CN102516572B - Bonding method of crystalline resin molding - Google Patents
Bonding method of crystalline resin molding Download PDFInfo
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- CN102516572B CN102516572B CN201110355223.6A CN201110355223A CN102516572B CN 102516572 B CN102516572 B CN 102516572B CN 201110355223 A CN201110355223 A CN 201110355223A CN 102516572 B CN102516572 B CN 102516572B
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- bonding
- molding
- caking agent
- resin
- solidifying
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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 that on 06 18th, 2008, application number are the divisional application of 200810125714.X, the denomination of invention application that is " adhering method of crystalloid resin forming body " the applying date.
Technical field
The present invention relates to the adhering method for utilizing 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 due to mechanical properties, electrical property and other physics-chem characteristic excellence, and processibility is good, therefore be generically and collectively referred to as engineering plastics, for the extensive use such as automobile, electrical and electronic parts.This POM, PBT, PPS can, separately for various molding, according to utilizing field difference, in order to improve its character, particularly mechanical properties, coordinate the improvement of the various compositions such as various reinforcers, additive and be widely used.But, the bonding strength of POM, PBT, PPS and other resin, particularly lower with the bonding strength of epoxy resin, therefore for example to utilize epoxy be between POM, PBT, the PPS molding of caking agent or when the sealing of the electrical and electronic parts that engages or utilize epoxy resin of the molding that these moldinies form with other material etc., for the low problem that often becomes of bonding strength of POM, PBT, PPS molding and the epoxy resin of cabinet etc.As the method addressing these problems, although inquired into POM, PBT, the polymkeric substance of PPS or the improvement of the upgrading of composition or caking agent or the optimization of adhering method, but each method does not all obtain sufficient bonding strength, there is the problem of complex procedures etc.
After Japanese kokai publication hei 5-177714 discloses and implemented Cement Composite Treated by Plasma etc. in the time of bonding PEEK (polyether-ether-ketone) resin, apply epoxy primer, carry out afterwards bonding pretreatment process, but owing to must preparing in addition the operation that plasma processing apparatus and priming paint etc. are very many, therefore having to need the problem of facility investment or extra manpower.
" プ ラ ス チ Star Network material ヘ is paying Fu Yu in Machine Agencies に Seki The Ru research ” Tu material research (research of " being given to the correlative study of mechanism adhering to of raw materials for plastics production " coating) No.143 Apr.2005 P8-15, is disclosing by the upper primer coating of polyolefin raw materials for plastics production (PP), cover with paint, lacquer, colour wash, etc. thereon; demonstrate the stripping strength raising of film, observe priming paint and soak into PP starting material.The method is given material owing to adhering to according to combination selection the best of every kind of coating and material, is prepared separately, therefore spends very much manpower and time, inefficent.
Summary of the invention
Problem of the present invention is to provide has abundant bonding force and the method for bonding crystalloid resin forming body simply.
The inventor etc. conduct in-depth research in order to solve above-mentioned problem, found that by bonding composition before caking agent solidifies and are impregnated in molding, can obtain higher bonding strength; Be impregnated between the concentration of bonding composition of molding bonding plane and bonding strength and there is positive correlation.On the other hand, in the adhering method in the past carrying out, bonding composition soaks into only micro-ly, cannot bring into play fully the performance of caking agent.Therefore, make bonding composition be impregnated into the operation of the bonding plane of molding by setting, than the adhering method conventionally carrying out, be impregnated in molding to bonding composition high density, result bonding strength increases substantially.
The invention provides and make crystalloid resin forming body carry out the adhering method of the crystalloid resin forming body of the solidification treatment of caking agent through following operation, described operation is: under prescribed condition, molding be impregnated in uncured caking agent; Under prescribed condition, molding be impregnated in the high solvent of the affinity of resinous principle that forms molding in; The operations such as the solvent that the affinity of the resinous principle of interpolation and formation molding is high in caking agent.
; the present invention is a kind of adhering method; it is characterized in that; using between Thermocurable caking agent bonding crystalloid resin forming body or when crystalloid resin forming body and other parts; after making bonding composition be impregnated into the operation of bonding plane of molding or with the operation that it is soaked into simultaneously, implement the solidification treatment of caking agent.
Accompanying drawing explanation
Fig. 1 is the figure that represents the determining bonding strength Test condition of carrying out in embodiment.
