CN105968001A - Carboxyl-containing reactive compound, hardened resin composition using same, and hardened substance - Google Patents
Carboxyl-containing reactive compound, hardened resin composition using same, and hardened substance Download PDFInfo
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- CN105968001A CN105968001A CN201610140971.5A CN201610140971A CN105968001A CN 105968001 A CN105968001 A CN 105968001A CN 201610140971 A CN201610140971 A CN 201610140971A CN 105968001 A CN105968001 A CN 105968001A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
- C07C69/75—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring of acids with a six-membered ring
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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
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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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- Organic Chemistry (AREA)
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- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Polyesters Or Polycarbonates (AREA)
- Epoxy Resins (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention provides a reactive material which is hardened through ultraviolet rays and other active energy rays, and the reactive material has high heat resistance and low colorability. The solution is to provide a carboxyl-containing reactive compound, a hardened resin composition using the same, and a hardened substance. The carboxyl-containing reactive compound is obtained by making multifunctional anhydride react with a compound which contains more than one polymerizable ethylene unsaturated radical and more than one hydroxyl in one molecule, the multifunctional anhydride being obtained by reacting hydrogenated trimellitic anhydride acyl halide or trimellitic anhydride acyl halide with polyatomic alcohol. The multifunctional reactant is obtained by reacting the carboxyl-containing reactive compound with a compound which contains more than one polymerizable ethylene unsaturated radical and more than one epoxy group in one molecule.
Description
Technical field
The present invention is about a kind of reactive compounds containing carboxyl and combinations thereof thing, purposes, and it is at polyol
Thing imports anhydride group, with molecule, there is more than 1 polymerizable ethylene unsaturated group and more than 1 hydroxyl the most further
Compound reaction and person.
Background technology
As representational solder resist material in display element photoresist representational in color filter, printed circuit board (PCB)
Material, has the reactivity containing carboxyl making the anhydride such as succinic anhydrides, tetrahydrochysene anhydride phthalic acid react and to obtain with acrylic acid epoxy ester etc.
Compound.Should the reactive compounds containing carboxyl be low acid value and the developability with excellence, and welding resistance print can be used in
In ink (patent documentation 1).
Owing to the modified acrylic acid epoxy ester series of existing acid has molecular weight distribution widely, therefore as minus resist material
When material uses, if making the dissolution of non-irradiated portion with the developer solution of alkalescence, then irradiation portion cannot be the most molten with the boundary in non-irradiated portion
Go out, and have the problem that the resolution of edge line deteriorates.
And, acid modified acroleic acid epoxy ester series uses epoxide as raw material.Therefore, manufacture epoxidation can be remained
Raw material during compound, for example originating from the halogenic ingredient of chloropropylene oxide.This acid modified acroleic acid epoxy ester series is used in solder resist etc.
During electronic circuit encapsulant, may be to long-term circuit having undesirable effect property of reliability by censuring this halogenic ingredient.
Furthermore, when the chromatic photoresist etc. of color filter uses acid modified acroleic acid epoxy ester series, acid modified acroleic acid ring
The usually use of oxygen esters derives from polyfunctional aromatic epoxies base class person.This is to maintain acid modified acroleic acid epoxy ester series
Thermostability.But, this acid modified acroleic acid esters has and produces the problem (patents such as xanthochromia in manufacturing step because of heat treated
Document 2).
At the anhydride that the manufacture of existing acid modified acroleic acid epoxy ester series is used, it is mainly used in 1 molecule containing 1
Individual anhydride group person.If using containing more than 2 anhydride group persons in 1 molecule, then due to acid modified acroleic acid epoxy ester series 1 molecule
In hydroxyl become many, carry out intermolecular cross-linking reaction, and be difficult to control to molecular weight.
In patent documentation 3, record a kind of method obtaining resist compositions, be 1 molecule to have 2 anhydride group from making
Compound and 1 molecule in there is the compound of hydroxyl and unsaturated group react and obtain half-esterification compound, make this half-esterification
Compound reacts with epoxide further, and obtains resist compositions, but, patent documentation 3 is not recorded such as this
The compound derived by the compound in 1 molecule with more than 3 anhydride group of invention or compositions.
[prior art literature]
[patent documentation]
Patent documentation 1: International Publication WO2008/004630 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2005-126674 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2005-206803 publication
Summary of the invention
[problem that invention to be solved]
The problem of the present invention is to provide a kind of reaction resin, and it has good photoreactivity, developability, is adapted as
Minus resist properties of materials.
[in order to solve the means of problem]
The present inventor in order to solve aforesaid problem, find the multifunctional anhydride (A) making to have particular configuration with in 1 molecule
There is compound (B) reaction of more than 1 polymerizable ethylene unsaturated group and more than 1 hydroxyl and obtain containing carboxyl
Reactive compounds (C), has resin characteristics excellent especially.
That is, the present invention about
(1) a kind of reactive compounds (C) containing carboxyl, makes at least have more than 3 hydroxyls in 1 molecule many
Unit's alcohol (a) hydrogenates trimellitic anhydride etheride (nuclear hydrogenated trimellitic with core
Anhydride halide) (b-1) or trimellitic anhydride etheride (trimellitic anhydride halide) (b-
2) react and obtain multifunctional anhydride (A), make that this multifunctional anhydride (A) and 1 molecule have more than 1 polymerizable second further
The compound (B) of alkene unsaturated group and more than 1 hydroxyl reacts and obtains.
(2) a kind of reactive compounds (C) containing carboxyl, makes at least have more than 3 hydroxyls in 1 molecule many
Unit's alcohol (a) reacts with core hydrogenation trimellitic anhydride etheride (b-1) or trimellitic anhydride etheride (b-2) and obtains
Multifunctional anhydride (A), makes have more than 1 polymerizable ethylene unsaturated group in this multifunctional anhydride (A) and 1 molecule further
And more than 1 hydroxyl compound (B) reaction and obtain, described polyhydric alcohol (a) be shown in following formula (1) in 1 molecule extremely
Contain the polyhydric alcohol (a-1) of 3 hydroxyls less:
(in formula, R1、R2、R3、R4、R5、R6The most independent, R1、R3、R4、R5、R6Represent hydrogen atom, hydroxyl, carbon number 1 to 11
Alkyl or the hydroxy alkyl of carbon number 1 to 4, R2Represent hydroxyl or the hydroxy alkyl of carbon number 1 to 4.L represents the integer of 0 to 11, m and n
Each represent the integer of 1 to 11).
(3) a kind of reactive compounds (C) containing carboxyl, makes at least have more than 3 hydroxyls in 1 molecule many
Unit's alcohol (a) reacts with core hydrogenation trimellitic anhydride etheride (b-1) or trimellitic anhydride etheride (b-2) and obtains
Multifunctional anhydride (A), makes have more than 1 polymerizable ethylene unsaturated group in this multifunctional anhydride (A) and 1 molecule further
And the compound (B) of more than 1 hydroxyl reacts and obtains, described polyhydric alcohol (a) is for making this polyhydric alcohol (a) and selected from alkylene oxide, ring
More than 1 reactions in shape ether and cyclic ester Suo Cheng group and the polyhydric alcohol (a-2) that obtains.
(4) a kind of multifunctional reactive compounds (E), is to make the reactive compounds containing carboxyl described in (1) or (2)
(C) there is the compound (D) of more than 1 polymerizable ethylene unsaturated group and more than 1 epoxy radicals react with 1 molecule and obtain
Person.
(5) a kind of multifunctional reactive compounds (E), be make described in (3) containing carboxyl reactive compound (C) and 1
Molecule has compound (D) reaction of more than 1 polymerizable ethylene unsaturated group and more than 1 epoxy radicals and obtains person.
(6) a kind of active energy beam hardened resin composition, it comprises the reactive compounds described in (1) or (2)
(C)。
(7) a kind of active energy beam hardened resin composition, it comprises the reactive compounds (C) described in (3).
(8) a kind of active energy beam hardened resin composition, it comprises the multifunctional reactive compounds described in (4)
(E)。
(9) a kind of active energy beam hardened resin composition, it comprises the multifunctional reactive compounds described in (5)
(E)。
(10) the active energy beam hardened resin composition as described in (6), is tunicle formation material.
(11) the active energy beam hardened resin composition as described in (7), is tunicle formation material.
(12) the active energy beam hardened resin composition as described in (8), is tunicle formation material.
(13) the active energy beam hardened resin composition as described in (9), is tunicle formation material.
(14) the active energy beam hardened resin composition as described in (6), is hardened by active energy beam
Painting material.
(15) the active energy beam hardened resin composition as described in (7), is hardened by active energy beam
Painting material.
(16) the active energy beam hardened resin composition as described in (8), is hardened by active energy beam
Painting material.
(17) the active energy beam hardened resin composition as described in (9), is hardened by active energy beam
Painting material.
(18) a kind of hardening thing, is the hardening thing of active energy beam hardened resin composition described in (6).
(19) a kind of hardening thing, is the hardening thing of active energy beam hardened resin composition described in (7).
(20) a kind of hardening thing, is the hardening thing of active energy beam hardened resin composition described in (8).
(21) a kind of hardening thing, is the hardening thing of active energy beam hardened resin composition described in (9).
(22) a kind of hardening thing, be described in (10) by the hardening thing of film formation material.
(23) a kind of hardening thing, be described in (11) by the hardening thing of film formation material.
(24) a kind of hardening thing, be described in (12) by the hardening thing of film formation material.
(25) a kind of hardening thing, be described in (13) by the hardening thing of film formation material.
