CN109689725A - Use for electronic equipment resin combination - Google Patents
Use for electronic equipment resin combination Download PDFInfo
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- CN109689725A CN109689725A CN201780056543.7A CN201780056543A CN109689725A CN 109689725 A CN109689725 A CN 109689725A CN 201780056543 A CN201780056543 A CN 201780056543A CN 109689725 A CN109689725 A CN 109689725A
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- epoxy resin
- methyl
- type epoxy
- resin
- resin combination
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G59/22—Di-epoxy compounds
- C08G59/223—Di-epoxy compounds together with monoepoxy compounds
-
- 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
- C08G59/40—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 curing agents used
- C08G59/50—Amines
-
- 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
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1339—Gaskets; Spacers; Sealing of cells
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nonlinear Science (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Epoxy Resins (AREA)
- Liquid Crystal (AREA)
Abstract
The present invention relates to a kind of use for electronic equipment resin combinations; it is to provide the use for electronic equipment resin combination of the low solidfied material of moisture permeability, contains the acrylated epoxy resin in part (methyl), (B) monofunctional epoxy compound, (C) amine system curing agent and (D) polymerization initiator of the epoxy resin of (A) 2 function or more.
Description
Technical field
The present invention relates to use for electronic equipment resin combinations.
Background technique
For the electronic devices such as organic electroluminescent, Electronic Paper, solar battery, liquid crystal display device, in order to anti-
The adverse effect only mainly generated by moisture, is sealed (sealing) using resin combination.
As such resin combination, it is widely used for using epoxy acrylate based compound as the radical polymerization of host agent
It closes reaction resin (for example, with reference to patent document 1).
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2007-297470 bulletin
Summary of the invention
Problems to be solved by the invention
But the moisture permeability of the solidfied material for the resin combination recorded in patent document 1 is not sufficiently low.Class of the invention
It inscribes and is to provide a kind of use for electronic equipment resin combination, can provide the low solidfied material of moisture permeability.
Means for solving the problems
The present invention includes following proposal.
[1] a kind of use for electronic equipment resin combination contains the part (methyl) of the epoxy resin of (A) 2 function or more
Acrylated epoxy resin, (B) monofunctional epoxy compound, (C) amine system curing agent and (D) polymerization initiator.
[2] the use for electronic equipment resin combination as described in [1], wherein (B) is following formula (1) compound represented.
X1-G (1)
[in formula, G is glycidoxy or methyl glycidoxy, X1For with or without substituent group aryl, have
Or the aryl-(O-R without substituent group1)n1Base (herein, R1For alkylidene, integer that n1 is 1~6), with or without taking
Aryl-the R of Dai Ji2Base (herein, R2For alkylidene), the heteroaryl with or without substituent group, with or without substituent group
Heteroaryl-(O-R3)n2Base (herein, R3For alkylidene, the integer that n2 is 1~6) or with or without the miscellaneous of substituent group
Aryl-R4Base (herein, R4For alkylidene).]
[3] the use for electronic equipment resin combination as described in [1] or [2], wherein the epoxide equivalent of (B) is 80~2,
000g/eq。
[4] resin combination as described in any one of [1]~[3], wherein (A) is selected from by bisphenol type epoxy tree
Rouge, bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy
Resin, phenol novolak type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F phenolic type epoxy resin, alicyclic epoxy resin, aliphatic chain
Shape epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, hydantoins type epoxy resin, isocyanide
One or more of the group of urea acid ester type epoxy resin and the phenol novolak type epoxy resin composition with triphenol methane skeleton
Epoxy resin part (methyl) acrylated epoxy resin.
[5] the use for electronic equipment resin combination as described in any one of [1]~[4], wherein relative to (A) and (B)
Total 100 mass parts, (B) are 1~40 mass parts.
[6] the use for electronic equipment resin combination as described in any one of [1]~[5] is liquid crystal drip-injection method with close
Seal agent.
The effect of invention
According to the present invention, a kind of use for electronic equipment resin combination is provided, can provide the low solidfied material of moisture permeability.
Specific embodiment
The following detailed description of the present invention.It should be noted that (methyl) acryloyl refers to methacryl in this specification
And/or acryloyl, (methyl) acrylate are methacrylate and/or acrylate." with or without substituent group "
Refer to " substituted or non-substituted ".Sometimes by the acrylated epoxy resin letter in the part (methyl) of epoxy resin more than (A) 2 function
It is denoted as (A).It is also same about (B), (C) and (D) etc..
[use for electronic equipment resin combination]
Use for electronic equipment resin combination (being hereinafter also referred to as " resin combination ") contains ring more than (A) 2 function
The acrylated epoxy resin in part (methyl) of oxygen resin, (B) monofunctional epoxy compound, (C) amine system curing agent and (D) it is poly-
Close initiator.
<part (methyl) acrylated epoxy resin of epoxy resin more than (A) 2 function>
(A) part (methyl) acrylated epoxy resin of epoxy resin more than 2 functions refers to one in epoxy resin
The resin that PART EPOXY base is reacted with (methyl) acrylic acid, that is, referring to has epoxy group and (methyl) propylene in resin
The resin of both acyl groups.
(A) it can react to obtain by more than 2 functions epoxy resin and (methyl) acrylic acid.More than 2 functions
The functional number of epoxy resin be not particularly limited, preferably 2~4.
Epoxy resin more than 2 functions is not particularly limited, bisphenol A type epoxy resin, bisphenol F type epoxy can be enumerated
Resin, bisphenol-s epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol-A phenolic
Type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, shrinks at bisphenol F phenolic type epoxy resin
Glycerol ester type epoxy resin, glycidyl amine type epoxy resin, hydantoins type epoxy resin, isocyanurate type asphalt mixtures modified by epoxy resin
Rouge, phenol novolak type epoxy resin with triphenol methane skeleton etc..In addition to this, two function phenols also can be used
2-glycidyl etherate, the 2-glycidyl etherate of two function alcohols and their halide, hydride etc..In addition, making
For the epoxy resin of 3 functions and 4 functions, the epoxy resin recorded in Japanese Unexamined Patent Publication 2012-077202 bulletin can be enumerated.
Epoxy resin more than 2 functions can be one kind or two or more combination.
For (A), relative to total molal quantity of (methyl) acryloyl group and epoxy group in resin, (methyl) third
Enoyl- is preferably 10~90 moles of %, more preferably 40~60 moles of %.(A) be included in a molecule in respectively containing 1 with
The compound of upper epoxy group and (methyl) acryloyl group.In addition, (A) can include: with epoxies more than 2 functions as raw material
Unreacted epoxide in resin is comparable, has 2 or more epoxy groups in a molecule and does not have (methyl) propylene
The compound of acyl group；With the compound phase reacted with whole epoxy groups of above-mentioned epoxide with (methyl) acrylic acid
When, in a molecule with 2 or more (methyl) acryloyl group and do not have epoxy group compound.
