonic acid one water and thing 1.2g, toluene 100mL, trimethylolpropane allyl ether (90%) 34g, at a reflux temperature reaction 15 hours.Reaction carries out sodium bicarbonate water cleaning after terminating, water cleans, concentration, with silica gel chromatography (hexane: ethyl acetate=80:20) purification, just obtain the 4 of light yellow liquid form, 5-7-oxa-bicyclo[4.1.0-1,2-dioctyl phthalate double; two (2,2-double; two (allyloxy methyl) butyl) ester 38g.
H-NMR(300MHz、CDCl3): δ=5.92～5.80 (m, 4H), 5.66 (s, 2H), 5.27～5.11 (m, 8H), 4.12～3.98 (m, 4H), 3.93～3.91 (m, 8H), 3.30 (s, 8H), 3.03 (m, 2H), 2.56～2.35 (m, 4H), 1.46～1.39 (q, 4H), 0.87～0.82 (t, 6H)
GC-MS (CI): m/z=563 (M+1).
In reactor, add double; two (2,2-double; two (allyloxy methyl) butyl)-4,5-7-oxa-bicyclo[4.1.0-1,2-dicarboxylic acid esters 35g, chloroform 300mL, metachloroperbenzoic acid 86g, react 2 days.After reaction terminates, make reaction terminating with sodium thiosulfate solution, add sodium bicarbonate water, extract.Solvent is distilled off, thus obtaining crude product from organic layer.With silica gel chromatography (hexane: ethyl acetate=50:50 → 10:90) purification, thus obtaining light yellow liquid 32g.
The compound obtained is 4,5-7-oxa-bicyclo[4.1.0-1,2-dioctyl phthalate double; two (2,2-double; two (2,3-glycidyl oxy methyl) butyl) ester, it is equivalent to the formula (4-3) corresponding with parent and the combination of the formula (2-1) corresponding with substituent group.
Viscosity is 2867mPa s at 25 DEG C.This epoxide is designated as (i-1).
H-NMR(300MHz、CDCl3): δ=4.11～3.98 (m, 4H), 3.74～3.68 (m, 4H), 3.42～3.30 (m, 12H), 3.23 (s, 2H), 3.13～3.08 (m, 4H), 2.92～2.89 (m, 2H), 2.79～2.76 (m, 4H), 2.59～2.56 (m, 4H), 2.35～2.22 (m, 4H), 1.46～1.39 (q, 4H), 0.88～0.83 (t, 6H)
GC-MS (CI): m/z=643 (M+1).
Synthesis example 2
The synthesis of 4,5-7-oxa-bicyclo[4.1.0-1,2-dioctyl phthalate double; two (double; two (2,3-glycidyl oxy methyl) propyl group of 3-(2,3-glycidoxy)-2,2-) ester
To with Dean-Stark apparatus, condenser reactor in add cis 4-cyclohexene-1,2-dicarboxylic acid anhydride 8.0g, p-methyl benzenesulfonic acid one water and thing 2.0g, toluene 150mL, pentaerythritol triallyl ether (70%) 39g, at a reflux temperature reaction 35 hours.Reaction carries out sodium bicarbonate water cleaning after terminating, water cleans, concentration, then with silica gel chromatography (hexane: ethyl acetate=90:10) purification, just obtain the 4 of colorless liquid, 5-7-oxa-bicyclo[4.1.0-1,2-dioctyl phthalate double; two (double; two (allyloxy methyl) propyl group of 3-(allyloxy) 2,2-) ester 17g.
H-NMR(300MHz、CDCl3): δ=5.92～5.79 (m, 6H), 5.66 (s, 2H), 5.26～5.11 (m, 12H), 4.25～4.10 (q, 4H), 3.94～3.91 (m, 12H), 3.49 (s, 12H), 3.03 (m, 2H), 2.61～2.54 (m, 2H), 2.39～2.31 (m, 2H)
GC-MS (CI): m/z=647 (M+1).
4,5-7-oxa-bicyclo[4.1.0-1 are added in reactor, 2-dioctyl phthalate double; two (double; two (allyloxy methyl) propyl group of 3-(allyloxy) 2,2-) ester 16g, chloroform 500mL, metachloroperbenzoic acid 60g, react 5 days.After reaction terminates, make reaction terminating with sodium thiosulfate solution, add sodium bicarbonate water, extract, organic layer is distilled off solvent, thus obtaining crude product.With silica gel chromatography (ethyl acetate=100) purification, thus obtaining colourless liquid 22g.
The compound obtained is 4,5-7-oxa-bicyclo[4.1.0-1, double; two (the 3-(2 of 2-dioctyl phthalate, 3-glycidoxy)-2,2-double; two (2,3-glycidyl oxy methyl) propyl group) ester, it is equivalent to the formula (4-3) corresponding with parent and the combination of the formula (2-2) corresponding with substituent group.
Viscosity is 15808mPa s at 25 DEG C.This epoxide is designated as (i-2).
H-NMR(300MHz、CDCl3): δ=4.22～4.10 (q, 4H), 3.74～3.69 (m, 6H), 3.53～3.44 (m, 12H), 3.36～3.31 (m, 6H), 3.24 (s, 2H), 3.13～3.08 (m, 6H), 2.93～2.89 (m, 2H), 2.78～2.75 (t, 6H), 2.59～2.56 (m, 6H), 2.32～2.24 (m, 4H)
LC-MS (ESI): m/z=759 (M+1).
