CN1033982C - Production of transparent solf seal adhesive with epoxy double component - Google Patents
Production of transparent solf seal adhesive with epoxy double component Download PDFInfo
- Publication number
- CN1033982C CN1033982C CN90102866A CN90102866A CN1033982C CN 1033982 C CN1033982 C CN 1033982C CN 90102866 A CN90102866 A CN 90102866A CN 90102866 A CN90102866 A CN 90102866A CN 1033982 C CN1033982 C CN 1033982C
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- component
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- epoxy
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Abstract
The present invention relates to a high molecular soft seal adhesive with epoxy double components, which belongs to the field of epoxy high molecular decoration and seal material. The present invention provides the preparation method and the adhesive preparing and molding technology of the material. The soft seal adhesive made by the method of the present invention can be used for decorating labels, printing wiring boards and flexibly packaging components. The present invention is used for decorating the labels to replace an imported polyurethanes flexible adhesive and is used for printing the wiring boards and flexibly packaging the components to replace imported material. After sealed and packaged, the printing boards and the components are integrated so as to greatly enhance the operating stability of the sealed components in severe conditions.
Description
The invention belongs to epoxies two-component-type polymer transparent soft decorates and the packaged material field.
The present invention is a kind of novel solf seal adhesive according to customer requirements and market requirement exploitation.Be used for label decoration aspect, before this, what the user used is the sizing material of Italian import, and this import glue is the soft glue of polyurethanes, costs an arm and a leg, and consumes foreign exchange, and per kilogram is more than 25 dollars.And when this sizing material carries out application, come supportingly with import equipment, Working environment requires low temperature, and the too high meeting of humidity causes that sizing material scraps, and uses import equipment, and the investment number is bigger.Domesticly do not see soft glue production as yet, the rigid polyester resin of photocuring is only arranged for commercially available.Polyester resin can only be confined to decorate on the hard label and use, and partial coating and paint are stung the lacquer phenomenon.During curing operation exposure sources will be arranged, storage characteristics is relatively poor, is no more than half a year.The soft encapsulation aspect that is used for printed circuit board and components and parts, the printed wiring board industry adopts surface mounting technology, is the external novel process of development in recent years.Printed board and components and parts make it integrated after encapsulation, thereby improve printed board job stability of (as high pressure, pulse jamming, humidity etc.) under some mal-condition greatly.With this soft glue encapsulation, do not resemble passing that some epoxy encapsulant can be in time and the shortcoming of hardening.The producer that has is used for the encapsulation of printed board with the soft encapsulating compound of U.S. Grace company, consumes foreign exchange, costs an arm and a leg, and per kilogram is more than 25 dollars.
The preparation method who the purpose of this invention is to provide a kind of epoxies two-component-type transparent soft glue, the soft glue that makes can be used for the encapsulation that printed board and various components and parts were decorated and be used for to label.Can substitute the import material.
Content of the present invention: this soft glue is formulated with 1: 1 (weight ratio) or other weight ratio by A component, two kinds of components of B component.
1, the preparation of A component:
The A component is formulated by Resins, epoxy, epoxide diluent, release agent, toughner.
Proportioning is: material name weight %
Resins, epoxy 85-95
Epoxide diluent 5-15
Release agent 0-1
Toughner 0-10
Resins, epoxy can be used: alicyclic ring or aromatic epoxy resin, and as E-54, E-51, E-44, E-42, E-35; Also available novolac epoxy, phenol formaldehyde Resins, epoxy, as F-51, F-48, F-44, JF-45, JF-43; Also available aliphatic epoxy resin, as B-63, the oxirane value of requirement is 0.03～0.6 equivalent/100g, for the thick liquid epoxy, viscosity is: in the time of 25 ℃, more than the 6000cps, for solids epoxy, softening temperature＜150 ℃.
The epoxy attenuant can be used: the epoxypropyl alkyl oxide, and the epoxypropyl aryl ethers, as 690,680,678,669,660,630,600 trades mark such as grade.The requirement oxirane value is 0.3～1.30 equivalent/100g, and viscosity is: in the time of 25 ℃, and＜10cps; Boiling range＞110 ℃.
Release agent can be with organosilyl monomeric ester class, as tetraethoxy, and butyl silicate etc.