In the manufacture of (A), the reacting dose of more than 2 functions epoxy resin and (methyl) acrylic acid is not limited especially
It is fixed, as long as to reach the amount of defined equivalent proportion.Epoxy resin more than 2 functions is reacted with (methyl) acrylic acid
In, catalyst can be used (for example, benzyl dimethylamine, triethylamine, benzyltrimethylammonium chloride, triphenylphosphine, antimony triphenyl
Deng) and polymerization inhibitor (for example, first quinone (methoquinone), quinhydrones, methylnaphthohydroquinone, phenthazine, dibutyl hydroxy toluene etc.).2
The reaction temperature of more than function epoxy resin and (methyl) acrylic acid for example can be set to 80~110 DEG C.Thereby, it is possible to make 2
It is acrylated that (methyl) occurs for a part of epoxy group of epoxy resin more than function.
Part (methyl) acrylated epoxy resin obtained from reacting bisphenol A type epoxy resin with (methyl) acrylic acid
I.e. (A) is for example obtained as follows.
Firstly, making bisphenol A type epoxy resin and (methyl) acrylic acid in basic catalyst, the organic phosphorus acidification of preferably trivalent
It reacts in the presence of conjunction object and/or amine compounds.Reaction ratio at this time is set as, relative to 1 equivalent of epoxy group, (methyl) third
Olefin(e) acid is the ratio of 10~90 equivalent %.Then, it for the reaction product, is handled by filtering, centrifuge separation and/or washing etc.
It removes basic catalyst and is refined.As above-mentioned basic catalyst, can be used in epoxy resin and (methyl) acrylic acid
Reaction used in well known basic catalyst.Alternatively, it is also possible to use basic catalyst to be carried on made of polymer
Polymer-supported basic catalyst.
It (A) can be one kind or two or more combination.
<(B) monofunctional epoxy compound>
(B) monofunctional epoxy compound is the ingredient for reducing the moisture permeability of the solidfied material of resin combination.Instead of (B)
Using it is more than 2 functions multi-functional epoxy compound and/or simple function acryloyl compounds in the case where, can not efficiently reduce
Moisture permeability.
(B) it is not particularly limited as long as the compound in molecule with 1 epoxy group, aromatic list can be enumerated
Functional epoxide compound and aliphatic monofunctional epoxy compound, the monofunctional epoxy compound of optimization aromatic.But
(B) for include in (A) monofunctional epoxy compound (that is, in a molecule containing 1 epoxy group, contain 1 or more (methyl) third
The compound of enoyl-) other than substance.
<<aromatic monofunctional epoxy compound>>
As long as the list in aromatic monofunctional epoxy compound molecule with aromatic group and/or heteroaromatic group
Functional epoxide compound is just not particularly limited, preferably following formula (1) compound represented.
X1-G (1)
[in formula, G is glycidoxy or methyl glycidoxy, X1For with or without substituent group aryl, have
Or the aryl-(O-R without substituent group1)n1Base (herein, R1For alkylidene, integer that n1 is 1~6), with or without taking
Aryl-the R of Dai Ji2Base (herein, R2For alkylidene), the heteroaryl with or without substituent group, with or without substituent group
Heteroaryl-(O-R3)n2Base (herein, R3For alkylidene, the integer that n2 is 1~6) or with or without the miscellaneous of substituent group
Aryl-R4Base (herein, R4For alkylidene).]
The preferred carbon atom number of aryl is 6~20, can enumerate phenyl, xenyl, naphthalene, terphenyl, anthryl, fluorenyl
Deng.From the aspect of further decreasing from the moisture permeability of solidfied material, X1In the preferred phenyl of aryl, xenyl and naphthalene, especially
It is preferred that phenyl.
The total atom number of heteroaryl be 5~30, for included at least other than carbon atom select free oxygen atom, sulphur atom and
1 or more heteroatomic monocycle or polycyclic heterocycle in the group of nitrogen-atoms composition, preferably carbon atom number are 5~20.Heteroaryl
Base can enumerate phthalimide-based, imidazole radicals, oxa- anthryl, thioxanthene base, thienyl, dibenzofuran group, benzopyrene
It mutters base, different thio benzopyranyl, dibenzo oxathiin base (Off ェ ノ キ サ チ イ ニ Le base), pyrrole radicals, pyrrole
Oxazolyl, pyrazinyl, pyrimidine radicals, pyridazinyl, indolizine base, isoindolyl, indyl, indazolyl, purine radicals, quinazinyl, isoquinoline
Quinoline base, quinolyl, phthalazinyl, naphthyridines base, quinoxalinyl, quinazolyl, cinnoline base, pteridyl, carbazyl, B-carboline base, phenanthrene
Piperidinyl, acridinyl, perimidinyl, Phen base, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furan
A word used for translation base, furyl etc..
The substituent group of aryl and heteroaryl can be enumerated selected from by alkyl, hydroxy alkyl, alkoxy, aryloxy group (preferably benzene
Oxygroup), aralkyl (preferably 1- methyl-1-phenylethyl), aralkyl oxy (preferably benzyloxy), formoxyl, acyl group (preferably benzene
Formoxyl), cyano, nitro, sulfo group, amide groups (preferably NH2One or more of CO yl) and the group of compositions such as halogen atom.
The preferred carbon atom number of alkyl is 1~20, is straight-chain or branched, can enumerate methyl, ethyl, propyl, isopropyl
Base, butyl, isobutyl group, sec-butyl, tert-butyl etc..Hydroxy alkyl is the alkyl being optionally substituted by a hydroxyl group, the alkyl portion in hydroxy alkyl
Divide as described above.Moieties in alkoxy are as described above.Halogen atom can enumerate fluorine atom, chlorine atom, bromine atom and iodine
Atom.
X1In the case where with substituent group, from the aspect of further decreasing from the moisture permeability of solidfied material, substituent group is preferred
For a kind in the group being made of alkyl, hydroxy alkyl, aryloxy group, aralkyl oxy, formoxyl, acyl group and halogen atom with
On.
The preferred carbon atom number of alkylidene is 1~6, is straight-chain or branched, can enumerate methylene, ethylidene, ethylidene
Base (ethane -1,1- diyl), trimethylene, propylidene (propane -1,2- diyl), propylidene (propane -1,1- diyl), different sub- third
Base (propane -2,2- diyl), tetramethylene, butylidene (butane -1,1- diyl), isobutylene (2- methylpropane -1,1- two
Base), pentamethylene, 2- methylpentane -1,5- diyl, hexa-methylene etc..
R1And R3It is preferred that ethylidene, trimethylene and propylidene.N1 and n2 be preferably 1~4 integer, particularly preferably 1.
R2And R4It is preferred that ethylidene and ethidine.
X1Aryl preferably with or without substituent group, the aryl-(O-R with or without substituent group1)n1Base or
Heteroaryl-R of the person with or without substituent group4Base.In addition, X1In the case where for the aryl with or without substituent group, more
The preferably non-substituted or aryl replaced above-mentioned preferred substituent group.
Aromatic monofunctional epoxy compound can be one kind or two or more combination.
<<aliphatic monofunctional epoxy compound>>
As long as in aliphatic monofunctional epoxy compound molecule have aliphatic group and do not have aromatic rings and/
Or the monofunctional epoxy compound of hetero-aromatic ring is just not particularly limited.That is, aliphatic monofunctional epoxy compound is in the molecule
There is no both aromatic rings and hetero-aromatic ring.Simple function ring shown in the aliphatic preferred following formula of monofunctional epoxy compound (2)
Oxygen compound.