Synthesis example 3
The synthesis of 1,2,3-propane tricarboxylic acid three (double; two (2,3-glycidyl oxy methyl) butyl of 2,2-) ester
To with Dean-Stark apparatus, condenser reactor in add propane-1,2,3-tricarboxylic acid 12g, p-methyl benzenesulfonic acid one water and thing 2.6g, toluene 200mL, trimethylolpropane allyl ether (90%) 49g, at a reflux temperature reaction 24 hours.Reaction carries out sodium bicarbonate water cleaning after terminating, water cleans, concentration, then with silica gel chromatography (hexane: ethyl acetate=80:20) purification, just obtain the 1 of yellow liquid form, 2,3-propane tricarboxylic acid three (2,2-double; two (allyloxy methyl) butyl) ester 46g.
H-NMR(300MHz、CDCl3): δ=5.92～5.79 (m, 6H), 5.27～5.12 (m, 12H), 4.06～4.05 (m, 6H), 3.93～3.91 (m, 12H), 3.30～3.23 (m, 13H), 2.82～2.74 (m, 4H), 1.47～1.39 (q, 6H), 0.87～0.82 (t, 9H)
GC-MS (CI): m/z=766 (M+1).
In reactor, add 1,2,3-propane tricarboxylic acid three (2,2-double; two (allyloxy methyl) butyl) ester 45g, chloroform 600mL, metachloroperbenzoic acid 87g, react 4 days.After reaction terminates, make reaction terminating with sodium thiosulfate solution, add sodium bicarbonate water, extract, organic layer is distilled off solvent, thus obtaining crude product.With silica gel chromatography (hexane: ethyl acetate=70:30) purification, thus obtaining colourless liquid 22g.
The compound obtained is 1,2,3-propane tricarboxylic acid three (2,2-double; two (2,3-glycidyl oxy methyl) butyl) ester, and it is equivalent to the formula (6-1) corresponding with parent and the combination of the formula (2-1) corresponding with substituent group.Viscosity is 5421mPa s at 25 DEG C.This epoxide is designated as (i-3).
H-NMR(300MHz、CDCl3): δ=4.05～4.04 (m, 6H), 3.73～3.68 (m, 6H), 3.42～3.24 (m, 19H), 3.12～3.10 (m, 6H), 2.83～2.80 (d, 2H), 2.78～2.75 (m, 6H), 2.65～2.63 (d, 2H), 2.59～2.56 (m, 6H), 1.46～1.39 (q, 6H), 0.88～0.83 (t, 9H)
LC-MS (ESI): m/z=861 (M+1).
Synthesis example 4
The synthesis of 1,2,3,4-ethylene-dimalonic acid four (double; two (2,3-glycidyl oxy methyl) butyl of 2,2-) ester
To with Dean-Stark apparatus, condenser reactor in add butane-1,2,3,4-tetracarboxylic acid dianhydride 7g, p-methyl benzenesulfonic acid one water and thing 0.7g, toluene 150mL, trimethylolpropane allyl ether (90%) 35g, at a reflux temperature reaction 51 hours.Reaction carries out sodium bicarbonate water cleaning after terminating, water cleans, concentration, then with silica gel chromatography (hexane: ethyl acetate=90:10) purification, just obtain the 1 of yellow liquid form, 2,3,4-ethylene-dimalonic acid four (2,2-double; two (allyloxy methyl) butyl) ester 20g.
H-NMR(300MHz、CDCl3): δ=5.92～5.79 (m, 8H), 5.27～5.12 (m, 16H), 4.13～4.00 (m, 8H), 3.95～3.91 (m, 16H), 3.32～3.30 (m, 18H), 2.85～2.76 (m, 2H), 2.40～2.35 (m, 2H), 1.45～1.41 (m, 8H), 0.87～0.81 (m, 12H)
TOF-MS (MALDI): m/z=1042 (M+Na).
Reactor adds 1,2,3,4-ethylene-dimalonic acid four (2,2-double; two (allyloxy methyl) butyl) ester 19g, chloroform 500mL, metachloroperbenzoic acid 42g, reacts 9 days.Reaction makes reaction terminating with sodium thiosulfate solution after terminating, and adds sodium bicarbonate water, extracts.Solvent is distilled off, thus obtaining crude product from organic layer.With silica gel chromatography (hexane: ethyl acetate=20:80) purification, add toluene 170g, activated carbon 3.4g after concentration, stir 3 hours.Filter out activated carbon, solvent is distilled off, thus obtaining light yellow liquid 16g.
The compound obtained is 1,2,3,4-ethylene-dimalonic acid four (2, double; two (2, the 3-glycidyl oxy methyl) butyl of 2-) ester, it is equivalent to the formula (6-2) corresponding with parent and the combination of the formula (2-1) corresponding with substituent group.
Viscosity is 12186mPa s at 25 DEG C.This epoxide is designated as (i-4).
H-NMR(300MHz、CDCl3): δ=4.15～3.97 (m, 8H), 3.72～3.68 (d, 8H), 3.42～3.32 (m, 26H), 3.13～3.09 (m, 8H), 2.85～2.82 (m, 2H), 2.78～2.75 (m, 8H), 2.59～2.56 (m, 8H), 2.45～2.39 (m, 2H), 1.45～1.41 (m, 8H), 0.88～0.82 (m, 12H)
TOF-MS (MALDI): m/z=1170 (M+Na).
Synthesis example 5
The synthesis of 1,3,5-tri-［ 2-(double; two (2,3-glycidyl oxy methyl) butoxy of 2,2-) carbonylethyl ］ isocyanuric acid ester
Trimethylolpropane allyl ether 45g, dichloromethane 360mL, 4-dimethylaminopyridine 23g, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride 36g, isocyanuric acid three (2-carboxy ethyl ester) 18g, room temperature reaction 3 days is added in reactor.After reaction terminates, organic layer hydrochloric acid, sodium bicarbonate water are cleaned, concentrates.With silica gel chromatography (hexane: ethyl acetate=80:20 → 50:50) purification, just obtain 1,3,5-tri-［ 2-(2,2-double; two (2,3-acrylic oxygen ylmethyl) butoxy) carbonylethyl ］ isocyanuric acid ester 27g of colorless liquid.