(26) a kind of hardening thing, is the hardening thing of the painting material hardened by active energy beam described in (14).
(27) a kind of hardening thing, is the hardening thing of the painting material hardened by active energy beam described in (15).
(28) a kind of hardening thing, is the hardening thing of the painting material hardened by active energy beam described in (16).
(29) a kind of hardening thing, is the hardening thing of the painting material hardened by active energy beam described in (17).
[invention effect]
The reactive compounds (C) containing carboxyl of the present invention and multifunctional reactive compounds (E) have excellence
Reactive, there is the developability of excellence in light drawing, and provide tough hardening thing.
The reactive compounds (C) containing carboxyl of the present invention and multifunctional reactive compounds (E) can be used for printing electricity
Road plate solder resist, conductor package substrate interlayer dielectic, flexible printed circuit solder resist, plating resist etc.
In.
Particularly use the feature of its high coloring and high-fire resistance, be also applied for chromatic photoresist useful in color filter etc.
Deng, black-matrix material, interval insulant etc..
And, the reactive compounds (C) containing carboxyl of the present invention and multifunctional reactive compounds (E) are used as
In purposes such as the fiber waveguides by light chartography.
Detailed description of the invention
The reactive compounds (C) containing carboxyl of the present invention, makes at least have more than 3 hydroxyls in 1 molecule
Polyhydric alcohol (a) reacts with core hydrogenation trimellitic anhydride etheride (b-1) or trimellitic anhydride etheride (b-2) and obtains
To multifunctional anhydride (A), make that this multifunctional anhydride (A) and 1 molecule have more than 1 polymerizable ethylene unsaturation further
The compound (B) of base and more than 1 hydroxyl reacts and obtains person.
The multifunctional reactive compounds (E) of the present invention is the reactive compounds (C) and 1 containing carboxyl making the present invention
Molecule has compound (D) reaction of more than 1 polymerisable ethylene unsaturated group and more than 1 epoxy radicals and obtains person.
The polyhydric alcohol (a) used in the present invention is at least to have more than 3 hydroxyl persons in 1 molecule.Hydroxyl is in 1 molecule
When being less than 2, firm crosslinked configuration cannot be constituted when becoming final hardening thing.
Polyhydric alcohol (a) in the present invention is more preferably for having the structure shown in following formula (1).
(in formula, R1、R2、R3、R4、R5、R6The most independent, R1、R3、R4、R5、R6Represent hydrogen atom, hydroxyl, carbon number 1 to 11
Alkyl or the hydroxy alkyl of carbon number 1 to 4, R2Represent hydroxyl or the hydroxy alkyl of carbon number 1 to 4.L represents the integer of 0 to 11, m with
N each represents the integer of 1 to 11).
In above-mentioned formula (1), when l or m is more than 2, for there is multiple R1、R3、R4、R6In, each R1、R3、R4、R6Can
For different substituent groups.Such as, during l=4,4 R existed1Can be 4 identical substituent groups, it is possible to be all different replacements
Base.R3、R4、R6Also with R1Identical.
As the concrete example of polyhydric alcohol (a), can enumerate: glycerol, trimethylolethane, trimethylolpropane, trihydroxy methyl
Butane, 1,2,4-butantriol, 2-hydroxy alkyl methyl isophthalic acid, 4-butanediol, 1,2,5-penta triol, 1,3,5-penta triol, 3-methyl
Pentane-1,3,5-triol, 1,2,6-hexanetriol, the pungent triol of 1,2,8--, 1,2,9-nonyl triol, 1,2,10-triol in the last of the ten Heavenly stems, trimerization are different
Three alcohols such as hydracid three-2-hydroxyethyl ester；Two (trimethylolpropanes), 1,1,2,2-second tetrol, erythritol, new penta 4
Alcohol, 1,2,3,5-penta tetrol, 1,2,4,5-penta tetrol, 1,1,5,5-penta tetrol, the own tetrol of 1,2,5,6-, 1,2,7,8-pungent four
Four alcohols such as alcohol, 1,2,9,10-tetrol in the last of the ten Heavenly stems；The polyhydric alcohol etc. such as double (new penta tetrols), polyglycereol.
Among such, when using the polyhydric alcohol to have 4 to 6 hydroxyls in the molecule shown in formula (1), obtained is hard
The excellent of compound.By the superperformance of hardening thing, material acquirement easness viewpoint from the point of view of, especially with new penta tetrol, two
(trimethylolpropane), double (new penta tetrols) are more preferably.
The polyhydric alcohol (a-2) of the present invention, refers to have in polyhydric alcohol (a) addition polymerization selected from alkylene oxide, cyclic ether and ring
The compound of the structure of more than 1 in Zhuan Zhisuocheng group.And, polyhydric alcohol (a-2) also visual purposes and by reactivity, firmly
The characteristic optimization of compound.
With R in formula (1)1Shown alkyl refers to the atomic group being only made up of carbon atom and hydrogen atom.
The carbon number of alkyl is more preferably 1 to 11.As concrete example, can enumerate: methyl, ethyl, n-pro-pyl, isopropyl, just
Butyl, isobutyl group, the tert-butyl group, the amyl group of straight or branched, the hexyl of straight or branched, the heptyl of straight or branched, straight chain or
The aliphatic hydroxyls such as the octyl group of side chain；The ester ring type alkyl such as cyclohexyl, methylcyclohexyl, ethylcyclohexyl；Phenyl, tolyl,
The aromatic series bases such as naphthyl, methyl naphthyl；The aromatic series such as benzyl, naphthyl methyl replaces alkyl etc..In the present invention, hard by the present invention
From the point of view of compound has good transparent viewpoint, this is more preferably aliphatic alkyl, ester ring type alkyl, by giving the hard of the present invention
From the viewpoint of the good obdurability of compound and thermostability, this is more preferably methyl and ethyl.
R1Or R2Shown hydroxy alkyl, refers to that the hydrogen atom of straight-chain or 1 of branched-chain alkyl or more than 2 is by hydroxyl
Substituted atomic group.
The carbon number of hydroxy alkyl is more preferably 1 to 4.As concrete example, can enumerate: methyl, ethyl, n-pro-pyl, isopropyl,
Normal-butyl and 1 of isobutyl group or the hydrogen atom person of being optionally substituted by a hydroxyl group of more than 2.In the present invention, by the viewpoint easily reacted
From the point of view of, more preferably for 1 hydrogen person of being optionally substituted by a hydroxyl group of end carbon.Good obdurability and thermostability is had by the hardening thing of the present invention
From the viewpoint of, this is more preferably hydroxymethyl, hydroxyethyl.
The alkylene oxide used in the present invention refers to the compound with the cyclic ether of 3 rings.
The carbon number of alkylene oxide is more preferably 2 to 8.Can enumerate such as: oxirane, expoxy propane, epoxy butane, Oxybenzene
Ethylene etc..Such alkylene oxide can be a kind, alternatively mix two or more person depending on required.Wherein, because of by obtaining easily and valency
Lattice are low, are the most more preferably at least one in oxirane, expoxy propane.
Relative to hydroxyl 1 equivalent of polyhydric alcohol (a), the usage amount of epoxide ring is usually the cyclic ether 0.1 to 6.0 of 3 rings
Equivalent, is more preferably 0.2 to 2.0 equivalent.If in this scope, thermostability and the obdurability of obtained hardening thing are good.
The cyclic ether used in the present invention, as long as the carbon of more than have in the cyclic hydrocarbon of more than 4 rings 1 is replaced
The compound of structure, i.e. without particularly limiting.
Cyclic ether is more preferably 4 to 6 rings, can enumerate oxetanes, oxolane, Pentamethylene oxide. as concrete example
Deng.Such cyclic ether can be a kind or be regarding two or more person of required mixing.Wherein, oxolane is because obtaining easy and price
Low, it is more preferably in the present invention.
The usage amount of cyclic ether, relative to hydroxyl 1 equivalent of polyhydric alcohol (a), generally ring-like ether is 0.1 to 6.0 equivalent, relatively
It is preferably 0.2 to 2.0 equivalent.If in this scope, then obtained hardening thing has good thermostability and obdurability.
The cyclic ester used in the present invention, as long as have in cyclic hydrocarbon the compound of structure containing ester bond, then without
Particularly limit.
The carbon number of cyclic ester is more preferably 2 to 6.As the concrete example of cyclic ester, can enumerate: in second lactone, propiolactone, fourth
Ester, valerolactone, caprolactone etc..Such cyclic ester can be a kind or be regarding two or more person of required mixing.Wherein, caprolactone is because taking
Obtain easily and price is low, be more preferably in the present invention.
The usage amount of cyclic ester, relative to hydroxyl 1 equivalent of polyhydric alcohol (a), generally ring-like ester is 0.1 to 6.0 equivalent, relatively
It is preferably 0.2 to 2.0 equivalent.If in this scope, then obtained hardening thing has good thermostability and obdurability.
The example of polyhydric alcohol (a-2), concrete illustration can enumerate: trimethylolpropane ethylene oxide adduct, trihydroxy methyl
Propane propylene oxide adduct, trimethylolpropane oxolane addition product, trimethylolpropane caprolactone addition product, new penta 4
Alcohol ethylene oxide adduct, new penta tetrol propylene oxide adduct, new penta tetrol oxolane addition product, new penta tetrol caprolactone
Addition product, double (new penta tetrol) ethylene oxide adduct, double (new penta tetrol) propylene oxide adduct, double (new penta tetrol) tetrahydrochysene
Furan addition product, double (new penta tetrol) caprolactone addition product etc..