X2-G (2)
[in formula, G is as defined in formula (1), X2For with or without substituent group alkyl, with or without
Alkyl-(the O-R of substituent group5)n3Base (herein, R5For alkylidene, integer that n3 is 1~6), the alkene with or without substituent group
Base, the alkenyl-(O-R with or without substituent group6)n4Base (herein, R6For alkylidene, integer that n4 is 1~6), have or
Alkynyl without substituent group or the alkynyl-(O-R with or without substituent group7)n5Base (herein, R7For alkylidene, n5
Integer for 1~6).]
Alkyl is as described above.The preferred carbon atom number of alkenyl be 2~20, be straight-chain or branched, can enumerate vinyl,
Allyl, 2- acrylic, 2- cyclobutenyl, 3- cyclobutenyl, 2- pentenyl, 3- pentenyl, 4- pentenyl, 2- hexenyl, 3- hexene
Base, 4- hexenyl, 5- hexenyl etc..The preferred carbon atom number of alkynyl is 2~20, is straight-chain or branched, can enumerate acetylene
Base, propargyl, 2- butynyl, 3- butynyl, valerylene base, 3- pentynyl, 4- pentynyl, 2- hexin base, 3- hexin base, 4- oneself
Alkynyl, 5- hexin base etc..The substituent group of alkyl, alkenyl and alkynyl can be enumerated selected from by formoxyl, acyl group, cyano, nitro, sulphur
One or more of groups of compositions such as base, amide groups and halogen.
R5、R6And R7With R1Meaning is identical, and preferred range is also identical.N3, n4 and n5 are identical as n1 meaning, preferred model
It encloses also identical.
X2Alkyl preferably with or without substituent group, the alkenyl with or without substituent group or have or
Alkynyl without substituent group.
Aliphatic monofunctional epoxy compound can be one kind or two or more combination.
<<preferred mode>>
(B) it is preferably only made of one or more of the group formed selected from disclosed in embodiment (b1)~(b18).
From the aspect of further decreasing from the moisture permeability of solidfied material, the epoxide equivalent of (B) is preferably 80~2,000g/
Eq, more preferably 100~1,000g/eq.
It (B) can be one kind or two or more combination.
<(C) amine system curing agent>
(C) amine system curing agent has primary amino group, secondary amino group and tertiary amino, and primary amino group and secondary amino group, which have, comes from these amino
Reactive hydrogen.(C) it is activated by heat, the epoxy reaction with resin combination solidifies resin combination.
Amine system curing agent is not particularly limited, poly- add-on type curing agent and catalyst type curing agent can be enumerated.As
Poly- add-on type curing agent can enumerate aromatic amine, organic acid dihydrazide compound, amine adduct, dicyandiamide, polynary amine system
Object, epoxy-modified polyamine etc. are closed, as catalyst type curing agent, imidazoles, the derivative of imidazoles, tertiary amine, tertiary amine can be enumerated
Poly- semicarbazides of salt etc..The preferred VDH of amine system curing agent (bis- (diazanyl the carbonyl ethyl) -5- isopropyl hydantoins of 1,3-), (oneself two by ADH
Acid dihydrazide), UDH (two carbohydrazide of 7,11- octadecane diene -1,18-) and LDH (octadecane -1,18- dicarboxyl acid dihydrazide) etc.
Organic acid dihydrazide；Polynary amine compound by ADEKA company as sale such as Adeka Hardener EH5030S；By
Ajinomoto Fine Techno company as Amicure PN-23, Amicure PN-30, Amicure MY-24,
The commercially available amine adduct such as Amicure MY-H.
It (C) can be one kind or two or more combination.
<(D) polymerization initiator>
(D) polymerization initiator is to become that (methyl) acryloyl group possessed by (A) is made to carry out optical free radical polymerization and/or heat
The ingredient of free radical generating source when free radical polymerization.As (D), can enumerate selected from by optical free radical polymerization initiator and heat
One or more of the group of radical polymerization initiator composition.By using optical free radical polymerization initiator, it is capable of forming and utilizes light
Make the cured solidification compound of resin combination with heat.By using hot radical polymerization initiator, it is capable of forming and utilizes heat
Make the cured solidification compound of resin combination.
<<optical free radical polymerization initiator>>
Optical free radical polymerization initiator can enumerate benzoin class, acetophenones, benzophenone, thioxanthene ketone class, α-acyl
Base oxime esters, phenylglyoxalates esters, benzil class, azo compound, diphenyl sulfide based compound, acylphosphine oxide system
Close object, benzoin ethers and Anthraquinones etc..Dissolubility of the optical free radical polymerization initiator preferably in liquid crystal is low, and its own
With the reactive group that decomposition product does not gasify when light irradiates.
It is being recorded in preferably WO2012/077720, as making containing at least two ring as optical free radical polymerization initiator
Compound obtained from the compound of oxygroup is reacted with dimethylaminobenzoic acid, with make the compound containing at least two epoxy group
The polymerization initiator of the mixture of compound obtained from being reacted with hydroxy thioxanthone.Herein, with the change of at least two epoxy group
It is as described above preferably as epoxy resin more than 2 functions to close object.
<<hot radical polymerization initiator>>
Hot radical polymerization initiator is generated free radicals by heating, initiated polymerization.Hot radical polymerization is drawn
Hair agent is not particularly limited, and can enumerate organic peroxide, azo-compound etc..Hot radical polymerization initiator can be 1
Kind or combination of more than two kinds.
It (D) can be one kind or two or more combination.
<further ingredient>
According to various characteristics required by the purposes of use for electronic equipment, resin combination can not damage effect of the present invention
In the range of comprising selected from by (E) photosensitizer, (F) further cure component (wherein except (A) and (B)), (G) filler with
(H) the further ingredient etc. of one or more of group of silane coupling agent composition.
<<(E) photosensitizer>>
In order to improve the sensitivity to light in photocuring, resin combination can further contain (E) photosensitizer.From admittedly
It sets out in terms of the property changed, (E) is it can be cited for example that carbonyls, sulfur-containing organic compound, persulfide, redox system
Close object, azo-compound, diazonium compound, halide, photo-reduction pigment etc..As photosensitizer, specifically, can lift
Out: the acridone derivatives of N- methylacridine ketone, N- butyl acridone etc；And α, α-diethoxy acetophenone, benzil,
Fluorenone, xanthone, uranyl compound etc..In addition, the substance that the example as optical free radical polymerization initiator is enumerated also includes
The substance functioned as photosensitizer.
It (E) can be one kind or two or more combination.
<<(F) further cure component (wherein except (A) and (B))>>
(F) it can be cited for example that the host agent as use for electronic equipment composition (preferably liquid crystal sealing agent) use it is existing
Compound with ethylenically unsaturated groups and/or epoxy group.
Compound with ethylenically unsaturated groups can enumerate (methyl) acrylate compounds, aliphatic propylene acyl
Amine compounds, ester ring type acrylamide compound include aromatic acrylamide compound or N- substituted acrylamide system
Close object.
