CN105524585B - A kind of adhesive and its preparation method and application - Google Patents
A kind of adhesive and its preparation method and application Download PDFInfo
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- CN105524585B CN105524585B CN201410679674.9A CN201410679674A CN105524585B CN 105524585 B CN105524585 B CN 105524585B CN 201410679674 A CN201410679674 A CN 201410679674A CN 105524585 B CN105524585 B CN 105524585B
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Abstract
The invention provides a kind of adhesive and preparation method thereof, the composition and percentage by weight of the adhesive are as follows：TPU 25 45%；Hydroxylated acrylic resin 8% 30%；Isocyanate curing agent 4% 6%；Diluent 30 50%；Auxiliary agent 1 5%.The invention provides the adhesive as binding agent between moulding and inserts application.The adhesive that the present invention is provided, is suitably selected by its component, obtains a gluing agent prescription with bonds well ability.By being directly pre-coated with the adhesive, in insert surface, to be subsequently molded again, it is ensured that form good bonding between inserts and moulding surface, and technique is greatly simplified.
Description
Technical field
The invention belongs to field of chemical preparation, more particularly to a kind of adhesive and its preparation method and application.
Background technology
In traditional handicraft, insert injection moulding typically by making buckle on inserts, is then molded again, makes inserts with rear injection
Mechanical bond between plastic cement by buckle is combined closely so as to be formed, it is ensured that bonding strength therebetween.And made on inserts
Structural member being applied to the method for making buckle, because its various buckle structure, handling ease deformation is not suitable for appearance member more.
In the prior art, also have using fine and closely woven micropore treatment is carried out to insert surface in advance, increase inserts and rear moulding
Between contact area so that post processing plastic cement and metal between form stronger adhesion.And insert surface is entered in advance
The fine and closely woven micropore treatment of row, its preprocessing process is complicated, and because the micropore very little of its formation is, it is necessary to the flowing of the plastic cement of rear injection
Property very well, it is narrower to the plastic cement of rear injection selection face, cause it to be used widely.
Therefore, a kind of method that contact forces are good and technique simplifies for seeking energy inserts and moulding simultaneously turns into when business
It is anxious.
The content of the invention
The present invention solve present in prior art after insert surface injection can not and meanwhile ensure inserts and moulding it
Between the technical problem that simplifies of good combination power and technique.
The invention provides a kind of adhesive, the composition and percentage by weight of the adhesive are as follows：
TPU 25-45%；
Hydroxylated acrylic resin 8%-30%；
Isocyanate curing agent 4%-6%；
Diluent 30-50%；
Auxiliary agent 1-5%.
Present invention also offers the preparation method of the adhesive, including after each component is mixed in proportion, it is uniformly dispersed,
Obtain the adhesive.
Finally, the invention provides the adhesive as binding agent between moulding and inserts application.
The adhesive that the present invention is provided, is suitably selected by its component, and obtaining one has bonds well ability
Gluing agent prescription, and injection of the plastic cement on inserts can be realized, be directly pre-coated with insert surface by by the adhesive,
Subsequently it is molded again, it is ensured that good bonding is formed between inserts and moulding surface, and technique is greatly simplified.
Specific embodiment
In order that technical problem solved by the invention, technical scheme and beneficial effect become more apparent, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to explain
The present invention, is not intended to limit the present invention.
Specifically, the invention provides a kind of adhesive, the composition and percentage by weight of the adhesive are as follows：
TPU 25%-45%；
Hydroxylated acrylic resin 8%-30%；
Isocyanate curing agent 4%-6%；
Diluent 30%-50%；
Auxiliary agent 1%-5%.
The adhesive that the present invention is provided, is suitably selected by its component, and obtaining one has bonds well ability
Gluing agent prescription, and injection of the plastic cement on inserts can be realized, be directly pre-coated with insert surface by by the adhesive,
Subsequently it is molded again, it is ensured that good bonding is formed between inserts and moulding surface, and technique is greatly simplified.