Toughner can be used α, and the ε dibasic alcohol is as butyleneglycol, hexylene glycol; Also available polyvalent alcohol, as TriMethylolPropane(TMP), tetramethylolmethane; Also available various softening agent, as dibutyl phthalate, dioctyl phthalate (DOP) etc.
The calculation formula of the oxirane value E of A component:
E＝C
1E
1＋C
2E
2＋……
E in the formula
1, E
2... be respectively the oxirane value of used various Resins, epoxy and epoxide diluent in the A component.C
1, C
2Be respectively the various Resins, epoxy of used correspondence in the A component and the weight fraction of epoxide diluent, C
1+ C
2=1.
Various raw materials at room temperature stir by the proportioning metering, are the A component.
2, the preparation of B component:
The B component is formed by solidifying agent, properties-correcting agent, catalyst preparation.Proportioning (weight ratio) is:
(solidifying agent+properties-correcting agent): catalyzer=1: 0.005～0.05:
Solidifying agent can be with fatty amine, arylamine class, imidazoles or modified imidazole class.
The fat amine curing agent, as quadrol, diethylenetriamine, triethylene tetramine, polyethylene polyamine etc.
Arylamine class solidifying agent is as, phenylenediamine, benzene dimethylamine, 4,4 '-diaminodiphenylmethane etc.
Imidazole curing agent is as imidazoles, 2-alkyl imidazole etc.
Properties-correcting agent epoxy available thinner, the epoxide diluent described in the preparation of using the A component.
Also available alkene esters of gallic acid, as methyl acrylic ester, esters of acrylic acid, for example butyl acrylate.
Catalyzer can be used aliphatic tertiary amine, alicyclic tertiary amine, aromatic series tertiary amine class.As triethylamine, tripropyl amine, N, N ' dimethyl benzylamine etc.
Solidifying agent and properties-correcting agent, press following conceptual design as the prescription of epoxide diluent:
[(N－Y)/(M
1＋yM
2)]×100＝E
In the formula: N is the reactive hydrogen number in the organic amine curing agent molecule.
Y is the stoichiometric coefficient of epoxide diluent in the B component.
M
1Molecular weight for organic amine curing agent.
M
2Molecular weight for epoxide diluent in the B component.
E is the oxirane value of A component.
By this conceptual design, reach A component and B composition weight and equate.The just in time equivalent reaction of the reactive hydrogen of the oxirane value of A component and B component.Just can make the stoichiometric coefficient y of epoxide diluent required the B component from above formula.Be that the stoichiometry of solidifying agent and epoxide diluent is 1 in the B component: y, both weight ratios are M
1: yM
2
In like manner, if A component and B component with W
A: W
BThe weight ratio preparation.Then press W
B[(N-Y)/(M
1+ yM
2)] * 100=W
A* E conceptual design is therefrom made the stoichiometric coefficient y of epoxide diluent required in the B component.
During reaction, can adopt under agitation condition solidifying agent to add in the epoxide diluent, or epoxide diluent adds in the solidifying agent, add the catalyzer of solidifying agent and epoxide diluent total amount 0.005-5% at last, temperature of reaction is controlled at 15～70 ℃, and the reaction times is 10～24 hours.
3, the preparation of soft glue and moulding.
Before joining glue, A, B component should be respectively preheating 20～30 minutes under 25～35 ℃ of conditions, put together then and stirred 5～10 minutes, through vacuum (700mmHg) deaeration 20 minutes, left standstill again 20 minutes, allow system viscosity reach proper range 10
2～10
4Cps, sealing is preserved stand-by then.During use the above-mentioned soft glue for preparing is coated on material surface, or uses die casting, through room temperature or middle low temperature (＜50 ℃) drying treatment, transparent, plentiful, soft decoration packaged material.
Advantage of the present invention: this soft glue is the epoxy glue of two-pack, have transparent, smooth, soft, warping strength characteristics, good to decoration or encapsulation adhesion, and various coating, paint nothing are stung the lacquer phenomenon, shelf lives is also grown (〉=1 year), can use on various base materials, and base material can be a metal, also can be various flexible substrates, as PVC, dacron chip base, ordinary rigid paper.
Embodiment 1:
A component preparation: 90 parts of 618 epoxy resins, 10 parts of 660A epoxide diluents, the tetraethoxy of total amount 2% in addition forms through fully stirring again.
