CN105085870A - Sealing material and prepreg - Google Patents
Sealing material and prepreg Download PDFInfo
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- CN105085870A CN105085870A CN201510140862.9A CN201510140862A CN105085870A CN 105085870 A CN105085870 A CN 105085870A CN 201510140862 A CN201510140862 A CN 201510140862A CN 105085870 A CN105085870 A CN 105085870A
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- sealing material
- polyvalent alcohol
- anhydride
- halogenide
- trimellitic anhydride
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Abstract
The invention provides a sealing material and a prepreg. The sealing material comprises polyfunctional anhydride obtained through reactions of mixtures of polyol (A)/polyol(B) and nuclear hydrogenated trimellitic anhydride halide, or nuclear hydrogenated trimellitic anhydride halide and trimellitic anhydride halide. The polyol (A) contains at least more than three hydroxyl groups in one molecule, and the polyol (B) is obtained through reactions of the polyol (A) with more than one selected from a group composed of an alkylene oxide, a cyclic ether and a cyclic ester. The sealing material and the prepreg have excellent transparency, heat resistance and toughness, and have characteristics suitable for optical parts.
Description
Technical field
The present invention relates to a kind of sealing material containing multifunctional acid anhydrides and the prepreg that are suitable for the sealing of electric and electronic material.Sealing material of the present invention has the characteristic of the transparency, thermotolerance, obdurability, coloring resistance excellence.
Background technology
So-called sealing material, refers to by sealing part, and with external environs and the material protected, is just widely using the thermosetting resin composition also comprising stiffening agent.The volatility when stiffening agent that uses in original sealing material exists sclerosis is high and cannot completely by element or this problem of linear sealing when sealing.For photodiode (LightEmittingDiode, LED), surface mount component (SurfaceMountDevice, the amount of resin of sealing SMD) is few, and therefore sometimes cause sealing to become incomplete because of the volatilization of stiffening agent, such as line exposes.In addition, except slight crack during Reflow Soldering, stripping etc., sclerosis becomes insufficient, therefore exists and is unable to undergo this problem of long-term lighting through the LED etc. of sealing.
As the stiffening agent used in original sealing material (acid anhydrides), what be widely known by the people is aromatic anhydride and ester ring type acid anhydrides.As the example of aromatic anhydride, include, for example acid three acid anhydride of patent documentation 1.But this compound is aromatic painted and easily absorb the light of short wavelength because being derived from, and cause the transparency and coloring resistance and insufficient.In addition, as the example of ester ring type acid anhydrides, include, for example the tetrahydrotoluene dicarboxylic anhydride of patent documentation 2, the tetracarboxylic dianhydride with three rings of patent documentation 3, the tetracarboxylic dianhydride with ester group of patent documentation 4.Although these hardening things provide high transparent, skeleton softness compared with aromatic anhydride, and then owing to being two senses, therefore thermotolerance is insufficient equally.In addition, although the isocyanurate compound of patent documentation 5 is trifunctionals, cause the transparency of provided hardening thing because being derived from the painted of isocyanuric acid ester and insufficient, and be not suitable for optical applications.
[prior art document]
[patent documentation]
[patent documentation 1] Japanese Patent Laid-Open 3-059031 publication
[patent documentation 2] Japanese Patent Laid-Open No. Sho 55-36406 publication
[patent documentation 3] Japanese Patent Laid-Open 2005-320383 publication
[patent documentation 4] Japanese Patent Laid-Open 2007-284414 publication
[patent documentation 5] Japanese Patent Laid-Open 2012-025670 publication
Summary of the invention
[inventing problem to be solved]
Problem of the present invention is the sealing material (sealing agent) obtaining a kind of flexibility, obdurability, thermotolerance, transparency excellence.
[technique means of dealing with problems]
The compound that the people such as the present inventor finds to make the polyvalent alcohol of the hydroxyl in a part with more than at least 3 and core hydrogenated trimellitic anhydride halogenide or core hydrogenated trimellitic anhydride halogenide and the halid mixture of trimellitic acid 1,2-anhydride to carry out reacting and obtain simultaneously maintains higher optical characteristics, one side provides the sealing material with flexibility, obdurability or thermotolerance (sealing agent), thus completes the present invention.
Namely, the present invention relates to a kind of sealing material, it comprises the multifunctional acid anhydrides making the polyvalent alcohol (A) containing the hydroxyl of more than at least 3 in a part and core hydrogenated trimellitic anhydride halogenide or core hydrogenated trimellitic anhydride halogenide and the halid mixture of trimellitic acid 1,2-anhydride carry out reacting and obtain, and described polyvalent alcohol (A) is represented by following general formula (1).
[changing 1]
(in formula, R
1, R
2, R
3, R
4, R
5, R
6independently, R
1, R
3, R
4, R
5, R
6represent hydrogen atom, hydroxyl, carbon number be 1 ~ 11 alkyl or carbon number be the hydroxyalkyl of 1 ~ 4, R
2represent that hydroxyl or carbon number are the hydroxyalkyl of 1 ~ 4.L represent 0 ~ 11, m and n represent respectively 1 ~ 11 integer)
And then, the present invention relates to described sealing material, it makes polyvalent alcohol (B) and core hydrogenated trimellitic anhydride halogenide or core hydrogenated trimellitic anhydride halogenide and the halid mixture of trimellitic acid 1,2-anhydride carry out reacting and obtaining, and described polyvalent alcohol (B) makes described polyvalent alcohol (A) carry out reacting and obtaining with more than a kind of being selected from the group that is made up of oxirane, cyclic ether and cyclic ester.
And then the present invention relates to described sealing material, it is the R making described polyvalent alcohol (A) or polyvalent alcohol (B)
1, R
2for carbon number is that the polyvalent alcohol of the hydroxyalkyl of 1 ~ 4 and core hydrogenated trimellitic anhydride halogenide or core hydrogenated trimellitic anhydride halogenide and the halid mixture of trimellitic acid 1,2-anhydride carry out reacting and obtain.
And then, the present invention relates to described sealing material, it makes described polyvalent alcohol (A) or polyvalent alcohol (B) and core hydrogenated trimellitic anhydride halogenide or core hydrogenated trimellitic anhydride halogenide and the halid mixture of trimellitic acid 1,2-anhydride carry out reacting and obtaining, and described polyvalent alcohol (A) is the R of general formula (1)
1, R
2, R
3, R
4, R
5, R
6for the polyvalent alcohol (A) that carbon number is the hydroxyalkyl of 1 ~ 4, described polyvalent alcohol (B) makes this polyvalent alcohol (A) carry out reacting and obtaining with more than a kind of being selected from the group that is made up of oxirane, cyclic ether and cyclic ester.
And then the present invention relates to described sealing material, wherein said polyvalent alcohol (A) is TriMethylolPropane(TMP) or Dipentaerythritol.
And then, the present invention relates to described sealing material, wherein said polyvalent alcohol (B) is Dipentaerythritol ethylene oxide adduct, Dipentaerythritol propylene oxide adduct, Dipentaerythritol tetrahydrofuran (THF) affixture, Dipentaerythritol caprolactone affixture.
And then, the present invention relates to described sealing material, wherein said polyvalent alcohol (B) is tetramethylolmethane 4 moles of ethylene oxide affixture, Dipentaerythritol 6 moles of ethylene oxide affixture, Dipentaerythritol 4 moles of caprolactone affixtures.
And then the present invention relates to a kind of sealing material, it comprises thermosetting resin composition, described thermosetting resin composition comprises in a part the compound and described multifunctional acid anhydrides with at least 1 epoxy group(ing).
And then, the present invention relates to a kind of sealing material, it comprises the thermosetting resin composition comprising described multifunctional acid anhydrides, and the compound in described a part with at least 1 epoxy group(ing) is be selected from more than a kind in aliphatics type epoxy resin, aromatic type epoxy resin and copoly type epoxy resin.
And then the present invention relates to a kind of sealing material, it comprises the thermosetting resin composition comprising described multifunctional acid anhydrides, and the compound in described a part with at least 1 epoxy group(ing) is aliphatics type epoxy resin and aromatic type epoxy resin.
And then the present invention relates to a kind of sealing material, it comprises the thermosetting resin composition comprising described multifunctional acid anhydrides, and described aliphatics type epoxy resin is the epoxy resin with cycloaliphatic ring structure.
And then, the present invention relates to a kind of sealing material, it comprises the thermosetting resin composition comprising described multifunctional acid anhydrides, and described aromatic type epoxy resin is for being selected from (4 (4 (1, two (the p-hydroxybenzene)-ethyl of 1-) alpha, alpha-dimethylbenzyl) phenol) in type epoxy resin and bisphenol A epoxide resin more than a kind.