The present inventor has found that the formula of the adhesive is in following preferred content scope by further experiment
Within when, its cementitiousness is more preferably：
TPU 30%-40%；
Hydroxylated acrylic resin 15%-20%；
Isocyanate curing agent 4%-6%；
Diluent 30%-40%；
Auxiliary agent 2%-4%.
In the present invention, the TPU is thermoplastic resin, i.e., it is the polyurethane resin of non-crosslinked type,
Reactive functional groups are not contained.After the TPU thermal spraying, cooling is capable of achieving solidification.Specifically, this hair
In bright, the glass transition temperature Tg of the TPU is 60-150 DEG C, more preferably 80-120 DEG C.The hydroxyl third
The hydroxyl value of olefin(e) acid resin is 65-120 KOHmg/g, more there is preferably 75-110 KOHmg/g.
The various isocyanates curing agent that the isocyanate curing agent is commonly used for those skilled in the art, for example can be with
Selected from toluene di-isocyanate(TDI)（TDI）, hexamethylene diisocyanate, isoflurane chalcone diisocyanate, 4,4 '-diphenyl methane
Diisocyanate（MDI）, one or more in XDI, but be not limited to this.
The various organic solvents that the diluent is commonly used for those skilled in the art, for example, can be selected from dimethylbenzene, methyl
One or more in isobutyl ketone, butyl glycol ether, butyl acetate, cyclohexanone, butanone, ethyl acetate, but it is not limited to this.
Under preferable case, in the present invention, the diluent is dimethylbenzene, methyl iso-butyl ketone (MIBK), butyl glycol ether, butyl acetate, hexamethylene
The mixed system of ketone, butanone.In the case of more preferably, in foregoing mixed system, the mass ratio of each component is 5:5:1:1:5:1.
The auxiliary agent is various auxiliary agents common in the art, including but not limited to defoamer, levelling agent.Wherein,
Defoamer is used to remove the bubble in adhesive, increases the bonding force between inserts and moulding.And levelling agent is then conducive to glue
Levelling of the glutinous agent in insert surface.In the case of more preferably, on the basis of the gross mass of the adhesive, the wherein content of defoamer
1 ~ 3wt%, the content of levelling agent is 1 ~ 2wt%.
The present inventor passes through further experiment and has been surprisingly found that, using titanium dioxide in the adhesive that the present invention is provided
During silicon, the bonding force between inserts and moulding can be further improved.It has been recognised by the inventors that this is due to adding dioxy in adhesive
In SiClx, after being coated insert surface, due to the presence of silica, the roughness of insert surface can be increased, so that can
Increase the contact area between inserts and rear moulding so that the bonding force enhancing between inserts and moulding.In addition, titanium dioxide
Silicon can also improve adhesive intensity in itself, so as to ensure combining closely for inserts and moulding.Under preferable case, with the glue
On the basis of the gross mass of glutinous agent, the content of silica is 5%-10%, more preferably 5%-8% in the adhesive.Inventor enters
One step finds that, when silica preferably uses nanometer grade silica, the bonding force between inserts and moulding is higher.Cause
This, in the present invention, the average grain diameter of the silica is preferably 0.1-30 μm.
The gluing agent prescription that the present invention is provided is simple, it is easy to prepare.Specifically, the invention provides the preparation of the adhesive
Method, including after each component is mixed in proportion, be uniformly dispersed, you can obtain the adhesive.The dispersion steps can be used
High speed dispersor is carried out.
It is dispersed in adhesive for ease of the TPU in the present invention, under preferable case, can
First TPU is scattered in polyurethane solutions are configured in diluent, then toward adding hydroxyl in the polyurethane solutions
Acrylic resin, isocyanate curing agent and auxiliary agent, are eventually adding silica.In the case of more preferably, polyurethane is being prepared
During solution, can also be heated, for example, be placed in infrared baking oven and heated, but be not limited to this.After the completion of heating also
Decentralized processing can be carried out using high speed dispersion agent.Finally, the invention provides the adhesive as between moulding and inserts
The application of binding agent.
