CN110054760A - One-component resin composition - Google Patents
One-component resin composition Download PDFInfo
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- CN110054760A CN110054760A CN201910048246.9A CN201910048246A CN110054760A CN 110054760 A CN110054760 A CN 110054760A CN 201910048246 A CN201910048246 A CN 201910048246A CN 110054760 A CN110054760 A CN 110054760A
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- component
- ingredient
- mercaptan
- resin composition
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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
- C08G59/40—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
- C08G59/66—Mercaptans
-
- 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
- C08G59/68—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 catalysts used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
Abstract
The subject of the invention is to provide the one-component resin compositions that the stress for shear direction and peeling direction this two side all has superior bonding force.Solution of the invention is a kind of one-component resin composition, it includes: epoxy resin, two functions are without multifunctional no ester mercaptan more than ester mercaptan and trifunctional.
Description
Technical field
The present invention relates to one pack system (one-component) resin combinations.
Background technique
Having used the compositions of thermosetting resin of epoxy resin has in mechanical property, electrical characteristic, thermal characteristics, chemically-resistant
The excellent performance of moral character and adhesive strength etc., so being used for coating, electric and electronic insulating materials and bonding all the time
The extensive purposes such as agent.As such resin combination, bi-component resin composition and one-component resin composition are developed.It is double
In component resin composition, epoxy resin is mixed with curing agent when in use, makes epoxy resin cure.On the other hand, single group
Divide in resin combination, in advance mix epoxy resin with curing agent, its solidification is made by heating etc. when in use.
In recent years, for the protection of the electronic component in the field of the sealing of semiconductor element etc., the densification of circuit
It is improved with the reliability of connection, one-component resin composition plays an important role.Especially for raising production efficiency, operation
Property, the cured requirement under the conditions of low-temperature short-time is improved.In addition, electronic component is increasingly miniaturized, various devices are realized
Removableization (portability), wearableization, the case where electronic equipment is as a result used under varied environment increases than previous
It is more.As a result, about fall-shock durable and high temperature and humidity resistance, also being required more higher than previous for resin combination
Reliability.
About describing respectively in above situation, such as patent document 1,2, the excellent low temperature of moisture-proof (moisture resistance) is quick
The one-component epoxy resin composition of curability describes the mercaptan compound with specific structure being used as consolidating for epoxy resin
Agent.
Existing technical literature
Patent document
Patent document 1: No. 2015/060440 bulletin of International Publication No.
Patent document 2: No. 2015/060439 bulletin of International Publication No..
Summary of the invention
The technical problems to be solved by the invention
In order to make the adhesive portion based on resin combination that there is enough tolerances to impact when falling, it is believed that need for cutting
Butt to either peeling direction to stress show enough bonding forces.But generally for performance high shear
Bonding force, it is effective for improving the elasticity modulus of resin combination, but peeling adhesion force declines to a great extent in this case.Another party
Face, generally for high peeling adhesion force is showed, it is effective for reducing the elasticity modulus of resin combination, but shearing is viscous in this case
Relay declines to a great extent.Accordingly, it is difficult to the resin combination that the bonding force for obtaining two sides is excellent.
In addition, proposing the ring that addition has flexible back bone in patent document 2 as the method for improving peeling adhesion force
The method of oxygen resin, but the usually reactivity of the epoxy resin with flexible back bone is low, therefore there are low-temperature fast-curing property differences
Problem.
Then, the issue of the present invention is to provide low-temperature fast-curing property is excellent, and then for shear direction and removing side
Superior bonding force is all had to the stress of this two side, and moisture-proof also excellent one-component resin composition.
Technical scheme applied to solve the technical problem
In order to solve the above problems, the present invention includes item below,
[1] a kind of one-component resin composition, which is characterized in that include following A, B and C ingredient,
A: epoxy resin
B: the mercaptan compound with 2 mercaptos and not ester-containing skeleton in the molecule
C: in the molecule with 3 or more mercaptos and the mercaptan compound of not ester-containing skeleton；
[2] the one-component resin composition according to above-mentioned [1], which is characterized in that it also include following D ingredients,
D: latent curing accelerator；
[3] the one-component resin composition according to above-mentioned [1] or [2], which is characterized in that the B component and the C at
Divide and does not have hydroxyl；
[4] the one-component resin composition according to any one of above-mentioned [1]~[3], which is characterized in that the C ingredient exists
Intramolecular has ring skeleton；
[5] the one-component resin composition according to any one of above-mentioned [1]~[4], which is characterized in that the B component exists
Intramolecular does not have ring skeleton；
[6] the one-component resin composition according to any one of above-mentioned [1]~[5], which is characterized in that the B component
Molecular weight is in the range of 130~1000；
[7] the one-component resin composition according to any one of above-mentioned [1]~[6], which is characterized in that by the B component
And the summation of the mercaptan radix of the C ingredient, when being set as 1, ratio shared by the mercaptan radix of the C ingredient be [the C ingredient
Total mercapto number/(total mercapto number of total mercapto number+C ingredient of the B component)] it is 0.1~0.9；
[8] a kind of bonding agent, which is characterized in that include one-component resin composition described in any one of above-mentioned [1]~[7]；
[9] bonding agent described in above-mentioned [8], which is characterized in that the bonding agent be used to be bonded the neodium magnet as adherend；
[10] a kind of sealing material, which is characterized in that include one-component resin combination described in any one of above-mentioned [1]~[7]
Object；
[11] a kind of solidfied material, which is characterized in that keep one-component resin composition described in any one of above-mentioned [1]~[7] hot
It is solidified to form；
[12] a kind of electronic component, which is characterized in that include solidfied material described in above-mentioned [11]；
[13] a kind of motor containing neodium magnet, which is characterized in that comprising adherend and for being bonded the above-mentioned of the adherend
[11] solidfied material described in；
[14] a kind of electronic component is the electronic component containing the motor containing neodium magnet, which is characterized in that comprising above-mentioned
[11] solidfied material described in.
The effect of invention
If can provide that low-temperature fast-curing property is excellent using the present invention, for shear direction and peeling direction this two side
Stress all has superior bonding force, and the one-component resin composition with moisture-proof.
Specific embodiment
The one-component resin composition that embodiments of the present invention are related to is dividing comprising (A ingredient) epoxy resin, (B component)
Mercaptan compound and (C ingredient) in sub with 2 mercaptos and not ester-containing skeleton are in the molecule with 3 or more mercaptan
The mercaptan compound of base and not ester-containing skeleton.Hereinafter, will " in the molecule with 2 mercaptos and not ester-containing skeleton it is Thiolation
Close object " be denoted as " two functions are without ester mercaptan ", will " in the molecule have 3 or more mercapto and not ester-containing skeleton it is Thiolation
Close object " it is denoted as " multifunctional no ester mercaptan ".The opinion of people according to the present invention, by and with two functions without ester mercaptan and multifunctional nothing
Ester mercaptan can get the one-component resin for all having excellent bonding force for shear direction and peeling direction this two side and combine
Object.In addition, being remarkably improved moisture-proof as curing agent (i.e. mercaptan compound) by using no ester mercaptan compound.