Core hydrogenation trimellitic anhydride etheride (b-1), is to import anhydride group in polyhydric alcohol (a) so that it is become
Use for multifunctional anhydride compound.Thereby, the esterification by ring opening of anhydride group can be not accompanied by and import anhydride group.In this specification
In, below core is hydrogenated trimellitic anhydride etheride (b-1) and is simply recited as " (b-1) ".
And, because hydrogenating through core, even if therefore under heat-resisting, fast light, also will not reduce coloring, its hardening thing can remain high
Optical characteristics, has the thermostability of excellence, obdurability simultaneously.
Trimellitic anhydride etheride (b-2) uses with identical purpose with (b-1).In this manual, below will be partially
Benzenetricarboxylic acid acid anhydride etheride (b-2) is simply recited as " (b-2) ".(b-2) there is the thermostability that relatively (b-1) is high.
(b-1) with (b-2) also can and use, coloring with the balance of thermostability visual purposes and modulate aptly.In this theory
In bright book, below (b-1) or (b-2) is all together and is recited as " etheride ".
As etheride, such as fluoride, acyl chlorides compound, acylbromide compound and acyl iodides etc. can be enumerated.Wherein, with reaction
Easness for, be more preferably chloro thing.
The synthesis of multifunctional anhydride (A), can be carried out by existing maneuver.In the reaction of polyhydric alcohol (a) and etheride
There is no particular restriction for the method for interpolation reagent, can use arbitrary additive process.Such as can use: by polyhydric alcohol (a) and basic species
Matter is dissolved in solvent, and instills the etheride dissolved through solvent in method therein lentamente；Or, exist on the contrary
Depending on required and in the solvent being dissolved with above-mentioned etheride, instill the side of polyhydric alcohol (a) and the mixture solution of alkaline matter
Method；In the etheride solution with polyhydric alcohol (a), the method instilling alkaline matter；And in the solution of polyhydric alcohol (a),
Instill the solution of etheride and the solution etc. of alkaline matter simultaneously.In this manual, below polyhydric alcohol (a) is simply recorded
For " (a) ".
(a) in the presence of alkaline matter and the reaction of etheride, be to carry out reacting generation alkaline matter neutralization simultaneously
And the hydrochlorate generated.This is filtered after removing, by concentrated filtrate, and obtain the multifunctional anhydride of purpose with high yield
(A) crude product.This crude product is dissolved with suitable solvent, concentrates after washing, then carry out drying under reduced pressure and obtain
Highly purified multifunctional anhydride (A).Further depending on required and carry out recrystallization with suitable solvent, thereby obtain higher alcoholic degree
Multifunctional anhydride (A).
A the usage amount of (), in terms of hydroxyl equivalent, is 1 relative to etheride, usually 0.6 to 1.0 equivalent is more preferably
0.8 to 1.0 equivalent.If this scope, then the hydroxyl of (a) the most esterified and will not the carboxylic acid halides of remained unreacted in system
Thing.
Spendable solvent in the etheride reaction with (a), as long as be that inertia person is i.e. not particularly limited to raw material,
And can enumerate: the ether solvents such as oxolane, 1,4-dioxane, 1,2-dimethoxy-ethane-bis-(2-methoxy ethyl) ether；First pyrrole
The aromatic amine solvent such as pyridine, pyridine；Such as ketone series solvents such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK)s；Such as toluene, dimethylbenzene
Etc. aromatic hydrocarbon solvents；If dichloromethane, chloroform, 1,2-dichloroethanes etc. are containing halogen solvent；As N-methyl-2-Pyrrolizidine ketone,
DMAC N,N' dimethyl acetamide, N, the amide series solvent such as N-diethyl acetamide, N,N-dimethylformamide；Such as hexamethyl phosphoramide
Etc. phosphorous solvent；Such as sulfur-bearing solvents such as dimethyl sulfoxides；Such as ester series solvents such as gamma-butyrolacton, ethyl acetate, butyl acetates；Such as 1,
The nitrogen-containing solvents such as 3-dimethyl-2-imidazolidine ketone；Phenol, orthoresol, metacresol, paracresol, orthomonochlorphenol, m-Chlorophenol, parachlorophenol etc.
There is the aromatic series series solvent etc. of hydroxyl.This equal solvent can be used alone, it is possible to 2 kind uses mixed above.
Listed herein in solvent, comprise the cyclic ether or cyclic ester used when being manufactured polyhydric alcohol (a-2) by (a), but
When making (a) to react with etheride, reaction temperature is-10 DEG C to 80 DEG C, is more preferably 0 DEG C to 70 DEG C, more preferably 10 DEG C
To 60 DEG C.If reaction temperature is higher than 80 DEG C, then when making (a) to react with cyclic ether or cyclic ester and to obtain polyhydric alcohol (a-2),
A the response rate of () and etheride can reduce.Response time is not particularly limited, and usually 10 minutes to 48 hours, is more preferably
30 minutes to 24 hours.Reaction is generally carried out at ambient pressure, can under elevated pressure or implement under decompression depending on required.
When making (a) to react with cyclic ether or cyclic ester and to manufacture polyhydric alcohol (a-2), reaction temperature is 80 DEG C to 250 DEG C, relatively
It is preferably 90 DEG C to 220 DEG C, more preferably 100 DEG C to 200 DEG C.Response time is not particularly limited, usually 10 minutes little to 48
Time, it is more preferably 30 minutes to 24 hours.Reaction is generally carried out at ambient pressure, can under elevated pressure or implement under decompression depending on required.
Molten value concentration in the reaction obtaining multifunctional anhydride (A), usually 5 mass % are to 50 mass %, are contemplated
The control of side reaction, the filtration step of precipitation, more preferably for carry out to 40 mass % with 10 mass %.More preferably with 10 matter
Scope below amount more than % and 40 mass % is carried out.
Reacting gas environment in the reaction obtaining multifunctional anhydride (A) is carried out the most under a nitrogen.Reaction vessel can be
Enclosed type reaction vessel, it is possible to for opening reaction vessel, but be inert gas environment to keep response system, for opening
Using during type can be with inert gas seal person.
Alkaline matter be in order in and use at the hydrochloric acid that produces of reaction simultaneously.The alkaline matter now used
Kind be not particularly limited, organic 3 grades of amines such as pyridine, triethylamine, DMA can be used；Potassium carbonate, hydrogen-oxygen
Change the inorganic base substances such as sodium.By the viewpoint that can cheaply obtain and good and make operation become readily and see to lipid soluble
From the point of view of Dian, it is more preferably pyridine, triethylamine.Also, from the viewpoint of by can cheaply obtain, be more preferably inorganic base substance.
The amount of the alkaline matter used is not particularly limited, but during owing to using too much, has alkaline matter and can be mixed into generation
Thing, refined load becomes big situation, is therefore usually the employing 1.0 mol times relative to etheride to 30 moles times
Number, be more preferably 1.2 mol times to 20 mol times, more preferably 1.5 mol times are to 10 mol times.
During water washing operations, although a part of multifunctional anhydride (A) can be hydrolyzed and become polybasic carboxylic acid, but by this is many
Unit's carboxylic acid under reduced pressure carries out heat treated, can easily make this part hydrolyze and the polybasic carboxylic acid that generates becomes polyfunctional acid again
Acid anhydride.The temperature that this heated under reduced pressure is used when processing step is 80 DEG C to 200 DEG C, is more preferably 100 DEG C to 180 DEG C, decompression
Degree is for below 10MPa, more preferably below 1MPa, and the upper limit of heat time heating time is without particular limitation, but usually 10 minutes to 48
Hour, it is more preferably 30 minutes to 24 hours.
So obtained multifunctional anhydride (A) can refine further.As process for purification now, can at random enter
Row recrystallization, distil, clean, activated carbon treatment, column chromatography etc..And, such method for refining may be repeated, it is possible to combination is real
Execute.The purity of the multifunctional anhydride (A) obtained by so, such as with regard to the analysis of gel permeation chromatography (hereinafter referred to as " GPC ") etc.
For the spectral peak area ratio of gained, usually more than 90 DEG C, it is more preferably more than 95 DEG C, more preferably more than 98 DEG C.
1 molecule shown in the present invention has more than 1 polymerisable ethylene unsaturated group and the change of more than 1 hydroxyl
Compound B, its purpose is to carry out half-esterification by anhydride group with the additive reaction of hydroxyl, imports unsaturated bond in the molecule, simultaneously
Produce free carboxyl, thereby give photoreactivity and the dissolubility to alkaline-based developer.
The hydroxyl that compound (B) has, more preferably for there to be 1 in 1 molecule.When containing more than 2, can become and have
Make the effect that (A) cross-links.Though this can make for improving molecular weight use energetically, if but excessively use, then can cause in viscosity
Rise, developability deteriorates.
Specifically, as the most obtainable 1 molecule has more than 1 polymerisable ethylene unsaturated group and 1
The compound (B) of individual above hydroxyl, can enumerate such as: (methyl) Hydroxyethyl Acrylate, (methyl) hydroxypropyl acrylate,
(methyl) dihydroxypropyl alkyl ester classes such as (methyl) hydroxy butyl acrylate.
Furthermore, can enumerate: new penta tetrol three (methyl) acrylate, two new penta tetrol three (methyl) acrylate etc. contain
Multifunctional (methyl) acrylate of hydroxyl.