And then the present invention relates to a kind of sealing material, it comprises the thermosetting resin composition comprising described multifunctional acid anhydrides, and the compound in described a part with at least 1 epoxy group(ing) is copoly type epoxy resin.
And then, the present invention relates to a kind of sealing material, it comprises thermosetting resin composition, and described thermosetting resin composition comprises and described polyvalent alcohol (A), described polyvalent alcohol (B), core hydrogenated trimellitic anhydride halogenide or core hydrogenated trimellitic anhydride halogenide and the inconsistent particle of the halid mixture of trimellitic acid 1,2-anhydride (C-1) or fiber (C-2).
And then the present invention relates to a kind of sealing material, it comprises described thermosetting resin composition, and described particle (C-1) is inorganic particulate.
And then the present invention relates to a kind of sealing material, it comprises described thermosetting resin composition, and described fiber (C-2) is glass fibre.
And then the present invention relates to a kind of sealing material, it comprises described thermosetting resin composition, and described fiber (C-2) is for spin to glass fibre, and then carries out the woven fiber glass weaved.
And then the present invention relates to a kind of sealing material, it is the prepreg described thermosetting resin composition being given to shape under semi-hardened state.
[effect of invention]
The transparency of sealing material of the present invention or obdurability, excellent heat resistance, be suitable for electric and electronic material, and then be suitable for the LED of requirement high transparent or the display unit of optical waveguides, liquid-crystal display, plasma display, electroluminescent (Electroluminescence, EL) indicating meter, portable machine etc. or the sealing of solar cell.
Embodiment
The polyvalent alcohol (A) used in the present invention refers to the structure with following general formula (1) and compound containing the hydroxyl of more than at least 3 in a part.
[changing 2]
(in formula, R
1, R
2, R
3, R
4, R
5, R
6independently, R
1, R
3, R
4, R
5, R
6represent hydrogen atom, hydroxyl, carbon number be 1 ~ 11 alkyl or carbon number be the hydroxyalkyl of 1 ~ 4, R
2represent that hydroxyl or carbon number are the hydroxyalkyl of 1 ~ 4.L represent 0 ~ 11, m and n represent respectively 1 ~ 11 integer)
In described general formula (1), when l or m is more than 2, becomes and there is multiple R
1, R
3, R
4, R
6in, each R
1, R
3, R
4, R
6different substituting groups can be adopted.Such as, as l=2, there is the R of 4
1can 4 be identical substituting group, also can a part identical and other are different, also can be different substituting groups.About R
3, R
4, R
6, also with R
1identical.
As the concrete example of polyvalent alcohol (A), can enumerate: glycerine, trimethylolethane, TriMethylolPropane(TMP), tri hydroxy methyl butane, 1, 2, 4-trihydroxybutane, 2-hydroxy-2-methyl-1, 4-butyleneglycol, 1, 2, 5-penta triol, 1, 3, 5-penta triol, 3-methylpentane-1, 3, 5-triol, 1, 2, 6-hexanetriol, 1, 2, the pungent triol of 8-, 1, 2, 9-triol in the ninth of the ten Heavenly Stems, 1, 2, three alcohols such as 10-triol in the last of the ten Heavenly stems, 1, 1, 2, 2-second tetrol, two-TriMethylolPropane(TMP), erythritol, tetramethylolmethane, 1, 2, 3, 5-penta tetrol, 1, 2, 4, 5-penta tetrol, 1, 1, 5, 5-penta tetrol, 1, 2, 5, the own tetrol of 6-, 1, 2, 7, the pungent tetrol of 8-, 1, 2, 9, four alcohols such as 10-tetrol in the last of the ten Heavenly stems, Dipentaerythritol, the polyvalent alcohols etc. such as Polyglycerine.
Among these, when there is the polyvalent alcohol of 4 ~ 6 hydroxyls in use a part, the excellent of the sealing material obtained.Especially with regard to the viewpoint of the formedness of the characteristic of sealing material, the acquisition easiness of material, preferred tetramethylolmethane, two-TriMethylolPropane(TMP), Dipentaerythritol.
In the present invention, so-called polyvalent alcohol (B), refers to have and makes polyvalent alcohol (A) and any one the above compound carrying out the structure of addition polymerization be selected from the group that is made up of oxirane, cyclic ether and cyclic ester.In addition, polyvalent alcohol (B) also can correspond to purposes and make the characteristic optimization of reactivity or hardening thing.
As the concrete example of polyvalent alcohol (B), can enumerate: TriMethylolPropane(TMP) ethylene oxide adduct, TriMethylolPropane(TMP) propylene oxide adduct, TriMethylolPropane(TMP) tetrahydrofuran (THF) affixture, TriMethylolPropane(TMP) caprolactone affixture, tetramethylolmethane ethylene oxide adduct, tetramethylolmethane propylene oxide adduct, tetramethylolmethane tetrahydrofuran (THF) affixture, tetramethylolmethane caprolactone affixture, Dipentaerythritol ethylene oxide adduct, Dipentaerythritol propylene oxide adduct, Dipentaerythritol tetrahydrofuran (THF) affixture, Dipentaerythritol caprolactone affixture etc.
R
1, R
3, R
4, R
5, R
6in alkyl refer to the atomic group only comprising carbon atom and hydrogen atom.
The carbon number of alkyl preferably 1 ~ 11.As concrete example, can enumerate: the aliphatic alkyl such as octyl group of the heptyl of the hexyl of the amyl group of methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, straight chain or branch, straight chain or branch, straight chain or branch, straight chain or branch, or the ester ring type alkyl such as cyclohexyl, methylcyclohexyl, ethylcyclohexyl, or the aromatic series bases such as phenyl, tolyl, naphthyl, methyl naphthyl, the aromatic series such as benzyl, naphthyl methyl substituted alkyl etc.Wherein, in the present invention, with regard to the viewpoint that the transparency of sealing material of the present invention is good, preferred aliphat alkyl or ester ring type alkyl, with regard to the viewpoint of obdurability and the good sealing material of the present invention of thermotolerance is provided, more preferably methyl and ethyl.
R
1, R
2, R
3, R
4, R
5, R
6in hydroxyalkyl refer to more than 1 of the hydrogen atom of straight-chain alkyl, branched-chain alkyl through hydroxyl replace atomic group.
The carbon number of hydroxyalkyl preferably 1 ~ 4.As concrete example, can enumerate: more than 1 or 2 of the hydrogen atom of methyl, ethyl, n-propyl, sec.-propyl, normal-butyl and isobutyl-replaces through hydroxyl.Wherein, in the present invention, just react with regard to easy viewpoint, preferably replace on end carbon and have 1 hydroxyl.With regard to the obdurability of sealing material of the present invention and the good viewpoint of thermotolerance, more preferably hydroxymethyl, hydroxyethyl.
The oxirane used in the present invention refers to the compound of the cyclic ether with triatomic ring.
The carbon number of oxirane preferably 2 ~ 8.Include, for example: oxyethane, propylene oxide, butylene oxide ring, Styrene oxide 98min. etc.These oxiranes can be a kind or optionally also two or more can be mixed.Wherein, if be selected from least a kind in oxyethane, propylene oxide, then easily to obtain and cheap, therefore preferred in the present invention.
About the usage quantity of oxirane, relative to hydroxyl 1 equivalent of polyvalent alcohol (A), the cyclic ether of usual triatomic ring is 0.1 equivalent ~ 6.0 equivalent, preferably 0.2 equivalent ~ 2.0 equivalent.If this scope, then thermotolerance and the obdurability of obtained hardening thing are good.
As long as the compound of the structure that the carbon that the cyclic ether used in the present invention has more than 1 of the cyclic hydrocarbon of more than 4 rings replaces through oxygen, be then not particularly limited.
Cyclic ether is 4 ring ~ 6 rings preferably, as concrete example, can enumerate: trimethylene oxide, tetrahydrofuran (THF), tetrahydropyrans etc.These cyclic ethers can be a kind or optionally also two or more can be mixed.Wherein, tetrahydrofuran (THF) due to easily obtain and cheap, therefore preferred in the present invention.
About the usage quantity of cyclic ether, relative to hydroxyl 1 equivalent of polyvalent alcohol (A), cyclic ether is 0.1 equivalent ~ 6.0 equivalent, preferably 0.2 equivalent ~ 2.0 equivalent.If this scope, then thermotolerance and the obdurability of obtained hardening thing are good.
As long as the cyclic ester used in the present invention has the compound of the structure containing ester bond in cyclic hydrocarbon, be then not particularly limited.
The carbon number of cyclic ester preferably 2 ~ 6.As the concrete example of cyclic ester, can enumerate: acetylactone, propiolactone, butyrolactone, valerolactone, caprolactone etc.These cyclic esters can be a kind or optionally also two or more can be mixed.Wherein, caprolactone due to easily obtain and cheap, therefore preferred in the present invention.
