CN102516572A - Bonding method of crystalline resin molding - Google Patents
Bonding method of crystalline resin molding Download PDFInfo
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- CN102516572A CN102516572A CN2011103552236A CN201110355223A CN102516572A CN 102516572 A CN102516572 A CN 102516572A CN 2011103552236 A CN2011103552236 A CN 2011103552236A CN 201110355223 A CN201110355223 A CN 201110355223A CN 102516572 A CN102516572 A CN 102516572A
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- bonding
- molding
- caking agent
- resin
- impregnated
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Abstract
The invention provides a bonding method of crystalline resin molding, At the bonding between crystalline resin moldings with each other or between the crystalline resin molding and other member with a thermally curable adhesive, the curing treatment of the adhesive is executed after the process for penetrating a bonding component into the bonding surface of the molding or simultaneously with the penetrating process.
Description
The application is to be on 06 18th, 2008, application number the dividing an application for the application of " adhering method of crystalloid resin forming body " that be 200810125714.X, denomination of invention the applying date.
Technical field
The present invention relates to be used to utilize the adhering method of the bonding difficult cementability crystalline resin of Thermocurable caking agent.
Background technology
Polyacetal resin (POM), polybutylene terephthalate resin (PB T), polyphenylene sulfide (PP S) are because mechanical properties, electrical property and other physics-chem characteristic are excellent; And processibility is good; Therefore be generically and collectively referred to as engineering plastics, be used for extensive uses such as automobile, electrical and electronic parts.This POM, PBT, PPS can be used for various molding separately, and be different according to utilizing the field, in order to improve its character, particularly mechanical properties, cooperates the improvement of various compositions such as various reinforcers, additive and be widely used.But; The bonding strength of POM, PBT, PPS and other resin, the particularly bonding strength with epoxy resin are lower; Therefore the engaging of the molding that for example to utilize epoxy be between the POM, PBT, PPS molding of caking agent or these moldinies and other material constitute, or when utilizing the sealing etc. of electrical and electronic parts of epoxy resin, the bonding strength that is used for POM, PBT, PPS molding and the epoxy resin of cabinet etc. is hanged down and is often become problem.As the method that addresses these problems; Though inquired into POM, PBT, the polymkeric substance of PPS or upgrading or the improvement of caking agent or the optimization of adhering method of composition; But each method does not all obtain sufficient adhesion strength, has the problem of complex proceduresization etc.
Japanese kokai publication hei 5-177714 discloses when bonding PEEK (polyetheretherketone) resin and to have implemented after the plasma treatment etc.; Apply epoxy primer; Carry out bonding pretreatment process afterwards; But owing to must prepare in addition very many operations such as plasma processing apparatus and priming paint, so has the problem that needs facility investment or extra manpower.
"Plastic su チ boots black material, heavy Full payment of the payment and institutional Concerning ru Study" Paint Full study ("the plastic material of attachment gives mechanism research" Coatings) No.143? Apr.2005? P8-15 discloses a method in the polyolefin Plastic material (PP) is coated on the primer coating on which to display the film peeling strength, was observed in the primer penetrates into the PP material.This method is given material owing to adhering to according to combination selection the best of every kind of coating and material, prepared separately, therefore spends very much manpower and time, and is inefficent.
Summary of the invention
Problem of the present invention is to provide has the abundant bonding force and the method for bonding crystalloid resin forming body simply.
The inventor etc. further investigate in order to solve above-mentioned problem, and the result finds to be impregnated in the molding through bonding composition before caking agent solidifies, and can obtain higher bonding strength; Be impregnated between concentration and the bonding strength of bonding composition of molding bonding plane and have positive correlation.On the other hand, in the adhering method that in the past carries out, bonding composition soaks into only micro-ly, can't bring into play the performance of caking agent fully.Therefore, make bonding composition be impregnated into the operation of the bonding plane of molding through setting, than the adhering method that carries out usually, be impregnated in the molding to bonding composition high density, bonding strength increases substantially as a result.
The present invention provides and makes crystalloid resin forming body carry out the adhering method of crystalloid resin forming body of the solidification treatment of caking agent through following operation, and said operation is: under prescribed condition, molding impregnated in the uncured caking agent; Under prescribed condition with molding impregnated in the high solvent of the affinity of resinous principle that constitutes molding in; In caking agent, add the high operations such as solvent of affinity with the resinous principle that constitutes molding.