Furthermore again, as in the chemical combination through carboxylic esterification of the unsaturated carboxylic acids such as epoxide addition (methyl) acrylic acid
Species, can enumerate: methyl glycidyl ether (methyl) acrylic acid adduct, ethyl ether (methyl) acrylic acid addition
Thing, octyl glycidyl ether (methyl) acrylic acid adduct, decyl glycidyl ether (methyl) acrylic acid adduct, stearyl contract
Water glycerin ether (methyl) acrylic acid adduct, phenyl glycidyl ether (methyl) acrylic acid adduct, butyl phenyl (+)-2,3-Epoxy-1-propanol
Ether (methyl) acrylic acid adduct, (methyl) glycidyl acrylate (methyl) acrylic acid adduct etc..
Additionally, be used as so-called ethylene glycol monovinyl ether, propylene glycol mono vinyl ether, butanediol mono vinyl ether
Deng monovinyl ether class.
Multifunctional anhydride (A) and the reaction of the compound (B) with ethylene unsaturated group and more than 1 hydroxyl, can make
Use existing method.
Now, in order to promote reaction, more preferably for using catalyst, relative to reactant, i.e. relative to multifunctional anhydride
(A) total amount of the reactant person, beyond compound (B) and the solvent that optionally adds, the usage amount of this catalyst is 0.1 to 10
Mass parts.Reaction temperature now is 60 to 150 DEG C, and the response time is more preferably 5 to 60 hours.Urge as spendable
The concrete example of agent, can enumerate such as: triethylamine, benzyldimethylamine, 2,4, triethyl ammonium chloride, benzyltrimethylammonium bromide,
Benzyltrimethylammonium iodide, triphenylphosphine, antimony triphenyl, methyl triphenyl antimony, octanoic acid chromium, zirconium caprylate etc..
This acid additive reaction, can be solvent-free under reaction, it is possible to for the reaction utilizing solvent to be diluted.Can make in this
Solvent, as long as this reaction is i.e. not particularly limited for inert solvent.More preferably solvent usage amount is visually obtained
The viscosity of resin or purposes and suitably adjust, but solid to divide be more preferably 90 to 30 quality %, more preferably 80 to 50 matter
Amount %.
Particular instantiation, include, for example: the aromatic hydrocarbon series solvents such as toluene, dimethylbenzene, ethylo benzene, durol；Hexane,
The aliphatic hydrocarbon series solvent such as octane, decane；And the petroleum ether of such mixture, unleaded gas, naphtha (petroleum
Naphtha) etc..
Also, as ester series solvent, can enumerate: the acetate alkyl esters such as ethyl acetate, propyl acetate, butyl acetate, γ-fourth
The ring-type esters such as lactone, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether monoacetate, diethylene glycol monoethyl ether list acetic acid
Ester, Triethylene glycol ethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol methyl ether acetate, butanediol list
Methyl ether acetates etc. are single or poly-alkane glycol monoalkyl ether monoacetate class, dialkyl glutarate, dialkyl succinate, oneself two
Polycarboxylic alkyl ester's classes etc. such as acid dialkyl ester.
Also, as ether series solvent, can enumerate: the alkyl ethers such as diethyl ether, ethyl butyl ether, glycol dimethyl ether, ethylene glycol
The alcohol ethers such as diethyl ether, dimethyl ether, dipropylene glycol diethyl ether, TRIGLYME, triethylene glycol diethyl ether, four
The ring-type ethers etc. such as hydrogen furan.
Also, as ketone series solvent, can enumerate: acetone, methyl ethyl ketone, Ketohexamethylene, different Buddhist ketone etc..
In the present invention, further to give reactivity, or for the purpose of adjusting the acid value given, and include making this
Invention containing carboxyl reactive compound (C) and 1 molecule have more than 1 polymerisable ethylene unsaturated group and 1
The multifunctional reactive compounds (E) that the compound (D) of above epoxy radicals reacts and obtains.The multifunctional reactivityization of the present invention
In compound (E), depending on 1 molecule that used has more than 1 polymerisable ethylene unsaturated group and more than 1 epoxy radicals
The response magnitude of compound (D), and include the multifunctional reactive compounds (E) with carboxyl, and not there are many officials of carboxyl
Can reactive compounds (E).
The epoxy radicals that described compound (D) is had, is more preferably to have 1 in 1 molecule.When containing more than 2, then can
Cross-link with reactive compounds (C).Though this can make for improving molecular weight use energetically, if but excessively use, then can
Cause viscosity to rise, developability deteriorates.
As 1 molecule has more than 1 polymerisable ethylene unsaturated group and the compound of more than 1 epoxy radicals
(D), specifically can enumerate: (methyl) glycidyl acrylate, (methyl) hydroxy butyl acrylate glycidyl ether, acrylic acid 4-
Hydroxybutyl glycidyl ether etc..
Reactive compounds (C) containing carboxyl can use existing method with the reaction of compound (D).In this reaction
In, identical catalyst, the solvent used when reacting can be used with described reactive compounds (C).Now, relative to reaction
Thing, i.e. relative to the total amount of the reactant beyond reactive compounds (C), compound (D) and the solvent optionally added,
The usage amount of this catalyst is 0.1 to 10 quality %.Reaction temperature is 60 to 150 DEG C, and the response time is more preferably 5 to 60
Hour.
Reactive compounds (C) containing the present invention or the active energy beam hardening resin of reactive compounds (E)
Compositions, is to represent that in response to various uses the material with other mixes, and then gives the compositions of the characteristic to application.
Can enumerate such as: other reactive compounds (F), active energy beam reactive initiators (G), coloring pigment
(H), extender pigment (I), sclerosing agent (J), other material etc..
As the concrete example of reactive compounds (F), the esters of acrylic acid of free-radical reactive, cationoid reaction can be enumerated
Property other epoxy compound species, for the so-called reactive oligomerization such as vinyl compound of both free radical and cation sensing
Species.
As spendable esters of acrylic acid, simple function (methyl) esters of acrylic acid, multifunctional (methyl) propylene can be enumerated
Esters of gallic acid, other epoxy acrylate class, polyester acrylate, amine ester acrylate etc..
As simple function (methyl) esters of acrylic acid, can enumerate: (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate,
(methyl) butyl acrylate, (methyl) lauryl acrylate, Polyethylene Glycol (methyl) acrylate, Polyethylene Glycol (methyl) propylene
Acid esters monomethyl ether, (methyl) phenylethyl acrylate, (methyl) acrylic acid different camphane ester, (methyl) cyclohexyl acrylate, (first
Base) acrylate, (methyl) tetrahydrofurfuryl acrylate etc..
As multifunctional (methyl) esters of acrylic acid, can enumerate: butanediol two (methyl) acrylate, hexanediol two (first
Base) acrylate, neopentyl glycol two (methyl) acrylate, nonanediol two (methyl) acrylate, glycol two (methyl) propylene
Acid esters, two (methyl) acrylic acid two stretch ethyl ester, Polyethylene Glycol two (methyl) acrylate, three (methyl) acryloyl group epoxide second
Base isocyanuric acid ester, polypropylene glycol two (methyl) acrylate, adipic acid epoxy radicals two (methyl) acrylate, bisphenol epoxies
Ethane two (methyl) acrylate, A Hydrogenated Bisphenol A oxirane (methyl) acrylate, bis-phenol two (methyl) acrylate, hydroxyl
Two (methyl) acrylate of the 6-caprolactone addition product of trimethylace tonitric neopentyl glycol, two new penta tetrols are anti-with 6-caprolactone
Answer poly-(methyl) acrylate of thing, two new penta tetrol poly-(methyl) acrylate, trimethylolpropane tris (methyl) acrylic acid
Ester, triethylol propane three (methyl) acrylate and ethylene oxide adduct thereof, new penta tetrol three (methyl) acrylate and
Its ethylene oxide adduct, new penta tetrol four (methyl) acrylate, two new penta tetrol six (methyl) acrylate and epoxies thereof
Ethane additive product etc..
As spendable vinyl compound, can enumerate: vinyl ethers, phenylethylene, other vinyl chemical combination
Thing.As vinyl ethers, can enumerate: ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, ethylene glycol bisthioglycolate
Vinyl ethers etc..As phenylethylene, can enumerate: styrene, methyl styrene, ethyl styrene etc..Ethylene as other
Based compound, can enumerate: cyamelide triallyl ester, cyamelide trimethyl allyl ester etc..
Furthermore, as so-called reactive oligomerization species, can enumerate: have in same intramolecular and can sense active energy beam
The amine ester acrylate of functional group and amine ester bond；There is the functional group that can sense active energy beam equally in same intramolecular
Polyester acrylate with ester bond；Derived by other epoxy resin, and have in same intramolecular and can sense active-energy and penetrate
The acrylic acid epoxy base ester of the functional group of line；Reactive oligomer etc. by such compound use.
And, as cationoid reaction monomer person, it is however generally that, as long as there is the compound of epoxy radicals i.e. without especially
Limit.Can enumerate such as: (methyl) glycidyl acrylate, methyl glycidyl ether, ethyl glycidyl ether, butyl
Glycidyl ether, bisphenol-A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate
(Union Carbide company's system " CYRACURE UVR-6110 " etc.), 3,4-epoxy cyclohexylethyl-3,4-epoxy basic ring
Cyclohexane carboxylic-acid ester, vinyl cyclohexene dioxide (Union Carbide company's system " ELR-4206 " etc.), limonene titanium dioxide
Thing (Daicel chemical industry limited company's system " CELLOXIDE 3000 " etc.), allyl cyclohexene dioxide, 3,4-
Epoxy radicals-4-methylcyclohexyl-2-expoxy propane, 2-(3,4-expoxycyclohexyl-5,5-spiral shell-3,4-epoxy radicals) hexamethylene-
M-dioxane, double (3,4-expoxycyclohexyl) adipate ester (Union Carbide company's system " CYRACURE UVR-6128 "
Deng), double (3,4-epoxycyclohexylmethyl) adipate ester, double (3,4-expoxycyclohexyl) ether, double (3,4-epoxycyclohexyethylSiOi
Ylmethyl) ether, double (3,4-expoxycyclohexyl) di-ethyl siloxane etc..