About the usage quantity of cyclic ester, relative to hydroxyl 1 equivalent of polyvalent alcohol (A), cyclic ester is 0.1 equivalent ~ 6.0 equivalent, preferably 0.2 equivalent ~ 2.0 equivalent.If this scope, then thermotolerance and the obdurability of obtained hardening thing are good.
The core hydrogenated trimellitic anhydride halogenide (hexanaphthene-1,2,4-tricarboxylic acid-1,2-acid anhydride halogenide) used in the present invention uses with the object identical with described trimellitic acid 1,2-anhydride halogenide.In addition, due to through core hydrogenation, even if therefore under heat-resisting, fast light, painted also few, its hardening thing maintains high optical characteristics, and obdurability is excellent.
The trimellitic acid 1,2-anhydride halogenide (1,2,4-benzene tricarboxylic acid-1,2-acid anhydride halogenide) used in the present invention makes multifunctional anhydride compound for anhydride group being directed in polyvalent alcohol.Thus, anhydride group can not be imported with the esterification by ring opening of anhydride group.In addition, owing to being be derived from aromatic upright and outspoken skeleton, therefore excellent heat resistance.
As trimellitic acid 1,2-anhydride halogenide and core hydrogenated trimellitic anhydride halogenide, include, for example fluorochemical, muriate, bromide and iodide etc., wherein, with regard to the easiness of reaction, preferred muriate.
The synthesis of the multifunctional acid anhydrides used in the present invention is undertaken by known method.There is no particular restriction for the addition means of the reagent in the reaction of polyvalent alcohol (A) or polyvalent alcohol (B) and core hydrogenated trimellitic anhydride halogenide or core hydrogenated trimellitic anhydride halogenide and the halid mixture of trimellitic acid 1,2-anhydride, can adopt arbitrary addition means.Such as following method etc. be can adopt: polyvalent alcohol (A) or polyvalent alcohol (B) and alkaline matter are dissolved in a solvent, dissolving described core hydrogenated trimellitic anhydride halogenide in a solvent or core hydrogenated trimellitic anhydride halogenide and the halid mixture of trimellitic acid 1,2-anhydride then dripped wherein lentamente; Or, in the described core hydrogenated trimellitic anhydride halogenide dissolved in a solvent or core hydrogenated trimellitic anhydride halogenide and the halid mixture of trimellitic acid 1,2-anhydride, optionally drip the mixing solutions of polyvalent alcohol (A) or polyvalent alcohol (B) and alkaline matter on the contrary; To the mixed solution and dripping alkaline matter of core hydrogenated trimellitic anhydride halogenide or core hydrogenated trimellitic anhydride halogenide and the halid mixture of trimellitic acid 1,2-anhydride and polyvalent alcohol (A) or polyvalent alcohol (B); And drip the solution of core hydrogenated trimellitic anhydride halogenide or core hydrogenated trimellitic anhydride halogenide and the halid mixture of trimellitic acid 1,2-anhydride and the solution of alkaline matter in the solution of polyvalent alcohol (A) or polyvalent alcohol (B) simultaneously.
Alkaline matter exists in the reaction of lower polyvalent alcohol (A) or polyvalent alcohol (B) and core hydrogenated trimellitic anhydride halogenide or core hydrogenated trimellitic anhydride halogenide and the halid mixture of trimellitic acid 1,2-anhydride, along with the carrying out of reaction, the hydrochloride that generation alkaline matter carries out neutralizing and generates.Carry out after filtration removes, concentrating filtrate to it, crude product as the multifunctional acid anhydrides of target can be obtained using high yield thus.If make this crude product be dissolved in suitable solvent, concentrate after washing, then carry out drying under reduced pressure, then can obtain the much higher sense acid anhydrides of purity.And then, optionally utilize suitable solvent to carry out recrystallize, the more much higher sense acid anhydrides of purity can be obtained thus.
Usually in hydroxyl equivalent, relative to core hydrogenated trimellitic anhydride halogenide or core hydrogenated trimellitic anhydride halogenide and the halid mixture 1 of trimellitic acid 1,2-anhydride, the usage quantity of polyvalent alcohol (A) or polyvalent alcohol (B) is 0.6 ~ 1.0, preferably 0.8 ~ 1.0.If this scope, then the hydroxyl of polyvalent alcohol (A) or polyvalent alcohol (B) all obtains esterification, and core hydrogenated trimellitic anhydride halogenide or trimellitic acid 1,2-anhydride halogenide can not remain in system.
In the present invention, if total mole number is set to 100, then the use molar ratio of trimellitic acid 1,2-anhydride halogenide and the halid mixture of core hydrogenated trimellitic anhydride is 1: 99 ~ 99: 1, preferably 30: 70 ~ 70: 30.The hydroxyl of polyvalent alcohol (A) or polyvalent alcohol (B) and trimellitic acid 1,2-anhydride halogenide and the halid reactive ratio of core hydrogenated trimellitic anhydride roughly with trimellitic acid 1,2-anhydride halogenide and the halid molar ratio of core hydrogenated trimellitic anhydride consistent.
Can be used for core hydrogenated trimellitic anhydride halogenide, or core hydrogenated trimellitic anhydride halogenide and the halid mixture of trimellitic acid 1,2-anhydride and polyvalent alcohol (A) or polyvalent alcohol (B) as long as the solvent of reaction be inertia relative to raw material, be then not particularly limited, can enumerate: tetrahydrofuran (THF), Isosorbide-5-Nitrae-diox, the ether solvents such as 1,2-glycol dimethyl ether-bis-(2-methoxy ethyl) ether, picoline, the aromatic amine solvents such as pyridine, as acetone, methyl ethyl ketone, ketone series solvent as methyl iso-butyl ketone (MIBK) etc., as toluene, aromatic hydrocarbon solvents as dimethylbenzene etc., as methylene dichloride, chloroform, halogen-containing solvent as 1,2-ethylene dichloride etc., as METHYLPYRROLIDONE, N,N-dimethylacetamide, N, N-diethyl acetamide, acid amides series solvent as DMF etc., as the phosphorous solvent as hexamethylphosphoramide etc., as the sulfur-bearing solvent as dimethyl sulfoxide (DMSO) etc., as gamma-butyrolactone, ethyl acetate, ester series solvent as butylacetate etc., as the nitrogen-containing solvent as 1,3-dimethyl-2-imidazolidone etc., phenol, ortho-cresol, meta-cresol, p-cresol, orthomonochlorphenol, m-Chlorophenol, P-Chlorophenol etc. have the aromatic series series solvent etc. of hydroxyl.These solvents can be used alone, also can be used in combination by two or more.
Solvent cited herein comprises the cyclic ether or cyclic ester that use when manufacturing polyvalent alcohol (B) by polyvalent alcohol (A), when making polyvalent alcohol (A) and core hydrogenated trimellitic anhydride halogenide or core hydrogenated trimellitic anhydride halogenide and the halid mixture of trimellitic acid 1,2-anhydride react, temperature of reaction is-10 DEG C ~ 80 DEG C, preferably 0 DEG C ~ 70 DEG C, more preferably 10 DEG C ~ 60 DEG C.If temperature of reaction is higher than 80 DEG C, then polyvalent alcohol (A) reacts with cyclic ether or cyclic ester, and obtaining polyvalent alcohol (B), polyvalent alcohol (A) declines with the reactivity of core hydrogenated trimellitic anhydride halogenide or core hydrogenated trimellitic anhydride halogenide and the halid mixture of trimellitic acid 1,2-anhydride.Reaction times, there is no particular restriction, but be generally 10 minutes ~ 48 hours, preferably 30 minutes ~ 24 hours.Reaction is carried out usually at ambient pressure, optionally also can implement under elevated pressure or under decompression.
Making polyvalent alcohol (A) carry out reaction to temperature of reaction when manufacturing polyvalent alcohol (B) with cyclic ether or cyclic ester is 80 DEG C ~ 250 DEG C, preferably 90 DEG C ~ 220 DEG C, more preferably 100 DEG C ~ 200 DEG C.Reaction times, there is no particular restriction, but be generally 10 minutes ~ 48 hours, preferably 30 minutes ~ 24 hours.Reaction is carried out usually at ambient pressure, optionally also can implement under elevated pressure or under decompression.
The concentration obtaining the solute in the reaction of multifunctional acid anhydrides is generally 5 quality % ~ 50 quality %, if consider the control of side reaction, the filtration step of precipitation, then preferably to carry out with 10 quality % ~ 40 quality %.More preferably carry out with the scope of more than 10 quality %, below 40 quality %.