In addition, in the present invention, so-called " one pack system " resin combination refers to mixes curing agent and epoxy resin in advance
Composition is with the composition by heating cured property.
[A ingredient: epoxy resin]
As epoxy resin, as long as being then not particularly limited with the resin of at least one epoxy group in the molecule.As epoxy
Resin, preferably using the resin of the epoxy group in average each molecule with 2 or more.
As epoxy resin, it can be mentioned, for example: keep bisphenol-A, Bisphenol F, bisphenol-A D, catechol, resorcinol etc. polynary
Polyglycidyl ether obtained by the polyalcohols such as phenol or glycerol, polyethylene glycol and epichlorohydrin reaction；Make P-hydroxybenzoic acid,
Glycidol ether-ether obtained by the hydroxycarboxylic acid and epichlorohydrin reaction of β oxynaphthoic acid etc；Make phthalic acid, right
More ethylene oxidic esters obtained by the polybasic carboxylic acid and epichlorohydrin reaction of phthalic acid etc；And epoxidized phenol phenolic aldehyde tree
Rouge (phenol novolac resin), epoxidized cresol phenolic resin (cresol novolac resin), epoxidation polyene
Hydrocarbon, ring type aliphatic epoxy resin and urethane-modified epoxy resin；Etc., it is not limited to these examples.
As epoxy resin, from the point of view of keeping the viewpoints such as high-fire resistance and low-moisture permeability, wherein preferably bisphenol type epoxy
Resin, bisphenol f type epoxy resin, phenol novolak type epoxy, biphenyl aralkyl-type epoxy resin, phenol aralkyl type ring oxygen
Resin, aromatic glycidyl amine type epoxy resin, epoxy resin with bicyclopentadiene structure etc., more preferably bisphenol-A type ring
Oxygen resin and bisphenol f type epoxy resin, further more preferably bisphenol A type epoxy resin.
The epoxide equivalent of epoxy resin is, for example, 50~500g/eq, preferably 100~300g/eq, more preferably 150~
200g/eq.Here, epoxide equivalent refers to the quality of the average corresponding epoxy resin of each epoxy group, it can be according to JIS K
7236 (2009) are measured.
Epoxy resin can be liquid, be also possible to solid-state, and both liquid resin and solid resin can be used.Here,
" liquid " and " solid-state " refers to the state of epoxy resin at room temperature.From the viewpoint of coating, processability, cementability, compared with
Be well using at least 10 mass % of all epoxy resin the above are liquid.As the specific example of the liquid-state epoxy resin,
It include: liquid bisphenol A type epoxy resin (Mitsubishi Chemical Ind's system " jER828EL ", Mitsubishi Chemical Ind's system " jER827 "), liquid
State bisphenol f type epoxy resin (Mitsubishi Chemical Ind's system " jER807 "), naphthalene type two functional epoxy resins (DIC corporation
" HP4032 ", " HP4032D "), liquid bisphenol A type epoxy resin/(aurification corporation is lived to bisphenol f type epoxy resin by Nippon Steel
" ZX1059 "), hydrogenation structure epoxy resin (Mitsubishi Chemical Ind's system " jERYX8000 ").Wherein, preferably high heat resistance and low
The Mitsubishi Chemical Ind's system " jER828EL " and Mitsubishi Chemical Ind's system " jER807 " of viscosity.
In addition, the specific example as solid epoxy resin, can enumerate: naphthalene type tetrafunctional epoxy resin (DIC corporation
" HP4700 "), dicyclopentadiene-type polyfunctional epoxy resin (DIC corporation " HP7200 "), naphthol type epoxy resin (Nippon Steel
Live in aurification corporation " ESN-475V "), epoxy resin (the Daicel chemical industrial company system " PB- with butadiene structure
3600 "), (Japanese chemical drug corporation " NC3000H ", " NC3000L ", the Mitsubishi Chemical Ind of the epoxy resin with biphenyl structural
Make " jERYX4000 ") etc..
In the case that the quality of resin combination entirety is set as 100 mass %, the content of the epoxy resin of A ingredient is for example
Preferably 5 mass % or more, more preferably 10 mass % or more, further more preferably 20 mass % or more, further more preferably 30 matter
% or more is measured, further more preferably 40 mass % or more, particularly preferably 45 mass % or more.In addition, preferably 95 mass % hereinafter,
More preferably 90 mass % hereinafter, further more preferably 85 mass % hereinafter, further more preferably 80 mass % hereinafter, further
More preferably 75 mass % are hereinafter, particularly preferably 70 mass % or less.
[B component: two functions are without ester mercaptan]
As B component two functions without ester mercaptan be in skeleton with 2 mercaptos and do not have ester bond compound.
It should be noted that ester bond refers to the key indicated with "-C (=O) O- " in the present invention.
From inhibit smell from the viewpoint of, molecular weight of two functions without ester mercaptan is preferably 130 or more, more preferably 140 with
On, further more preferably 150 or more, preferably 160 or more.
In addition, molecular weight of two functions without ester mercaptan is for example from the viewpoint of obtaining good rapidly-curable
1000 hereinafter, preferably 500 hereinafter, more preferably 300 hereinafter, further more preferably 230 or less.
In addition, two functions may be at the model obtained by arbitrarily selecting in the above-mentioned upper limit and lower limit without the molecular weight of ester mercaptan
In enclosing, for example, 130~1000, preferably 140 or more and 500 hereinafter, more preferably 150 or more and 300 hereinafter, preferably 160
Above and 230 or less.
Preferably two functions do not have hydroxyl without ester mercaptan in the molecule.In the case where not having hydroxyl in the molecule, deposit
In the tendency for being easy to get good working life (pot life), it is easy to take into account the service life and rapid curing of resin combination
Property.
Preferably two functions do not have ring skeleton without ester mercaptan in the molecule.In the case where ring skeleton, skeleton becomes
Obtain soft, the available superior resin combination of peel strength.