Among such, as reactive compounds (F) person, the most preferably esters of acrylic acid of free radical atherosclerotic type.If
During cationic, owing to carboxylic acid can react with epoxy radicals, therefore must be as 2 liquid mixed types.
The active energy beam hardened resin composition of the present invention, the reactivity containing carboxyl comprised in the composition
Compound (C) or multifunctional reactive compounds (E) are 97 to 5 quality %, are more preferably 87 to 10 quality %, and other is reactive
Compound (F) is 3 to 95 quality %, more preferably 3 to 90 quality %.Also other composition can be contained depending on required.
As the active energy beam reactive initiators (G) used in the present invention, can enumerate such as: benzoin, benzene
The benzoin classes such as acyloin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether；Acetophenone, 2,2-diethyl
Epoxide-2-phenyl acetophenone, 1,1-ww-dichloroacetophenone, 2-hydroxy-2-methyl-phenyl-propane-1-ketone, diethoxy acetophenone,
The acetophenone classes such as 1-hydroxycyclohexylphenylketone, 2-methyl isophthalic acid-[4-(methylsulfany) phenyl]-2-morpholinyl-propane-1-ketone；
The Anthraquinones such as 2-ethyl-anthraquinone, 2-tributyl anthraquinone, 2-chloroanthraquinone, 2-amyl anthraquinone；2,4-diethyl phenoxathiin ketone, 2-
The phenoxathiin ketones such as isopropyl phenoxathiin ketone, 2-chlorine phenoxathiin ketone；Acetophenone dimethyl ketal, benzyl dimethyl contract
The ketal classes such as ketone；Benzophenone, 4-benzoyl-4 '-methyldiphenyl sulfide, 4,4 '-bis-methylamino benzophenone etc.
Benzophenone；2,4,6-trimethylbenzoyldiphenyl oxide, double (2,4,6-trimethylbenzoyl)-Phenylphosphine
The existing general free radical type photoreaction initiator classes such as phosphine oxide class such as oxide.
And, can enumerate: lewis acidic diazol, lewis acidic salt, lewis acidic sulfonium salt, lewis acid
Salt, other etheride, triazine series initiators, borate series initiators and other cation series initiators class, light
Acid producing agent class etc..
As lewis acidic diazol, can enumerate: p-methoxyphenyl diazonium fluoride phosphonate, N, N-diethyl
Aminocarbonyl phenyl diazonium hexafluorophosphonate (three new chemical industrial company SUN-AID SI-60L/SI-80L/SI-100L etc.)
Deng；As lewis acidic salt, can enumerate: diphenyl hexafluorophosphonate, diphenyl hexafluoro antimonate etc.；As Louis
The sulfonium salt of this acid, can enumerate: triphenylsulfonium hexafluorophosphonate (Union Carbide company Cyracure UVI-6990 etc.),
Triphenylsulfonium hexafluoro antimonate (Union Carbide company Cyracure UVI-6974 etc.) etc.；As lewis acidic
Salt, can enumerate: triphenyl hexafluoro antimonate etc..
As other etheride, can enumerate: 2,2,2-tri-chloro-[1-4 '-(dimethyl ethyl) phenyl] ethyl ketone (AKZO
Company Trigonal PI etc.), 2,2-bis-chloro-1-4-(Phenoxyphenyl) ethyl ketone (Sandoz company Sandray 1000
Deng), α, α, α-trisbromomethyl phenyl sulfone (Zhi Tie chemical company BMPS etc.).As triazine series initiators, can enumerate: 2,4,
6-three (trichloromethyl)-three, 2,4-trichloromethyl-(4 '-methoxyphenyl)-6-three (Panchim company Triazine A
Deng), 2,4-trichloromethyl-(4 '-methoxyl-styrene-6-triazine (Panchim company Triazine PMS etc.), 2,4-
Trichloromethyl-(piperonyl)-6-triazine (Panchim company Triazine PP etc.), 2,4-trichloromethyl-(4 '-methoxyl group
Naphthyl)-6-triazine (Panchim company Triazine B etc.), 2-[2 '-(5 "-methylfuran base) ethylidene]-4,6-be double
(trichloromethyl)-sym-triazine (three and chemical company etc.), 2-(2 '-furylethylidene)-4,6-double (trichloromethyl)-all-
Triazine (three and chemical company etc.).
Borate-based initiator can be enumerated: Japan photopigment NK-3876 and NK-3881 etc., other light acid producing agent
Deng, can enumerate: 9-phenylacridine, 2,2 '-bis-(o-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl-1, (dark fund is melted into 2-bisglyoxaline
The bisglyoxaline etc. of company), double (2-amido-propane) dihydrochloride (with Guang Chun medicine company V50 etc.) of 2,2-azo, 2,2-idol
Nitrogen double [2-(imidazoline-2-base) propane] dihydrochloride (with Guang Chun medicine company VA044 etc.), [η-5-2-4-(ring pentadecyl)
(1,2,3,4,5,6, η)-(Methylethyl)-benzene] ferrum (II) hexafluorophosphonate (Ciba Geigy company Irgacure 261
Deng), double (y5-cyclopentadienyl groups) double [the fluoro-3-of 2,6-bis-(1H-pyridine-1-base) phenyl] titanium (company of Ciba Geigy company system
CGI-784 etc.) etc..
Other, it is possible to and with thermoinduction peroxides such as azo series initiators, benzoyl peroxide such as azobis isobutyronitriles
Compound system free radical type initiator etc..Furthermore, it is also possible to and with free base system and two kinds of initiators of cation system.Initiator is permissible
It is used alone a kind, it is also possible to and use two or more.
The coloring pigment (H) used in the present invention, is that the active energy beam resin combination making the present invention becomes
The user for coloured material.It is categorized as organic pigment and inorganic pigment according to constituting, but aim colour or purposes can be coordinated and fit
Preferably select.
Organic pigment person is to classify according to its basic framework.Can enumerate such as: isoindolinone system, isoindoline system, secondary
Methyl-system, anthraquinone system, anthrone system, xanthene system, diketopyrrolo-pyrrole system, be, purple cyclic ketones (perinone) is, quinoline
The polycyclic pigment classes such as Azone system, indigo system, diazine system, phthalein green grass or young crops prime system, monoazo system, bisazo system, condensation bisazo system etc. are even
Nitrogen pigment class, mordant pigment class, daylight fluorescent pigment class.
Inorganic salt material class can be enumerated: titanium dioxide, calcium carbonate, barium sulfate, zinc oxide, Muscovitum, carbon black, colcother, aluminium flake etc..
And, the extender pigment (I) shown in the present invention represents not to be colored as the pigment of purpose, and to obtain compositions
Viscosity or mobility, hardening thing mechanical property for the purpose of and user.
Can enumerate such as: barium sulfate, calcium carbonate, Talcum, clay, sheet glass, bead, graphite, aluminium oxide, hydroxide
Aluminum, polystyrene bead, polyethylene beads, polypropylene pearl, polytetrafluoro ethane pearl etc..
And, use for the purpose of the sclerosing agent (J) shown in the present invention is the degree of cross linking to improve hardening thing further.Example
When using as resist material such as the compositions of: the present invention, if remaining carboxyl after development completes, then can make resistance to water, heat-resisting
Property etc. deteriorate.Therefore, allocate the compound with epoxy radicals as sclerosing agent, after development completes, carry out heating steps, mat
The carboxyl coming from the reactive compounds (C) containing carboxyl or multifunctional reactive compounds (E) is used as sclerosing agent by this
(J) the compound etc. with epoxy radicals carries out carboxylic esterification, and can seek the improvement of characteristic.
Furthermore, as other material, so that the active energy beam hardened resin composition of the present invention is suitable to various use
For the purpose of in Tu, it is also possible to 70 weight % are that the upper limit adds other composition.Other composition can be enumerated: does not shows active energy beam
Show the resinae of reactivity, various additive or for the purpose of investing application adaptive etc. for adjusting viscosity and waving of adding
The property sent out solvent etc..Other composition spendable illustrated below.
Other does not show the resinae (so-called inert polymer (inert of reactivity to active energy beam
Polymer)), such as can use: other epoxy resin, phenol resin, amine ester resin, polyester resin, ketone formaldehyde resin, cresol tree
Fat, xylene resin, diallyl phthalate ester resin, styrene resin, guanamines (guanamine) resin, natural and
Synthetic rubber, acrylic resin, vistanex and such modification thing.Such to use till 40 weight % in the range of relatively
Preferably.
Other additive such as can use: the thixotropy such as thermmohardening catalyst, Aerosil such as tripolycyanamide invest agent, silicon
Polymerization inhibitor, tranquilizer, the antioxidants etc. such as ketone system, the leveling agent of fluorine system and defoamer, hydroquinone, Hydroquinone monomethylether.
And according to application target, for the purpose of can adjusting viscosity, and it is molten to add volatility in the resin combination of the present invention
Agent 50 mass %, to add to till 35 mass % in the range of more preferably.