The reaction environment obtaining the reaction of multifunctional acid anhydrides is generally and carries out under a nitrogen.Reaction vessel can be hermetic type reaction vessel, also can be opening reaction vessel, but in order to reactive system is remained inert environments, uses the reaction vessel sealed by rare gas element when style of opening.
The hydrogenchloride that alkaline matter is used for producing the carrying out along with reaction neutralizes.The kind of now used alkaline matter is not particularly limited, and can use the organic tertiary amine classes such as pyridine, triethylamine, DMA, the alkaline matter that salt of wormwood, sodium hydroxide etc. are inorganic.The viewpoint that just can obtain at an easy rate, or be just rich in solvability in a liquid, therefore operation becomes easy viewpoint, preferred pyridine or triethylamine.In addition, with regard to the viewpoint that can obtain at an easy rate, preferably inorganic alkaline matter.
There is no particular restriction for the amount of the alkaline matter used, if but use superfluously, then be mixed into product or refining load becomes large, therefore relative to core hydrogenated trimellitic anhydride halogenide or core hydrogenated trimellitic anhydride halogenide and the halid mixture of trimellitic acid 1,2-anhydride, usual employing 1.0 moles doubly ~ 30 moles doubly, preferred employing 1.2 moles doubly ~ 20 moles doubly, more preferably adopt 1.5 moles doubly ~ 10 moles doubly.
When water washing operations, a part for multifunctional acid anhydrides is hydrolyzed, and is changing into ester ring type polycarboxylic acid, but by carrying out heated under reduced pressure process to it, and the ester ring type polycarboxylic acid that can easily make a part be hydrolyzed generated reverts to multifunctional acid anhydrides.The temperature adopted during this heated under reduced pressure treatment step is 80 DEG C ~ 200 DEG C, preferably 100 DEG C ~ 180 DEG C, and degree of decompression is below 10kPa, preferred below 1kPa, there is no particular restriction for the upper limit of heat-up time, but be generally 10 minutes ~ 48 hours, preferably 30 minutes ~ 24 hours.
Also can the described multifunctional acid anhydrides obtained in this way be refined further.As the process for purification in this situation, at random recrystallize, distillation, cleaning, activated carbon treatment, column chromatography etc. can be carried out.In addition, even if repeat these method for refining, also can be combined to implement.The purity for multifunctional acid anhydrides of the present invention obtained in this way is such as (following by gel permeation chromatography, be called " GPC ") etc. the area ratio of peak value that obtains of analysis, be generally more than 90%, preferably more than 95%, more preferably more than 98%.
About the preservation of multifunctional acid anhydrides, in order to prevent the open loop of the anhydride rings caused by hydrolysis, it is desirable to preserve under the low temperature avoiding high humidity.Specifically, if utilize refrigerator to carry out keeping in the container that stopping property is good, then long preservation is stood.In addition, about multifunctional acid anhydrides, in order to prevent moisture absorption, can immediately for ensuing polyreaction after refining.Within shelf time is now generally 100 hours, preferably within 50 hours, more preferably within 24 hours.
Also can combine and carry out the compound of sclerous reaction to form thermosetting resin composition with described multifunctional acid anhydrides.Now, as long as have by heat and carry out the compound of the functional group reacted with anhydride group, be then not particularly limited, especially can use the compound with epoxy group(ing) aptly.
Now, in order to obtain suitable thermosetting resin composition, in suitable use 1 molecule containing more than at least 2 can carry out the compound of the functional group reacted with anhydride group.
As long as have the compound of at least 1 epoxy group(ing) in compound 1 molecule with epoxy group(ing) shown in the present invention, then can use arbitrary compound.Below, as the compound in 1 molecule of the present invention with at least 1 epoxy group(ing) can be suitably used for, aromatic type epoxy resin, aliphatics type epoxy resin, copoly type epoxy resin are described.
As aromatic type epoxy resin, can enumerate: cresol novolak type epoxy resin, phenol novolak type epoxy resin, biphenyl-phenolic resin varnish type epoxy resin such as phenol type epoxy resin, naphthol type epoxy resin, the bisphenol-type epoxy resins such as bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, tris-phenol type epoxy resin, oxalic dialdehyde type epoxy resin, (4 (4 (1, two (the p-hydroxybenzene)-ethyl of 1-) alpha, alpha-dimethylbenzyl) phenol) type epoxy resin etc.Among these, in the present invention, if consider thermotolerance, photostabilization, then preferred bisphenol A type epoxy resin, (4 (4 (1, two (the p-hydroxybenzene)-ethyl of 1-) alpha, alpha-dimethylbenzyl) phenol) type epoxy resin.
As aliphatics type epoxy resin, can enumerate: there is the epoxy resin of cycloaliphatic ring structure and not there is the epoxy resin of cycloaliphatic ring structure.The feature with the epoxy resin of cycloaliphatic ring structure is: the annular aliphatic structure in a part with at least more than one.Include, for example: terpenes diphenol, or phenols (phenol, alkyl substituted phenol, naphthols, alkyl-substituted naphthaline phenol, dihydroxy-benzene, dihydroxy naphthlene etc.) and aliphatic ring structure diene (Dicyclopentadiene (DCPD) or norbornadiene, hexahydroxy-indenes etc.) polycondensate and the glycidyl ether compound that derives from their modifier, A Hydrogenated Bisphenol A (dihydroxyphenyl propane, Bisphenol F) type epoxy resin, alicyclic epoxy resin etc., there is in molecule the epoxy resin of cyclohexyl structure, there is the epoxy resin of Dicyclopentadiene (DCPD) structure, there is the epoxy resin etc. of triglycidyl group isocyanurate structure.Specifically, include, for example: cylohexanediol diglycidyl ether, 3,4-epoxycyclohexyethylSiOi enylmethyl-3 ', 4 '-epoxycyclohexyethylSiOi olefinic carboxylic acid ester, 2,1,2-epoxy group(ing)-4-(2-Oxyranyle) the hexanaphthene affixture etc. of two (the hydroxyalkyl)-n-butyl alcohol of 2-.
As the compound etc. containing at least 1 epoxy group(ing) in 1 molecule without cycloaliphatic ring structure, the Racemic glycidol ethers that hexane diglycidylether etc. derives from straight chain alcohol or branched-chain alcoho can be enumerated.
As copoly type epoxy resin, represent and have the monomer of unsaturated double-bond and epoxy group(ing) concurrently, such as expression makes the monomers such as (methyl) glycidyl acrylate, (methyl) Hydroxyethyl Acrylate glycidyl ether, (methyl) hydroxy butyl acrylate glycidyl ether and other monomers with unsaturated group that can carry out being polymerized carry out copolymerization.As other monomers, be not particularly limited, as long as copolymerization can be carried out with the described monomer having unsaturated double-bond and epoxy group(ing) concurrently, then can use any monomer.Include, for example: ethene, propylene, vinylbenzene, vinyl-acetic ester, the vinyl compound classes such as vinylchlorid, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) Ethyl acrylate, (methyl) Octyl acrylate, (methyl) lauryl acrylate, (methyl) alkyl-acrylates such as (methyl) stearyl acrylate base ester, (methyl) Hydroxyethyl Acrylate, glycol ethers list (methyl) esters of acrylic acids such as (methyl) hydroxy butyl acrylate, ethylene glycol monomethyl ether (methyl) acrylate, poly glycol monomethyl ether (methyl) acrylate, polyethyleneglycol ether (methyl) acrylate, glycol ethers monoalky lether (methyl) esters of acrylic acids etc. such as polypropylene glycol monomethyl ether (methyl) acrylate.
Sealing material of the present invention can comprise particle (C-1) and/or fiber (C-2).
The particle (C-1) used in the present invention include, for example the polymethylmethacrylate as organic filler, polystyrene, nylon etc., as the talcum of inorganic particulate, calcined clay, non-calcined clay, the silicate such as mica and glass, titanium oxide, zirconium white, aluminum oxide, the oxide compound such as silicon-dioxide and fused silica, calcium carbonate, the carbonate such as magnesiumcarbonate and hydrotalcite, aluminium hydroxide, the oxyhydroxide such as magnesium hydroxide and calcium hydroxide, barium sulfate, the vitriol such as calcium sulfate and calcium sulfite or sulphite, zinc borate, barium metaborate, aluminum borate, the borate such as lime borate and Sodium Tetraborate, aluminium nitride, the nitride such as boron nitride and silicon nitride etc., magnesium fluoride, the fluorochemicals such as Calcium Fluoride (Fluorspan), can be used as not obtain from market containing the micropowder of dispersion solvent or dispersion colloidal solution in a solvent and use.In addition, a kind of described particle or two or more is used in combination can be used.As long as dispersion solvent selectes the ketones such as methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone, N,N-DIMETHYLACETAMIDE, the ester such as ethyl acetate, butylacetate class, the non-polar solvent such as toluene, dimethylbenzene etc. dissolve using of each composition of sealing material of the present invention.In addition, with regard to the viewpoint of dimensional stability, preferred inorganic particulate.Especially, with regard to the viewpoint of versatility or cheapness, preferential oxidation aluminium, silicon-dioxide.