As it was previously stated, between inserts and moulding by snapping connection when, buckle structure is various, and inserts is easily deformed,
And inserts is surface-treated to increase the contact area of the two, complicated process steps and injection moulding plastic species is limited, not
Can be used widely.Therefore, the invention provides a kind of adhesive of new formulation, it can be realized between inserts and moulding
Bonds well.
Specifically, cleaning treatment first can be carried out to insert surface, the adhesive of present invention offer is provided, treat the gluing
The injection step of moulding can be carried out after agent solidification, the inserts-note with good binding agent can be obtained after the completion of injection
Plastic combination product.
The adhesive provided using the present invention realizes the bonds well between inserts and moulding, and it need not enter to inserts
The complicated machining of row and surface micropore treatment, the flatness of one side guarantee inserts, another aspect high working efficiency, and it is right
The plastic cement species of follow-up injection is not limited, and can obtain extensive use.
In the present invention, the inserts can be glass, or metal, and other various need to carry out surface injection
Treat moulding, the present invention is not particularly limited.
Explanation is further explained to the present invention by the following examples.Raw material passes through employed in embodiment and comparative example
It is commercially available, the present invention is not particularly limited.
Embodiment 1
The formula of the adhesive S1 of the present embodiment is：Tg is 80 DEG C of TPU 40%；Hydroxy acrylic acid
Resin（Hydroxyl value is 110 KOHmg/g） 18% ；MDI curing agent 4%；Silica（Average grain diameter is 7 μm） 5%；Auxiliary agent（Disappear
Infusion） 3%；Diluent 30%, foregoing content is weight/mass percentage composition.
Wherein, diluent is dimethylbenzene, methyl iso-butyl ketone (MIBK), butyl glycol ether, butyl acetate, cyclohexanone, butanone by matter
Amount is than being 5:5:1:1:5:1 mixed system.
Its manufacture craft is：（1）TPU is placed in 8h is soaked in diluent, be then placed in infrared baking oven
0.5h is heated at interior 60 DEG C, 0.5h is stirred with the rotating speed of 1000r/min on high speed dispersor afterwards, obtain polyurethane solutions；
（2）Hydroxylated acrylic resin, MDI curing agent and auxiliary agent are added toward foregoing polyurethane solutions, and is continued on high speed dispersor
0.5h is stirred with the rotating speed of 1500r/min, silica is added while stirring, obtain the adhesive of the present embodiment, be designated as S1.
Embodiment 2
The formula of the adhesive S2 of the present embodiment is：Tg is 80 DEG C of TPU 30%；Hydroxy acrylic acid
Resin（Hydroxyl value is 110 KOHmg/g） 25% ；TDI curing agent 6%；Silica（Average grain diameter is 3 μm） 6%；Auxiliary agent（Stream
Flat agent） 1%；Diluent 32%, foregoing content is weight/mass percentage composition.
Wherein, diluent is dimethylbenzene, methyl iso-butyl ketone (MIBK), butyl glycol ether, butyl acetate, cyclohexanone, butanone by matter
Amount is than being 5:5:1:1:5:1 mixed system.
Its manufacture craft is：TPU is placed in 8h is soaked in diluent, be then placed in infrared baking oven
0.5h is heated at 60 DEG C, 0.5h is stirred with the rotating speed of 1000r/min on high speed dispersor afterwards, obtain polyurethane solutions；（2）
Add Hydroxylated acrylic resin, MDI curing agent and auxiliary agent toward foregoing polyurethane solutions, and continue on high speed dispersor with
The rotating speed stirring 0.5h of 1500r/min, adds silica while stirring, obtain the adhesive of the present embodiment, is designated as S2.
Embodiment 3
The formula of the adhesive S3 of the present embodiment is：Tg is 120 DEG C of TPU 34%；Hydroxy acrylic acid
Resin（Hydroxyl value is 75 KOHmg/g） 20% ；MDI curing agent 5%；Silica（Average grain diameter is 15 μm） 8%；Auxiliary agent：Disappear
Infusion 2%+ levelling agents 1%；Diluent 30%, foregoing content is weight/mass percentage composition.