The active energy beam hardened resin composition of the present invention hardens easily by active energy beam.Herein,
As the concrete example of active energy beam, can enumerate: ultraviolet, visible light rays, infrared ray, X-ray, γ (gamma) ray,
The electromagnetic waves such as laser light ray, the particle ray etc. such as alpha ray, β ray, electron ray.If considering the Suitable applications of the present invention, then
With ultraviolet, laser light ray, visible light rays or electron ray for more preferably among such.
Tunicle formation material in the present invention, refers to be coated on the material of substrate surface.Concrete purposes can be enumerated: intaglio plate
The ink materials such as ink, soft version ink, silk screen ink, registering ink, hard painting, top coat, finishing varnish, clear dope (clear
The coating material such as coat), lamination, other then material such as various solids, sticker of laser disc, solder resist, resist,
The resist materials etc. such as micro-machine resist.Furthermore, tunicle formation material is temporarily painted on fissility base material and filming
After, it is fitted on the base material as original purpose and is formed the so-called dry film of tunicle, fall within tunicle formation material.
The reactive compounds (C) containing carboxyl of the present invention and there is the multifunctional reactive compounds (E) of carboxyl,
It is to promote the adherence to base material with carboxyl, and is applicable to the tunicle formation material of plastic rubber substrate or metal base.Do not have
The multifunctional reactive compounds (E) of carboxyl also can give hardness, adherence and the impact that hardening thing is excellent, therefore is suitable for as quilt
Film formation material.
Furthermore, due to the reactive compounds (C) containing carboxyl and the multifunctional reactive compounds (E) with carboxyl
Dissolve in alkaline aqueous solution, therefore can use as by the drawing material compositions of active energy beam.
By the painting material of active energy beam in the present invention, refer to be formed on base material said composition tunicle layer it
After, carry out local irradiation with ultraviolet isoreactivity energy-ray, utilize irradiation portion, work that the physical difference of non-irradiation unit is charted
The compositions of property energy-ray induction type.Specifically, by irradiation portion or non-irradiation unit someways, such as with solvent etc.,
Alkaline solutions etc. are dissolved etc. and are removed, the compositions used for the purpose of charting.
Such material that can be applicable to various patternable, is particularly suitable for the example solder resist material, increases layer (build-up)
The layer insulation material of engineering method, furthermore, it is possible to be used in as fiber waveguide such as printed circuit board (PCB), optoelectronic substrate or photopolymer substrate
Electrical/electronics/light base material etc..
For particularly suitable purposes, it is the feature applying flexibly high-fire resistance, high transparent, and applicable as colourama
Resistance material or fiber waveguide loop form material.
The method that tunicle is formed is not particularly limited, and can use: the letterpress sides such as intaglio printing mode, soft version such as intaglio plate
The planography ways such as the porous printing mode such as formula, silk screen, registering, roller coat cloth, cutter coating, the coating of die coating cloth, curtain type, rotation
The various application modes such as coating.
The hardening thing of the active energy beam hardened resin composition of the present invention, refers to the active energy beam to the present invention
Hardened resin composition irradiates active energy beam and the person of being hardened.
[embodiment]
Hereinafter, the present invention is described in more detail by embodiment, but the invention is not limited in these embodiments.
Synthesis example: the synthesis 1 of multifunctional anhydride (A)
With blender, reflux cooling pipe, agitating device flask in, impose nitrogen and rinse, while such as table
Described in measure in the etheride described in table of (being 1.1 equivalents relative to the hydroxyl of (a)) and add THF 45g, and become equal
Even solution.After stirring this solution while being cooled to 5 DEG C, pyrrole will be added in (a) described in the table of amount as described in table
Pyridine (being 1.2 equivalents relative to the hydroxyl of (a)) and the homogeneous solution of THF 54g, be maintained at liquid temperature 10 DEG C with next
Limit instills lentamente.After completing to instill, to be stirred at room temperature 1 hour, then it is warming up to 50 DEG C, and sustained response 8 hours.Then,
Reactant liquor is cooled to 20 DEG C, after filtering the pyridine hydrochloride removing insoluble composition, concentrated filtrate.Concentrate is dissolved in second
In acetoacetic ester 120ml, after cleaning 3 times with the water of 30ml, it is dried with anhydrous magnesium sulfate.Filter after removing anhydrous magnesium sulfate, will filter
Liquid concentrates, and is dissolved in the ethyl acetate of 15ml by the concentrate obtained, then obtains product with toluene recrystallization.At compound
Synthesis in, by gel permeation chromatography (hereinafter referred to as " GPC ") confirm raw material alcohols disappear time point, with this time point
For having reacted.
The relatively synthesis of synthesis example 1-1:2 official energy anhydride
Two sense anhydride are synthesized according to synthesis example 1.Its result and synthesis example 1 are shown in following table in the lump.
[table 1]
| Synthesis example | (a) | Sense radix | (b) | Productivity |
| Synthesis example 1-1 | TMP(13.4g) | N=3 | HTAC(59.4g) | 75% |
| Synthesis example 1-2 | PE(13.6g) | N=4 | HTAC(79.3g) | 80% |
| Synthesis example 1-3 | DPE(25.4g) | N=4 | HTAC(118.9g) | 75% |
| Synthesis example 1-4 | DPE6EO(25.9g) | N=6 | HTAC(59.4g) | 70% |
| Synthesis example 1-5 | DPE6CL(29.5g) | N=6 | HTAC(35.7g) | 70% |
| Synthesis example 1-6 | PE4EO(31.2g) | N=6 | HTAC(79.3g) | 65% |
| Synthesis example 1-7 | PE(13.6g) | N=4 | HTAC/TMAC(77.9g)* | 75% |
| Synthesis example 1-8 | PE(13.6g) | N=4 | TMAC(76.6g) | 75% |
| Synthesis example 1-9 | THI(26.1g) | N=3 | HTAC(59.4g) | 60% |
| Relatively synthesis example 1-1 | BPA2EO(31.6g) | N=2 | HTAC(39.6g) | 70% |
Table is called for short
TMP: trimethylolpropane
PE: new penta tetrol
DPE: two new penta tetrols
DPE6EO: two new penta tetrol 6 moles of ethylene oxide addition products
DPE6CL: two new 6 moles of caprolactone addition products of penta tetrol
PE4EO: new penta tetrol 4 moles of ethylene oxide addition product
BPA2EO: bisphenol-A 2 moles of ethylene oxide addition product
THI: trimerization different hydracid three-2-hydroxyethyl ester
HTAC: core hydrogenation trimellitic anhydride acyl chlorides
TMAC: trimellitic anhydride acyl chlorides
* HTAC/TMAL (mol ratio)=1/1
The modulation of the embodiment 1 reactive compounds (C) containing carboxyl
With blender, reflux cooling pipe, agitating device flask in, the multifunctional anhydride will modulated with synthesis example 1
(A) add 20mmol (quality is recorded in table), propylene glycol monomethyl ether is added the total amount relative to (A) Yu (B)
Become solid and divide the amount of 60 mass %, and using 0.3 mass % of the pyridine interpolation solvent-laden total amount of bag as catalyst, and stir
Mix dissolving.
Add further as 1 molecule has more than 1 polymerisable ethylene unsaturated group and more than 1 hydroxyl
The compound described in table of compound (B), and carry out reacting 10 hours with 100 DEG C.
It is cooled to after having reacted, measures the acid value (AV, mgKOH/g) in solution, be converted into solid point acid value the most really
Recognize reaction end.
Measuring of acid value is implemented according to the method for JIS K0070:1992.
The modulation of the comparative example 1 reactive compounds containing 2 functional carboxyl groups
Same as in Example 1, other 2 officials described in use table can react by anhydride 20mmol.
[table 2]
| Embodiment | Compound (A) | Compound (B) | Actual measurement AV | Theoretical AV |
| Embodiment 1-1 | Synthesis example 1-1 (13.5g) | HEA7.66g(66mmol) | 171 | 165 |
| Embodiment 1-2 | Synthesis example 1-2 (17.1g) | HEA10.22g(88mmol) | 175 | 170 |
| Embodiment 1-3 | Synthesis example 1-3 (26.7g) | HEA15.3g(132mmol) | 172 | 166 |
| Embodiment 1-4 | Synthesis example 1-4 (32.0g) | HEA15.3g(132mmol) | 155 | 147 |
| Embodiment 1-5 | Synthesis example 1-5 (41.3g) | HEA15.3g(132mmol) | 129 | 122 |
| Embodiment 1-6 | Synthesis example 1-6 (20.7g) | HEA10.2g(88mmol) | 154 | 150 |
| Embodiment 1-7 | Synthesis example 1-7 (16.9g) | HEA10.2g(88mmol) | 177 | 171 |
| Embodiment 1-8 | Synthesis example 1-8 (16.7g) | HEA10.2g(88mmol) | 178 | 173 |
| Embodiment 1-9 | Synthesis example 1-2 (17.1g) | PE3A57.3g(88mmol) | 69 | 65 |
| Embodiment 1-10 | Synthesis example 1-2 (17.1g) | GMA-AA18.9g(88mmol) | 136 | 131 |
| Embodiment 1-11 | Synthesis example 1-2 (17.1g) | PGE-AA19.6g(88mmol) | 134 | 129 |
| Embodiment 1-12 | Synthesis example 1-9 (16.0g) | HEA7.66g(66mmol) | 155 | 146 |
| Comparative example 1-1 | Relatively synthesis example 1-1 (13.5g) | HEA5.1g(88mmol) | 129 | 124 |
| Comparative example 1-2 | TMEG-100(8.2g) | HEA5.1g(88mmol) | 180 | 174 |
Table is called for short
HEA: Hydroxyethyl Acrylate, OHV=116g/OHeq
PE3A: new penta tetrol triacrylate and the mixture of new penta tetra-acrylate, new penta tetrol three acrylic acid
Ratio=about 50/50 (mole) of ester/new penta tetra-acrylate, OHV=650g/OHeq
GMA-AA: glycidyl ether-acrylic carboxylate's compound, chemistry limited company of common prosperity society LIGHT
ESTER G-201P, OHV=214g/OHeq
PGE-AA: phenyl glycidyl ether-acrylic carboxylate's compound, Japan chemical medicine KAYARAD R-128H, OHV
=222g/OHeq
TMEG-100: ethylene glycol bis trimellitic anhydride, new Japan Chemical RIKACID TMEG-100
Embodiment 2: the modulation of reactive compounds (E)
With blender, reflux cooling pipe, agitating device flask in, in add with embodiment 1 modulation reactivity
In the reaction solution 0.01mol (quality divides scaled value to be recorded in table with solid) of compound (C), will have 1 as in 1 molecule
The compound described in table of the compound (D) of individual above polymerisable ethylene unsaturated group and more than 1 epoxy radicals is with table
In record amount be added, and be added propylene glycol methyl ether acetate adjusting so that final solid is divided into 60 matter
After amount %, make it react 24 hours with 100 DEG C, obtain reactive compounds (E).