The fiber (C-2) used in the present invention can be enumerated: carbon fiber, glass fibre, casein fiber, ground nut fiber, Zein fibers, soybean fiber, seaweed fiber, chitin fiber, mannosans fiber, rubber fibre, cellulosic fibre, nylon fiber, Saran, thermovyl, trevira, polyacrylonitrile fibre, modified acryl fibre, polyethylene fibre, polypropylene fibre, styroflex, polyether ester fibre, polyurethane fibre etc.1 kind of described fiber or two or more is used in combination can be used.Wherein, with regard to the viewpoint of versatility, preferred glass fibers.In addition, have multiple for the weaving cotton cloth of glass fibre, tNonwovens, cloth etc., in the present invention, there is no particular restriction for its kind, but in order to obtain the hardening thing of the excellent in dimensional stability when making sealing material impregnation of the present invention and hardening, it is suitable that woven fiber glass.If consider and the adhesion of sealing material of the present invention, then glass fibre preferably utilizes silane coupling agent to carry out processing.
Particle (C-1) and fiber (C-2), corresponding to required performance, only can use any one, also can use two kinds.
In sealing material of the present invention, also can comprise other compositions.As other compositions described, can enumerate: antioxidant, photostabilizer, UV light absorber etc.
In sealing material of the present invention, in order to promote the reaction caused by heat, and promote reaction in order to induction heat or adjust stiffening temperature, usually also adding hardening catalyst.As long as described hardening catalyst has the function promoting described sclerous reaction, then can use known general hardening catalyst.
As the antioxidant of sealing material used in the present invention, as long as known general antioxidants such as phenol system antioxidant, sulphur system antioxidant, phosphorous antioxidants, then also unrestricted.But, if in view of feature of the present invention, then preferably select colourless, even and if heat when hardening or long-time be used as sealing after circuit substrate, be also difficult to painted.
As phenol system antioxidant, can enumerate: single phenols, bisphenols and polymer phenols etc.
As the concrete example of sulphur system antioxidant, can enumerate: dilauryl-3,3 '-thiodipropionate, myristyl-3,3 '-thiodipropionate, distearyl-3,3 '-thiodipropionate etc.
As phosphorous antioxidant, can enumerate: phosphorous acid esters, oxa-phospho hetero phenanthrene are oxide-based.
These antioxidants can be used alone respectively, but also two or more combination can be come and uses.Relative to sealing material 100 mass parts of the present invention, the usage quantity of antioxidant is generally 0.008 mass parts ~ 1 mass parts, preferably 0.01 mass parts ~ 0.5 mass parts.In addition, in the present invention, the antioxidant of preferred phosphorus system.
As the photostabilizer of sealing material used in the present invention, known general photostabilizer can be used, be not particularly limited.But, if in view of feature of the present invention, then preferably select colourless, even and if heat when hardening or when long-time use, be also difficult to painted material.
As the representative example of these materials, hindered amines etc. can be enumerated.
As the UV light absorber of sealing material used in the present invention, known general UV light absorber can be used, be not particularly limited.As UV light absorber, benzotriazole system, hydroxyphenyltriazinuv system etc. can be enumerated, also can use with described photostabilizer.
In the present invention, preferably use through time the low UV light absorber of tint permanence.Include, for example: propionic acid-2-[4-[4,6-two ([1,1 '-biphenyl]-4-base)-1,3,5-triazine-2-base]-3-hydroxy phenyl]-different monooctyl ester (refined (Tinuvin) 479 of such as slave, Japanese vapour bar (CibaJapan) (share) manufactures) etc.
When the photostabilization of sealing material of the present invention will be promoted, hydroxyphenyltriazinuv system UV light absorber and hindered amine system photostabilizer are used.
In sealing material of the present invention, also can in the scope of the characteristics such as the harmless transparency or hardness, optionally add the resinous principles such as butyraldehyde system resin, acetal system resin, acrylic resin, epoxy-nylon system resin, paracril (NitrileButadieneRubber, NBR)-phenol resin, epoxy-NBR system resin, polyamide series resin, polyimide system resin, silicone-based resin.
In sealing material of the present invention, also can add silane coupling agent, releasing agent, flow agent, interfacial agent, dyestuff, pigment, organically light diffusion filler, diluting solvent etc.
In sealing material of the present invention, also can add known general metal-salt.Include, for example: the metallic compounds etc. such as carboxylic metallic salt (zinc salt of 2 ethyl hexanoic acid, stearic acid, behenic acid, tetradecanoic acid etc., pink salt, zirconates) or phosphate metal salt (zinc salt of octylphosphonic acid, stearyl phosphoric acid etc.), metal alkoxides salt (tri-butyl aluminum, tetrapropyl zirconium etc.), acetylacetonate (methyl ethyl diketone zirconium chelate, acetylacetone titanium chelate etc.).These metal-salts can be used alone or use two or more.By adding metal-salt, and thermotolerance, the photostabilization of sealing material of the present invention can be promoted.
In sealing material of the present invention, in order to promote the reaction caused by heat, and promote reaction in order to induction heat or adjust stiffening temperature, usually also adding hardening catalyst.As long as described hardening catalyst has the function promoting described sclerous reaction, then can use known general hardening catalyst.
As hardening catalyst, include, for example: glyoxal ethyline, 2-phenylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1 benzyl 2 methyl imidazole, 1-cyano ethyl-glyoxal ethyline, 1-cyano ethyl-2-phenylimidazole, 1-cyano ethyl-2-undecyl imidazole, 2,4-diamino-6 (2 '-Methylimidazole (1 ')) ethyl-s-triazine, 2,4-diamino-6 (2 '-undecyl imidazole (1 ')) ethyl-s-triazine, 2,4-diamino-6 (2 '-ethyl, 4-methylimidazole (1 ')) ethyl-s-triazine, 2,4-diamino-6 (2 '-Methylimidazole (1 ')) ethyl-s-triazine isocyanuric acid affixture, the 2:3 affixture of glyoxal ethyline isocyanuric acid, 2-phenylimidazole isocyanuric acid affixture, 2-phenyl-3,5-dihydroxyalkyl imidazoles, 2-phenyl-4-hydroxyalkyl-5-Methylimidazole, the various imidazoles such as 1-cyano ethyl-2-phenyl-3,5-dicyano ethoxyl methyl imidazoles, and described imidazoles and phthalic acid, m-phthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, naphthalic acid, maleic acid, the salt of the polycarboxylic acids such as oxalic acid, the amidess such as dicyandiamide, 1, 8-diaza-dicyclo (5,4,0) hendecene-7 diaza compound such as grade and their tetraphenyl borate salts, the salt of phenol novolacs etc., with the salt of described polycarboxylic acid class or phosphonic acid based, Tetrabutylammonium bromide, cetrimonium bromide, the ammonium salt classes such as bromination tricaprylmethylammonium, triphenylphosphine, three (toluyl) phosphine, tetraphenylphosphonibromide bromide squama, tetraphenyl squama tetraphenyl borate salts, phosphine class or the squama compounds such as hexafluoro antimony squama salt, the phenols such as 2,4,6-triamino methylphenols, stannous octoate, cobalt octoate, zinc octoate, zirconium caprylate, nickel octoate, the organometallic compounds etc. such as cobalt naphthenate.And then, the microcapsule-type hardening catalyst etc. making hardening accelerator become microcapsule can be enumerated.
Any should being suitable for according to required characteristic of these hardening catalysts is used to select.Relative to all resins 100 mass parts in sealing material of the present invention, usually in the scope of 0.001 mass parts ~ 15 mass parts, use hardening catalyst.
In sealing material of the present invention, may correspond in the form used containing solvent.As long as solvent used in the present invention is inertia for the composition of sealing material of the present invention, then be not particularly limited, include, for example with the solvent phase of the reaction that can be used for core hydrogenated trimellitic anhydride halogenide or core hydrogenated trimellitic anhydride halogenide and the halid mixture of trimellitic acid 1,2-anhydride and polyvalent alcohol (A) or polyvalent alcohol (B) with.