The functionality of (methyl) acrylate compounds can be more than mono-functional, two functionalities or trifunctional more
Functionality.
As (methyl) acrylate compounds of mono-functional, aliphatic (methyl) acrylate can be enumerated, containing virtue
(methyl) acrylate of fragrant ring etc. is preferably selected from from the viscosity for ensuring resin combination, flexible aspect by (methyl)
Hydroxy-ethyl acrylate, (methyl) benzyl acrylate, (methyl) tetrahydrofurfuryl acrylate, (methyl) Isooctyl acrylate monomer, (methyl)
Cyclohexyl acrylate, (methyl) isobornyl acrylate, (methyl) dicyclopentanyl acrylate, (methyl) acrylate oxygroup second
Ester, (methyl) acrylic acid bicyclopentyl oxygroup ethyl ester, (methyl) acrylic acid dicyclopentadienyl oxygroup ethyl ester, (methyl) acrylic acid
Different myristin, (methyl) lauryl acrylate, (methyl) tert-butyl acrylate, diethylene glycol monoethyl ether (methyl) acrylic acid
Ester, to cumylphenoxy ethylene glycol (methyl) acrylate, ethoxylation (methyl) phenyl acrylate and (methyl) acrylic acid
The compound of one or more of the group of ethylene oxidic ester composition.
As (methyl) acrylate compounds of two functionalities, from ensure resin combination viscosity, it is flexible in terms of
It sets out, is preferably selected from by Tricyclodecane Dimethanol two (methyl) acrylate, dihydroxymethyl bicyclopentane two (methyl) acrylic acid
Ester, EO modified 1,6-hexylene glycols two (methyl) acrylate, EO modified bisphenol A two (methyl) acrylate, PO modified bisphenol A two
(methyl) acrylate, polyester two (methyl) acrylate (for example, ARONIX M-6100, the manufacture of East Asia Synesis Company), poly- second
Glycol two (methyl) acrylate (for example, chemical industrial company, the village 4G, Xin Zhong manufactures) and organosilicon two (methyl) acrylic acid
The compound of one or more of the group of ester (for example, EBECRYL 350, the manufacture of Daicel-Allnex company) composition.Wherein, excellent
It selects without hydroxyl and with (methyl) acrylate of bisphenol A skeleton, as such (methyl) acrylate, by common prosperity society
Chemical Co., Ltd. sale has LIGHT ACRYLATE BP-4EAL (the EO addition product diacrylate of bisphenol-A), BP-4PA (double
The PO addition product diacrylate of phenol A) etc..Herein, " EO " refers to ethylene oxide, and " PO " refers to propylene oxide.
As trifunctional or multi-functional (methyl) acrylate compounds, from ensure resin combination viscosity,
Flexible aspect is set out, and is preferably selected from by EO modified glycerol three (methyl) acrylate (trifunctional), three (first of PO modified glycerol
Base) acrylate (trifunctional), pentaerythrite three (methyl) acrylate (trifunctional), dipentaerythritol six (methyl) acrylic acid
The compound of one or more of the group of ester (six functions) and pentaerythrite four (methyl) acrylate (tetrafunctional) composition.
As the compound with epoxy group, can enumerate as epoxy resin substances as described above more than 2 functions.
It (F) can be one kind or two or more combination.
It should be noted that include in resin combination has epoxy group and/or ethylenic bond not in resin combination
The ingredient of saturated group can be only made of (A), (B) and (C) according to circumstances.In this case, resin combination does not include
(F) (that is, further cure component in addition to (A) and (B)).Specifically, can be with epoxy group and ethylenic bond not
The ingredient of saturated group is only made of a part of (A), is also possible to epoxy group and does not have ethylenically unsaturated groups
Ingredient be only made of a part of (A) and (B), or be only made of a part of (A), (B) and (C), and/or, can also be with
It is without epoxy group and there is the ingredient of ethylenically unsaturated groups to be only made of a part of (A).It should be noted that tool
In the case where having the ingredient of epoxy group and/or ethylenically unsaturated groups to include (C), there is the case where epoxy group for (C).
<<(G) filler>>
The intensity of solidfied material made of solidifying resin combination for the viscosity of control resin combination, raising is logical
The purpose of inhibiting linear expansivity and improving the bonding reliability of resin combination is spent, is added (G).(G) is not particularly limited, it can
To enumerate the well known inorganic filler and organic filler that use for the composition comprising epoxy resin.It, can as inorganic filler
To enumerate calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, alumina silicate, titanium oxide, aluminium oxide, zinc oxide, silica, kaolinite
Soil, talcum, bead, sericite, atlapulgite, bentonite, aluminium nitride and silicon nitride.As organic filler, can enumerate
Polymethyl methacrylate, polystyrene keep copolymer obtained from the monomer for constituting them and other monomers copolymerization, polyester micro-
Grain, polyurethane particulate and rubber particle, particularly preferred inorganic filler, such as silica and talcum.
It (G) can be one kind or two or more combination.
<<(H) silane coupling agent>>
(H) be for it is further improve with the purpose of the cementability of liquid crystal display substrate and add.To silane coupling agent
It is not particularly limited, gamma-amino propyl trimethoxy silicane, γ mercaptopropyitrimethoxy silane, γ-isocyanide can be enumerated
Acid esters propyl trimethoxy silicane and 3- glycidoxypropyltrime,hoxysilane etc..
It (H) can be one kind or two or more combination.
(composition)
Relative to total 100 mass parts of (A) and (B), the content of (B) in resin combination is preferably 1~40 mass
Part, more preferably 2~35 mass parts, particularly preferably 2.5~15 mass parts.If the content of (B) in resin combination is upper
Range is stated, the reducing effect of the moisture permeability by (B) solidfied material generated can be given full play of.
Relative to total 100 mass parts of (A) and (B), the content of (C) in resin combination is preferably 1~40 mass
Part, more preferably 3~35 mass parts.Wherein, in the case that (C) is only made of poly- add-on type curing agent, in resin combination
(C) amount that amounts to 0.6~1.2 times of the amount of the content preferably reactive hydrogen of (C) relative to the epoxy group of (A) and (B),
More preferably reach 0.7~1.1 times of amount.If the amount of the reactive hydrogen of (C) adds up to 1.2 relative to the epoxy group of (A) and (B)
Again hereinafter, can reduce the amount of the amino in the solidfied material of resin combination.The solidfied material of resin combination is in water as a result,
Solubility further decreases, and can further decrease the moisture permeability of solidfied material.In addition, if the amount of the reactive hydrogen of (C) is relative to (A)
The epoxy group of (B) adds up to 0.6 times or more, can effectively promote curing reaction.
Relative to total 100 mass parts of (A) and (B), the content of (D) in resin combination is preferably 0.1~25 matter
Measure part, more preferably 0.5~15 mass parts.
In the case that resin combination includes (E), relative to 100 mass parts of (D), the content of (E) is preferably 0.5~40
Mass parts, more preferably 1~20 mass parts.
In the case that resin combination includes (F), relative to total 100 mass parts of (A) and (B), the content of (F) is preferred
For 1~30 mass parts, more preferably 2~20 mass parts.