The preparation of B component: solidifying agent diethylenetriamine (DETA), with epoxypropyl butyl ether (660) epoxide diluent modification.Reaction formula is:
In the A component: the oxirane value E of epoxy 618
1=0.50, the oxirane value E of epoxy 660
2=0.70, so the oxirane value E=0.9 * 0.50+0.1 * 0.7=0.52 of A component is in the B component: diethylenetriamine molecular weight M
1=103, reactive hydrogen number N=5, epoxy 660 molecular weight M
2=130, according to
Y=2.66, so the weight ratio of diethylenetriamine and 660 is 103:2.66 * 130=1: 3.36, so get 23 parts of diethylenetriamines, 77 parts of 660 epoxies add stirring in 660 with diethylenetriamine, add the back that finishes and add 2 parts of triethylamines, 50 ℃ of temperature of reaction, reaction times 20hr.
Join glue: at 30 ℃,, stir then and join glue, stirred 20 minutes, left standstill again 20 minutes with A.B two component preheatings 25 minutes.
Embodiment 2 ruby shellacs
The preparation of A component: 95 parts of epoxy E-51 resins, 5 parts of epoxy propane butyl ethers are stirred well to evenly, leave standstill, and can use.
The preparation of B component; 25.4 part diethylenetriamine, 74.6 parts of epoxy propane butyl ethers after finishing, add 2 parts of triethylamines again, place three strength flasks to heat, and temperature is controlled at about 60 ℃, and fully stir 10 hours reaction times.
The technical indicator of A component, B component:
Limpid in sight, transparent, water-white
Viscosity (25 ℃, CPS): A component＜500, B component＜350
Proportion (g/cm
3): A component 1.02～1.05, B component 0.97～0.99
Join glue and moulding:
1. join the preparation before the glue: used container in the time of will joining glue, cleaning is dry, mixes up the weighing balance, label cleaning surfaces, drying.As temperature (＜10 ℃) on the low side, should preheating in baking oven (30～35 ℃) half an hour, join glue again.
2. join glue with A component and B component, by weight 100 than weighing up the same container of back injection, stir, static 1 hour (＜30 ℃) were to 2 hours (below 25 ℃ time).When if temperature is lower than 10 ℃, can be in baking oven (40 ℃) preheating 20 minutes, use after taking out static half an hour.The viscosity of glue increases in time.
3. application will be controlled the glue after the viscosity, evenly drop on the label with small beaker or syringe, and edge can stir with little pin, makes glue be uniformly coated on the surface.
4. the label after static gel coats should static its gel that makes, and the time is more than 25 ℃ 3 hours, below 20 ℃ 4 hours to 5 hours.
5. condition of cure room temperature 24 hours (25 ℃)～36 hours
43 ℃ 12 hours～18 hours
60 ℃ of 43 ℃ of conditions of cure of suggestion 2 hours 1 hour
Note thing top: A, sizing material answered weighing accurate when the B component was mixed, and weight ratio such as pressed and mixed, join what how much used.Excessive glue is mixing above 6 hours gels that promptly lost efficacy, and it is all invalid to add other any thinners.Batch mixes can not add other thinners, in order to avoid produce bubble and reduce intensity.
Storage requirement:
1, storage at should keep cool place, ventilation, dry, stow away from heat, and ruby shellac is not being opened under the situation of lid, and be 1 year storage period below 25 ℃.
2, unnecessary mixed A, B component can not be poured in A or the B component, in order to avoid make it to lose efficacy.
The cured article index
| Outward appearance | The water white transparency elastomerics |
| Free monomer content | ????＜0.8％ |
| Bubble | There is not obvious bubble |
| Transmittance | ＞90% (visible-range) |
| Stripping strength | With metal, paper substrates bonding＞1.5KN/cm 2 |
| Intensity (25 ℃ of Shao Shi) | ????35-45℃ |
Embodiment 3: the printed board packaging plastic.
The preparation of A component, 97 parts of 618 epoxy resins, 3 parts of epoxy propane butyl ethers are stirred well to evenly, leave standstill, and can use.
The preparation of B component: 35.4 parts of positive hexanediamines, 64.6 parts of butyl acrylates after finishing, add 2 parts of triethylamines again, place three strength flasks to heat, and temperature is controlled at about 70 ℃, and fully stir 12 hours reaction times.