H-NMR(300MHz、CDCl3): δ=5.93～5.80 (m, 6H), 5.28～5.12 (m, 12H), 4.21～4.11 (m, 6H), 4.01 (s, 6H), 3.95～3.92 (m, 12H), 3.31 (s, 12H), 2.70～2.65 (m, 6H), 1.47～1.40 (m, 6H), 0.88～0.83 (m, 9H)
LC-MS (ESI): m/z=935 (M+1).
In reactor, add 1,3,5-tri-［ 2-(2,2-double; two (2,3-acrylic oxygen ylmethyl) butoxy) carbonylethyl ］ isocyanuric acid ester 27g, chloroform 530mL, metachloroperbenzoic acid 50g, react 3 days under room temperature.Reaction makes reaction terminating with sodium thiosulfate solution after terminating, and cleans with sodium bicarbonate water, water.Solvent is distilled off, thus obtaining crude product from organic layer.With silica gel chromatography (hexane: ethyl acetate=40:60 → 0:100) purification, concentrate, be subsequently adding toluene 250mL, activated carbon 5g, stirring.Filter out activated carbon, solvent is distilled off, thus obtaining colourless liquid 23g.
The compound obtained is 1,3,5-tri-［ 2-(2,2-double; two (2,3-glycidyl oxy methyl) butoxy) carbonylethyl ］ isocyanuric acid ester, it is equivalent to the formula (5-2) corresponding with parent and the combination of the formula (2-1) corresponding with substituent group.
Viscosity is 14464mPa s at 30 DEG C.This epoxide is designated as (i-5).
H-NMR(300MHz、CDCl3): δ=4.20～4.16 (m, 6H), 4.06 (s, 6H), 3.73～3.67 (m, 6H), 3.44～3.31 (m, 18H), 3.14～3.08 (m, 6H), 2.79～2.76 (m, 6H), 2.71～2.66 (m, 6H), 2.59～2.57 (m, 6H), 1.47～1.40 (m, 6H), 0.89～0.84 (m, 6H)
MALDI-TOFMS:m/z=1052.82 (M+Na)
Synthesis example 6
The synthesis of 1,3,5-tri-[2-(double; two (2,3-glycidyl oxy methyl)-3-(2,3-glycidoxy) propoxyl group of 2,2-) carbonylethyl] isocyanuric acid ester
In reactor, add tetramethylolmethane 56g, dichloromethane 400mL, 4-dimethylaminopyridine 29g, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride 46g, isocyanuric acid three (2-carboxy ethyl) ester 25g, at room temperature react a night.Organic layer hydrochloric acid, sodium bicarbonate water are cleaned after terminating by reaction, concentrate.With silica gel chromatography (hexane: ethyl acetate=90:10 → 80:20 → 60:40) purification, just obtain the 1 of colorless liquid, 3,5-tri-[2-(2,2-double; two (2,3-acrylic oxygen ylmethyl)-3-(2,3-acrylic oxygen base) propoxyl group) carbonylethyl] isocyanuric acid ester 24g.
H-NMR(300MHz、CDCl3): δ=5.92～5.79 (m, 9H), 5.27～5.12 (m, 18H), 4.18 (m, 12H), 3.95～3.92 (m, 18H), 3.43 (s, 18H), 2.70～2.65 (m, 6H)
TOF-MS (MALDI): m/z=1082.43 (M+Na)
1,3,5-tri-[2-(2 is added in reactor, 2-double; two (2,3-acrylic oxygen ylmethyl)-3-(2,3-acrylic oxygen base) propoxyl group) carbonylethyl] isocyanuric acid ester 23g, chloroform 1L, metachloroperbenzoic acid 63g, at room temperature reaction 6 days.Reaction makes reaction terminating with sodium thiosulfate solution after terminating, and cleans with sodium bicarbonate water, water.Solvent is distilled off, thus obtaining crude product from organic layer.With silica gel chromatography (hexane: ethyl acetate=20:80 → 0:100) purification, concentrate, be subsequently adding toluene 500mL, activated carbon 4g, be stirred.Filter out activated carbon, solvent is distilled off, thus obtaining colourless liquid 33g.
The compound obtained is 1,3,5-tri-[2-(2,2-double; two (2,3-glycidyl oxy methyl)-3-(2,3-glycidoxy) propoxyl group) carbonylethyl] isocyanuric acid ester, it is equivalent to the formula (5-2) corresponding with parent and the combination of the formula (2-2) corresponding with substituent group.
Viscosity is 15462mPa s at 30 DEG C.This epoxide is designated as (i-6).
H-NMR(300MHz、CDCl3): δ=4.20～4.15 (m, 12H), 3.74～3.31 (m, 36H), 3.12～3.08 (m, 9H), 2.79～2.57 (m, 24H)
TOF-MS (MALDI): m/z=1226.52 (M+Na)
Synthesis example 7
The synthesis of 1,3,5-tri-[2-(1-(2,3-glycidyl oxy methyl)-2-(2,3-glycidoxy) ethyoxyl) carbonylethyl] isocyanuric acid ester
In reactor, add isocyanuric acid three (2-carboxyethyl) 55g, DMF 170mL, after confirming dissolving, drip thionyl chloride 63g.At room temperature stirring 1 hour, filters the solid separated out, and cleans with chloroform, dries, thus obtaining 1,3,5-tri-(2-chloroformyl ethyl) isocyanuric acid ester 54g of white solid forms.