As preferred two function without ester mercaptan, the compound indicated with following formula 1 can be enumerated；
(formula 1): HS-R1-SH
It should be noted that in formula 1, R1Indicate the bivalent hydrocarbon radical of the linear chain or branched chain of carbon number 3~16, preferably 4~12.It can in alkyl
Bivalent group shown in following (1a)~(1c) comprising 1 or more.R1Preferably straight-chain alkyl or include 1 or more
With the straight-chain alkyl of following (1a) bivalent group indicated；
[changing 1]
[changing 2]
[changing 3]
As two functions indicated with above-mentioned formula 1 without ester mercaptan, specific enumerable Isosorbide-5-Nitrae-succinimide mercaptans, 1,6- ethanthiol, 1,
Pungent two mercaptan of 8-, 1, the 10- last of the ten Heavenly stems, two mercaptan, pungent two mercaptan of 3,6- dioxa -1,8- and bis- (2- mercaptoethyl) thioethers etc., preferably
Pungent two mercaptan of 1,8-, two mercaptan of the 1,10- last of the ten Heavenly stems and pungent two mercaptan of 3,6- dioxa -1,8-.
(B component) two function in resin combination is not particularly limited without the content of ester mercaptan, can according to epoxy resin and
The type etc. of multifunctional no ester mercaptan is adjusted.
For example, (B component) two function is without ester sulphur in the case that the content of (A ingredient) epoxy resin is set as 100 mass parts
The content of alcohol is preferably 0.1~100 mass parts, more preferably 1~60 mass parts, further more preferably 10~40 mass parts.
[C ingredient: multifunctional no ester mercaptan]
As long as the multifunctional no ester mercaptan as C ingredient has 3 or more mercaptos in skeleton (i.e. more than trifunctional)
And do not have the compound of ester bond, then it is not particularly limited.
Preferably multifunctional no ester mercaptan is trifunctional~six functions, more preferably trifunctional~tetrafunctional without ester mercaptan.
Preferably multifunctional no ester mercaptan does not have hydroxyl in the molecule.In the case where not having hydroxyl in the molecule, deposit
In the tendency for being easy to get good working life, it is easy to take into account the service life and rapidly-curable of resin combination.
Preferably multifunctional no ester mercaptan is the compound with ring skeleton.The ring skeleton can be alicyclic ring skeleton, aromatic ring
Any one of skeleton, heteroaryl ring skeleton, heterocyclic skeleton, preferably aromatic ring frame, heteroaryl ring skeleton, heterocyclic skeleton, more preferably
Heterocyclic skeleton.In the case where ring skeleton, shear bond power is improved.As such compound with heterocyclic skeleton, can arrange
Citing as 5~8 member rings, as annular atom include at least one nitrogen-atoms monocyclic or two ring type compounds.It is more specific next
It says, as the compound with heterocyclic skeleton, the compound comprising isocyanuric acid ring skeleton or glycoluril skeleton can be enumerated.
For example, the compound indicated with following formula 2 can be enumerated as preferred multifunctional no ester mercaptan；
[changing 4]
In equation 2 above, R2、R3And R4Separately indicate the divalent hydrocarbon of the linear chain or branched chain of carbon number 1~6, preferably carbon number 1~5
Base.It also may include bivalent group shown in 1 or more following (2a)~(2c) in alkyl；
[changing 5]
[changing 6]
[changing 7]
As the multifunctional no ester mercaptan indicated with above-mentioned formula 2, specific enumerable three (3- mercaptopropyi) isocyanuric acid ester.
Alternatively, the compound indicated with following formula 3 can be enumerated as other preferred multifunctional no ester mercaptan；
[changing 8]
In equation 3 above, R5、R6、R7And R8Separately indicate the two of the linear chain or branched chain of carbon number 1~6, preferably carbon number 1~4
Valency alkyl.It may include bivalent group shown in 1 or more following (3a)~(3c) in alkyl；
[changing 9]
[changing 10]
[changing 11]
As the multifunctional no ester mercaptan indicated with above-mentioned formula 3, specific enumerable 1,3,4,6- tetra- (2- mercaptoethyl) glycolurils etc..
The content of (C ingredient) multifunctional no ester mercaptan in resin combination is not particularly limited, can according to epoxy resin and
Type etc. of two functions without ester mercaptan is adjusted.
For example, in the case that the content of (A ingredient) epoxy resin is set as 100 mass parts, (C ingredient) multifunctional no ester sulphur
The content of alcohol is preferably 0.1~100 mass parts, more preferably 1~60 mass parts, further more preferably 10~50 mass parts.
When the summation of B component contained by composition and the mercaptan radix of C ingredient is set as 1, shared by the mercaptan radix of C ingredient
Ratio [total mercapto number of C ingredient/(total mercapto number of total mercapto number+C ingredient of B component)] be, for example, 0.1~
0.9, preferably 0.2~0.8, more preferably 0.3~0.7.
Here, the mass parts of mercaptan contained in so-called mercaptan radix representation composition are worth divided by obtained by mercapto equivalent
(mass parts of mercaptan/mercapto equivalent).It should be noted that comprising a variety of as B component or the feelings of the mercaptan of C ingredient in composition
Under condition, indicate the mass parts of each mercaptan divided by the summation of value obtained by respective mercapto equivalent.
In addition, mercapto equivalent is the value for indicating the quality of the average corresponding mercaptan compound of each mercapto, be by
The molecular weight of mercaptan compound is worth divided by obtained by mercaptan radix contained by the molecule compound.
In addition, " summation of the mercaptan radix of B component and C ingredient " is opposite in resin combination of the present embodiment
It is preferably in the ratio (total epoxy radix of C ingredient and total mercapto number/A ingredient of B component) of " the epoxy radix of A ingredient "
0.2~2.0, more preferably 0.6~1.2.
Here, the mass parts of epoxy resin contained in so-called epoxy radix representation composition are obtained divided by epoxide equivalent
Value (mass parts/epoxide equivalent of epoxy resin).It should be noted that including the epoxy resin of a variety of A ingredients in composition
In the case of, it indicates the mass parts of each epoxy resin divided by the summation of value obtained by respective epoxide equivalent.
[D ingredient: latent curing accelerator]
Resin combination preferably of the present embodiment includes latent curing accelerator.Latent curing accelerator is tool
Have and the solidification of epoxy resin is not helped at room temperature (20 DEG C ± 15 DEG C (JISZ8703)) and promotes asphalt mixtures modified by epoxy resin when heating
The additive of the cured function of rouge.
As latent curing accelerator, solid dispersing latent curing accelerator is preferably used.Solid dispersing
Latent curing accelerator refers at room temperature for the solid insoluble in epoxy resin, becomes solvable by heating, as ring
The compound that the curing accelerator of oxygen resin plays a role.
As solid dispersing latent curing accelerator, it can be mentioned, for example be at room temperature solid imidazolium compounds,
And solid dispersing amine adduct class latent curing accelerator, it is not limited to these examples.Wherein, preferably solid divides
Dissipate type amine adduct class latent curing accelerator.