Promptly; The present invention is a kind of adhering method; It is characterized in that; Using between the bonding crystalloid resin forming body of Thermocurable caking agent or crystalloid resin forming body during with other parts, through after making bonding composition be impregnated into the operation of bonding plane of molding, or with make its operation of soaking into simultaneously, the solidification treatment of enforcement caking agent.
Description of drawings
The figure of the determining bonding strength Test condition that Fig. 1 carries out among the embodiment for expression.
Embodiment
Among the present invention, the employed crystalline resin of crystalloid resin forming body is difficult cementability crystalline resin, and preferred especially resin can be enumerated polyacetal resin, polybutylene terephthalate resin, polyphenylene sulfide etc.These resins have carried out the various countermeasures that are used to improve cementability such as effort that resin upgrading, prescription are formed, but according to the present invention, even if do not implement this countermeasure, bonding strength still can improve.In addition, implemented the resin material of this countermeasure through use, bonding strength further improves.
Crystalloid resin forming body as long as bonding plane can not reduce the effect of soaking into of bonding composition, then can be different shape or implemented processing.For example, can be the molding that utilizes through the Mold Making of gauffer processing or mirror finish, also can be molding through sandblasting, uviolizing, plasma treatment, chemical treatment etc.In addition, when being made into body, preferably die temperature is set in the temperature that is lower than typical temperature through injection forming etc.
As not having special qualification, can enumerate between this molding or be example as other high-molecular weight polymers of other parts, glass, metal, timber, fabric, paper, leather etc. with the bonding parts of crystalloid resin forming body.Metal is aluminium, iron etc., does not have special qualification.As high-molecular weight polymer, it is resin etc. that polyester based resin, polyamide-based resin, acrylic resin, phenylethylene resin series, phenolic aldehyde are arranged, and does not have special qualification.In addition, the form as these moldinies or other parts also is not limited to stereo structure, sheet, film like etc.
It is caking agent, silicone-based caking agent etc. that the Thermocurable caking agent that the present invention uses can be enumerated epoxy.
The Thermocurable caking agent is that curable resin (host) and solidifying agent, packing material appropriate combination are formed, when curable resin solidifies owing to heat with molding or other parts through chemical or physically combine to carry out bonding.Among the present invention bonding composition be meant this caking agent contained with solidify the relevant curable resin and the general name of solidifying agent.
When being caking agent for epoxy; For example can enumerate Thermocurable bisphenol A type epoxy resin as heat-curable epoxy resin, bisphenol f type epoxy resin, novolac epoxy resin, cresols novolac epoxy resin, alicyclic epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, NSC 9226 type epoxy resin, isocyanuric acid ester type epoxy resin, acrylic modified epoxy resin etc. as curable resin, be that caking agent can suitably use separately or combination is used according to epoxy.
In addition; Solidifying agent is the solidified material that can be used for epoxy resin, and for example can enumerate aliphatic amide is that solidifying agent, ester ring type amine are that solidifying agent, secondary amine or tertiary amine are that solidifying agent, aromatic amine are that solidifying agent, acid anhydrides are solidifying agent, Dyhard RU 100, boron trifluoride amine complex, imidazolium compounds etc.These materials can use separately, can also be also with more than 2 kinds.
In addition, the use level of solidifying agent is decided according to epoxy resin, and in the normally used scope of solidifying agent, suitably adjusts according to molding condition or characteristic etc.
Bonding pre-treatment of the present invention has at caking agent and under prescribed condition, molding not impregnated in bonding composition under the solidified condition; Specifically; When using the isolating 2 liquid type caking agents of host and solidifying agent, be meant in more than 60 ℃ molding being impregnated in more than 1 hour as the host of bonding composition or solidifying agent.About time of immersion; When the 1 liquid type caking agent that the 2 liquid type caking agents that use to mix host and solidifying agent or host and solidifying agent have been pre-mixed, be meant molding impregnated in more than 60 ℃ and below the solidification value of caking agent in the caking agent more than 1 hour.Here, the low or time of immersion of dipping temperature in short-term, host or solidifying agent are few to the amounts of saturation of molding, can't expect fully that bonding strength improves effect.When impregnated in host or solidifying agent, owing to can set dipping temperature higher, therefore bring into play dipping effect further, but bonding composition is because heat takes place to solidify or when going bad, can not bring into play and soak into effect, so should be noted that.In addition, when being mixed with host and solidifying agent, when setting dipping temperature than the highland, bonding composition solidifies earlier before fully soaking into, and therefore when making temperature too high, opposite treatment effect can reduce.Be necessary to keep not solidified state of bonding composition in the dipping.Through these bonding pre-treatment, bonding composition increases to the amounts of saturation of molding, is impregnated into the curing that reacts in the solidification process of the inner bonding composition of molding after caking agent applies, and therefore shows high bonding strength at the interface at molding/caking agent.