In reactor, add chloroform 100mL, glycerol-α, α '-diallyl ether 37g, pyridine 17g, then stir, add 1,3,5-tri-(2-chloroformyl ethyl) isocyanuric acid ester 20g bit by bit.React 3 hours at 65 DEG C.After solvent is distilled off, the salt separated out is filtered to remove, in filtrate, adds chloroform, clean with water.Organic layer is concentrated, then with silica gel chromatography (hexane: ethyl acetate=70:30 → 50:50) purification, just obtain the 1 of colorless liquid, 3,5-tri-[2-(1-(2,3-acrylic oxygen ylmethyl)-2-(2,3-acrylic oxygen base) ethyoxyl) carbonylethyl] isocyanuric acid ester 27g.
H-NMR(300MHz、CDCl3): δ=5.94～5.80 (m, 6H), 5.29～5.12 (m, 15H), 4.20～4.16 (m, 6H), 4.04～3.98 (m, 12H), 3.60～3.58 (d, 12H), 2.74～2.69 (t, 6H)
1 is added in reactor, 3,5-tri-[2-(1-(2,3-acrylic oxygen ylmethyl)-2-(2,3-acrylic oxygen base) ethyoxyl) carbonylethyl] isocyanuric acid ester 27g, chloroform 1L, metachloroperbenzoic acid 59g, at room temperature reaction 4 days.Reaction makes reaction terminating with sodium thiosulfate solution, is carried out with sodium bicarbonate water, water after terminating.Solvent is distilled off, thus obtaining crude product from organic layer.By silica gel chromatography (hexane: ethyl acetate=70:30 → 50:50 → 30:70 → 10:90 → 0:100) purification, add toluene 120mL, activated carbon 2g after concentration, be stirred.Filter out activated carbon, solvent is distilled off, thus obtaining colourless liquid 12g.
The compound obtained is 1,3,5-tri-[2-(1-(2,3-glycidyl oxy methyl)-2-(2,3-glycidoxy) ethyoxyl) carbonylethyl] isocyanuric acid ester, it is equivalent to the formula (5-2) corresponding with parent and the combination of the formula (2-3) corresponding with substituent group.
Viscosity is 18061mPa s at 30 DEG C.This epoxide is designated as (i-7).
H-NMR(300MHz、CDCl3): δ=5.15～5.12 (m, 3H), 4.21～4.16 (m, 6H), 3.83～3.35 (m, 24H), 3.14～3.13 (m, 6H), 2.80～2.58 (m, 18H)
LC-MS (ESI): m/z=905 (M+H)
Synthesis example 8
The synthesis of 1,3,5-tri-(double; two (2,3-glycidoxy) propyl group of 2,3-) isocyanuric acid ester
In reactor, add isocyanuric acid 30g, tetramethyl ammonium chloride 5g, 1,3-dimethyl-2-imidazolidinone 300mL, allyl glycidyl ether 95g, react 5 hours at 100 DEG C.After reaction terminates, extract by ethyl acetate, organic layer sodium bicarbonate water is cleaned, concentrates.With silica gel chromatography (hexane: ethyl acetate=30:70) purification, just obtain 1,3,5-tri-(2-hydroxyl-3-(2,3-acrylic oxygen base) propyl group) isocyanuric acid ester 37g of colorless liquid.
H-NMR(300MHz、CDCl3): δ=5.94～5.85 (m, 3H), 5.31～5.18 (m, 6H), 4.27～3.93 (m, 15H), 3.57～3.45 (m, 6H), 2.67～2.65 (m, 3H)
GC-MS (CI): m/z=471 (M)
In reactor, add sodium hydride 11g, dimethylformamide 700mL, stir at 0 DEG C and drip 1,3,5-tri-(2-hydroxyl-3-(2,3-acrylic oxygen base) propyl group) isocyanuric acid ester 35g, allyl bromide, bromoallylene 54g, at room temperature reaction 1 day.Reaction makes reaction terminating with water after terminating, and with methylbenzene extraction, is cleaned by organic layer saline solution, concentrates.With silica gel chromatography (hexane: ethyl acetate=80:20 → 50:50) purification, just obtain 1,3,5-tri-(2,3-double; two (2,3-acrylic oxygen base) propyl group) isocyanuric acid ester 13g of colorless liquid.
H-NMR(300MHz、CDCl3): δ=5.94～5.79 (m, 6H), 5.27～5.11 (m, 12H), 4.19～3.94 (m, 18H), 3.86～3.83 (m, 3H), 3.52～3.51 (m, 6H)
GC-MS (CI): m/z=592 (M+2)
1,3,5-tri-(2,3-double; two (2,3-acrylic oxygen base) propyl group) isocyanuric acid ester 21g, chloroform 630mL, metachloroperbenzoic acid 59g, at room temperature reaction 4 days are added in reactor.Reaction makes reaction terminating with sodium thiosulfate solution, is carried out with sodium bicarbonate water, water after terminating.Organic layer is distilled off solvent, thus obtaining crude product.With silica gel chromatography (hexane: ethyl acetate=20:80) purification, add toluene 320mL, activated carbon 7g after concentration, be stirred.Filter out activated carbon, solvent is distilled off, thus obtaining colourless liquid 30g.
The compound obtained is 1,3,5-tri-(2,3-double; two (2,3-glycidoxy) propyl group) isocyanuric acid ester, and it is equivalent to the formula (5-6) corresponding with parent and the combination of the formula (2-4) corresponding with substituent group.
Viscosity is 17011mPa s at 25 DEG C.This epoxide is designated as (i-8).
H-NMR(300MHz、CDCl3): δ=4.09～3.76 (m, 15H), 3.66～3.32 (m, 12H), 3.16～3.08 (m, 6H), 2.79～2.71 (m, 6H), 2.62～2.57 (m, 6H)
LC-MS (ESI): m/z=688 (M+1).