[table 3]
| Embodiment | Compound (C) | Compound (D) | Actual measurement AV | Theoretical AV |
| Embodiment 2-1 | Embodiment 1-2 (13.2g) | GMA2.8g(0.005mmol) | 66 | 60 |
| Embodiment 2-2 | Embodiment 1-2 (13.2g) | GMA1.14g(0.002mmol) | 100 | 95 |
| Embodiment 2-3 | Embodiment 1-2 (13.2g) | GMA5.6g(0.0098mmol) | 4.4 | 2.4 |
| Embodiment 2-4 | Embodiment 1-6 (15.0g) | GMA1.42g(0.0025mmol) | 87 | 82 |
| Embodiment 2-5 | Embodiment 1-2 (13.2g) | 4HBGE 2.0g(0.0025mmol) | 85 | 79 |
Table is called for short
GMA: glycidyl methacrylate
4HBAGE: acrylic acid 4-hydroxybutyl glycidyl ether
Embodiment 3: the modulation of white minus resist compositions
The embodiment 1 being scaled 7g (actual loadings is that solid is divided divided by 60 mass % persons) will be divided with solid and compare
The reactive compounds (E) that reactive compounds (C) solution containing carboxyl synthesized in example 1 or embodiment 2 are modulated
Solution, free radical atherosclerotic type monomer DPHA (two new penta tetrol six acrylic acid of the reactive compounds as other (F) of 4g
Ester, Japan's chemical medicine limited company system), (chemical industry share is limited for the barium sulfate B-30 as extender pigment (I) of 5g
Company's system), the titanium oxide pigments TIPAQUE CR-90 as coloring pigment (H) (stone originates in industry limited company system) of 3g,
The TEPIC-SP as sclerosing agent (J) (trimerization different hydracid three glycidyl ester, Nissan Chemical limited company system) of 4g,
The IRGACURE 907 as active energy beam reactive initiators (G) of 0.5g (BASF JAPAN limited company
System), the propylene glycol methyl ether acetate as solvent of 4g, use three-roll grinder carry out kneading, obtain white minus resist
Use compositions.
The inhibitor composition of gained is carried out application with silk screen print method on patch copper-cover laminated plate, and with the baking box of 80 DEG C
Within 15 minutes, solvent is made to volatilize.Then, (ORC makes limited company of institute system, model HMW-to use ultraviolet exposure apparatus according
680GW) there is the shade of circuit pattern and in order to estimate that the Kodak rank of sensitivity become plate (step tablet) through description
No.2, irradiates 500mJ/cm2Ultraviolet.Afterwards, the film on dry film peeled off and confirm stripping state.After, with 1% carbonic acid
Sodium water solution carries out spray development, removes the resin in non-irradiation ultraviolet radiation portion.After washing and drying, by printed circuit board (PCB) with 150 DEG C
Air drier carry out heat hardening in 60 minutes reaction and obtain cured film.
The evaluation item of white inhibitor composition
<sensitivity assessment>
The Concentration portion till which can be remained at the exposure portion being perforated through rank and becoming plate when sensitivity is to develop in stage and
Judge.The big person of number of stages (value) is judged to high sensitivity (unit: section) with the dense portion of plate.
<developability assessment>
Developability is when the exposure portion making to be perforated through pattern shade develops, complete to pattern form portion after spray developing liquid
Time till full development, i.e. with so-called developing time (break time) assessment developability (unit: second).It is more preferably 20
Second was to about 40 seconds.
<analyticity assessment>
Analyticity is to use optical microscope to judge distance between centers of tracks pattern (the Line and space that pattern shade is comprised
Pattern) pattern (unit: μm) whether is formed subtly.It is worth little person to can determine that as fine pattern.
<xanthochromia assessment>
Xanthochromia be by 150 DEG C of sclerous reactions after resist insert further in the hot-blast oven of 180 DEG C 72 hours, observe
Heat-resisting coloring.Xanthochromia is to visually evaluate.Assessment benchmark is as follows:
◎: without variable color
Zero: the most slightly turn yellow
△: confirm to become yellow
×: become brown
<light resistance assessment>
Light resistance is to use SUPER UV testing machine (the rugged electric system of rock) to irradiate ultraviolet the resist after 150 DEG C of sclerous reactions
Light 20 hours, to visually evaluate the coloring of the white resist after having irradiated.Assessment benchmark is as follows:
◎: without variable color
Zero: the most slightly turn yellow
△: confirm to become yellow
×: become brown
<thermostability assessment>
Thermostability is that the substrate being made with the photoresistance film after 150 DEG C of sclerous reactions floats in the solder bath of 260 DEG C 1 point
Zhong Hou, inserts in water and cools down rapidly.Repeat this operation 3 times after, put X shape scar under with cutter, carried out by adhesive tape
Adherence is assessed.
Zero: without peeling off
△: only have, in X word portion, the vestige slightly peeled off
×: there is stripping
[table 4]
Table is called for short
CCR-1218H: cresol novolak type acid modified acroleic acid epoxy radicals ester (Japan's chemical medicine system)
ZCR-1569H: biphenyl type acid modified acroleic acid epoxy radicals ester (Japan's chemical medicine system)
ASP-010: methyl methacrylate, butyl methacrylate, methacrylic acid copolymer (Japan's chemical medicine system)
As can be known from the above results, the reactive compounds (C) containing carboxyl of the present invention and multifunctional reactivityization
The sensitivity of compound (E), developability, analyticity are excellent, and can obtain further xanthochromia, light resistance, thermostability balance the most excellent
Different hardening thing.
Embodiment 4: metal coating material composition
Load to divide with solid and be scaled adjusting with embodiment 1 of 10g (actual loadings being that solid is divided divided by 60 mass %)
System the reactive compounds (C) containing carboxyl or embodiment 2 modulation reactive compounds (E), 15g as other
The bisphenol epoxies ethane diacrylate of reactive compounds (F), 15g tri-(propylene glycol) diacrylate, 10g amine ester acrylic acid
Ester (UX-5000, Japan's chemical medicine system), 1.5g are as the IRGACURE 184 (BASF of active energy beam reactive initiators (G)
JAPAN system), and fully kneading is to uniformly, modulates atherosclerotic type compositions.
The compositions of gained is painted on TFS substrate (tin plate) with bar coating machine #8, and with 100 DEG C of baking boxs 10
Minute solvent is made to volatilize.Afterwards, 500mJ/cm is irradiated2Ultraviolet carry out sclerous reaction, obtain cured film.
The metal assessment being coated with cloth material
<hardening assessment>
After hardening, the hardness of film is estimated according to pencil hardness test (JIS-K5600-5-4:1999).
<adherence assessment>
The adherence of metal base is entered according to cross-cut tester (cross-cut) disbonded test (JIS-K5600-5-6:1999)
Row assessment.
Assessment benchmark is also estimated by following classification according to JIS-5600:
Classification 0: without peeling off, well
Classification 1: only corner portion peels off slightly
Classification 2: corner portion peels off
Classification 3: the grid of stripping does not reaches half
Classification 4: the grid of stripping is more than half
Classification 5: almost all is peeled off, for the best
<resistance to impact assessment>
The resistance to impact of film is estimated according to Du Pont's impact test (JIS-K5600-5-6:1999).It is to be with hammer
500g, strike mould are 6.35mm, height of fall is that 250mm implements.
Zero: crack-free
△: though there being micro rupture, but without peeling off
×: there is stripping
[table 5]
Table is called for short
HOA-HH: Hydroxyethyl Acrylate hexahydrophthalic acid monoesters
TPGDA: three (propylene glycol) diacrylate
Shown by above result, comprise the reactive compounds (C) containing carboxyl of the present invention and/or multifunctional reaction
The resin combination of property compound (E) can become the coating composition of adherence, hardening, excellent impact resistance.
[industrial applicability]
The reactive compounds (C) containing carboxyl of the present invention and multifunctional reactive compounds (E) variable color is few, resolve
Property high, thermostability high.Therefore be particularly well suited for use in the skin film formation material outside solder resist material, require water white transparency or
To be colored as the hardening material of purpose, such as, it is adapted for use with: the painting cloth material of active energy beam atherosclerotic type, printing print
Ink.