[embodiment]
Secondly, the present invention is illustrated in greater detail by embodiment.Moreover the present invention is not by the following any restriction of embodiment.In the synthesis of compound, confirmed that by gel permeation chromatography (hereinafter referred to as " GPC ") time point of the disappearance of raw material alcohols is set to reaction and terminates.Moreover, in an embodiment, TMAC represents trimellitic anhydride chloride, and HTAC represents core hydrogenated trimellitic anhydride muriate, and THF represents tetrahydrofuran (THF), TMP represents TriMethylolPropane(TMP), DPE represents Dipentaerythritol, and PE4EO represents tetramethylolmethane 4 moles of ethylene oxide affixture, and DE6EO represents Dipentaerythritol 6 moles of ethylene oxide affixture, DPE4C represents Dipentaerythritol 4 moles of caprolactone affixtures, and MEK represents methyl ethyl ketone.
Synthesis example 0: the synthesis of Dipentaerythritol 4 moles of caprolactone affixtures (DPE4C)
In the flask possessing stirrer, reflux cooling pipe, whipping appts, one side implements nitrogen wash, one adds caprolactone 45.66g (400mmol) in Dipentaerythritol 25.43g (100mmol), then stir 12 hours at 180 DEG C, and obtain Dipentaerythritol 4 moles of caprolactone affixture 71.09g.
Synthesis example 1-1: the synthesis 1 of multifunctional acid anhydrides
In the flask possessing stirrer, reflux cooling pipe, whipping appts, one side implements nitrogen wash, and one adds THF36g and makes homogeneous solution in HTAC23.34g (108mmol).This solution faced by one carries out after till stirring one side is cooled to 5 DEG C, liquid temperature is remained less than 10 DEG C by one side, and one side drips lentamente to TMP4.44g (33mmol) middle interpolation pyridine 10.08g (127.5mmol) and THF54g and makes uniform solution.After dropping terminates, at room temperature stir 1 hour, be then warming up to till 50 DEG C, and make reaction continue 8 hours.Then, reaction solution is cooled to till 20 DEG C, using after the pyridine hydrochloride elimination of not solvent components, filtrate is concentrated.Make enriched material be dissolved in ethyl acetate 120ml, after utilizing the water of 30ml to carry out 3 cleanings, utilize anhydrous magnesium sulfate to carry out drying.After anhydrous magnesium sulfate elimination, filtrate is concentrated, and make obtained enriched material be dissolved in the ethyl acetate of 15ml, then utilize toluene to carry out recrystallize, and obtain product 16.7g (productive rate is 75.2%).
Synthesis example 1-2 ~ synthesis example 1-8 and compare synthesis example 1-1: the synthesis 2 ~ synthesis 9 of multifunctional acid anhydrides
Be set to except following table 1 except by TMAC, HTAC, polyvalent alcohol (A)/polyvalent alcohol (B), obtain multifunctional acid anhydrides in the mode identical with synthesis example 1-1.
Synthesis 2 ~ the synthesis 9 of the multifunctional acid anhydrides of table 1
Embodiment 1-1: the preparation 1 of sealing material
By the multifunctional acid anhydrides 35g making to obtain in synthesis example 1-1, (Daicel (Daicel) (share) manufactures aliphatics type epoxy resin EHPE-3150, epoxy equivalent (weight) is 181) 10g, as (4 (4 (1 of aromatic type epoxy resin, two (the p-hydroxybenzene)-ethyl of 1-) α, α-dimethylbenzyl) phenol) (epoxy equivalent (weight) is 206 to type epoxy resin, total chlorine amount is 550ppm) 27g, equally as RE-310S (Japanese chemical drug (share) manufacture: aqueous bisphenol A epoxide resin of aromatic type epoxy resin, epoxy equivalent (weight) is 185, total chlorine amount 500ppm) 23g, as the zinc octoate 0.3g of other compositions, what the MEK41g as diluting solvent mixed heats to 70 DEG C, and mix, and obtain the sealing material that solids component is 70 quality %.
Embodiment 1-2: the preparation 2 of sealing material
Except the multifunctional acid anhydrides obtained in synthesis example 1-2 is set to 34g, MEK is set to beyond 40g, obtains in the mode identical with embodiment 1-1 the sealing material that solids component is 70 quality %.
Embodiment 1-3: the preparation 3 of sealing material
What multifunctional acid anhydrides 41g, MEK43g of making to obtain in synthesis example 1-3 are mixed heats to 50 DEG C, and mixes, and obtains the sealing material that solids component is 70 quality %.
Embodiment 1-4: the preparation 4 of sealing material
Except the multifunctional acid anhydrides obtained in synthesis example 1-4 is set to 46g, MEK is set to beyond 46g, obtains in the mode identical with embodiment 1-1 the sealing material that solids component is 70 quality %.
Embodiment 1-5: the preparation 5 of sealing material
Except the multifunctional acid anhydrides obtained in synthesis example 1-5 is set to 46g, MEK is set to beyond 46g, obtains in the mode identical with embodiment 1-1 the sealing material that solids component is 70 quality %.
Embodiment 1-6: the preparation 6 of sealing material
Except the multifunctional acid anhydrides obtained in synthesis example 1-6 is set to 46g, MEK is set to beyond 46g, obtains in the mode identical with embodiment 1-1 the sealing material that solids component is 70 quality %.
Embodiment 1-7: the preparation 7 of sealing material
Except the multifunctional acid anhydrides obtained in synthesis example 1-7 is set to 35g, MEK is set to beyond 41g, obtains in the mode identical with embodiment 1-1 the sealing material that solids component is 70 quality %.
Embodiment 1-8: the preparation 8 of sealing material
Except the multifunctional acid anhydrides obtained in synthesis example 1-8 is set to 35g, MEK is set to beyond 41g, obtains in the mode identical with embodiment 1-1 the sealing material that solids component is 70 quality %.
Comparative example 1-1: the preparation 9 of sealing material
Except being set to 35g by comparing the multifunctional acid anhydrides obtained in synthesis example 1-1, MEK is set to beyond 41g, with the mode identical with embodiment 1-1 obtain solids component be 70 quality % relatively use sealing material.
Comparative example 1-2: the preparation 10 of sealing material
Except 4-methylhexahydrophthalic anhydride is set to 17g, MEK is set to beyond 33g, with the mode identical with embodiment 1-1 obtain solids component be 70 quality % relatively use sealing material.
Comparative example 1-3: the preparation 11 of resin combination
Except 1,2,4,5-cyclopentanetetracarboxylic dianhydride is set to 17g, the acetone as diluting solvent is set to beyond 33g, with the mode identical with embodiment 1-1 obtain solids component be 70 quality % relatively use sealing material.
Embodiment 2 and comparative example 2: the evaluation of hardening thing characteristic
Utilize heat-resisting demoulding adhesive tape to make the mould of 40mm × 25mm × 1mm on the glass substrate, the curable resin composition of curable resin composition of the present invention and comparative example be poured into thickness respectively and be about till 800 μm, and carry out at 80 DEG C 50 minutes dry.In drying way, carry out 1 vacuum defoamation, and bubble is removed.Thereafter till being cooled to room temperature, and acknowledgement state, result sealing material of the present invention is at room temperature solid.
Then, at 150 DEG C, utilize drying machine to carry out sclerosis in 3 hours, and obtain hardening thing of the present invention.Glass transition temperature, obdurability, coloring resistance are measured respectively to obtained hardening thing.
For the evaluation method of resin combination and cured film and metewand as described below.
(1) thermotolerance: in determination of viscoelasticity system (DMS-6000: Seiko electronic industry (SeikoInstruments & Electronics) (share) manufactures), measure the glass transition temperature (Tg) of the sealing material through sclerosis with stretch mode, frequency 1Hz.Determinating reference is as described below.
◎: Tg is more than 195 DEG C
Zero: Tg is more than 185 DEG C, less than 194 DEG C
Δ: Tg is more than 175 DEG C, less than 184 DEG C
×: Tg is less than 174 DEG C
(2) obdurability: the two ends fixing the cured film of the sealing material through sclerosis with hand, and the state of observing cured film when pressing central part.Determinating reference is as described below.
◎: even if press consumingly, also can not crack, and can not break.
Zero: even if press slightly, also can not crack, and can not break, if but press consumingly, then can crack.
Δ: if press slightly, then can crack, if press consumingly, then can break.
×: if press slightly, then can break.
(3) coloring resistance: utilize spectrophotometer (U-3900H: Hitachi's new and high technology (HitachiHigh-Technologies) (share) manufactures (yellow chromaticity is JISK7105/JISK7373) and measure the initial yellow chromaticity (YI) of the cured film of the sealing material through sclerosis and place the yellow chromaticity (YI) after 20 minutes at 230 DEG C, and obtains its poor (xanthochromia degree: Δ YI).Determinating reference is as described below.