As it is described be at room temperature solid imidazolium compounds, it can be mentioned, for example 2- heptadecyl imidazoles, 2- phenyl-
4,5- hydroxymethyl-imidazole, 2- undecyl imidazole, 2 phenyl 4 methyl 5 hydroxy methylimidazole, 2- phenyl -4- benzyl -5- hydroxyl
Methylimidazole, 2,4- diamino -6- (2-methylimidazole base-(1))-ethyl-s-triazine, 2,4- diamino -6- (2'- methyl miaow
Oxazolyl-(1) ')-ethyl-s-triazine isocyanuric acid adduct, 2-methylimidazole, 2- phenylimidazole, 2- phenyl -4- methyl miaow
Azoles, 1-cyanoethyl-2-phenylimidazole, 1- 1-cyanoethyl-2-methylimidazole trimellitic acid salt, 1-cyanoethyl-2-phenylimidazole are inclined
Benzenetricarboxylic acid salt, N- (2-methylimidazole base -1- ethyl) urea, N, N'- (2-methylimidazole base-(1)-ethyl) adipamide
(N, N'- (2-methylimidazolyl- (1)-ethyl) adipoyl diamide) etc., it is not limited to these examples.
As the example of solid dispersing amine adduct class latent curing accelerator, amine compounds and epoxidation can be enumerated
Close reaction product (amine-epoxy adduction species), the reaction product of amine compounds and isocyanate compound or carbamide compound of object
(urea type adduction species) etc..
As can be used as the solid dispersing amine adduct class latent curing accelerator (amine-epoxy adduction species)
The epoxide for manufacturing one of raw material, it can be mentioned, for example: make the polyphenol such as bisphenol-A, Bisphenol F, catechol, resorcinol,
Or polyglycidyl ether obtained by the polyalcohol and epichlorohydrin reaction of glycerol or polyethylene glycol etc；Make para hydroxybenzene first
Glycidol ether-ether obtained by the hydroxycarboxylic acid and epichlorohydrin reaction of acid, β oxynaphthoic acid etc；Make phthalic acid,
More ethylene oxidic esters obtained by the polybasic carboxylic acid and epichlorohydrin reaction of terephthalic acid (TPA) etc；Make 4,4'- diamino hexichol
Methylmethane or m-aminophenol etc. and glycidol amine compounds obtained by epichlorohydrin reaction；And epoxidized phenol phenolic aldehyde
The multi-functional epoxides such as resin, epoxidized cresol phenolic resin, epoxidized polyolefin or butyl glycidyl ether,
Mono-functionals' epoxide such as phenyl glycidyl ether, glycidyl methacrylate；Etc., it is not limited to these
Example.
It can be used as the amine compounds of the manufacture raw material of the solid dispersing amine adduct class latent curing accelerator, only
If in the molecule with 1 or more can with epoxy group occur addition reaction reactive hydrogen and at least in the molecule have 1 with
On functional group in primary amino group, secondary amino group and tertiary amino compound.As such amine compounds, example can be enumerated
Such as: diethylenetriamines, trien, n-propylamine, 2- hydroxyethylamino propylamine, cyclohexylamine ,-two hexamethylene of 4,4'- diamino
The aliphatic amine of methylmethane etc；The aromatic amine compounds such as 4,4'- diaminodiphenyl-methane, 2-aminotoluene；2- ethyl-
The heterocyclic compound of the nitrogen atoms such as 4-methylimidazole, 2-ethyl-4-methylimidazole quinoline, 2,4- methylimidazole quinoline, piperidines, piperazine
Object；Etc., it is not limited to these examples.
In addition, wherein especially the compound with tertiary amino is to provide with excellent solidification promotion ability in the molecule
Latent curing accelerator raw material, as the example of such compound, it can be mentioned, for example dimethylaminopropylamines, diethylamino
The aminations such as base propylamine, two n-propylamine base propylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylamino-ethylamine, N methyl piperazine
Close imidazolium compounds such as object or 2-methylimidazole, 2- ethyl imidazol(e), 2-ethyl-4-methylimidazole, 2- phenylimidazole etc
In the molecule with the primary amine class or secondary amine class of tertiary amino；2-dimethylaminoethanol, 1- methyl -2-dimethylaminoethanol, 1- benzene
Oxygroup methyl -2-dimethylaminoethanol, 2-diethylaminoethanol, 1- butoxymethyl -2-dimethylaminoethanol, 1- (2- hydroxyl -
3- phenoxy propyl) -2-methylimidazole, 1- (2- hydroxyl -3- phenoxy propyl) -2-ethyl-4-methylimidazole, 1- (2- hydroxyl -
3- butoxypropyl) -2-methylimidazole, 1- (2- hydroxyl -3- butoxypropyl) -2-ethyl-4-methylimidazole, 1- (2- hydroxyl -
3- phenoxy propyl) -2- benzylimidazoline, 1- (2- hydroxyl -3- butoxypropyl) -2-methylimidazole quinoline, 2- (dimethylamino first
Base) phenol, 2,4,6- tri- (dimethylamino methyl) phenol, N- beta-hydroxy ethyl morpholine, 2- dimethylamino ethyl mercaptan, 2- sulfydryl pyrrole
Pyridine, 2- benzimidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 4- mercaptopyridine, N, N- dimethylaminobenzoic acid, N,
N- dimethylglycine, niacin, isonicotinic acid, pyridine carboxylic acid, N, N- dimethylglycinamidyl hydrazine, N, N- dimethyl propylene hydrazides, nicotinoyl
In the molecule with alcohols, phenols, thio-alcohol, carboxylic acids and the hydrazides of tertiary amino as hydrazine, isonicotinic acid hydrazide etc.；Etc..
When making the epoxide and amine compounds that addition reaction manufacture latent curing accelerator occur, also
Active dydrogen compounds in the molecule with 2 or more reactive hydrogens can be added.As such active dydrogen compounds, example can be enumerated
Such as: bisphenol-A, Bisphenol F, bisphenol S, quinhydrones, catechol, resorcinol, pyrogallol, phenol novolacs polyatomic phenol,
The polyalcohols such as trimethylolpropane, the polybasic carboxylic acids class such as adipic acid, phthalic acid, 1,2- dimercaptoethane, 2- sulfydryl second
Alcohol, 1- sulfydryl -3- phenoxy group -2- propyl alcohol, thioacetic acid, ortho-aminobenzoic acid, lactic acid etc., it is not limited to these examples.
Isocyanic acid as the manufacture raw material that can be used as the solid dispersing amine adduct class latent curing accelerator
Ester compounds can be used for example: n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, benzyl isocyanate ester etc.