As other method that increases the amounts of saturation of caking agent in crystalloid resin forming body, have to use to be added with the organic solvent high and (to be 8J with the difference of the SP SP of crystalline resin with the affinity of crystalloid resin forming body
1/2/ cm
3/2Below) caking agent carry out bonding processing; Perhaps before bonding processing under prescribed condition with molding be immersed in the organic solvent high with the molding affinity (with the difference of the SP value of crystalline resin be 8J
1/2/ cm
3/2Below) in back method such as adhesive.
Through these methods; Same during with above-mentioned pre-treatment; Because the amounts of saturation of bonding composition in molding increases, is impregnated into the curing that in solidification process, reacts of the inner bonding composition of molding, thereby shows high bonding strength at the interface at molding/caking agent.Here, when using difference with the SP value of crystalline resin greater than 8J
1/2/ cm
3/2Organic solvent the time, the effect that the infiltration capacity of bonding composition in molding increases is few, the effect that improves of bonding strength is low as a result.
In addition, in the time must forming the anneal of article, preferably carrying out the laggard capable anneal of bonding processing.Because anneal obstruction caking agent soaks into to molding, therefore can not give full play to effect of the present invention, must prolong necessary above time of immersion or raising dipping temperature or solidification value in order to obtain necessary bonding strength.
Embodiment
Below through embodiment the present invention is described in further detail, but the present invention is not limited thereto.In addition, the measuring method of the bonding strength shown in the following example is described below.
Bonding strength
Handle: as shown in Figure 1, it is 2 sections that ASTM tension test sheet is blocked in centre, fully removes deburring.For the thickness with caking agent is adjusted to about 0.2mm, paste PTFE sheet material (NITOFLON adhesive tape 973UL day east electrician's system), making bond area is 1.3cm
2(the wide 1.3cm of test film * overlapping 1.0cm) carries out bonding.After using crocodile clip CP-104 (production of plus company) fixing, under the condition of cure of regulation, be cured.
Measure: measure tensile strength, with the tensile strength of per unit bond area as the tensile shear bonding strength.In addition, failure mode is as follows.
Cohesion failure: caking agent lost efficacy.
Interface peel: the generation unsticking at the interface between crystalloid resin forming body and caking agent (peeling off).
Tensile shear(ing) test (according to JIS K6850)
Machine: ORIENTEC Co., the Tensilon RTC-1325 trial speed 10mm/min that LTD produces
Adhering method: diagram (Fig. 1)
The swelling amount
Handle: sample at room temperature impregnated in the solvent 200 hours.After solvent impregnated, take out sample, gravimetry after removing the surface attachment solvent will be than increment part of the example weight before solvent impregnated as swelling amount (wt%)
Bonding composition amounts of saturation
Handle: remove the caking agent on the adhesive test postforming surface, every separated certain thickness (10 μ m) cuts out ultrathin section(ing) from the top layer to use the ultrathin section(ing) cutter.Use Py-GC/MS, every kind of molding kind is obtained bonding composition (in the situation of bisphenol A type epoxy resin, being the peak from the dihydroxyphenyl propane composition) the MS area in the ultrathin section(ing) as relative ratio respectively.
Machine: Py-GC/MS GC6890N/HS5975 (Agilent Technologies production)
Embodiment 1
Use DX 2002 (Polyplastics Co., Ltd.'s system, polybutylene terephthalate), use host XNR5002/ solidifying agent XNH5002 (Nagase ChemteX Corporation system) as molding as caking agent.As bonding pre-treatment, molding impregnated among the host XNR5002, flooded 1 hour down at 150 ℃.After the pre-treatment, use common adhering method to carry out bonding processing, under 150 ℃, 3 hours condition of cure, be cured.After the curing, after 24 hours, implement the bonding strength test.
Embodiment 2
Except using DN M90-44 (Polyplastics Co., Ltd.'s system, polyacetal),, solidify the back and after 24 hours, implement the bonding strength test through carrying out bonding pre-treatment, bonding processing with embodiment 1 same method as the molding.