◎: Δ YI is less than 0.4
Zero: Δ YI is more than 0.5, less than 0.7
Δ: Δ YI is more than 0.8, less than 1.0
×: Δ YI is more than 1.1
(4) reliability: utilize silk screen printing (silkscreen) method, the polyimide substrate of comb-type electrode forming line/space=50/50 micron makes the film that thickness is roughly 25 microns.Put into the voltage of the after-applied 100V of high temperature groove to 120 DEG C of 85% relative humidity, and compare the transition of its resistance value.Measure from on-test resistance value lower than the time of the time point of 1 megohm.Determinating reference is as described below.
◎: resistance value is more than 200 hours lower than the time point of 1 megohm
Zero: resistance value is more than 150 hours, less than 199 hours lower than the time point of 1 megohm
Δ: resistance value is more than 100 hours, less than 149 hours lower than the time point of 1 megohm
×: resistance value is less than 99 hours lower than the time point of 1 megohm
The Property comparison of table 2 hardening thing
| Embodiment | Sealing material | Thermotolerance | Obdurability | Coloring resistance | Reliability |
| Embodiment 2-1 | Embodiment 1-1 | ○ | ○ | ◎ | ◎ |
| Embodiment 2-2 | Embodiment 1-2 | ◎ | ○ | ○ | ◎ |
| Embodiment 2-3 | Embodiment 1-3 | ○ | ◎ | ◎ | ○ |
| Embodiment 2-4 | Embodiment 1-4 | ◎ | ◎ | ○ | ○ |
| Embodiment 2-5 | Embodiment 1-5 | ○ | ◎ | ○ | ◎ |
| Embodiment 2-6 | Embodiment 1-6 | ◎ | ○ | ○ | ◎ |
| Embodiment 2-7 | Embodiment 1-7 | ◎ | ○ | ○ | ◎ |
| Embodiment 2-8 | Embodiment 1-8 | ◎ | ○ | Δ | ◎ |
| Comparative example 2-1 | Comparative example 1-1 | ◎ | Δ | × | ◎ |
| Comparative example 2-2 | Comparative example 1-2 | × | × | ◎ | × |
| Comparative example 2-3 | Comparative example 1-3 | Δ | × | ◎ | Δ |
As clear and definite according to above result, the thermotolerance of sealing material of the present invention, obdurability, coloring resistance, excellent in reliability.Multifunctional acid anhydrides for the sealing material of embodiment 2 has the acid anhydrides of more than trifunctional, and then the alcohol becoming parent nucleus is aliphatics and molecular weight is also large, therefore can think the thermotolerance of sealing material of the present invention and obdurability excellence.In addition, this multifunctional acid anhydrides also has many saturated alicyclic rings, therefore can think that coloring resistance is excellent, owing to comprising woven fiber glass etc., therefore can think that dimensional stability is also excellent.In contrast, the multifunctional acid anhydrides of comparative example 1-1 is not owing to having saturated alicyclic ring, the therefore coloring resistance of sealing material insufficient.In addition, the multifunctional acid anhydrides used in comparative example 1-2 is low molecule, therefore can think the thermotolerance of sealing material and obdurability not good enough.The multifunctional acid anhydrides used in comparative example 1-3 is two senses and for low molecule, therefore can think the thermotolerance of sealing material and obdurability not good enough.
The preparation 1 of embodiment 3-1:LED point lantern test sealing material
The multifunctional acid anhydrides obtained in synthesis example 1-1 is set to 34g, using as 3 of epoxy resin, 4-epoxycyclohexyl-methyl-3,4-epoxycyclohexylcarboxylate (UVR-6105 that DOW Chemical (TheDowChemical) manufactures) is set to 38g, cetyltrimethylammonium hydroxide (Tokyo changes into 25% methanol solution that industry (share) manufactures) as stiffening agent is set to 0.09g, the MEK as diluting solvent is set to 20g to obtain sealing material.
The preparation 2 of embodiment 3-2:LED point lantern test sealing material
Except the multifunctional acid anhydrides obtained in synthesis example 1-3 is set to 34g, UVR-6105 is set to beyond 33g, obtains sealing material in the mode identical with embodiment 3-1.
The preparation 3 of embodiment 3-3:LED point lantern test sealing material
Except being set to except 34g by the multifunctional acid anhydrides obtained in synthesis example 1-6, obtain sealing material in the mode identical with embodiment 3-2.
The preparation 4 of embodiment 3-4:LED point lantern test sealing material
Except being set to except 34g by the multifunctional acid anhydrides obtained in synthesis example 1-7, obtain sealing material in the mode identical with embodiment 3-2.
The preparation 5 of embodiment 3-5:LED point lantern test sealing material
Except being set to except 34g by the multifunctional acid anhydrides obtained in synthesis example 1-8, obtain sealing material in the mode identical with embodiment 3-2.
The preparation 6 of comparative example 3-1:LED point lantern test sealing material
Except being set to 34g by comparing the multifunctional acid anhydrides obtained in synthesis example 1-1, UVR-6105 being set to beyond 39g, obtaining to compare in the mode identical with embodiment 3-1 and use sealing material.
The preparation 7 of comparative example 3-2:LED point lantern test sealing material
4-methylhexahydrophthalic anhydride is set to 17g, UVR-6105 is set to 20g, cetyltrimethylammonium hydroxide is set to 0.06g, MEK is set to 10g to obtain to compare and uses sealing material.
Embodiment 4 and comparative example 4:LED point lantern test
After vacuum defoamation in 60 minutes is implemented to the sealing material obtained in embodiment 3 and comparative example 3, the lead frame being equipped with the surface mounting LED (SMD type 5mm φ rated current is 30mA) that emission wavelength is the luminous element of 465nm is configured on mould, being poured into by resin to mould by transfer molding processes and carried out heating and pressurizing makes it harden, and obtains a some lantern test LED thus.Point lantern test utilizes the electric current of 2 times as the 30mA of rated current to carry out a lantern test.Below represent detailed condition.As mensuration project, use integrating sphere to measure the illumination of lighting 200 hours front and back, and calculate the conservation rate of the illumination of test LED.Show the result in table 3.
Lighting detailed conditions
Emission wavelength: center emission wavelength, 465nm
Type of drive: constant current behavior, 60mA (luminous element rated current is 30mA) series connection also lighting 3 simultaneously
Drive environment: 85 DEG C, lighting in 85% damp and hot machine
Evaluate: the illumination conservation rate after 200 hours
Determinating reference is as described below.
◎: illumination conservation rate is more than 75%
Zero: illumination conservation rate is more than 70%, less than 74%
Δ: illumination conservation rate is more than 65%, less than 69%
×: illumination conservation rate is less than 65%
The LED point lamp test of table 3 sealing material is compared
| Embodiment | Composition | Illumination conservation rate |
| Embodiment 4-1 | Embodiment 3-1 | ◎ |
| Embodiment 4-2 | Embodiment 3-2 | ◎ |
| Embodiment 4-3 | Embodiment 3-3 | ○ |
| Embodiment 4-4 | Embodiment 3-4 | ○ |
| Embodiment 4-5 | Embodiment 3-5 | ○ |
| Comparative example 4-1 | Comparative example 3-1 | × |
| Comparative example 4-2 | Comparative example 3-2 | Δ |
According to above result, the illumination conservation rate showing sealing material of the present invention is good.
Embodiment 5: the preparation of solar battery element seal test prepreg
Embodiment 1-1, embodiment 1-3, embodiment 1-6, embodiment 1-7, embodiment 1-8, comparative example 1-1, comparative example 1-2 is made (to be equivalent to electronic circuit interconnects and encapsulation association (TheInstituteforInterconnectingandPackagingElectronicCirc uits containing being immersed in the woven fiber glass comprising E-glass, IPC) specification 106) in, in the baking oven of 100 DEG C, drying in 10 minutes carried out to solvent thereafter and obtain the prepreg that thickness is 50 μm.They are set to respectively embodiment 5-1 ~ embodiment 5-3 and comparative example 5-1 ~ comparative example 5-2.
Embodiment 6 and comparative example 6: the making and the evaluation thereof that seal organic solar battery element (photo-electric conversion element)
Utilizing tin indium oxide (IndiumTinOxide, ITO) Polyethylene Naphthalate (Polyethylenenaphthalate of conduction processing is implemented, PEN) sheet material makes the film of poly-3-hexyl thiophene (Price card (Plexcore) OSP3HT, Sigma-Aldrich (Sigma-Aldrich) manufactures).Then, this substrate is arranged in vacuum deposition apparatus, and is exhausted until the vacuum tightness in device becomes 2 × 10
-3till below Pa.By resistive heating evaporation, C60 evaporation is become the thickness of 30nm, and 2,9-dimethyl-4,7-phenylbenzene-1, the 10-phenanthroline of evaporation 10nm.And then, become the thickness of 100nm to form negative electrode aluminium-vapour deposition across shadow mask (shadowmask), and make the round organic photovoltaic cell element that diameter is 2mm.