In the case that resin combination includes (G), relative to total 100 mass parts of (A) and (B), the content of (G) is preferred
For 2~40 mass parts, more preferably 3~30 mass parts.
In the case that resin combination includes (H), relative to total 100 mass parts of (A) and (B), the content of (H) is preferred
For 0.1~10 mass parts, more preferably 0.3~2 mass parts.
The content of (A) and (B) in resin combination be preferably 40 mass % or more, particularly preferably 60 mass % with
On.In addition, the content of (A), (B), (C) and (D) in resin combination be preferably 40 mass of mass %~100 %, more preferably
For 50 mass of mass %~97 %, particularly preferably 60 mass of mass %~95 %.
[manufacture of resin combination]
Resin combination can be by that will be used as (A)~(D) of neccessary composition and other compositions as optional member are mixed
It closes and manufactures.
[curing method]
Resin combination can pass through the method including heating or the method including heating and active energy beam irradiates
Solidified.In the case where carrying out heating and active energy beam irradiates the two, heating can be in the photograph of active energy beam
Before penetrating, simultaneously, and/or carry out later, preferably carried out later.The preferred ultraviolet light of active energy beam, luminous ray.Activity
The exposure of energy-ray is preferably 50~10,000mJ/cm2, more preferably 100~6,000mJ/cm2.The temperature of heating is preferred
It is 50~200 DEG C, particularly preferably 80~150 DEG C.The time of heating is preferably 10 minutes~5 hours, particularly preferably 30 points
Clock~3 hour.
[purposes]
Resin combination may be used as the sealant for protecting electronic device from moisture damage.As electronic device,
Organic electroluminescent, Electronic Paper, solar battery and liquid crystal display device etc. can be enumerated.In particular, resin combination is preferred
As liquid crystal drip-injection method sealant.Thus, it is possible to be used as the sealing of low, liquid crystal display characteristic the high reliablity of moisture permeability
Agent.About having used the liquid crystal drip-injection method sealant of epoxy resin, such as it is referred to Japanese Unexamined Patent Publication 2012-077202
Bulletin.
Embodiment
Hereinafter, illustrate the present invention by embodiment, but the present invention and it is not limited to these examples.It needs to illustrate
, (A) and (D) used in embodiment and comparative example is manufactured as follows.
[(A): the manufacture of the acrylated bisphenol A type epoxy resin of part methyl]
By bisphenol A type epoxy resin (EXA-850CRP, Dainippon Ink Chemicals's manufacture) 340.0g, methacrylic acid (Tokyo
Manufactured at Industrial Co., Ltd) 90.4g, triphenylphosphine (Tokyo Chemical Industry Co., Ltd's manufacture) 0.5g and BHT (dibutyl
Hydroxy-methylbenzene) 100mg mixing, it is stirred 6 hours at 100 DEG C.Obtain the part methyl propylene of 418.0g light yellow clear dope
Acylated bisphenol A type epoxy resin a1.
[(D): the manufacture of polymerization initiator]
Polymerization initiator used in embodiment and comparative example manufactures as follows.
<manufacture of polymerization initiator d1>
By Denacol EX-830 (diglycidyl ether Nagase chemteX Co., Ltd. of PEG400 manufactures) 26.8g
(0.10 equivalent/epoxy group), 4- dimethylaminobenzoic acid 16.5g (1.0 equivalent), (0.20 works as benzyltrimethylammonium chloride 3.7g
Amount), MIBK (methyl iso-butyl ketone (MIBK)) 25.0g be packed into flask, 110 DEG C stir 24 hours.Reaction mixture is cooled to room temperature,
It is dissolved in chloroform 50g, is cleaned 6 times with water 100ml.The solvent under reduced pressure of organic phase is distilled off, 35.3g polymerization is obtained and causes
Agent d1.
<manufacture of polymerization initiator d2>
By Denacol EX-830 (diglycidyl ether Nagase chemteX Co., Ltd. of PEG400 manufactures) 26.8g
(0.10 equivalent/epoxy group), 2- hydroxyl -9H- thioxanthene-9-one 22.8g (1.0 equivalent), benzyltrimethylammonium chloride 3.7g (0.20
Equivalent), MIBK40.0g be packed into flask, 110 DEG C stir 72 hours.Reaction mixture is cooled to room temperature, chloroform is dissolved in
In 50g, cleaned 6 times with water 100ml.The solvent under reduced pressure of organic phase is distilled off, 36.2g polymerization initiator d2 is obtained.
[(B): monofunctional epoxy compound]
It is the structural formula of (B) used in embodiment, as follows with ProductName or manufacturing method.
[changing 1]
[changing 2]
B1:EX-141: phenyl glycidyl ether (manufacture of Nagase chemteX Co., Ltd.)
B2:OPP-G:2- phenylphenol glycidol ether (Sanko Co., Ltd.'s manufacture)
B3:EX-146:4- tert-butyl-phenyl glycidol ether (manufacture of Nagase chemteX Co., Ltd.)
<manufacture of monofunctional epoxy compound b4>
1- naphthols 200g, epoxychloropropane 1283g, dimethyl sulfoxide 125g loading are equipped with thermometer, cooling tube, enlightening
In the 2L three neck round bottom flask for pacifying Stark trap (Dean-Stark Trap), dropping funel, blender.Then, it will mix
Object is heated to about 50 DEG C under the decompression of 50 supports (torr) while stirring, and 48% sodium hydroxide of 208g was added dropwise with 2 hours
Aqueous solution.In the water distillated by azeotropic/epoxychloropropane mixture, epoxychloropropane is returned into reaction system one on one side
While continuing to stir.After addition, continue stirring 2 hours.Then, reaction mixture is cooled to room temperature and toluene is added
1000g is cleaned 5 times with the water of 1.5L.Magnesium sulfate is added in organic phase, after dry, solid component is filtered out by filtering etc., it will
Obtained organic layer is removed by vacuum distillation, obtains 253g monofunctional epoxy compound b4.
<manufacture of monofunctional epoxy compound b5>
4- α-cumyl phenol 200g, epoxychloropropane 871g, dimethyl sulfoxide 85g loading are equipped with thermometer, cooling
Pipe, Dean-Stark water segregator (Dean-Stark Trap), dropping funel, blender 2L three neck round bottom flask in.Then,
Mixture is heated to about 50 DEG C under the decompression of 50 supports (torr) while stirring, 48% hydrogen of 141g was added dropwise with 2 hours
Aqueous solution of sodium oxide.In the water distillated by azeotropic/epoxychloropropane mixture, epoxychloropropane is returned into reaction on one side
System continues to stir on one side.After addition, continue stirring 2 hours.Then, reaction mixture is cooled to room temperature and first is added
Benzene 1000g is cleaned 5 times with the water of 1.5L.Magnesium sulfate is added in organic phase, after dry, solid component is filtered out by filtering etc.,
Obtained organic layer is removed by vacuum distillation, obtains 250g monofunctional epoxy compound b5.