Embodiment 3
Except using FN 0220A9 (Polyplastics Co., Ltd.'s system, polyphenylene sulfide),, solidify the back and after 24 hours, implement the bonding strength test through carrying out bonding pre-treatment, bonding processing with embodiment 1 same method as the molding.
Embodiment 4
Use DX 2002 (Polyplastics Co., Ltd.'s system, polybutylene terephthalate), use host XNR5002/ solidifying agent XNH5002 (Nagase ChemteX Corporation system) as molding as caking agent.As bonding pre-treatment, molding impregnated in the toluene, at room temperature flooded 1 hour.After the pre-treatment, use common adhering method to carry out bonding processing, under 150 ℃, 3 hours condition of cure, be cured.After the curing, after 24 hours, implement the bonding strength test.
Embodiment 5
Use DX 2002 (Polyplastics Co., Ltd.'s system, polybutylene terephthalate), use as caking agent and in host XNR5002/ solidifying agent XNH5002 (Nagase ChemteX Corporation system), add the material that 20wt% toluene forms as molding.Use common adhering method to carry out bonding processing, under 150 ℃, 3 hours condition of cure, be cured.After the curing, after 24 hours, implement the bonding strength test.
Embodiment 6
Except as bonding pre-treatment be with molding impregnated among the host XNR5002,60 ℃ following 1 hour, through carrying out bonding processing, solidify the back and after 24 hours, implement the bonding strength test with embodiment 1 same method.
Embodiment 7
Except as bonding pre-treatment be with molding impregnated among the host XNR5002,60 ℃ following 5 hours, through carrying out bonding processing, solidify the back and after 24 hours, implement the bonding strength test with embodiment 1 same method.
Embodiment 8
Use DX 2002 (Polyplastics Co., Ltd.'s system, polybutylene terephthalate), use 1 liquid type epoxy adhesive XN1244SR (Nagase ChemteX Corporation system) as molding as caking agent.As bonding pre-treatment, with molding impregnated among the XN 1244SR, 60 ℃ following 1 hour.After the pre-treatment, use common adhering method to carry out bonding processing, under 150 ℃, 1 hour condition of cure, be cured.Solidify the back and after 24 hours, implement the bonding strength test.
Embodiment 9
Except as bonding pre-treatment being impregnated in molding in the 1-propyl alcohol, following 1 hour of the room temperature, through carrying out bonding processing with embodiment 4 same methods, solidifies the back and after 24 hours, implement the bonding strength test.
Embodiment 10
Except as bonding pre-treatment be with molding impregnated among the solidifying agent XNH5002,100 ℃ following 1 hour, through carrying out bonding processing, solidify the back and after 24 hours, implement the bonding strength test with embodiment 1 same method.
Comparative example 1
Except not carrying out the bonding pre-treatment,, solidify the back and after 24 hours, implement the bonding strength test through carrying out bonding processing with embodiment 1 same method.
Comparative example 2
Except not carrying out the bonding pre-treatment,, solidify the back and after 24 hours, implement the bonding strength test through carrying out bonding processing with embodiment 2 same methods.
Comparative example 3
Except not carrying out the bonding pre-treatment,, solidify the back and after 24 hours, implement the bonding strength test through carrying out bonding processing with embodiment 3 same methods.
Comparative example 4
Except as bonding pre-treatment be with molding impregnated among the host XNR5002,150 ℃ following 10 minutes, through carrying out bonding processing, solidify the back and after 24 hours, implement the bonding strength test with embodiment 1 same method.
Comparative example 5
Except as bonding pre-treatment being impregnated in molding in the toluene, following 10 minutes of the room temperature, through carrying out bonding processing with embodiment 4 same methods, solidifies the back and after 24 hours, implement the bonding strength test.
Comparative example 6
Except use ethanol to replace the toluene as immersion solvent,, solidify the back and after 24 hours, implement the bonding strength test through carrying out bonding processing with embodiment 4 same methods.
Comparative example 7
Except use ethanol to replace the toluene as the solvent that makes an addition to caking agent,, solidify the back and after 24 hours, implement the bonding strength test through carrying out bonding processing with embodiment 5 same methods.
Comparative example 8
Except not carrying out the bonding pre-treatment,, solidify the back and after 24 hours, implement the bonding strength test through carrying out bonding processing with embodiment 7 same methods.
These results are shown in table 1～table 4.
Table 4
Notes) the caking agent degree of soaking in each resin is used in resin and is represented with the ratio that comparative example 1,2,3 was made as 100 o'clock respectively.