Furthermore, due to the reactive compounds (C) containing carboxyl of the present invention and have the multifunctional reactivity of carboxyl
Compound (E) contains carboxyl in the molecule, therefore is also applied for the minus light by alkali develops and charts.Therefore, the present invention is suitable for making
It is used in resist material, the chromatic photoresist requiring that coloring is few, is particularly suitable for the chromatic photoresist of LCD, black matrix", a deadening
Agent, optical waveguide material etc..
Claims (21)
1. containing the reactive compounds of carboxyl, be the polyhydric alcohol a making at least to have more than 3 hydroxyls in 1 molecule with
The multifunctional anhydride that core hydrogenation trimellitic anhydride etheride b-1 or trimellitic anhydride etheride b-2 reacts and obtains
The compound B in A, with 1 molecule with more than 1 polymerizable ethylene unsaturated group and more than 1 hydroxyl reacts and obtains.
2. containing the reactive compounds of carboxyl, be the polyhydric alcohol a making at least to have more than 3 hydroxyls in 1 molecule with
The multifunctional anhydride that core hydrogenation trimellitic anhydride etheride b-1 or trimellitic anhydride etheride b-2 reacts and obtains
The compound B in A, with 1 molecule with more than 1 polymerizable ethylene unsaturated group and more than 1 hydroxyl reacts and obtains, described
Polyhydric alcohol a is the polyhydric alcohol a-1 at least containing 3 hydroxyls in 1 molecule shown in following formula (1):
In formula, R1、R2、R3、R4、R5、R6The most independent, R1、R3、R4、R5、R6Represent hydrogen atom, hydroxyl, the alkyl of carbon number 1 to 11
Or the hydroxy alkyl of carbon number 1 to 4, R2Represent hydroxyl or the hydroxy alkyl of carbon number 1 to 4；L represents the integer of 0 to 11, m with n is each
Represent the integer of 1 to 11.
3. containing the reactive compounds of carboxyl, be the polyhydric alcohol a making at least to have more than 3 hydroxyls in 1 molecule with
The multifunctional anhydride that core hydrogenation trimellitic anhydride etheride b-1 or trimellitic anhydride etheride b-2 reacts and obtains
The compound B in A, with 1 molecule with more than 1 polymerizable ethylene unsaturated group and more than 1 hydroxyl reacts and obtains, described
Polyhydric alcohol a be make the polyhydric alcohol a described in claim 1 or 2 with selected from alkylene oxide, cyclic ether and cyclic ester in groups in
More than 1 reactions and the polyhydric alcohol a-2 that obtains.
4. a multifunctional reactive compounds, is to make the reactive compounds containing carboxyl and 1 described in claim 1 or 2
Molecule has the compound D reaction of more than 1 polymerizable ethylene unsaturated group and more than 1 epoxy radicals and obtains.
5. a multifunctional reactive compounds, is to make the reactive compounds containing carboxyl described in claim 3 and 1 molecule
In have more than 1 polymerizable ethylene unsaturated group and more than 1 epoxy radicals compound D reaction and obtain.
6. an active energy beam hardened resin composition, it comprises the reactive compounds described in claim 1 or 2.
7. active energy beam hardened resin composition as claimed in claim 6, is tunicle formation material.
8. active energy beam hardened resin composition as claimed in claim 6, is the description by active energy beam
Material.
9. an active energy beam hardened resin composition, it comprises the reactive compounds described in claim 3.
10. active energy beam hardened resin composition as claimed in claim 9, is tunicle formation material.
11. active energy beam hardened resin compositions as claimed in claim 9, are the descriptions by active energy beam
Material.
12. 1 kinds of active energy beam hardened resin compositions, it comprises the multifunctional reactive chemical combination described in claim 4
Thing.
13. active energy beam hardened resin compositions as claimed in claim 12, are tunicle formation materials.
14. active energy beam hardened resin compositions as claimed in claim 12, are retouching by active energy beam
Paint material.
15. 1 kinds of active energy beam hardened resin compositions, it comprises the multifunctional reactive chemical combination described in claim 5
Thing.
16. active energy beam hardened resin compositions as claimed in claim 15, are retouching by active energy beam
Paint material.
17. active energy beam hardened resin compositions as claimed in claim 15, are tunicle formation materials.
18. 1 kinds of hardening things, are the hardening things of active energy beam hardened resin composition described in claim 6.
19. 1 kinds of hardening things, are the hardening things of active energy beam hardened resin composition described in claim 7.
20. 1 kinds of hardening things, are the hardening things of active energy beam hardened resin composition described in claim 8.
21. 1 kinds of hardening things, are the hardening things of active energy beam hardened resin composition described in claim 9.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015050776A JP6362272B2 (en) | 2015-03-13 | 2015-03-13 | Carboxyl group-containing reactive compound, curable resin composition using the same, and use thereof. |
| JP2015-050776 | 2015-03-13 |
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| Publication Number | Publication Date |
|---|---|
| CN105968001A true CN105968001A (en) | 2016-09-28 |
| CN105968001B CN105968001B (en) | 2020-05-08 |
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| CN201610140971.5A Active CN105968001B (en) | 2015-03-13 | 2016-03-11 | Carboxyl group-containing reactive compound, curable resin composition using same, and cured product |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6362272B2 (en) |
| KR (1) | KR20160110139A (en) |
| CN (1) | CN105968001B (en) |
| TW (1) | TWI681984B (en) |
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| JP2007246830A (en) * | 2006-03-17 | 2007-09-27 | Stanley Electric Co Ltd | Thermo-setting resin composition, light transmitting cured product obtained by thermosetting the same, and light emitting diode sealed with the cured product |
| WO2009025190A1 (en) * | 2007-08-21 | 2009-02-26 | Nippon Kayaku Kabushiki Kaisha | Reactive carboxylate compound, active-energy-ray-curable resin composition utilizing the same, and use of the same |
| JP2009249607A (en) * | 2008-04-11 | 2009-10-29 | Nippon Kayaku Co Ltd | Photosensitive resin composition and cured product of the same |
| CN102212246A (en) * | 2010-04-07 | 2011-10-12 | 信越化学工业株式会社 | Epoxy composition for encapsulating an optical semiconductor element, manufacturing method thereof and cured product |
| CN104220478A (en) * | 2012-03-19 | 2014-12-17 | Dic株式会社 | Active energy ray-curable composition, active energy ray-curable coating material using same, and active energy ray-curable printing ink using same |
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| DE3425183A1 (en) * | 1984-07-09 | 1986-01-16 | Henkel KGaA, 4000 Düsseldorf | UNSATURATED POLYESTER |
| GB2405875B (en) * | 2002-02-26 | 2005-09-14 | Nippon Kayaku Kk | Photosensitive resin, resin composition and cured product thereof |
| JP2005126674A (en) | 2003-09-30 | 2005-05-19 | Mitsubishi Chemicals Corp | Colored resin composition, color filter and liquid crystal displaying device |
| JP3965183B2 (en) | 2003-12-22 | 2007-08-29 | 日本ユピカ株式会社 | An acid-modified epoxy (meth) acrylate compound, a photosensitive thermosetting resin composition containing the acid-modified epoxy (meth) acrylate compound, and a cured product thereof. |
| JPWO2008004630A1 (en) | 2006-07-06 | 2009-12-03 | 日本化薬株式会社 | Active energy ray-curable optical composition and high refractive index resin |
| JP6136322B2 (en) | 2013-02-06 | 2017-05-31 | 日産自動車株式会社 | Releasing and heat insulation switching structure of vehicle drive device |
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2015
- 2015-03-13 JP JP2015050776A patent/JP6362272B2/en active Active
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2016
- 2016-03-07 KR KR1020160026839A patent/KR20160110139A/en not_active Application Discontinuation
- 2016-03-11 TW TW105107520A patent/TWI681984B/en active
- 2016-03-11 CN CN201610140971.5A patent/CN105968001B/en active Active
Patent Citations (6)
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|---|---|---|---|---|
| CN1478219A (en) * | 2000-12-04 | 2004-02-25 | ѧУ�������δ���ѧ | Photocurable and thermosetting resin composition |
| JP2007246830A (en) * | 2006-03-17 | 2007-09-27 | Stanley Electric Co Ltd | Thermo-setting resin composition, light transmitting cured product obtained by thermosetting the same, and light emitting diode sealed with the cured product |
| WO2009025190A1 (en) * | 2007-08-21 | 2009-02-26 | Nippon Kayaku Kabushiki Kaisha | Reactive carboxylate compound, active-energy-ray-curable resin composition utilizing the same, and use of the same |
| JP2009249607A (en) * | 2008-04-11 | 2009-10-29 | Nippon Kayaku Co Ltd | Photosensitive resin composition and cured product of the same |
| CN102212246A (en) * | 2010-04-07 | 2011-10-12 | 信越化学工业株式会社 | Epoxy composition for encapsulating an optical semiconductor element, manufacturing method thereof and cured product |
| CN104220478A (en) * | 2012-03-19 | 2014-12-17 | Dic株式会社 | Active energy ray-curable composition, active energy ray-curable coating material using same, and active energy ray-curable printing ink using same |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201632565A (en) | 2016-09-16 |
| CN105968001B (en) | 2020-05-08 |
| JP2016169326A (en) | 2016-09-23 |
| TWI681984B (en) | 2020-01-11 |
| KR20160110139A (en) | 2016-09-21 |
| JP6362272B2 (en) | 2018-07-25 |
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