Monofunctional isocyanates compound；Hexamethylene diisocyanate, toluene di-isocyanate(TDI), 1,5- naphthalene diisocyanate, hexichol
Methylmethane -4,4'- diisocyanate, isophorone diisocyanate, benzene dimethylene diisocyanate, to benzene diisocyanate
The polyfunctional isocyanate compounds such as ester, 1,3,6- hexa-methylene triisocyanate, norbornane triisocyanate；And these
Compound containing terminal isocyanate group obtained by polyfunctional isocyanate compound is reacted with active dydrogen compounds；Etc..Make
For the example of such compound containing terminal isocyanate group, can enumerate: by toluene di-isocyanate(TDI) and trimethylolpropane
Reaction obtain the additive compound with terminal isocyanate group, reacting by toluene di-isocyanate(TDI) and pentaerythrite
The obtained additive compound etc. with terminal isocyanate group, it is not limited to these examples.
In addition, the urea as the manufacture raw material that can be used as the solid dispersing amine adduct class latent curing accelerator
Compound, it can be mentioned, for example urea (urea), thiocarbamides etc., it is not limited to these examples.
Solid dispersing latent curing accelerator can be for example readily available by following methods: above-mentioned manufacture is former
Material properly mixes, room temperature to 200 DEG C at a temperature of make its react after, cooled and solidified, then crushed, or in first
Base ethyl ketone, dioxanes make its reaction in tetrahydrofuran equal solvent, after desolventizing, comminuted solids ingredient.
About as the commercially available representative example of solid dispersing latent curing accelerator, for example, as amine-epoxy adduction
Species (amine adduct class) can enumerate " Ajicure PN-23 " (Ajinomoto Fine-Techno corporation trade name),
(Asahi Chemical Industry is public by " Ajicure PN-H " (Ajinomoto Fine-Techno corporation trade name), " Novacure HX-3742 "
Take charge of trade name processed), " Novacure HX-3721 " (Asahi Kasei Corporation's trade name) etc., and can be enumerated as urea type adduction species
" Fujicure FXR-1020 " (Fuji is melted into corporation trade name), " Fujicure FXR-1030 " (Fuji is melted into corporation
Trade name) etc., it is not limited to these examples.
In the case that the content of (A ingredient) epoxy resin is set as 100 mass parts, (D ingredient) latent curing accelerator
Content be preferably 0.1~100 mass parts, more preferably 1~60 mass parts, further more preferably 5~30 mass parts.
[E ingredient: stabilizer]
In order to realize excellent storage stability, resin combination of the present embodiment is preferably also comprising being selected from borate
Compound, titanate compound, aluminic acid ester compounds, zirconic acid ester compounds, isocyanate compound, carboxylic acid, acid anhydrides and sulfydryl
The stabilizer (E ingredient) of one or more of organic acid.
As the boric acid ester compound, it can be mentioned, for example: trimethylborate, triethyl borate, three n-propyl of boric acid, boron
Sour three isopropyl esters, tri-n-butyl borate, triamylborate, boric acid triallyl, the own ester of boric acid three, tricyclohexyl borate, boric acid
Three monooctyl esters, three nonyl ester of boric acid, boric acid three last of the ten Heavenly stems ester, boric acid three (dodecyl) ester, boric acid three (cetyl) ester, boric acid three (ten
Eight alkyl) ester, three (2- ethyl hexyl oxy) borines, bis- (tetra- oxaundecyl of 1,4,7,10-) (five oxa-s of 1,4,7,10,13-
Myristyl) (1,4,7- trioxaundecane base) borine, boric acid tribenzyl ester, boric acid triphen base ester, boric acid tri-o-tolyl
Ester, boric acid three toluene base esters, triethanolamine borates etc..
As the titanate compound, it can be mentioned, for example: tetraethyl titanate, metatitanic acid orthocarbonate, tetraisopropyl titanate, titanium
Sour four butyl esters, four monooctyl ester of metatitanic acid etc..
As the aluminic acid ester compounds, it can be mentioned, for example: aluminic acid triethyl, three propyl ester of aluminic acid, three isopropyl ester of aluminic acid, aluminium
Sour tributyl, three monooctyl ester of aluminic acid etc..
As the zirconic acid ester compounds, it can be mentioned, for example: zirconic acid tetra-ethyl ester, zirconic acid orthocarbonate, zirconic acid tetra-isopropyl, zirconium
Sour four butyl esters etc..
As the isocyanate compound, it can be mentioned, for example: n-butyl isocyanate, isopropyl isocyanate, 2- chlorine
Ethyl isocyanate, phenyl isocyanate, parachlorobenzyl isocyanic ester, benzyl isocyanate ester, hexamethylene diisocyanate, 2-
Ethylphenyl isocyanates, 2,6- dimethylphenyl isocyanate, 2,4 toluene diisocyanate, toluene di-isocyanate(TDI), 2,
6- toluene di-isocyanate(TDI), 1,5- naphthalene diisocyanate, diphenyl methane -4,4'- diisocyanate, tolidine diisocyanate
Ester, isophorone diisocyanate, benzene dimethylene diisocyanate, paraphenylene diisocyanate, norbornane triisocyanate
Deng.
As the carboxylic acid, it can be mentioned, for example: the representative examples of saturated aliphatic unitary such as formic acid, acetic acid, propionic acid, butyric acid, caproic acid, octanoic acid
Acid；The unsaturated aliphatics monoacid such as acrylic acid, methacrylic acid, butenoic acid；The halogenated aliphatics such as chloroacetic acid, dichloroacetic acid
Acid；The unitary oxyacid such as glycolic, lactic acid；Aliphatic aldehyde-acids and the ketone acids such as glyoxalic acid, grape sour (racemic tartaric acid)；Grass
The aliphatic polybasic acids such as acid, malonic acid, succinic acid, maleic acid；Benzoic acid, halogen benzoic acid, methyl benzoic acid, phenylacetic acid, meat
The aromatic monoamines such as cinnamic acid, mandelic acid acid；Aromatic polyacids such as phthalic acid, trimesic acid etc..
As the acid anhydrides, it can be mentioned, for example: succinic anhydride, dodecyl succinic anhydride, maleic anhydride, methyl ring penta 2
The aliphatic such as the adduct of alkene and maleic anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride or aliphatic are more
First acid anhydrides etc.；Aromatic polybasics acid anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride etc..
As the sulfydryl organic acid, it can be mentioned, for example: thioacetic acid, mercaptopropionic acid, mercaptobutyric acid, mercapto succinic acid,
The mercapto aliphatics monocarboxylic acid such as dimercaptosuccinic acid, the sulfydryl obtained by the esterification of hydroxy organic acid and sulfydryl organic acid
Aliphatic monocarboxylic acid, sulfydryls aromatic monocarboxylate such as mercaptobenzoic acid etc..