Claims (5)
1. an adhering method is characterized in that, is using between the bonding crystalloid resin forming body of Thermocurable caking agent or when crystalloid resin forming body and other parts, is 8J through the difference that molding is immersed in the SP SP value of molding
1/2/ cm
3/2In the following organic solvent, make bonding composition be impregnated into the bonding plane of molding.
2. adhering method according to claim 1; It is characterized in that; Use said organic solvent bonding composition is impregnated into molding bonding plane method in this organic solvent with after the bonding plane at least of molding dipping is more than 1 hour, adhesive on bonding plane.
3. adhering method according to claim 1 is characterized in that, the method for using said organic solvent bonding composition to be impregnated into the bonding plane of molding is added with the caking agent of organic solvent for coating on the bonding plane of molding.
4. according to each described adhering method of claim 1～3, it is characterized in that crystalloid resin forming body is processed by polyacetal resin, polybutylene terephthalate resin or polyphenylene sulfide.
5. according to each described adhering method of claim 1～3, it is characterized in that the Thermocurable caking agent is that epoxy is a caking agent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007-159716 | 2007-06-18 | ||
| JP2007159716A JP5236216B2 (en) | 2007-06-18 | 2007-06-18 | Method for bonding crystalline resin molding |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200810125714XA Division CN101328274B (en) | 2007-06-18 | 2008-06-18 | Sticking method of crystalloid resin forming body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102516572A true CN102516572A (en) | 2012-06-27 |
| CN102516572B CN102516572B (en) | 2014-06-18 |
Family
ID=40204301
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200810125714XA Expired - Fee Related CN101328274B (en) | 2007-06-18 | 2008-06-18 | Sticking method of crystalloid resin forming body |
| CN201110355223.6A Expired - Fee Related CN102516572B (en) | 2007-06-18 | 2008-06-18 | Bonding method of crystalline resin molding |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200810125714XA Expired - Fee Related CN101328274B (en) | 2007-06-18 | 2008-06-18 | Sticking method of crystalloid resin forming body |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP5236216B2 (en) |
| CN (2) | CN101328274B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104903389A (en) * | 2013-04-18 | 2015-09-09 | 住友电木株式会社 | Film for covering steel sheet |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7088624B2 (en) * | 2016-04-05 | 2022-06-21 | グンゼ株式会社 | clothing |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1670105A (en) * | 2004-03-19 | 2005-09-21 | 中国科学院理化技术研究院 | Modified epoxy resin adhesive used under low temperature |
| JP2006028474A (en) * | 2004-06-16 | 2006-02-02 | Hori Glass Kk | Adhering method of hardly adhesive resin adherend and adhesive structure of hardly adhesive resin adherend |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5616175B2 (en) * | 1974-02-28 | 1981-04-15 | ||
| JPS5959726A (en) * | 1982-09-30 | 1984-04-05 | Mitsui Petrochem Ind Ltd | Coating of polyolefin |
| JPS60181134A (en) * | 1984-02-29 | 1985-09-14 | Hitachi Ltd | Bonding of polyacetal resin |
| JPS6243429A (en) * | 1985-08-21 | 1987-02-25 | Asahi Chem Ind Co Ltd | Bonding of polyoxymethylene |
| KR100499001B1 (en) * | 2002-06-27 | 2005-07-01 | 주식회사 동성엔에스씨 | Surface treatment method to enhance the bonding of polyolefine resin |
-
2007
- 2007-06-18 JP JP2007159716A patent/JP5236216B2/en active Active
-
2008
- 2008-06-18 CN CN200810125714XA patent/CN101328274B/en not_active Expired - Fee Related
- 2008-06-18 CN CN201110355223.6A patent/CN102516572B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1670105A (en) * | 2004-03-19 | 2005-09-21 | 中国科学院理化技术研究院 | Modified epoxy resin adhesive used under low temperature |
| JP2006028474A (en) * | 2004-06-16 | 2006-02-02 | Hori Glass Kk | Adhering method of hardly adhesive resin adherend and adhesive structure of hardly adhesive resin adherend |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104903389A (en) * | 2013-04-18 | 2015-09-09 | 住友电木株式会社 | Film for covering steel sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101328274A (en) | 2008-12-24 |
| JP2008307836A (en) | 2008-12-25 |
| CN102516572B (en) | 2014-06-18 |
| CN101328274B (en) | 2012-05-23 |
| JP5236216B2 (en) | 2013-07-17 |
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