<manufacture of monofunctional epoxy compound b6>
4- metoxyphenol 100g, epoxychloropropane 745g, benzyltrimethylammonium chloride 15g loading are equipped with temperature
The 2L three neck round bottom flask of meter, cooling tube, Dean-Stark water segregator (Dean-Stark Trap), dropping funel, blender
In.Then, mixture is heated to about 50 DEG C under the decompression of 50 supports (torr) while stirring, with 3 hours dropwise addition 121g
48% sodium hydrate aqueous solution.In the water distillated by azeotropic/epoxychloropropane mixture, epoxychloropropane is returned on one side
Reaction system is returned to continue to stir on one side.After addition, continue stirring 2 hours.Then, reaction mixture is cooled to room temperature
And toluene 500g is added, it is cleaned 5 times with the water of 1.0L.Magnesium sulfate is added in organic phase, after dry, is filtered out by filtering etc. solid
Obtained organic layer is removed by vacuum distillation, obtains 103g monofunctional epoxy compound b6 by body ingredient.
<manufacture of monofunctional epoxy compound b7>
4- hydroxy benzaldehyde 100g, epoxychloropropane 757g, benzyltrimethylammonium chloride 15g loading are equipped with temperature
The 2L three neck round bottom flask of meter, cooling tube, Dean-Stark water segregator (Dean-Stark Trap), dropping funel, blender
In.Then, mixture is heated to about 50 DEG C under the decompression of 50 supports (torr) while stirring, with 3 hours dropwise addition 123g
48% sodium hydrate aqueous solution.In the water distillated by azeotropic/epoxychloropropane mixture, epoxychloropropane is returned on one side
Reaction system is returned to continue to stir on one side.After addition, continue stirring 2 hours.Then, reaction mixture is cooled to room temperature
And toluene 500g is added, it is cleaned 4 times with the water of 1.0L.Magnesium sulfate is added in organic phase, after dry, is filtered out by filtering etc. solid
Obtained organic layer is removed by vacuum distillation, obtains 111g monofunctional epoxy compound b7 by body ingredient.
<manufacture of monofunctional epoxy compound b8>
By 4- hydroxy-phenylformonitrile 25g, epoxychloropropane 194g, benzyltrimethylammonium chloride 4g loading be equipped with thermometer,
Cooling tube, Dean-Stark water segregator (Dean-Stark Trap), dropping funel, blender 0.5L three neck round bottom flask in.
Then, mixture is heated to about while stirring under the decompression of 50 supports (torr) 50 DEG C, was added dropwise 32g's with 3 hours
48% sodium hydrate aqueous solution.In the water distillated by azeotropic/epoxychloropropane mixture, epoxychloropropane is returned on one side
Continue to stir on one side to reaction system.After addition, continue stirring 2 hours.Then, reaction mixture is cooled to room temperature simultaneously
Toluene 150g is added, is cleaned 4 times with the water of 0.3L.Magnesium sulfate is added in organic phase, after dry, solid is filtered out by filtering etc.
Obtained organic layer is removed by vacuum distillation, obtains 36g monofunctional epoxy compound b8 by ingredient.
<manufacture of monofunctional epoxy compound b9>
4- fluorophenol 100g, epoxychloropropane 850g, benzyltrimethylammonium chloride 17g loading are equipped with thermometer, cold
But in the 2L three neck round bottom flask of pipe, Dean-Stark water segregator (Dean-Stark Trap), dropping funel, blender.It connects
, mixture is heated to about 50 DEG C under the decompression of 50 supports (torr) while stirring, was added dropwise the 48% of 138g with 3 hours
Sodium hydrate aqueous solution.In the water distillated by azeotropic/epoxychloropropane mixture, on one side by epoxychloropropane back to instead
System is answered to continue to stir on one side.After addition, continue stirring 5 hours.Then, reaction mixture is cooled to room temperature and is added
Toluene 500g is cleaned 4 times with the water of 1.0L.Be added magnesium sulfate in organic phase, after dry, by filter etc. filter out solid at
Point, obtained organic layer is removed by vacuum distillation, obtains 130g monofunctional epoxy compound b9.
<manufacture of monofunctional epoxy compound b10>
By 4- phenoxy phenyl 25g, epoxychloropropane 124g, benzyltrimethylammonium chloride 3g loading be equipped with thermometer,
Cooling tube, Dean-Stark water segregator (Dean-Stark Trap), dropping funel, blender 0.5L three neck round bottom flask in.
Then, mixture is heated to about while stirring under the decompression of 50 supports (torr) 50 DEG C, was added dropwise 20g's with 3 hours
48% sodium hydrate aqueous solution.In the water distillated by azeotropic/epoxychloropropane mixture, epoxychloropropane is returned on one side
Continue to stir on one side to reaction system.After addition, continue stirring 2 hours.Then, reaction mixture is cooled to room temperature simultaneously
Toluene 150g is added, is cleaned 4 times with the water of 0.3L.Magnesium sulfate is added in organic phase, after dry, solid is filtered out by filtering etc.
Obtained organic layer is removed by vacuum distillation, obtains 32g monofunctional epoxy compound b10 by ingredient.
<manufacture of monofunctional epoxy compound b11>
2- phenoxetol 100g, epoxychloropropane 670g, benzyltrimethylammonium chloride 13g loading are equipped with temperature
The 2L three neck round bottom flask of meter, cooling tube, Dean-Stark water segregator (Dean-Stark Trap), dropping funel, blender
In.Then, mixture is heated to about while stirring under the decompression of 50 supports (torr) 50 DEG C, was added dropwise 20g's with 3 hours
48% sodium hydrate aqueous solution.In the water distillated by azeotropic/epoxychloropropane mixture, epoxychloropropane is returned on one side
Continue to stir on one side to reaction system.After addition, continue stirring 3 hours.Then, reaction mixture is cooled to room temperature simultaneously
Toluene 500g is added, is cleaned 3 times with the water of 1.0L.Magnesium sulfate is added in organic phase, after dry, solid is filtered out by filtering etc.
Obtained organic layer is removed by vacuum distillation, obtains 70g monofunctional epoxy compound b11 by ingredient.
<manufacture of monofunctional epoxy compound b12>
(1) synthesis of hydroxyethyl addition product
2- phenylphenol 100g, ethylene carbonate 62g, N,N-dimethylformamide 300g, potassium carbonate 97g are packed into flask
In, it is stirred 24 hours at 100 DEG C.It is cooled to room temperature, toluene 500g is added, is cleaned 5 times with the water of 1.0L.It is added in organic phase
Magnesium sulfate, after dry, filters out solid component by filtering etc., and obtained organic layer is removed by vacuum distillation, is obtained
2- phenylphenol-hydroxyethyl addition product.
(2) synthesis of epoxy resin
By obtained 2- phenylphenol-hydroxyethyl addition product 100g, epoxychloropropane 432g, benzyl trimethyl chlorination
Ammonium 9g loading is equipped with thermometer, cooling tube, Dean-Stark water segregator (Dean-Stark Trap), dropping funel, blender
1L three neck round bottom flask in.Then, mixture is heated to about 50 DEG C under the decompression of 50 supports (torr) while stirring,
48% sodium hydrate aqueous solution of 70g was added dropwise with 3 hours.In the water distillated by azeotropic/epoxychloropropane mixture, on one side
Epoxychloropropane is continued to stir on one side back to reaction system.After addition, continue stirring 3 hours.Then, reaction is mixed
It closes object and is cooled to room temperature and is added toluene 500g, with 4 cleaning of water of 1.0L.Magnesium sulfate is added in organic phase, it is dry
Afterwards, solid component is filtered out by filtering etc., obtained organic layer is removed by vacuum distillation, obtains 121g simple function ring
Oxygen compound b12.