Embodiment
In the present invention, the crystalline resin that crystalloid resin forming body uses is difficult cementability crystalline resin, and particularly preferred resin can be enumerated polyacetal resin, polybutylene terephthalate resin, polyphenylene sulfide etc.It is various for improving the countermeasure of cementability that these resins have carried out the effort of resin upgrading, formula composition etc., 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 by 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, can be different shape or implemented processing.For example, can be the molding utilizing through the Mold Making of gauffer processing or mirror finish, can be also the molding through sandblasting, uviolizing, Cement Composite Treated by Plasma, chemical treatment etc.In addition, while being made into body by injection forming etc., preferably die temperature is set in to the temperature lower than typical temperature.
As being not particularly limited with the bonding parts of crystalloid resin forming body, can enumerating between this molding or be example as other high-molecular weight polymers of other parts, glass, metal, timber, fabric, paper, leather etc.Metal is aluminium, iron etc., is not particularly limited.As high-molecular weight polymer, having polyester based resin, polyamide-based resin, acrylic resin, phenylethylene resin series, phenolic aldehyde is resin etc., is not particularly limited.In addition, be also not limited to stereo structure, sheet, film like etc. as the form of these moldinies or other parts.
It is caking agent, silicone-based caking agent etc. that the Thermocurable caking agent that the present invention uses can be enumerated epoxy.
Thermocurable caking agent be by curable resin (host) and solidifying agent, packing material is appropriately combined forms, in the time that curable resin solidifies due to heat with molding or other parts by chemical or be physically combined carry out bonding.In the present invention bonding composition refer to this caking agent contained with solidify relevant curable resin and the general name of solidifying agent.
While being caking agent for epoxy, can enumerate for example the 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, glycolylurea type epoxy resin, isocyanuric acid ester type epoxy resin, acrylic modified epoxy resin etc. as curable resin, be that caking agent can suitably be used singly or in combination according to epoxy.
In addition, solidifying agent is can be for the curing material of 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 and use two or more.
In addition, the use level of solidifying agent is determined according to epoxy resin, and suitably adjusts according to molding condition or characteristic etc. in the normally used scope of solidifying agent.
Bonding pre-treatment of the present invention has and under the condition of not solidifying at caking agent, molding be impregnated in to bonding composition under prescribed condition, specifically, in the time of the 2 liquid type caking agent that uses host to separate with solidifying agent, refer to and more than 60 ℃, molding be impregnated in the host of bonding composition or solidifying agent more than 1 hour.About dipping time, using while mixing the 1 liquid type caking agent that 2 liquid type caking agents of host and solidifying agent or host and solidifying agent have been pre-mixed, refer to more than 60 ℃ and below the solidification value of caking agent, molding be impregnated in to caking agent in more than 1 hour.Here, in short-term, host or solidifying agent are few to the amounts of saturation of molding for the low or dipping time of dipping temperature, cannot expect fully that bonding strength improves effect.In the time impregnated in host or solidifying agent, owing to can dipping temperature being set highlyer, therefore bring into play further dipping effect, but bonding composition is because heat occurs when curing or rotten, can not bring into play and soak into effect, therefore should be noted that.In addition, while being mixed with host and solidifying agent, in the time setting dipping temperature compared with highland, bonding composition first occurs to solidify before fully soaking into, and therefore, in the time making excess Temperature, contrary treatment effect can reduce.In dipping, be necessary the state that keeps bonding composition not solidify.By these bonding pre-treatment, bonding composition increases to the amounts of saturation of molding, reacts curing in the solidification process of the bonding composition that is impregnated into molding inside after caking agent applies, and therefore shows high bonding strength in molding/caking agent interface.
As increase caking agent other method to the amounts of saturation in crystalloid resin forming body, have use be added with the organic solvent high with the affinity of crystalloid resin forming body (with the difference of the solubility parameter SP of crystalline resin be 8J
1/2/ cm
3/2caking agent below) carries out bonding processing; Or before bonding processing, under prescribed condition, molding is immersed in the organic solvent high with molding affinity (with the difference of the SP value of crystalline resin be 8J
1/2/ cm
3/2after below), apply the methods such as caking agent.