Wherein, diluent is dimethylbenzene, methyl iso-butyl ketone (MIBK), butyl glycol ether, butyl acetate, cyclohexanone, butanone by matter
Amount is than being 5:5:1:1:5:1 mixed system.
Its manufacture craft is：TPU is placed in 8h is soaked in diluent, be then placed in infrared baking oven
0.5h is heated at 60 DEG C, 0.5h is stirred with the rotating speed of 1000r/min on high speed dispersor afterwards, obtain polyurethane solutions；（2）
Add Hydroxylated acrylic resin, MDI curing agent and auxiliary agent toward foregoing polyurethane solutions, and continue on high speed dispersor with
The rotating speed stirring 0.5h of 1500r/min, adds silica while stirring, obtain the adhesive of the present embodiment, is designated as S3.
Embodiment 4
The formula of the adhesive S4 of the present embodiment is：Tg is 90 DEG C of TPU 25%；Hydroxy acrylic acid
Resin（Hydroxyl value is 95 KOHmg/g） 30% ；MDI curing agent 5%；Silica（Average grain diameter is 7 μm） 4%；Auxiliary agent（Disappear
Infusion） 1%；Diluent 35%, foregoing content is weight/mass percentage composition.
Wherein, diluent is that methyl iso-butyl ketone (MIBK), butyl glycol ether, butyl acetate, cyclohexanone are 5 in mass ratio:1:1:
2 mixed system.
Its manufacture craft is：TPU is placed in 8h is soaked in diluent, be then placed in infrared baking oven
0.5h is heated at 60 DEG C, 0.5h is stirred with the rotating speed of 1000r/min on high speed dispersor afterwards, obtain polyurethane solutions；（2）
Add Hydroxylated acrylic resin, MDI curing agent and auxiliary agent toward foregoing polyurethane solutions, and continue on high speed dispersor with
The rotating speed stirring 0.5h of 1500r/min, adds silica while stirring, obtain the adhesive of the present embodiment, is designated as S4.
Embodiment 5
The formula of the adhesive S5 of the present embodiment is：Tg is 90 DEG C of TPU 45%；Hydroxy acrylic acid
Resin（Hydroxyl value is 75 KOHmg/g） 8% ；MDI curing agent 6%；Silica（Average grain diameter is 7 μm） 4%；Auxiliary agent（Froth breaking
Agent） 2%；Diluent 35%, foregoing content is weight/mass percentage composition.
Wherein, diluent is that dimethylbenzene, butyl glycol ether, butyl acetate, butanone are 5 in mass ratio:1:1:3 mixture
System.
Its manufacture craft is：（TPU is placed in 8h is soaked in diluent, be then placed in infrared baking oven
0.5h is heated at 60 DEG C, 0.5h is stirred with the rotating speed of 1000r/min on high speed dispersor afterwards, obtain polyurethane solutions；（2）
Add Hydroxylated acrylic resin, MDI curing agent and auxiliary agent toward foregoing polyurethane solutions, and continue on high speed dispersor with
The rotating speed stirring 0.5h of 1500r/min, adds silica while stirring, obtain the adhesive of the present embodiment, is designated as S5.
Embodiment 6
The formula of the adhesive S6 of the present embodiment is：Tg is 90 DEG C of TPU 35%；Hydroxy acrylic acid
Resin（Hydroxyl value is 75 KOHmg/g） 18% ；MDI curing agent 5%；Auxiliary agent（Defoamer） 2%；Diluent 40%, foregoing content
It is weight/mass percentage composition.
Wherein, diluent is dimethylbenzene, methyl iso-butyl ketone (MIBK), butyl glycol ether, butyl acetate, cyclohexanone, ethyl acetate
In mass ratio it is 5:5:1:1:5:1 mixed system.