Be placed on the organic photovoltaic cell device substrate obtained in this way after prepreg made in embodiment 5 is removed the electrode part of element evaluation respectively.And then mounting thickness is that the film comprising tetrafluoroethylene-ethylene copolymer of 100 μm is as peel ply.One side under vacuo, is pressurizeed to this element by vacuum pressing, and one side carries out heat hardening in 3 hours at 130 DEG C, and obtains sealing element.
Detailed conditions
Radiation illumination: 100mW/cm
2
Drive environment: the thermal cycling of-20 DEG C, 15 minutes → 25 DEG C, 5 minutes → 100 DEG C, 15 minutes → 25 DEG C, 5 minutes is repeated 20 times.
Evaluate: the photoelectric transformation efficiency conservation rate after test
Determinating reference is as described below.
◎: photoelectric transformation efficiency conservation rate is more than 80%
Zero: photoelectric transformation efficiency conservation rate is more than 70%, less than 79%
Δ: photoelectric transformation efficiency conservation rate is more than 60%, less than 69%
×: photoelectric transformation efficiency conservation rate is less than 59%
The Property comparison of table 4 sealing material
| Embodiment | Composition | Photoelectric transformation efficiency conservation rate |
| Embodiment 7-1 | Embodiment 6-1 | ◎ |
| Embodiment 7-2 | Embodiment 6-2 | ◎ |
| Embodiment 7-3 | Embodiment 6-3 | ◎ |
| Embodiment 7-4 | Embodiment 6-4 | ◎ |
| Embodiment 7-5 | Embodiment 6-5 | ◎ |
| Comparative example 7-1 | Comparative example 6-1 | × |
| Comparative example 7-2 | Comparative example 6-2 | × |
According to above result, the photoelectric transformation efficiency conservation rate showing sealing material of the present invention is good.
[utilizability in industry]
Sealing material of the present invention is suitable for the sealing material used in the display unit or solar cell etc. of liquid-crystal display, plasma display, EL indicating meter, portable machine etc.
Claims (10)
1. a sealing material, it is characterized in that: comprise the multifunctional acid anhydrides making the polyvalent alcohol (A) containing the hydroxyl of more than at least 3 in a part and core hydrogenated trimellitic anhydride halogenide or core hydrogenated trimellitic anhydride halogenide and the halid mixture of trimellitic acid 1,2-anhydride carry out reacting and obtain, described polyvalent alcohol (A) is represented by following general formula (1)
In formula, R
1, R
2, R
3, R
4, R
5, R
6independently, R
1, R
3, R
4, R
5, R
6represent hydrogen atom, hydroxyl, carbon number be 1 ~ 11 alkyl or carbon number be the hydroxyalkyl of 1 ~ 4, R
2represent that hydroxyl or carbon number are the hydroxyalkyl of 1 ~ 4; 1 expression 0 ~ 11, m and n represents the integer of 1 ~ 11 respectively.
2. a sealing material, it is characterized in that: comprise the multifunctional acid anhydrides making polyvalent alcohol (B) and core hydrogenated trimellitic anhydride halogenide or core hydrogenated trimellitic anhydride halogenide and the halid mixture of trimellitic acid 1,2-anhydride carry out reacting and obtain, described polyvalent alcohol (B) makes polyvalent alcohol according to claim 1 (A) carry out reacting and obtaining with more than a kind of being selected from the group that is made up of oxirane, cyclic ether and cyclic ester.
3. a sealing material, it is characterized in that: comprise the multifunctional acid anhydrides making polyvalent alcohol (A) and core hydrogenated trimellitic anhydride halogenide or core hydrogenated trimellitic anhydride halogenide and the halid mixture of trimellitic acid 1,2-anhydride carry out reacting and obtain, described polyvalent alcohol (A) is in general formula according to claim 1 (1), R
1, R
2, R
3, R
4, R
5, R
6for the polyvalent alcohol (A) that carbon number is the hydroxyalkyl of 1 ~ 4.
4. a sealing material, it is characterized in that: comprise the multifunctional acid anhydrides making polyvalent alcohol (B) and core hydrogenated trimellitic anhydride halogenide or core hydrogenated trimellitic anhydride halogenide and the halid mixture of trimellitic acid 1,2-anhydride carry out reacting and obtain, described polyvalent alcohol (B) makes polyvalent alcohol according to claim 3 (A) carry out reacting and obtaining with more than a kind of being selected from the group that is made up of oxirane, cyclic ether and cyclic ester.
5. a sealing material, is characterized in that: comprise thermosetting resin composition, and described thermosetting resin composition comprises in a part the compound and multifunctional acid anhydrides according to any one of claim 1 to 4 with at least 1 epoxy group(ing).
6. sealing material according to any one of claim 1 to 5, is characterized in that: also comprise and polyvalent alcohol (A), trimellitic acid 1,2-anhydride halogenide and core hydrogenated trimellitic anhydride halogenide or core hydrogenated trimellitic anhydride halogenide and the inconsistent particle of the halid mixture of trimellitic acid 1,2-anhydride (C-1) or fiber (C-2).
7. sealing material according to claim 6, is characterized in that: described particle (C-1) is inorganic particulate.
8. sealing material according to claim 6, is characterized in that: described fiber (C-2) is glass fibre.
9. sealing material according to claim 6, is characterized in that: described fiber (C-2) for spin to glass fibre, and then carries out the woven fiber glass weaved.
10. a prepreg, is characterized in that: under semi-hardened state, give shape to the sealing material according to any one of claim 5 to 9 form.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014-099793 | 2014-05-13 | ||
| JP2014099793 | 2014-05-13 | ||
| JP2015040923 | 2015-03-03 | ||
| JP2015-040923 | 2015-03-03 | ||
| JP2015040922A JP6362558B2 (en) | 2014-05-13 | 2015-03-03 | Polyfunctional acid anhydride and thermosetting resin composition |
| JP2015-040922 | 2015-03-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105085870A true CN105085870A (en) | 2015-11-25 |
Family
ID=54567261
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510140862.9A Pending CN105085870A (en) | 2014-05-13 | 2015-03-27 | Sealing material and prepreg |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105085870A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110283561A (en) * | 2019-05-30 | 2019-09-27 | 天津德高化成科技有限公司 | A kind of LED display patch type discrete device potting resin composition and application thereof |
| CN117070158A (en) * | 2023-08-16 | 2023-11-17 | 东莞中能膜业科技有限公司 | Protective film applied to new energy battery shell and preparation method thereof |
| CN117070158B (en) * | 2023-08-16 | 2024-05-10 | 东莞中能膜业科技有限公司 | Protective film applied to new energy battery shell and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003041182A (en) * | 2001-07-27 | 2003-02-13 | New Japan Chem Co Ltd | Epoxy resin powder coating composition |
| JP2007246830A (en) * | 2006-03-17 | 2007-09-27 | Stanley Electric Co Ltd | Thermo-setting resin composition, light transmitting cured product obtained by thermosetting the same, and light emitting diode sealed with the cured product |
| CN104558544A (en) * | 2013-10-15 | 2015-04-29 | 日本化药株式会社 | Polyfunctional acid anhydride, a thermosetting resin composition and its cured prepreg |
-
2015
- 2015-03-27 CN CN201510140862.9A patent/CN105085870A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003041182A (en) * | 2001-07-27 | 2003-02-13 | New Japan Chem Co Ltd | Epoxy resin powder coating composition |
| JP2007246830A (en) * | 2006-03-17 | 2007-09-27 | Stanley Electric Co Ltd | Thermo-setting resin composition, light transmitting cured product obtained by thermosetting the same, and light emitting diode sealed with the cured product |
| CN104558544A (en) * | 2013-10-15 | 2015-04-29 | 日本化药株式会社 | Polyfunctional acid anhydride, a thermosetting resin composition and its cured prepreg |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110283561A (en) * | 2019-05-30 | 2019-09-27 | 天津德高化成科技有限公司 | A kind of LED display patch type discrete device potting resin composition and application thereof |
| CN110283561B (en) * | 2019-05-30 | 2021-09-10 | 天津德高化成科技有限公司 | Packaging resin composition for LED display screen patch type discrete device and application thereof |
| CN117070158A (en) * | 2023-08-16 | 2023-11-17 | 东莞中能膜业科技有限公司 | Protective film applied to new energy battery shell and preparation method thereof |
| CN117070158B (en) * | 2023-08-16 | 2024-05-10 | 东莞中能膜业科技有限公司 | Protective film applied to new energy battery shell and preparation method thereof |
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Application publication date: 20151125 |