Synthesis example 9
The synthesis of double; two (double; two (2,3-glycidyl oxy methyl) butyl of 2,2-)-diamantane (obsolete)-1,3-dicarboxylic acid esters
1,3-adamantane acid 20g, methanol 200g, concentrated sulphuric acid 0.8g is added, at a reflux temperature reaction 2 hours in reactor.Reactant liquor is concentrated, adds toluene 200mL, first with sodium bicarbonate water, be carried out followed by with water.Organic layer is concentrated, then with silica gel chromatography (hexane: ethyl acetate=3:1) purification, just obtains 1,3-adamantane acid methyl ester 21g of white solid forms.
H-NMR(300MHz、CDCl3): δ=3.66 (s, 6H), 2.15～1.68 (m, 14H)
GC-MS (CI): m/z=253 (M+H)
1,3-adamantane acid methyl ester 20g, p-methyl benzenesulfonic acid water and thing 12g, toluene 200mL, trimethylolpropane allyl ether (90%) 70g is added, at a reflux temperature reaction 26 days in reactor.Reactant liquor is concentrated, is carried out with sodium bicarbonate water, sodium hydrate aqueous solution.Organic layer is concentrated, then with silica gel chromatography (hexane: ethyl acetate=100:0 → 95:5 → 80:20) purification, just obtain double; two (2,2-double; two (propenyloxy group methyl) butyl)-diamantane (obsolete)-1 of brown liquid form, 3-dicarboxylic acid esters 14g.
H-NMR(300MHz、CDCl3): δ=5.91～5.82 (m, 4H), 5.27～5.13 (m, 8H), 3.97 (s, 4H), 3.94～3.92 (m, 8H), 3.32 (s, 8H), 2.16～1.69 (m, 14H), 1.46～1.43 (q, 4H), 0.88～0.83 (t, 6H)
GC-MS (CI): m/z=618 (M+H)
Double; two (2,2-double; two (propenyloxy group methyl) butyl)-diamantane (obsolete)-1,3-dicarboxylic acid esters 13g, chloroform 500mL, metachloroperbenzoic acid 47g, at room temperature reaction 3 days are added in reactor.After reaction terminates, make reaction terminating with sodium thiosulfate solution, be carried out with sodium bicarbonate water, water.Solvent is distilled off, thus obtaining crude product from organic layer.With silica gel chromatography (hexane: ethyl acetate=70:30 → 50:50 → 30:70 → 10:90) purification, add toluene 130mL, activated carbon 3g after concentration, be stirred.Filter out activated carbon, solvent is distilled off, thus obtaining light yellow liquid 9g.
The compound obtained is double; two (2,2-double; two (2,3-glycidyl oxy methyl) butyl)-diamantane (obsolete)-1,3-dicarboxylic acid esters, it is equivalent to the formula (4-1) corresponding with parent and the combination of the formula (2-1) corresponding with substituent group.
Viscosity is 2609mPa s at 25 DEG C.This epoxide is designated as (i-9).
H-NMR(300MHz、CDCl3): δ=4.00 (s, 4H), 3.72～3.67 (m, 4H), 3.44～3.32 (m, 12H), 3.10 (s, 4H), 2.79～2.76 (m, 4H), 2.59～2.57 (m, 4H), 2.02～1.69 (m, 14H), 1.46～1.43 (q, 6H), 0.89～0.83 (t, 4H)
LC-MS (ESI): m/z=682 (M+H)
Relatively synthesis example 1
The synthesis of double; two (2,3-glycidyl) ester of 4,5-7-oxa-bicyclo[4.1.0-1,2-dioctyl phthalate
Cis-4-cyclohexene-1,2-dioctyl phthalate 15g, potassium carbonate 37g, dimethylformamide 255mL, allyl bromide, bromoallylene 32g, at room temperature reaction 15 hours are added in reactor.After reaction terminates, filter, add toluene and water extracts.Carry out water cleaning, concentration, with silica gel chromatography (hexane: ethyl acetate=75:25) purification, just obtain 4-cyclohexene-1 of light yellow liquid form, double; two (2-acrylic) the ester 21g of 2-dioctyl phthalate.
H-NMR(300MHz、CDCl3): δ=5.96～5.82 (m, 2H), 5.68～5.67 (m, 2H), 5.33～5.19 (m, 4H), 4.60～4.58 (m, 4H), 3.11～3.07 (m, 2H), 2.62～2.55 (m, 2H), 2.41～2.33 (m, 2H)
GC-MS (CI): m/z=250 (M).
4-cyclohexene-1 is added in reactor, 2-dioctyl phthalate double; two (2-acrylic) ester 21g, chloroform 300mL, it is cooled to 0-10 DEG C, is subsequently adding metachloroperbenzoic acid 87g, be warmed up to room temperature, react 5 days.After reaction terminates, make reaction terminating with sodium thiosulfate solution, add sodium bicarbonate water, extract.Cleaned by organic layer sodium bicarbonate water, water cleans, and then dries, is distilled off by solvent, thus obtaining crude product.With silica gel chromatography (hexane: ethyl acetate=50:50 → 10:90) purification, thus obtaining colourless liquid 20g.
The compound obtained is double; two (2,3-glycidyl) ester of 4,5-7-oxa-bicyclo[4.1.0-1,2-dioctyl phthalate.
Viscosity is 1992mPa s at 25 DEG C.This epoxide is designated as (i-10).
H-NMR(300MHz、CDCl3): δ=4.51～4.41 (m, 2H), 3.96～3.84 (m, 2H), 3.25～3.19 (m, 4H), 3.01～2.98 (m, 2H), 2.84～2.81 (m, 2H), 2.66～2.61 (m, 2H), 2.27～2.20 (m, 4H)
GC-MS (CI): m/z=298 (M).