<manufacture of monofunctional epoxy compound b13>
4- dihydroxy benaophenonel 25g, epoxychloropropane 117g, benzyltrimethylammonium chloride 2g loading are equipped with temperature
The 0.5L three neck round bottom flask of meter, cooling tube, Dean-Stark water segregator (Dean-Stark Trap), dropping funel, blender
In.Then, mixture is heated to about while stirring under the decompression of 50 supports (torr) 50 DEG C, was added dropwise 19g's with 3 hours
48% sodium hydrate aqueous solution.In the water distillated by azeotropic/epoxychloropropane mixture, epoxychloropropane is returned on one side
Continue to stir on one side to reaction system.After addition, continue stirring 12 hours.Then, reaction mixture is cooled to room temperature
And toluene 200g is added, it is cleaned 4 times with the water of 0.3L.Magnesium sulfate is added in organic phase, after dry, is filtered out by filtering etc. solid
Obtained organic layer is removed by vacuum distillation, obtains 26g monofunctional epoxy compound b13 by body ingredient.
<manufacture of monofunctional epoxy compound b14>
4- (benzyloxy) phenol 100g, epoxychloropropane 462g, benzyltrimethylammonium chloride 9g loading are equipped with temperature
The 1L three neck round bottom flask of meter, cooling tube, Dean-Stark water segregator (Dean-Stark Trap), dropping funel, blender
In.Then, mixture is heated to about while stirring under the decompression of 50 supports (torr) 50 DEG C, was added dropwise 75g's with 3 hours
48% sodium hydrate aqueous solution.In the water distillated by azeotropic/epoxychloropropane mixture, epoxychloropropane is returned on one side
Continue to stir on one side to reaction system.After addition, continue stirring 12 hours.Then, reaction mixture is cooled to room temperature
And toluene 400g is added, it is cleaned 3 times with the water of 1.0L.Magnesium sulfate is added in organic phase, after dry, is filtered out by filtering etc. solid
Obtained organic layer is removed by vacuum distillation, obtains 82g monofunctional epoxy compound b14 by body ingredient.
B15: Glycidyl methyl ether (Tokyo Chemical Industry Co., Ltd's manufacture)
B16: butyl glycidyl ether (Tokyo Chemical Industry Co., Ltd's manufacture)
B17: furfuryl glycidyl ether (manufacture of Acros Organics company)
<manufacture of monofunctional epoxy compound b18>
2- (4- hydroxy phenyl) ethyl alcohol 100g, epoxychloropropane 402g, dimethyl sulfoxide 65g loading are equipped with temperature
The 2L three neck round bottom flask of meter, cooling tube, Dean-Stark water segregator (Dean-Stark Trap), dropping funel, blender
In.Then, mixture is heated to about while stirring under the decompression of 50 supports (torr) 50 DEG C, was added dropwise 60g's with 3 hours
48% sodium hydrate aqueous solution.In the water distillated by azeotropic/epoxychloropropane mixture, epoxychloropropane is returned on one side
Continue to stir on one side to reaction system.After addition, continue stirring 2 hours.Then, reaction mixture is cooled to room temperature simultaneously
Toluene 200g, 3- methyl -2- butanone 200g is added, is cleaned 3 times with the water of 0.5L.Magnesium sulfate is added in organic phase, after dry,
Solid component is filtered out by filtering etc., obtained organic layer is removed by vacuum distillation, obtains 108g monofunctional epoxy
Compound b18.
[other: 2 functional epoxide compounds and simple function (methyl) acrylate compounds]
2 functional epoxide compounds used in comparative example and simple function (methyl) acrylate compounds are as described below.
B ' 1:EXA-850CRP: bisphenol A type epoxy resin (Dainippon Ink Chemicals's manufacture)
B ' 2: phenyl methacrylate (Tokyo Chemical Industry Co., Ltd's manufacture)
[Examples 1 to 22 and comparative example 1~4]
By the acrylated bisphenol A type epoxy resin a1 of part methyl, each monofunctional epoxy compound or 2 functional epoxyizatioies
Close object or simple function (methyl) acrylate compounds, Photoepolymerizationinitiater initiater d1 and d2, amine system curing agent c1 (polynary amine system
Close object, EH-5030S (Asahi Denka Co., Ltd.'s manufacture)) it is sufficiently kneaded according to blend amount shown in following table 1 (mass parts), it obtains
The resin combination of Examples 1 to 22 and comparative example 1~4.
About synthesis example and compare each compound manufactured in synthesis example and these each resin combinations, utilization are following
Test evaluated.
[experimental condition]
(1) epoxide equivalent (WPE) measures
It is measured under conditions of record in JIS K 7236:2001.
(2) moisture permeability
For resin combination, by diameter be 3.6mm~3.8mm, with a thickness of 0.28mm~0.32mm in the way of, utilize
100mm × 100mm, thickness 0.1mm PET (polyethylene terephthalate) film clamped, with 100mW/cm2It is ultraviolet
Line irradiates illumination, by being respectively 1500mJ/cm2Luminous energy two sides is irradiated, it is small to carry out 1 with 120 DEG C of hot-air ovens
When heat cure, the sample of moisture permeability measurement is made.Measured about moisture permeability, according to JIS K 0208:1976, using 65 DEG C/
95% constant temperature and humidity cabinet, by being calculated using the weight change of moisture-inhibiting agar diffusion method.The unit of moisture permeability is g/ (m2·24h)。
Above evaluation result and the mixture composition of the resin combination of Examples 1 to 22 and comparative example 1~4 are shown together
In following table 1 and 2.It should be noted that other than embodiment 4, using (C) reactive hydrogen amount relative to (A) and (B)
The amount of (C) for adding up to 1 times of epoxy group.In addition, in embodiment 4, using (C) reactive hydrogen amount relative to (A) and (B)
The amount of (C) for adding up to 0.83 times of epoxy group.
[table 1]
[table 2]
The resin combination of embodiment is the resin combination that can provide the low solidfied material of moisture permeability.
By the comparison of embodiment 3,6 and 9 it is found that in X1In the case where for non-substituted aryl, if the epoxide equivalent of (B) subtracts
Small, moisture permeability further decreases.By the comparison of embodiment 19 and 20 it is found that about X2It the case where for non-substituted alkyl, can also
Think same result.It is thought that because since epoxide equivalent is small, becoming more in conjunction with number, crosslinking becomes fine and close.
By embodiment 6~10 it is found that adding up to 100 mass parts relative to (A) and (B), if (B) compared with embodiment 11
Content increase then solidfied material moisture permeability reduce.But total 100 mass parts relative to (A) and (B), if the content of (B)
For the effect saturation for reducing the moisture permeability of solidfied material.
By embodiment 3 compared with embodiment 4 it is found that epoxy group relative to (A) and (B) it is total, even if at (C)
In the case that the amount of reactive hydrogen is few, it may have the effect for reducing the moisture permeability of solidfied material.