By these methods, same during with above-mentioned pre-treatment, the bonding composition that increases, is impregnated into molding inside to the amounts of saturation in molding due to bonding composition reacts curing in solidification process, thereby shows high bonding strength in molding/caking agent interface.Here, when use and the difference of the SP value of crystalline resin are greater than 8J
1/2/ cm
3/2organic solvent time, the effect that bonding composition increases to the infiltration capacity in molding is few, the effect that result bonding strength improves is low.
In addition, in the time must forming the anneal of product, preferably carrying out the laggard row anneal of bonding processing.Because anneal hinders caking agent to the soaking into of molding, therefore can not give full play to effect of the present invention, must extend necessary above dipping time or improve dipping temperature or solidification value in order to obtain necessary bonding strength.
embodiment
The present invention is described by the following examples in further detail, but the present invention is not limited thereto.The measuring method of the bonding strength in addition, shown in example is as described below.
Bonding strength
Process: as shown in Figure 1, it is 2 sections that ASTM tension test sheet is blocked in centre, fully except deburring.For the thickness of 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, using the tensile strength of per unit bond area as tensile shear bonding strength.In addition, failure mode is as follows.
Cohesion failure: caking agent lost efficacy.
Interface peel: unsticking (peeling off) occurs the interface between crystalloid resin forming body and caking agent.
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)
Swelling
Process: sample at room temperature be impregnated in solvent to 200 hours.After solvent impregnated, take out sample, removing gravimetry after surface attachment solvent, using increment part of the example weight than before solvent impregnated as swelling (wt%)
Bonding composition amounts of saturation
Process: remove the caking agent on adhesive test postforming surface, (10 μ m) cut out ultrathin section(ing) from top layer every certain thickness to use 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 dihydroxyphenyl propane composition) the MS area in 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 caking agent as molding.As bonding pre-treatment, molding be impregnated in host XNR5002, at 150 ℃, flood 1 hour.After pre-treatment, use common adhering method to carry out bonding processing, under the condition of cure of 150 ℃, 3 hours, be cured.After solidifying, after 24 hours, implement bonding strength test.
embodiment 2
Except using DN M90-44 (Polyplastics Co., Ltd.'s system, polyacetal) as molding, carry out bonding pre-treatment, bonding processing by method similarly to Example 1, after solidifying, after 24 hours, implement bonding strength test.
embodiment 3
Except using FN 0220A9 (Polyplastics Co., Ltd.'s system, polyphenylene sulfide) as molding, carry out bonding pre-treatment, bonding processing by method similarly to Example 1, after solidifying, after 24 hours, implement bonding strength test.
embodiment 4
Use DX 2002 (Polyplastics Co., Ltd.'s system, polybutylene terephthalate), use host XNR5002/ solidifying agent XNH5002 (Nagase ChemteX Corporation system) as caking agent as molding.As bonding pre-treatment, molding be impregnated in toluene, at room temperature flood 1 hour.After pre-treatment, use common adhering method to carry out bonding processing, under the condition of cure of 150 ℃, 3 hours, be cured.After solidifying, after 24 hours, implement bonding strength test.
embodiment 5
Use DX 2002 (Polyplastics Co., Ltd.'s system, polybutylene terephthalate), use and in host XNR5002/ solidifying agent XNH5002 (Nagase ChemteX Corporation system), add the material that 20wt% toluene forms as caking agent as molding.Use common adhering method to carry out bonding processing, under the condition of cure of 150 ℃, 3 hours, be cured.After solidifying, after 24 hours, implement bonding strength test.
embodiment 6
Except as bonding pre-treatment being impregnated in molding in host XNR5002, at 60 ℃ 1 hour, carries out bonding processing by method similarly to Example 1, after solidifying, after 24 hours, implement bonding strength test.
embodiment 7
Except as bonding pre-treatment being impregnated in molding in host XNR5002, at 60 ℃ 5 hours, carries out bonding processing by method similarly to Example 1, after solidifying, after 24 hours, implement bonding strength test.
embodiment 8
Use DX 2002 (Polyplastics Co., Ltd.'s system, polybutylene terephthalate), use 1 liquid type epoxy adhesive XN1244SR (Nagase ChemteX Corporation system) as caking agent as molding.As bonding pre-treatment, by molding impregnated in XN 1244SR, at 60 ℃ 1 hour.After pre-treatment, use common adhering method to carry out bonding processing, under the condition of cure of 150 ℃, 1 hour, be cured.After solidifying, after 24 hours, implement bonding strength test.