Its manufacture craft is：TPU is placed in 8h is soaked in diluent, be then placed in infrared baking oven
0.5h is heated at 60 DEG C, 0.5h is stirred with the rotating speed of 1000r/min on high speed dispersor afterwards, obtain polyurethane solutions；（2）
Add Hydroxylated acrylic resin, MDI curing agent and auxiliary agent toward foregoing polyurethane solutions, and continue on high speed dispersor with
The rotating speed stirring 0.5h of 1500r/min, adds silica while stirring, obtain the adhesive of the present embodiment, is designated as S6.
Comparative example 1
Directly it is designated as the adhesive of this comparative example using the 025GT of the beautiful China of common finished product adhesive on the market
DS1。
Comparative example 2
The formula of the adhesive DS2 of this comparative example is：Tg is 90 DEG C of TPU（ 50%；Hydroxy
Acid resin（Hydroxyl value is 75 KOHmg/g） 20% ；MDI curing agent 4%；Auxiliary agent（Defoamer） 1%；Diluent 25%, it is foregoing to contain
It is weight/mass percentage composition to measure.
Wherein, diluent is dimethylbenzene, methyl iso-butyl ketone (MIBK), butyl glycol ether, butyl acetate, cyclohexanone, butanone by matter
Amount is than being 5:5:1:1:5:1 mixed system.
Its manufacture craft is：TPU is placed in 8h is soaked in diluent, be then placed in infrared baking oven
0.5h is heated at 60 DEG C, 0.5h is stirred with the rotating speed of 1000r/min on high speed dispersor afterwards, obtain polyurethane solutions；（2）
Add Hydroxylated acrylic resin, MDI curing agent and auxiliary agent toward foregoing polyurethane solutions, and continue on high speed dispersor with
The rotating speed stirring 0.5h of 1500r/min, adds silica while stirring, obtain the adhesive of this comparative example, is designated as DS2.
Comparative example 3
The formula of the adhesive DS3 of this comparative example is：Tg is 90 DEG C of TPU 20%；Hydroxy acrylic acid
Resin（Hydroxyl value is 75 KOHmg/g） 30% ；MDI curing agent 6%；Silica（Average grain diameter is 7 μm） 10%；Auxiliary agent（Disappear
Infusion） 4%；Diluent 30%, foregoing content is weight/mass percentage composition.
Wherein, diluent is dimethylbenzene, methyl iso-butyl ketone (MIBK), butyl glycol ether, butyl acetate, cyclohexanone, butanone by matter
Amount is than being 5:5:1:1:5:1 mixed system.
Its manufacture craft is：TPU is placed in 8h is soaked in diluent, be then placed in infrared baking oven
0.5h is heated at 60 DEG C, 0.5h is stirred with the rotating speed of 1000r/min on high speed dispersor afterwards, obtain polyurethane solutions；（2）
Add Hydroxylated acrylic resin, MDI curing agent and auxiliary agent toward foregoing polyurethane solutions, and continue on high speed dispersor with
The rotating speed stirring 0.5h of 1500r/min, adds silica while stirring, obtain the adhesive of this comparative example, is designated as DS3.
Performance test
Cleaning glass substrate surface, then sprays beauty China EP-501PT as primer respectively in the glass substrate surface,
Adhesive S1-S6 and DS1-DS3 are sprayed again after primer solidification, glue solidification is baked to, and then there is solidification glue in glass baseplate
One surface of liquid is molded, and obtains glass-plastic cement composite members, and S10-S60 and DS10-DS30 is designated as respectively.
Cleaning aluminum alloy substrate surface, then sprays beauty China EP-501PT the bottom of as respectively on the aluminum alloy base material surface
Glue, adhesive S1-S6 and DS1-DS3 are sprayed after primer solidification again, are baked to glue solidification, are then had in aluminum alloy base material solid
A surface for changing glue is molded, and obtains aluminium alloy-plastic cement composite members, and S11-S66 and DS11-DS33 is designated as respectively.
（1）Pull-out test
By tool be assemblied in plug force tester vice on, then by foregoing glass-plastic cement composite members S10-S60,
DS10-DS30 and aluminium alloy-plastic cement composite members S11-S66, DS11-DS33 are sandwiched in tool respectively, with the speed of 10mm/min
Carry out drawing, maximum, force when record product is broken.Test result is as shown in table 1.