By the comparison of embodiment 3,7,9,10~14,17~18,22 it is found that in X1For can be with substituted aryl the case where
Under, if the non-substituted or aryl replaced preferred substituent group, then the moisture permeability of solidfied material further decreases.
By the comparison of embodiment 7 and 22 it is found that and X1It is compared for the case where alkyl-substituted aryl, for by hydroxyl alkane
In the case where the aryl that base replaces, the moisture permeability of solidfied material is further decreased.
By the comparison of embodiment 3 and 15 and embodiment 8 and 16 it is found that with ring structure and ring comprising aromatic group
The resin combination for the epoxide that oxygen propoxyl group is combined by oxyalkylene alkyl is compared, the ring knot comprising aromatic group
The moisture permeability of the solidfied material of the resin combination for the epoxide that structure and glycidoxy are bound directly further decreases.
Even if by the comparison of embodiment 19~21 it is found that the carbon atom in conjunction with glycidoxy is the carbon original of aliphatic
Son, the moisture permeability of the solidfied material of the resin combination comprising the aromatic epoxy compound with aromatic group also further drop
It is low.
In comparative example 1, since resin combination is free of (B), thus the moisture permeability of solidfied material is high.
In comparative example 2, and resin combination includes 2 functional epoxide compounds instead of monofunctional epoxy compound, therefore admittedly
The reduction of the moisture permeability of compound is insufficient.
In comparative example 3 and 4, resin combination includes simple function (methyl) acrylate compounds and replaces monofunctional epoxy
Compound.Relative to the embodiment 2 and 3~4 for having used same amount of monofunctional epoxy compound, the solidfied material of comparative example 3 and 4
Moisture permeability reduction it is insufficient.
Industrial applicibility
Resin combination is the use for electronic equipment resin combination that can provide the low solidfied material of moisture permeability.Resin group as a result,
The industry that object is closed as the sealant, particularly liquid crystal drip-injection method sealant of the use for electronic equipment for requiring low moisture permeability is practical
Property it is high.
Claims (6)
1. a kind of use for electronic equipment resin combination contains part (methyl) acryloyl of the epoxy resin of (A) 2 function or more
Change epoxy resin, (B) monofunctional epoxy compound, (C) amine system curing agent and (D) polymerization initiator.
2. use for electronic equipment resin combination as described in claim 1, wherein (B) is following formula (1) compound represented,
X1-G(1)
In formula,
G be glycidoxy or methyl glycidoxy,
X1For the aryl with or without substituent group, the aryl-(O-R with or without substituent group1)n1Base has or does not have
Aryl-the R of substituted base2Base, the heteroaryl with or without substituent group, the heteroaryl-(O- with or without substituent group
R3)n2Base or heteroaryl-R with or without substituent group4Base, herein, R1For alkylidene, the integer that n1 is 1~6, R2For
Alkylidene, R3For alkylidene, the integer that n2 is 1~6, R4For alkylidene.
3. use for electronic equipment resin combination as claimed in claim 1 or 2, wherein the epoxide equivalent of (B) is 80~2,
000g/eq。
4. resin combination according to any one of claims 1 to 3, wherein (A) be selected from by bisphenol A type epoxy resin,
Bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy tree
Rouge, phenol novolak type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F phenolic type epoxy resin, alicyclic epoxy resin, aliphatic chain
Epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, hydantoins type epoxy resin, isocyanide urea
One or more of the group of sour ester type epoxy resin and the phenol novolak type epoxy resin composition with triphenol methane skeleton
Part (methyl) acrylated epoxy resin of epoxy resin.
5. use for electronic equipment resin combination as described in any one of claims 1 to 4, wherein relative to (A) and (B)
Total 100 mass parts, (B) are 1~40 mass parts.
6. being sealed such as use for electronic equipment resin combination according to any one of claims 1 to 5 for liquid crystal drip-injection method
Agent.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016225997 | 2016-11-21 | ||
| JP2016-225997 | 2016-11-21 | ||
| PCT/JP2017/037979 WO2018092508A1 (en) | 2016-11-21 | 2017-10-20 | Resin composition for electronic device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109689725A true CN109689725A (en) | 2019-04-26 |
| CN109689725B CN109689725B (en) | 2020-07-14 |
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| CN201780056543.7A Active CN109689725B (en) | 2016-11-21 | 2017-10-20 | Resin composition for electronic device |
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| JP (1) | JP6518894B2 (en) |
| KR (1) | KR102149717B1 (en) |
| CN (1) | CN109689725B (en) |
| TW (1) | TWI710597B (en) |
| WO (1) | WO2018092508A1 (en) |
Cited By (4)
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|---|---|---|---|---|
| CN109320918A (en) * | 2018-11-07 | 2019-02-12 | 中国科学院宁波材料技术与工程研究所 | Recyclable carbon-fibre reinforced epoxy resin composite material, preparation method and application |
| CN113811559A (en) * | 2019-05-14 | 2021-12-17 | 协立化学产业株式会社 | Sealant for liquid crystal dropping method |
| CN115433146A (en) * | 2022-09-16 | 2022-12-06 | 西安思摩威新材料有限公司 | Compound for sealing film, composition and sealing film formed by using composition |
| CN113811559B (en) * | 2019-05-14 | 2024-05-31 | 协立化学产业株式会社 | Sealant for liquid crystal instilling method |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20220133967A (en) | 2020-05-29 | 2022-10-05 | 미쓰이 가가쿠 가부시키가이샤 | Sealing agent for display devices |
| KR102630372B1 (en) * | 2021-11-30 | 2024-01-30 | 한국화학연구원 | Gas barrier polymer coating film prepared using co-solvent and Manufacturing method thereof |
| WO2023182358A1 (en) * | 2022-03-25 | 2023-09-28 | 三井化学株式会社 | Thermosetting resin composition, sealant for display devices, and display device |
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- 2017-10-20 WO PCT/JP2017/037979 patent/WO2018092508A1/en active Application Filing
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| JP2009019099A (en) * | 2007-07-11 | 2009-01-29 | Showa Highpolymer Co Ltd | Resin composition for fiber-reinforced composite material, molding material using the same, and fiber-reinforced composite material |
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| CN113811559A (en) * | 2019-05-14 | 2021-12-17 | 协立化学产业株式会社 | Sealant for liquid crystal dropping method |
| CN113811559B (en) * | 2019-05-14 | 2024-05-31 | 协立化学产业株式会社 | Sealant for liquid crystal instilling method |
| CN115433146A (en) * | 2022-09-16 | 2022-12-06 | 西安思摩威新材料有限公司 | Compound for sealing film, composition and sealing film formed by using composition |
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Also Published As
| Publication number | Publication date |
|---|---|
| KR102149717B1 (en) | 2020-08-31 |
| KR20190080859A (en) | 2019-07-08 |
| TWI710597B (en) | 2020-11-21 |
| TW201829610A (en) | 2018-08-16 |
| CN109689725B (en) | 2020-07-14 |
| JP6518894B2 (en) | 2019-05-29 |
| WO2018092508A1 (en) | 2018-05-24 |
| JPWO2018092508A1 (en) | 2019-04-18 |
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