Relatively synthesis example 2
The synthesis of four (2,3-glycidyl)-1,2,3,4-ethylene-dimalonic acid ester
1,2,3,4-ethylene-dimalonic acid 53g, potassium carbonate 155g, DMF 892mL, allyl bromide, bromoallylene 177g is added, reaction 11 hours under 68 degree in reactor.After reaction terminates, clean with toluene, and be carried out with water, concentration, then with silica gel chromatography (hexane: ethyl acetate=80:20) purification, just obtains the 1 of light yellow liquid form, 2,3,4-ethylene-dimalonic acid four (2-acrylic) ester 71g.
H-NMR(300MHz、CDCl3): δ=5.94～5.82 (m, 4H), 5.35～5.22 (m, 8H), 4.61～4.58 (m, 8H), 3.41～3.37 (m, 2H), 2.90～2.81 (m, 2H), 2.50～2.43 (m, 2H)
GC-MS (CI): m/z=395 (M+H),
In reactor, add four (2-acrylic)-1,2,3,4-ethylene-dimalonic acid ester 40g, chloroform 800mL, after being cooled to 0-10 DEG C, add metachloroperbenzoic acid 112g, be warmed up to room temperature, react 96 hours.After reaction terminates, make reaction terminating with sodium thiosulfate solution, add sodium bicarbonate water, extract.Organic layers with water being cleaned, solvent being distilled off, thus obtaining crude product.With silica gel chromatography (hexane: ethyl acetate=20:80) purification, thus obtaining colourless liquid 22g.At room temperature place, with regard to crystallization, with ethanol purge, thus obtaining white solid.Measure the fusing point of crystallization with DSC, result is 49.6 DEG C.The compound obtained is 1,2,3,4-ethylene-dimalonic acid four (3,4-glycidyl) ester.
This epoxide is designated as (i-11).
H-NMR(300MHz、CDCl3): δ=4.52～4.42 (m, 4H), 4.00～3.90 (m, 4H), 3.44～3.41 (m, 2H), 3.25～3.18 (m, 4H), 2.93～2.83 (m, 6H), 2.67～2.63 (m, 4H), 2.55～2.49 (m, 2H)
LC-MS (ESI): m/z=481.2 (M+Na).
Relatively synthesis example 3
The synthesis of double; two (2,3-glycidyl)-diamantane (obsolete)-1,3-dicarboxylic acid esters
In reactor, add 1,3-adamantane acid 20g, potassium carbonate 32g, DMF 500mL, allyl bromide, bromoallylene 32g, react 4 hours at 65 DEG C.By reacting liquid filtering, in filtrate, add toluene, be carried out with water.The organic layer concentration that will obtain, just obtains double; two (2,3-acrylic)-diamantane (obsolete)-1 of yellow liquid form, 3-dicarboxylic acid esters 28g.
H-NMR(300MHz、CDCl3): δ=5.97～5.84 (m, 2H), 5.33～5.20 (m, 4H), 4.58～4.55 (m, 4H), 2.17～1.69 (m, 14H)
GC-MS (CI): m/z=304 (M).
Diamantane (obsolete)-1 is added in reactor, 3-dioctyl phthalate double; two (2,3-acrylic) ester 27g, metachloroperbenzoic acid 62g, chloroform 500mL, at room temperature reaction 5 days.After reaction terminates, make reaction terminating with sodium thiosulfate solution, add sodium bicarbonate water, extract.Organic layers with water being cleaned, solvent being distilled off, thus obtaining crude product.With silica gel chromatography (hexane: ethyl acetate=70:30 → 50:50) purification, add toluene 250mL, activated carbon 5g after concentration, be stirred.Filter out activated carbon, solvent is distilled off, thus obtaining colourless liquid 20g.
The compound obtained is double; two (2,3-glycidyl) ester of diamantane (obsolete)-1,3-dioctyl phthalate.
Viscosity is 207mPa s at 25 DEG C.This epoxide is designated as (i-12).
H-NMR(300MHz、CDCl3): δ=4.43～4.38 (m, 2H), 3.96～3.90 (m, 2H), 3.23～3.17 (m, 2H), 2.86～2.83 (m, 2H), 2.66～2.63 (m, 2H), 2.18～1.70 (m, 14H)
GC-MS (CI): m/z=336 (M)
As aqueous epoxide, prepare 3 ', 4 '-epoxycyclohexyl formic acid 3,4-epoxycyclohexyl-methyl ester of formula (7-5).This epoxide is designated as (i-13).
The hydrogenated bisphenol A type diglycidyl ether of formula (7-3) is prepared as aqueous epoxide.This epoxide is designated as (i-14).
(preparation of photoacid generator)
Polypropylene carbonate ester solution (formula (8-2), effective ingredient 50%, trade name CPI-101A, サ Application ア プ ロ Co., Ltd. system) as sulfonium salt.It is designated as photoacid generator (ii-1).
Prepare the polypropylene carbonate ester solution (formula (8-1), effective ingredient 50%, trade name CPI-100P, サ Application ア プ ロ Co., Ltd. system) of sulfonium salt, be designated as photoacid generator (ii-2).
(preparation of solidification compound and photo-curable test)
Embodiment 1
Epoxide and photoacid generator are coordinated with the ratio shown in table 1, with can be stirred device with deaeration (trade name: あ わ and り Taro, シ Application キ Co., Ltd. system) carry out mixing, deaeration, and make solidification compound.Use level is all recorded with mass parts, and what epoxide and photoacid generator were recorded is the mass parts of effective ingredient.For the photoacid generator (ii-1) of polypropylene carbonate ester solution, (ii-2), it is made directly use.
From the distance of 9.5cm, the solidification compound that makes is irradiated UV (ultraviolet), observe photocuring variation with flow graph (viscometer), storage modulus is reached the 4 power Pa (1 × 10 of 104Pa) time (second) is defined as hardening time (second).UV irradiates and carries out 600 seconds.