As E ingredient, from the viewpoint of versatility and highly-safe, raising storage stability, wherein preferably boric acid
Ester compounds, more preferably triethyl borate, three n-propyl of boric acid, triisopropyl borate ester, tri-n-butyl borate, more preferably boric acid three
Ethyl ester.As long as the storage stability of resin improves, the content of E ingredient is not particularly limited, by the content of the epoxy resin of A ingredient
In the case where being set as 100 mass parts, the content of E ingredient is preferably 0.001~50 mass parts, more preferably 0.05~30 mass parts,
Further more preferably 0.1~10 mass parts.
May be used also other than cooperating simultaneously with A ingredient~D ingredient as fitting method of the E ingredient into resin combination
The latent curing accelerator of D ingredient is mixed with E ingredient in advance.It, can be by Methylethyl as mixed method at this moment
In ketone, toluene equal solvent, perhaps make the two contact to carry out in the epoxy resin of liquid or in the absence of a solvent.
(F ingredient: other compositions)
Common filler (example can be added as needed in the field of the invention in the one-component resin composition of present embodiment
Such as fumed silica (fumed silica)), diluent, solvent, pigment, flexibility imparting agent, coupling agent, antioxidant, touching
It is denaturalized the various additives such as imparting agent, dispersing agent.
A~C ingredient described above and D~F ingredient as any ingredient are used as raw material to prepare present embodiment
The one-component resin composition being related to is not especially difficult, can carry out according to currently known method.For example, Henschel can be used
(Henschel) mixing machines such as mixing machine mix each ingredient to prepare one-component resin composition.
In addition, the solidification of resulting one-component resin composition is not also especially difficult, this can also be according to currently known
Method carries out.For example, can more than room temperature at a temperature of, solidified by heating resulting one-component resin composition.
For heating, it is appropriate that in such as 70~150 DEG C, preferably 75~120 DEG C, more preferably 80~100 DEG C of temperature
Under, carry out the time of such as 1~60 minute, preferably 3~30 minutes, more preferably 5~15 minutes.Especially if 80 or
Solidified at 100 DEG C by heating below in 10 minutes, then can determine whether as the low-temperature fast-curing property with appropriateness.
Also comprising also wrapping by heating resin cured matter obtained by above-mentioned one-component resin composition in present embodiment
Containing the functional article containing the resin cured matter.As functional article, it can be mentioned, for example bonding agent, cast agent, sealer,
Sealant, fibre strengthening resin, coating agent or coating etc..
In addition, for example to can be used for the magnet in the motor containing neodium magnet bonding with shell for the epoxy resin cured product,
Or the bonding agent as the electronic component-use for being equipped with the motor containing neodium magnet.In general, magnet causes because of heat
Demagnetization it is big.Resin combination of the invention can be by computer heating control when being bonded in 80 DEG C of low temperature below, therefore is suitable for: will
The neodium magnet purposes Nian Jie with other components；In the electronic component for being equipped with neodium magnet, by the component (structure other than neodium magnet
Component) purposes that is bonded to each other；And purposes in the bonding process of the electronic component after the component mounting containing neodium magnet etc..
It is heated, shrinks, the cooled property then expanded in addition, neodium magnet has, therefore the component for being used as adherend with other
Line expansion is different, generates internal stress in bonding.Therefore, the stripping on bonding interface occurs due to be easy the impact because falling etc.
From.About this point, resin combination of the invention for either shear direction and peeling direction to stress all have
High bonding force, therefore be not susceptible to remove, it is particularly suitable for the bonding of neodium magnet.
In addition, above-mentioned (B component) two function can make epoxy resin (A without ester mercaptan and (C ingredient) multifunctional no ester mercaptan
Ingredient) solidification, therefore their mixture can be used as hardener for epoxy resin.That is, asphalt mixtures modified by epoxy resin of the present embodiment
Rouge curing agent includes above-mentioned (B component) two function without ester mercaptan and (C ingredient) multifunctional no ester mercaptan.
Embodiment
Hereinafter, the present invention will be more specifically described based on examples, but the present invention is not limited to implementations below
Example.
[preparation of one-component resin composition]
According to mixing each ingredient shown in Tables 1 and 2 with being combined into, Examples 1 to 7 is prepared and tree that comparative example 1~7 is related to
Oil/fat composition.It should be noted that the use level of each ingredient refers to mass parts in Tables 1 and 2.In addition, each Examples and Comparative Examples
In, the ratio between epoxy radix and mercaptan radix in resin combination substantially 1:1.
Specifically, the material of amount shown in Tables 1 and 2 is weighed into dedicated plastic containers.Then, using rotation public affairs
Turn de-airing mixer " THINKY MIXER " (あ わ と り And-chain Taro) (Xin Ji corporation；ARE-250), at room temperature with
2000rpm is sufficiently mixed, and then deaeration 1 minute, obtains target resin combination.
It should be noted that the material used is described in detail below；
[epoxy resin]
JER828EL: Mitsubishi Chemical Ind's system, bisphenol A-type (BPA type) epoxy resin, epoxide equivalent 186g/eq
JER807: Mitsubishi Chemical Ind's system, bisphenol-f type (BPF type) epoxy resin, epoxide equivalent 165g/eq.
[two functions are without ester mercaptan]
1,8- pungent two mercaptan: Tokyo chemical conversion industry corporation, mercapto add up to equivalent 89g/eq, molecular weight 178
[changing 12]
。
1, the 10- last of the ten Heavenly stems, two mercaptan: Tokyo chemical conversion industry corporation, mercapto add up to equivalent 103g/eq, molecular weight 206
[changing 13]
。
Pungent two mercaptan of 3,6- dioxas -1,8-: Tokyo chemical conversion industry corporation, mercapto add up to equivalent 91g/eq, molecule
Amount 182
[changing 14]
。
[the ester-containing mercaptan of two functions]
EGTP: shallow lake chemical company system, ethylene glycol two (3-thiopropionate), mercapto add up to equivalent 124g/eq.