（2）Shearing test
Using plug force tester, clamping foregoing glass-plastic cement composite members S10-S60, DS10-DS30 and aluminium are closed respectively
Two of gold-plastic cement composite members S11-S66, DS11-DS33, carries out drawing, when record product is broken with the speed of 10mm/min
Maximum, force.Test result is as shown in table 1.
Table 1
。
By upper table 1 as can be seen that the adhesive S1-S6 that provides of the present invention is between glass and plastic cement and aluminium alloy
Good cementitiousness is respectively provided between plastic cement, hence it is evident that better than the adhesive sample DS1-DS3 in comparative example.
Presently preferred embodiments of the present invention is the foregoing is only, is not intended to limit the invention, it is all in essence of the invention
Any modification, equivalent and improvement made within god and principle etc., should be included within the scope of the present invention.
Claims (11)
1. a kind of adhesive, it is characterised in that the composition and percentage by weight of the adhesive are as follows：
Wherein, the glass transition temperature Tg of the TPU is 60 DEG C -150 DEG C；The Hydroxylated acrylic resin
Hydroxyl value is 65-120KOHmg/g.
2. adhesive according to claim 1, it is characterised in that the composition and percentage by weight of the adhesive are as follows：
3. adhesive according to claim 1 and 2, it is characterised in that described on the basis of the gross mass of the adhesive
The also silica containing 5%-10% in adhesive.
4. adhesive according to claim 3, it is characterised in that the average grain diameter of the silica is 0.1-30 μm.
5. adhesive according to claim 1, it is characterised in that the isocyanate curing agent is selected from toluene diisocynate
Ester, hexamethylene diisocyanate, isoflurane chalcone diisocyanate, 4,4 '-methyl diphenylene diisocyanate, phenylenedimethylidyne
One or more in diisocyanate.
6. adhesive according to claim 1, it is characterised in that the diluent be selected from dimethylbenzene, methyl iso-butyl ketone (MIBK),
One or more in butyl glycol ether, butyl acetate, cyclohexanone, butanone.
7. adhesive according to claim 1, it is characterised in that the auxiliary agent is selected from the one kind in defoamer, levelling agent
Or two kinds.
8. the preparation method of the adhesive described in claim 1, including after each component is mixed in proportion, be uniformly dispersed, obtain
The adhesive.
9. the adhesive described in claim 1 as binding agent between moulding and inserts application.
10. the application according to its profit requires 9, the inserts is glass.
11. application according to its profit requires 9, the inserts is metal.
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| CN201410679674.9A CN105524585B (en) | 2014-11-24 | 2014-11-24 | A kind of adhesive and its preparation method and application |
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| CN105524585B true CN105524585B (en) | 2017-07-04 |
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| CN107033792A (en) * | 2016-11-25 | 2017-08-11 | 启东市百汇机械制造有限公司 | One kind is used for machinery labeling adhesive |
| CN107987249B (en) * | 2017-12-06 | 2020-11-13 | 中国建筑材料科学研究总院有限公司 | Polycarbonate and polymethyl methacrylate laminated adhesive resin, preparation method and application thereof |
| CN110885661B (en) * | 2019-11-22 | 2022-05-24 | 江西奇信集团股份有限公司 | Stone back adhesive and preparation method thereof |
| CN111231405B (en) * | 2020-03-02 | 2022-01-04 | 东莞协旺彩印有限公司 | Cosmetic packaging box and preparation method thereof |
| CN111484797B (en) * | 2020-04-30 | 2021-10-22 | 上海嘉宝莉涂料有限公司 | Hydroxy acrylic resin material composition and preparation method and application thereof |
| CN113963842A (en) * | 2021-10-13 | 2022-01-21 | 瑞安复合材料(深圳)有限公司 | High partial discharge insulating material for oil-cooled motor and preparation method thereof |
| CN114536886A (en) * | 2022-01-05 | 2022-05-27 | 深圳市信维通信股份有限公司 | Soft-packing rubber injection molding process and metal part |
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