Limpid in sight, transparent, little Huang
Viscosity (25 ℃, CPS): A component＜300, B component＜250
Proportion (g/cm
3): A component 0.98～1.05, B component 0.98～1.05
Volume specific resistance (Ω cm) A component＞10
10, B component 1.5～2.0 * 10
9
Join glue and moulding:
1. join glue: correct weighing A component and B component, inject same clean container, stir, until evenly, preheating 20 minutes in 30 ℃ of baking ovens then.
2. mould: cast generally should be carried out in mould, and mould can be made of metallic substance such as steel or aluminium.Should be smooth as far as possible, smooth with the sizing material contact position, can improve the smooth finish of pouring piece.Before the cast, should apply supporting releasing agent one to two time, and standby after half an hour 100 ℃ of bakings.
3. cast: the end that should note printed board in the cast injects, and should there be venting hole at another place, avoids colloid to wrap up in the air inlet bubble, influences outward appearance and quality.
4. condition of cure: room temperature 2 days
45 ℃ 18 hours
60 ℃ 6 hours
5. some explanation: in most cases the curing quality is better under 60 ℃ of temperature, and this temperature is less to making sheet and components and parts influence, can improve the ratio of first-grade products, can enhance productivity simultaneously.In addition, this solf seal adhesive also can be used for the encapsulation of (＜500 volts) on some other low voltage electrical equipment, can improve the reliability that electrical equipment uses, can cut with a knife out simultaneously, change or the detection components and parts, avoid improper, cause the shortcoming of scrapping after the cast because of printed board processing before pouring into a mould.
Storage requirement:
Solf seal adhesive should be adorned in the vinyon bucket of dry seal, and it is shady and cool, dry that storage at should keep, and be 1 year storage period in the time of 25 ℃.
Soft surface encapsulation glue technical indicator:
Color and luster: limpid, transparent, little Huang.
Proportion: 1.05g/cm
3
Shore hardness: 35 °～45 °
Specific inductivity: 4.28～4.90
Dielectric loss factor: 0.08～0.105
Volume specific resistance:＞10
3Ω cm
Claims (11)
1, it is formulated by Resins, epoxy, epoxide diluent, release agent, toughner that a kind of preparation method of epoxies two-component-type transparent soft glue, feature of the present invention are the A components, and proportioning is:
Material name weight %
Resins, epoxy 85-95
Epoxide diluent 5-15
Release agent 0-1
Toughner 0-10
The calculation formula of A component oxirane value E:
E＝C
1E
1＋C
2E
2＋……
E in the formula
1, E
2... be respectively the oxirane value of used various Resins, epoxy and epoxide diluent in the A component, C
1, C
2Be respectively the various Resins, epoxy of used correspondence in the A component and weight fraction, the C of epoxide diluent
1+ C
2=1;
The B component is formed by solidifying agent, properties-correcting agent, catalyst preparation, and proportioning (weight ratio) is: (solidifying agent+properties-correcting agent): catalyzer=1: 0.005-0.05:
If A component and B component are with W
A: W
BThe weight ratio preparation, then solidifying agent is 1 with the stoichiometric coefficient ratio of epoxide diluent: y, y calculates with following formula:
W
B[(N－Y)/(M
1＋yM
2)]×100＝W
A×E
In the formula: N is the reactive hydrogen number in the organic amine curing agent molecule
Y is the stoichiometric coefficient of epoxide diluent in the B component
M
1Molecular weight for organic amine curing agent
M
2Molecular weight for epoxide diluent in the B component
E is the oxirane value in the A component,
The preparation of soft glue and moulding: A component, B component should put together stirring then respectively through preheating, then through vacuum defoamation, leave standstill, and system viscosity is 10
2-10
4CPS seals stand-byly, during use the soft glue for preparing is coated on material surface or uses die casting, gets final product through room temperature or middle cryodrying.
2, preparation method as claimed in claim 1, it is characterized in that used Resins, epoxy can be with alicyclic ring or aromatic epoxy resin, also available novolac epoxy, phenol formaldehyde Resins, epoxy, also available aliphatic Resins, epoxy, the oxirane value of requirement are 0.03-0.6 equivalent/100g, for the thick liquid epoxy, viscosity is: in the time of 25 ℃, more than the 6000CPS, for solids epoxy, softening temperature is less than 150 ℃.
3, preparation method as claimed in claim 1, it is characterized in that used epoxide diluent epoxy available propane alkyl oxide, propylene oxide aryl ethers, requiring oxirane value is 0.3-1.30 equivalent/100g, and viscosity is: in the time of 25 ℃, less than 10CPS, boiling range is greater than 110 ℃.