embodiment 9
Except as bonding pre-treatment being impregnated in molding in 1-propyl alcohol, lower 1 hour of room temperature, carries out bonding processing by method similarly to Example 4, after solidifying, after 24 hours, implement bonding strength test.
embodiment 10
Except as bonding pre-treatment being impregnated in molding in solidifying agent XNH5002, at 100 ℃ 1 hour, carries out bonding processing by method similarly to Example 1, after solidifying, after 24 hours, implement bonding strength test.
comparative example 1
Except not carrying out bonding pre-treatment, carry out bonding processing by method similarly to Example 1, after solidifying, after 24 hours, implement bonding strength test.
comparative example 2
Except not carrying out bonding pre-treatment, carry out bonding processing by method similarly to Example 2, after solidifying, after 24 hours, implement bonding strength test.
comparative example 3
Except not carrying out bonding pre-treatment, carry out bonding processing by method similarly to Example 3, after solidifying, after 24 hours, implement bonding strength test.
comparative example 4
Except as bonding pre-treatment being impregnated in molding in host XNR5002, at 150 ℃ 10 minutes, carries out bonding processing by method similarly to Example 1, after solidifying, after 24 hours, implement bonding strength test.
comparative example 5
Except as bonding pre-treatment being impregnated in molding in toluene, lower 10 minutes of room temperature, carries out bonding processing by method similarly to Example 4, after solidifying, after 24 hours, implement bonding strength test.
comparative example 6
Except using ethanol to replace toluene as immersion solvent, carry out bonding processing by method similarly to Example 4, after solidifying, after 24 hours, implement bonding strength test.
comparative example 7
Except using ethanol to replace toluene as the solvent that makes an addition to caking agent, carry out bonding processing by method similarly to Example 5, after solidifying, after 24 hours, implement bonding strength test.
comparative example 8
Except not carrying out bonding pre-treatment, carry out bonding processing by method similarly to Example 7, after solidifying, after 24 hours, implement bonding strength test.
These be the results are shown in to table 1～table 4.
Table 4
Note) the caking agent degree of soaking in each resin uses and is made as the ratio of 100 o'clock with comparative example 1,2,3 respectively in resin and represents.
Claims (3)
1. an adhering method, it is characterized in that, using between Thermocurable caking agent bonding crystalloid resin forming body or when crystalloid resin forming body and other parts, be 8J by least bonding plane of molding being immersed in the difference of the solubility parameter SP value of molding
1/2/ cm
3/2in following organic solvent 1 hour above after, on bonding plane, apply caking agent, or apply the caking agent that is added with organic solvent on the bonding plane of molding.
2. adhering method according to claim 1, is characterized in that, crystalloid resin forming body is made up of polyacetal resin, polybutylene terephthalate resin or polyphenylene sulfide.
3. adhering method according to claim 1 and 2, is characterized in that, Thermocurable caking agent is that epoxy is 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 CN102516572A (en) | 2012-06-27 |
| CN102516572B true CN102516572B (en) | 2014-06-18 |
Family
ID=40204301
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110355223.6A Expired - Fee Related CN102516572B (en) | 2007-06-18 | 2008-06-18 | Bonding method of crystalline resin molding |
| CN200810125714XA Expired - Fee Related CN101328274B (en) | 2007-06-18 | 2008-06-18 | Sticking method of crystalloid resin forming body |
Family Applications After (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)
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|---|---|
| JP (1) | JP5236216B2 (en) |
| CN (2) | CN102516572B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5741878B2 (en) * | 2013-04-18 | 2015-07-01 | 住友ベークライト株式会社 | Steel sheet coating film |
| JP7088624B2 (en) * | 2016-04-05 | 2022-06-21 | グンゼ株式会社 | clothing |
Citations (1)
| 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 |
Family Cites Families (6)
| 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 |
| 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 |
-
2007
- 2007-06-18 JP JP2007159716A patent/JP5236216B2/en active Active
-
2008
- 2008-06-18 CN CN201110355223.6A patent/CN102516572B/en not_active Expired - Fee Related
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Patent Citations (1)
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| JP特开2006-28474A 2006.02.02 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101328274B (en) | 2012-05-23 |
| JP2008307836A (en) | 2008-12-25 |
| CN102516572A (en) | 2012-06-27 |
| CN101328274A (en) | 2008-12-24 |
| JP5236216B2 (en) | 2013-07-17 |
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