Flow graph uses レ オ ロ ジ カ company's system (trade name VAR-50 type), and lamp uses Hg-Xe lamp, and the UV wavelength of irradiation is 365nm, and irradiation dose is 20mW/cm2.Illumination window material in UV irradiation uses hard glass thick for 3mm, solidification compound the thickness of the film formed is 50 μm.Measure the cure times of solidification compound, be recorded in table 1.
Embodiment 2～embodiment 8 and comparative example 1～comparative example 5
In the way of same with above-described embodiment 1, prepare solidification compound with the mixing ratio shown in table 1～table 4, measure the cure times of solidification compound, be recorded in table 1～table 4.
[table 1]
[table 2]
[table 3]
[table 4]
Embodiment 9
The 75 μm of applicators of solidification compound made in the way of same with above-described embodiment 1, with the mixing ratio shown in table 5 are applied in PET film (Japan spins A4100125 μm), irradiate UV (ultraviolet) with following accumulated light from the distance of 26.5cm, after irradiation, do not glue test (finger touches test drying time) at once.
UV irradiating machine uses the batch type of furnace ultraviolet curing device of 2kW × 1 lamp (ア イ グ ラ Off ィ ッ Network ス company system), and lamp use Hg lamp (H02-L412.0kW ア イ グ ラ Off ィ ッ Network ス company system), illumination is 20mW/cm2(365nm).Illumination window material in UV irradiation uses quartz glass.The not viscous time of solidification compound is evaluated, is recorded in table 5.
Embodiment 10, comparative example 6～comparative example 9
Prepare solidification compound in mode in the same manner as above-described embodiment 9 with the mixing ratio shown in table 5, evaluate the not viscous time of solidification compound, be recorded in table 5.
It should be noted that, metewand in table 5 be point below 5 class be evaluated: solidify (◎), somewhat tacky (zero), leave finger mark (△), although surface cure but internal uncured (△ ×), uncured (×).
[table 5]
(being made of thermosetting compound)
Embodiment 11
The anhydride curing agent リ カ シ ッ De MH-700 mixture of mol ratio 70:30 of 4-methylhexahydrophthalic anhydride and hexahydrophthalic anhydride (trade name, new Japan Chemical company system, the composition are) of the epoxide (i-1) of 24.6g and 31.3g is added, under decompression, at room temperature stirring deaeration 30 minutes in reactor.(trade name, Japan's synthetic chemical industry company system, composition are the tetrabutyls to add the ヒ シ U リ Application PX-4ET of 0.25g as curing acceleratorDiethyl dithiophosphate), and then stir deaeration 5 minutes.This mixture is injected the silicone rubber that clips 3mm processed with releasing agent glass plate (use releasing agent SR-2410 (trade name), east レ ダ ウ conning company, processed 1 hour at 150 DEG C.) between, at 100 DEG C, carrying out precuring in 2 hours, main solidification is the solidification carried out at 150 DEG C 5 hours.
Embodiment 12
The ヒ シ U リ Application PX-4ET of the epoxide (i-2) of 9.4g, リ カ シ ッ De MH-700,0.10g of 14.3g is added in the way of same with above-described embodiment 1, thus obtaining solidfied material.
Embodiment 13
The ヒ シ U リ Application PX-4ET of the epoxide (i-3) of 16.5g, リ カ シ ッ De MH-700,0.17g of 18.7g is added in the way of same with above-described embodiment 1, thus obtaining solidfied material.
Embodiment 14
The ヒ シ U リ Application PX-4ET of the epoxide (i-4) of 10.2g, リ カ シ ッ De MH-700,0.11g of 11.7g is added in the way of same with above-described embodiment 1, thus obtaining solidfied material.
Embodiment 15
The ヒ シ U リ Application PX-4ET of the epoxide (i-5) of 5.02g, リ カ シ ッ De MH-700,0.063g of 4.66g is added in the way of same with above-described embodiment 1, thus obtaining solidfied material.
Embodiment 16
The ヒ シ U リ Application PX-4ET of the epoxide (i-6) of 13.5g, リ カ シ ッ De MH-700,0.13g of 16.6g is added in the way of same with above-described embodiment 1, thus obtaining solidfied material.
Embodiment 17
The ヒ シ U リ Application PX-4ET of the epoxide (i-7) of 7.66g, リ カ シ ッ De MH-700,0.078g of 8.38g is added in the way of same with above-described embodiment 1, thus obtaining solidfied material.
Embodiment 18
The ヒ シ U リ Application PX-4ET of the epoxide (i-8) of 14.2g, リ カ シ ッ De MH-700,0.15g of 20.0g is added in the way of same with above-described embodiment 1, thus obtaining solidfied material.
Comparative example 10
The ヒ シ U リ Application PX-4ET of the epoxide (i-5) of 14.7g, リ カ シ ッ De MH-700,0.15g of 24.1g is added in the way of same with above-described embodiment 1, thus obtaining solidfied material.
Comparative example 11
The ヒ シ U リ Application PX-4ET of the epoxide (i-6) of 14.6g, リ カ シ ッ De MH-700,0.15g of 20.9g is added in the way of same with above-described embodiment 1, thus obtaining solidfied material.
The solidfied material obtained is measured bend test (bending strength and the modulus of elasticity in static bending), absorbance, linear expansivity, glass transition temperatures at 3.
(mensuration of flexural property)
It is measured by universal testing machine based on JISK-6911.
Examination measures the height and width testing sheet, props up test piece, with pressurization wedge to its central authorities' imposed load, measures load when test piece has been rolled over, calculates bending strength (σ).
Bending strength σ: (MPa) { kgf/mm2}
P: the load (N) { kgf } when test piece has been rolled over
L: distance between the fulcrum (mm)
W: the width (mm) of test piece
H: the height (mm) of test piece.