4, preparation method as claimed in claim 1 is characterized in that used release agent can be with organosilyl monomeric ester class.
5, preparation method as claimed in claim 1 is characterized in that used toughner can use α, ε dibasic alcohol, also available polyvalent alcohol, also available various softening agent.
6, preparation method as claimed in claim 1 is characterized in that used solidifying agent can use fatty amine, also available arylamine class or imidazoles.
7, preparation method as claimed in claim 1 is characterized in that used catalyzer can use aliphatic tertiary amine, alicyclic tertiary amine, aromatic series tertiary amine class.
8, preparation method as claimed in claim 1 is characterized in that properties-correcting agent epoxy available thinner used in the B component, described in claim 3, and also available alkene esters of gallic acid.
9, preparation method as claimed in claim 1 is characterized in that the preparation technology of A component measures by proportioning for various raw materials, at room temperature stirs.
10, preparation method as claimed in claim 1, the preparation technology who it is characterized in that the B component is that various raw materials are by the proportioning weighing, can adopt under agitation condition solidifying agent to add in the properties-correcting agent, or properties-correcting agent adds in the solidifying agent, dropwise the back and add catalyzer, temperature of reaction 15-70 ℃ reaction times 10-24 hour.
11, preparation method as claimed in claim 1, it is characterized in that the preparation and the moulding of soft glue, the preheating temperature 25-35 of A component, B component ℃, 20-30 minute warm up time, A, B component put together and stirred vacuum defoamation 20 minutes, vacuum tightness 700mmHg during deaeration 5-10 minute, left standstill 20 minutes, drying temperature is less than 50 ℃ during moulding.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN90102866A CN1033982C (en) | 1990-05-28 | 1990-05-28 | Production of transparent solf seal adhesive with epoxy double component |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN90102866A CN1033982C (en) | 1990-05-28 | 1990-05-28 | Production of transparent solf seal adhesive with epoxy double component |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1056887A CN1056887A (en) | 1991-12-11 |
| CN1033982C true CN1033982C (en) | 1997-02-05 |
Family
ID=4877749
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN90102866A Expired - Fee Related CN1033982C (en) | 1990-05-28 | 1990-05-28 | Production of transparent solf seal adhesive with epoxy double component |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1033982C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100446953C (en) * | 2005-01-28 | 2008-12-31 | 赵启林 | Epoxy resin and flyash composite plastes and forming method thereof |
| CN102181043B (en) * | 2011-03-23 | 2012-10-24 | 吴江固德电材系统股份有限公司 | latent curing agent with multiple storage stability |
| CN102363722B (en) * | 2011-10-17 | 2012-12-19 | 山东同大镍网有限公司 | Water-soluble insulating cement, cylinder fetal membrane with application of insulating cement and preparation method thereof |
| CN104087124B (en) * | 2014-07-25 | 2017-05-03 | 厦门双瑞船舶涂料有限公司 | Phenol aldehyde epoxy paint with chemical medium resistance and preparation method thereof |
| CN105958169A (en) * | 2016-05-31 | 2016-09-21 | 安徽省瑞洋通讯设备有限公司 | Method for using closing glue to close double-frequency circuit breaker cavity port |
| CN107185506A (en) * | 2017-07-12 | 2017-09-22 | 诺圆环保科技（苏州）有限公司 | Inhale color chips aftertreatment technology |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4225479A (en) * | 1979-07-30 | 1980-09-30 | Celanese Corporation | Cationic epoxide-amine reaction products |
| EP0245559A2 (en) * | 1985-11-26 | 1987-11-19 | Loctite Corporation | Two component curable epoxy resin composition having a long pot life |
| US4769400A (en) * | 1983-04-09 | 1988-09-06 | Basf Farben + Fasern Ag | Heat-curable binder mixture |
-
1990
- 1990-05-28 CN CN90102866A patent/CN1033982C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4225479A (en) * | 1979-07-30 | 1980-09-30 | Celanese Corporation | Cationic epoxide-amine reaction products |
| US4769400A (en) * | 1983-04-09 | 1988-09-06 | Basf Farben + Fasern Ag | Heat-curable binder mixture |
| EP0245559A2 (en) * | 1985-11-26 | 1987-11-19 | Loctite Corporation | Two component curable epoxy resin composition having a long pot life |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1056887A (en) | 1991-12-11 |
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