[multifunctional no ester mercaptan]
TMPIC:Ajinomoto Fine-Techno corporation, three (3- mercaptopropyi) isocyanuric acid esters, mercapto add up to equivalent
117g/eq
[changing 15]
。
TS-G: four countries are melted into corporation, 1,3,4,6- tetra- (2- mercaptoethyl) glycoluril, and mercapto adds up to equivalent 103g/eq
[changing 16]
。
[multifunctional ester-containing mercaptan]
TMTP: shallow lake chemical company system, trimethylolpropane tris (3-thiopropionate), mercapto add up to equivalent 140g/eq
[latent curing accelerator]
PN-23:Ajinomoto Fine-Techno corporation, amine-epoxy adduction species curing agent
[stabilizer]
TEB: Tokyo is melted into corporation, triethyl borate
[filler]
AEROSIL 200: Japanese AEROSIL corporation, fumed silica
[evaluation of low-temperature fast-curing property]
For each embodiment and each comparative example, thought poorly of by measuring the gelling time (gelation time) based on JISC6521
Warm rapidly-curable.Specifically, firstly, by hot plate type gelation exerciser (GT-D: day new science corporation), to each reality
The time that the resin combination for applying example and comparative example becomes no longer wire drawing at 80 DEG C is measured.It more specifically, will about 0.5g
Sample (resin combination) be placed on hot plate type gelation testing machine.Conduct at the time of being up to 80 DEG C (80 DEG C of gelling times)
Starting point is repeated close circular motion (1 circle of rotation in 1 second) to the resin combination using the scraper of the wide 5mm in front end, makes resin
Composition is in the range of being contained in diameter 25mm on hot plate.By resin combination from hot plate vertical-lift 30mm, with filiform
As terminal when disconnection, will be considered as the time for reaching gelation from the time of the origin-to-destination is measured.It should be noted that
Scraper is not promoted during resin viscosity is low, again constantly from hot plate vertical-lift about 30mm after viscosity rising, this is repeated
It moves up and down until filiform disconnects.Measurement is repeated 2 times, its average value is used as a result.It is believed that gelling time is shorter,
Then low-temperature fast-curing property is better.
[evaluation of initial bond strenght]
(i) initial tensile shear bond strength
The test piece for preparing 2 pieces of low carbon steel plates (mild steel plate) (JISG3141, SPCC), wipes oil with the cloth waste of acetone-wet.Into
And the surface of the bonding plane of the low carbon steel plate is ground using endless belt #120.Low carbon steel plate abradant surface with the thickness of about 1mm
Equably it is coated with resin combination.2 pieces of test pieces, 2 clip fittings are compressed in such a way that coated face is overlapped about 12mm.At this moment,
The resin combination of spilling is wiped with cloth waste at once.Test piece is equably arranged in baking oven, is heating and curing at 80 DEG C 60 minutes,
Make its bonding.2 pieces of test pieces are prepared respectively for same resin.For resulting test piece, TENSILON universal testing machine is used
(TOYO BALDWIN corporation, UTM-5T) measures tensile shear adhesive strength (determination of the environment: temperature according to JIS-K-6850
25 DEG C/humidity 60%, tensile speed: 5mm/min).Based on the peak load (N) that test piece is destroyed, bond area is measured
(mm2), tensile shear adhesive strength A is calculated by following formula；
(formula): tensile shear adhesive strength A (N/mm2)=peak load (N)/bond area (mm2)。
(ii) adhesive strength is initially removed
The cloth waste of the test piece acetone-wet of steel plate (25mm × 150mm × 0.4mm) is wiped, oil is wiped.In turn, using ring
Shape grinds the surface of the bonding plane of the steel plate with #120.Tree is coated with equably with about 20~30 μm of thickness in the abradant surface of steel plate
Oil/fat composition.It is overlapped another block of steel plate, is compressed with 4 clip fittings.At this moment, the resin combination of spilling is wiped at once.It will examination
Piece is equably arranged in baking oven, is heating and curing 60 minutes at 80 DEG C, is made its bonding.Same resin combination is prepared respectively
2 pieces of test pieces.For resulting test piece, using TENSILON universal testing machine (ORIENTEC corporation, RTM-500) according to JIS-
K-6854-3 measures tensile strength (determination of the environment: 25 DEG C/humidity of temperature 60%, tensile speed: 50mm/min).With average removing
The corresponding removing adhesive strength A of every 25mm width is calculated based on load (N).
[evaluation of moisture-proof]
(i) tensile shear adhesive strength
The same step of evaluation with initial tensile shear bond strength prepare respectively 2 pieces in addition made of test piece.It is setting
Be set to 121 DEG C, 100%RH saturation condition high pressure accelerated aging (Pressure Cooker) testing machine in place 24 hours
Afterwards, for resulting test piece, using TENSILON universal testing machine (TOYO BALDWIN corporation, UTM-5T), with cementability
Similarly according to JIS-K-6850 measurement tensile shear adhesive strength, (determination of the environment: 25 DEG C/humidity of temperature 60% stretches speed for test
Degree: 5mm/min).Based on the peak load (N) that test piece is destroyed, bond area (mm is measured2), the evaluation with cementability
Similarly calculate tensile shear adhesive strength B；
Tensile shear adhesive strength B (N/mm2)=peak load (N)/bond area (mm2)。
[tensile shear adhesive strength conservation rate]
In order to evaluate humidity influence caused by adhesive strength, strength retention is calculated.Strength retention is cut according to above-mentioned stretching
The value for cutting adhesive strength A and tensile shear adhesive strength B calculates as follows；
[strength retention]=[tensile shear adhesive strength B]/[tensile shear adhesive strength A] × 100
It should be explained that, it is believed that the value of strength retention is bigger, then test piece more has tolerance to high humility.
[removing adhesive strength]
The same step of the evaluation with initial removing adhesive strength prepare respectively 2 pieces in addition made of test piece.By each test piece
After being placed 24 hours in being set as the high pressure accelerated life test machine of condition of 121 DEG C, 100%RH saturation, for resulting examination
Piece is stretched strong using TENSILON universal testing machine (ORIENTEC corporation, RTM-500) according to JIS-K-6854-3 measurement
It spends (determination of the environment: 25 DEG C/humidity of temperature 60%, tensile speed: 50mm/min).It is calculated based on average peel load (N) every
The corresponding removing adhesive strength B of 25mm width.
[removing adhesive strength conservation rate]
In order to evaluate humidity influence caused by removing adhesive strength, strength retention is calculated.Strength retention is according to above-mentioned stripping
Value from adhesive strength A and removing adhesive strength B calculates as follows;
[strength retention]=[removing adhesive strength B]/[removing adhesive strength A] × 100
It is believed that the value of strength retention is bigger, then test piece more has tolerance to high humility.
[storage stability]
About 5g resin combination is enclosed in plastic containers and in 25 DEG C/humidity of temperature by example each for Examples 1 to 7 respectively
After being placed 24 hours in 60% thermostatic chamber, breaks a seal and confirm mobility.
As a result, available spatula is stirred in any one of Examples 1 to 7.I.e., it is thus identified that Examples 1 to 7 relates to
And resin combination all have excellent storage stability.
[investigation of evaluation result]
The above-mentioned result respectively evaluated is shown in table 1 and table 2.Know the resin combination of Examples 1 to 7 and the resin combination of comparative example
Object is compared, and shows good shear bond power, peeling adhesion force, moisture-proof, low-temperature fast-curing property.