σ=(3PL)/(2Wh2)
The modulus of elasticity in static bending (E) refers to (MPa) { kgf/mm2, F/Y refers to the slope (N/mm) { kgf/mm } of the straight line portion of load-strain curve,
E=(L3/(4Wh3)〕×〔F/Y〕
(mensuration of absorbance)
Use the absorbance of spectrophotometer 400nm.
(mensuration of linear expansivity)
The mensuration of linear expansivity, is measured based on JISK-6911.
The thickness of Accurate Determining test piece, expands compression method with TMA (thermo-mechanical analysis) and is measured with the condition of load 0.05N, programming rate 5 DEG C/minute.
Linear expansion coefficient α 1, is length (the L) × 50=α 1 at the initial stage of variable quantity (Δ the L1)/test piece of the length of 30～80 DEG C.
(mensuration of glass transition temperature (Tg))
The thickness of Accurate Determining test piece, is measured with the condition of load 0.05N, programming rate 5 DEG C/minute with the compression method that expands of TMA.The curve of the front and back of glass transition point is drawn tangent line, obtains Tg according to the intersection point of this tangent line.
[table 6]
Industry utilizability
The solidification compound of the epoxide containing the present invention, there is light and heat curable, there is the high close attachment of opposing substrate, high transparent (transparency of relative visible ray), the firmly advantageous feature such as painting property, high-fire resistance, it is possible to for electronic unit, optics, precision mechanism parts covering or bonding.May be used for the bonding of the parts etc. of the engine interior of the such as magnet assembly of hard disk of the parts of the optical element of the lens of mobile portable phone, camera, light emitting diode (LED), semiconductor laser (LD) etc., liquid crystal panel, biochip, the lens of camera, prism etc., computer etc., CD, the reading part (part of the optical information that dish reflects can be read) of DVD player, the oscillating plate of rising tune device and line, the Magnetitum of motor, circuit substrate, electronic unit, automobile etc.
Hard coat material as the surface protection for car body, lamp, appliances, building materials, plastics etc., it is possible to for lens or illuminator, the plastic lens of glasses, mobile portable phone, game machine, blooming, the ID card etc. of the such as car body of automobile, motorcycle, headlight.
As being used on metal, the plastics etc. such as aluminum the ink material of printing, it is possible to list for the card class such as the credit card, membership card, appliances, the switch of office equipment, keyboard printing black, black for the ink-jet printer of CD, DVD etc..
In addition, the solidification compound of the present invention can combine with 3 Vc AD, the technology of the stereoscopic article of complexity is made for making resin solidify, in the light appearance such as the modelling for industrial product, it is possible to list the coating for optical fiber, bonding, fiber waveguide, thick film resist (MEMS uses) etc..

Claims (14)

1. the epoxide represented by following formula (1),
In formula (1), A represents that the unsaturated alkyl of the carbon number 2～10 of (n4) valency, the cyclic hydrocarbon group of carbon number 4～20 of (n4) valency, (n4) valency are containing azo-cycle base, the chain alkyl of the carbon number 3～10 of (n4) valency or their (n4) valency groups of combining, R1And R2Separately represent the alkyl of hydrogen atom or carbon number 1～10, R3Representing (n3+1) valency alkyl, n1 represents that integer 2, n2 represents that integer 1, n3 represents integer 2～5, and n4 represents integer 2～8,
When A represents the chain alkyl of the carbon number 3～10 of the unsaturated alkyl of the carbon number 2～10 of (n4) valency, the cyclic hydrocarbon group of carbon number 4～20 of (n4) valency, (n4) valency, n5 represents that integer 1, n6 represents integer 1；
When A represents (n4) valency containing azo-cycle base, n5 represents integer 0 or 1, and n6 represents integer 0 or 1.
2. epoxide as claimed in claim 1, when A represents (n4) valency group that the unsaturated alkyl of the carbon number 2～10 of (n4) valency, the cyclic hydrocarbon group of carbon number 4～20 of (n4) valency, (n4) valency chain alkyl containing azo-cycle base, the carbon number 3～10 of (n4) valency combine, n5 represents that integer 1, n6 represents integer 1.
3. epoxide as claimed in claim 1 or 2, described A remove (n4) individual hydrogen atom from ethylene, propylene or norborene after (n4) valency unsaturated alkyl.
4. epoxide as claimed in claim 1 or 2, described A from Tetramethylene., Pentamethylene., hexamethylene, 7-oxa-bicyclo[4.1.0, removed (n4) valency cyclic hydrocarbon group after (n4) individual hydrogen atom by alkyl substituted 7-oxa-bicyclo[4.1.0, double-heptene, bicyclooctene or diamantane (obsolete).
5. epoxide as claimed in claim 1 or 2, described A remove (n4) individual hydrogen atom from trialkyl isocyanuric acid ester after (n4) valency containing azo-cycle base.
6. epoxide as claimed in claim 1 or 2, described A remove (n4) individual hydrogen atom from propane, butane, pentane or hexane after (n4) valency chain alkyl.
7. a solidification compound, epoxide described in any one containing claim 1～6 and firming agent.
8. solidification compound as claimed in claim 7, described firming agent is anhydride, amine, phenolic resin, polyamide, imidazoles or multi-thiol.
9. solidification compound as claimed in claim 7 or 8, relative to epoxy radicals 1 equivalent of described epoxide, contains described firming agent with the ratio of 0.5～1.5 equivalent.
10. a solidification compound, epoxide described in any one containing claim 1～6 and acid agent.
11. solidification compound as claimed in claim 10, described acid agent is photoacid generator or thermal acid generator.
12. solidification compound as claimed in claim 11, described acid agent isSalt.
13. solidification compound as claimed in claim 11, described acid agent is sulfonium salt compound or iodineSalt compound.
14. the solidification compound as described in any one of claim 10～13, relative to the quality of described epoxide, contain described acid agent with the ratio of 0.1～20 mass %.
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