Specifically, if Examples 1 to 5 and comparative example 1 being compared, the initial removing adhesive strength of comparative example 1
For 6 (1N/25mm), in contrast, Examples 1 to 5 is 15 (1N/25mm) or more.It is used only that is, can distinguish with as curing agent
The case where multifunctional no ester mercaptan (comparative example 1), is compared, and (implements by and with two functions without ester mercaptan and multifunctional no ester mercaptan
Example 1~5), initial removing adhesive strength significantly improves.It should be noted that by the type of multifunctional no ester mercaptan and embodiment 1~
5 different embodiments 6 are compared with corresponding comparative example 2, also show same tendency.
In addition, each comparative example compares each embodiment if embodiment 2,4,5 is compared with comparative example 3~5 respectively,
Initial tensile shear bond strength A is considerably lower.That is, can distinguish and the case where two functions are without ester mercaptan is used only as curing agent
(comparative example 3~5) is compared, and by and with two functions and polyfunctional no ester mercaptan, can improve initial tensile shear bond strength.
Then, if Examples 1 to 7 and comparative example 6 and 7 being compared, each embodiment shows considerably higher moisture-proof
Property.That is, can distinguish by using no ester mercaptan rather than ester-containing mercaptan as curing agent, so that moisture-proof significantly improves.
In addition, gelling time has good low-temperature fast-curing within 3 minutes in any one of Examples 1 to 7
Property.
[table 1]
。
[table 2]
。
Claims (14)
1. a kind of one-component resin composition, which is characterized in that include following A, B and C ingredient,
A: epoxy resin
B: the mercaptan compound with 2 mercaptos and not ester-containing skeleton in the molecule
C: in the molecule with 3 or more mercaptos and the mercaptan compound of not ester-containing skeleton.
2. one-component resin composition according to claim 1, which is characterized in that it also include following D ingredients,
D: latent curing accelerator.
3. one-component resin composition according to claim 1 or 2, which is characterized in that the B component and the C ingredient
Without hydroxyl.
4. one-component resin composition described according to claim 1 ~ any one of 3, which is characterized in that the C ingredient is dividing
There is ring skeleton in sub.
5. one-component resin composition described according to claim 1 ~ any one of 4, which is characterized in that the B component is being divided
Do not have ring skeleton in sub.
6. one-component resin composition described according to claim 1 ~ any one of 5, which is characterized in that point of the B component
Son amount is in the range of 130~1000.
7. one-component resin composition described according to claim 1 ~ any one of 6, which is characterized in that by the B component and
When the summation of the mercaptan radix of the C ingredient is set as 1, ratio shared by the mercaptan radix of the C ingredient [the C ingredient it is total
Mercaptan radix/(the total mercapto number of total mercapto number+C ingredient of the B component)] it is 0.1~0.9.
8. a kind of bonding agent, which is characterized in that include one-component resin composition described in any one of claim 1 ~ 7.
9. bonding agent according to claim 8, which is characterized in that the bonding agent be used to be bonded the neodymium magnetic as adherend
Iron.
10. a kind of sealing material, which is characterized in that include one-component resin composition described in any one of claim 1 ~ 7.
11. a kind of solidfied material, which is characterized in that make one-component resin composition thermosetting described in any one of claim 1 ~ 7
Change.
12. a kind of electronic component, which is characterized in that include the solidfied material described in claim 11.
13. a kind of motor containing neodium magnet, which is characterized in that the right comprising adherend and for being bonded the adherend is wanted
Solidfied material described in asking 11.
14. a kind of electronic component is the electronic component containing the motor containing neodium magnet, which is characterized in that want comprising right
Solidfied material described in asking 11.
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| JP2018006499A JP6983380B2 (en) | 2018-01-18 | 2018-01-18 | One-component resin composition |
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| CN113788936A (en) * | 2021-10-22 | 2021-12-14 | 韦尔通(厦门)科技股份有限公司 | Light/heat dual-curing resin composition and preparation method and application thereof |
| CN113943420A (en) * | 2021-10-22 | 2022-01-18 | 韦尔通(厦门)科技股份有限公司 | UV (ultraviolet) light-cured resin composition and preparation method and application thereof |
| CN114525099A (en) * | 2022-03-09 | 2022-05-24 | 上海回天新材料有限公司 | Moisture-heat-resistant low-temperature curing single-component epoxy adhesive |
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| KR20210080363A (en) * | 2018-10-17 | 2021-06-30 | 나믹스 가부시끼가이샤 | resin composition |
| JP2021004229A (en) * | 2019-06-25 | 2021-01-14 | 川口化学工業株式会社 | Novel isocyanurate compound having thiol groups and use thereof |
| US20220372249A1 (en) * | 2019-10-30 | 2022-11-24 | Threebond Co., Ltd. | Resin composition |
| KR102242440B1 (en) * | 2019-11-25 | 2021-04-20 | 주식회사 케이씨씨 | Adhesive composition |
| JP7415717B2 (en) | 2020-03-24 | 2024-01-17 | 味の素株式会社 | resin composition |
| US11453743B2 (en) * | 2020-06-05 | 2022-09-27 | Chanda Chemical Corp. | Thermoset epoxy resin, its preparing composition and making process thereof |
| JP7437695B2 (en) | 2020-07-30 | 2024-02-26 | パナソニックＩｐマネジメント株式会社 | Thermosetting composition, cured product, device, and method for manufacturing the device |
| TW202328261A (en) * | 2021-10-28 | 2023-07-16 | 日商日產化學股份有限公司 | epoxy resin composition |
| JP2023166744A (en) * | 2022-05-10 | 2023-11-22 | 四国化成工業株式会社 | Thiol compound and uses thereof |
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| CN113788936A (en) * | 2021-10-22 | 2021-12-14 | 韦尔通(厦门)科技股份有限公司 | Light/heat dual-curing resin composition and preparation method and application thereof |
| CN113943420A (en) * | 2021-10-22 | 2022-01-18 | 韦尔通(厦门)科技股份有限公司 | UV (ultraviolet) light-cured resin composition and preparation method and application thereof |
| CN113788936B (en) * | 2021-10-22 | 2022-05-10 | 韦尔通(厦门)科技股份有限公司 | Light/heat dual-curing resin composition and preparation method and application thereof |
| WO2023065803A1 (en) * | 2021-10-22 | 2023-04-27 | 韦尔通科技股份有限公司 | Photo/thermal dual-curing resin composition, and preparation method therefor and use thereof |
| CN114525099A (en) * | 2022-03-09 | 2022-05-24 | 上海回天新材料有限公司 | Moisture-heat-resistant low-temperature curing single-component epoxy adhesive |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110054760B (en) | 2023-05-05 |
| TW201936776A (en) | 2019-09-16 |
| JP6983380B2 (en) | 2021-12-17 |
| JP2019123824A (en) | 2019-07-25 |
| TWI811288B (en) | 2023-08-11 |
| KR20190088426A (en) | 2019-07-26 |
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