CN101146837A - Adherent composition and method of temporarily fixing member therewith - Google Patents
Adherent composition and method of temporarily fixing member therewith Download PDFInfo
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- CN101146837A CN101146837A CNA2005800491464A CN200580049146A CN101146837A CN 101146837 A CN101146837 A CN 101146837A CN A2005800491464 A CNA2005800491464 A CN A2005800491464A CN 200580049146 A CN200580049146 A CN 200580049146A CN 101146837 A CN101146837 A CN 101146837A
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Abstract
A method of temporary fixing at working of an optical member; and a resin composition suitable therefor. There is provided a composition characterized by containing (meth)acrylate of = 500 molecular weight (A1) having one or more (meth)acryloyl groups at its molecular end or side chain, polyfunctional (meth)acrylate (B1), (meth)acrylate (C1) other than the (meth)acrylates (A1) and (B1) and photopolymerization initiator (D1). Further, there is provided a method of temporarily fixing a member, characterized by temporarily adhesion fixing a member with the use of the composition, followed by working of the temporarily fixed member, immersing of the worked member in hot water of = 90 DEG C and removing of the resin composition hardened.
Description
Technical field
The present invention relates to a kind of method of temporarily fixing of member when processing various member, and be applicable to the adhesive composition and the tackiness agent of this method.Specifically, when the present invention relates to a kind of processing optical and using member, the method for this member of working fastening and the light solidified tackiness agent that is applicable to this purposes.
Background technology
The working fastening of optical mirror slip, bevelled mirror, array (array), silicon chip, semi-conductor installation parts etc. sticks with glue agent, usually use double faced adhesive tape and hot melt adhesive, utilize the bonding or laminated member of this type of tackiness agent, after becoming desired shape by machining, remove tackiness agent and can manufacture tool member.As, for the semi-conductor installation parts, this base part utilizes double faced adhesive tape to be fixed in after the base material, and machining becomes required parts, peels off double faced adhesive tape by irradiation ultraviolet radiation from parts again.Also have, when using hot melt adhesive, behind the combination member, by heating tackiness agent is permeated after the gap, the member that machining is required is peeled off tackiness agent then in organic solvent.
But there are the following problems when using double faced adhesive tape, promptly is difficult to guarantee the precision of thickness, or because bond strength is low, cutting is relatively poor during tool member, or is not heated to more than 100 ℃ then not peelable, or when peeling off by ultraviolet ray, the penetrance of adherend attachment is relatively poor problem such as to be difficult to peel off.
When using hot melt adhesive, need be heated to when bonding more than 100 ℃, therefore spendable member kind is restricted.Simultaneously, need with an organic solvent when peeling off, except the clean complex process of basic solvent or halogen organic solvent, its operating environment also becomes problem.
In order to solve the problems of the technologies described above, the working fastening that has proposed to contain water-soluble cpdss such as water-soluble vinyl monomer is with light-cured type or heating type glue stick, this type of adhesive compound has solved the separability in the water, but the bond strength of stationary member is low, the poor dimensional precision of the member after the machining.Also proposed, and improved the fusible while by using specific high-hydrophilic (methyl) acrylate, the working fastening that improves separability by swelling or part dissolving sticks with glue agent.Therefore but when machining, cutting tool generation frictional heat such as parts and blade or diamond cutter need be cooled off with a large amount of water, and described high-hydrophilic composition is when cutting, and cured article swelling and become softness is difficult to reach high dimensional accuracy.Also have, residual a part of dissolved cured article on the member of peeling off diminishes outward appearance (referring to Patent Document 1,2,3).
Patent documentation 1: Japanese patent laid-open 6-116534 communique
Patent documentation 2: Japanese patent laid-open 11-71553 communique
Patent documentation 3: the Japanese Patent spy opens the 2001-226641 communique
The announcement of invention
In order to improve the scantling precision after the machining, particularly in the purposes field of optics, need a kind of tool hydrophobicity, high bond strength, and separability is good in water, simultaneously, peel off the back and do not stay residue, the light-cured type tackiness agent that environment or operation are all good on the member.
The present invention is, in order to solve above-mentioned prior art problem, carried out after the research, found to utilize specific hydrophobicity (methyl) propenyl monomer, by making up this monomer, make and have high bond strength and the good adhesive compound of the separability in water or in the warm water, can reach purpose of the present invention, thereby finish the present invention.
The present invention has following main points.
1. composition (claim example I); it is characterized in that; contain (A1): it is (methyl) acrylate more than 500 that the end of molecule or side chain have (methyl) acryl, molecular weight more than 1; (B1): multifunctional (methyl) acrylate; (C1): described (A1), (B1) (methyl) acrylate in addition, and (D1): contain Photoepolymerizationinitiater initiater.
2. the composition of 1 record as described is characterized in that, (A1) for being selected from polyhutadiene, PI and described both more than a kind of arbitrary hydride.
3. the compositions of 1 or 2 records as described, wherein, (A1), (B1) and (C1) have a hydrophobicity.
4. the composition of each record in 1 to 3 as described contains (A1) 5～80 mass parts, (B1) 1～50 mass parts, (C1) 5～80 mass parts, (D1) 0.1～20 mass parts.
5. composition (claim example II); it is characterized in that; contain (A2): it is (methyl) acrylate more than 500 that the end of molecule or side chain have (methyl) acryl, molecular weight more than 1; (B2): multifunctional (methyl) acrylate; (C2): described (A2), (B2) (methyl) acrylate in addition; (D2) Photoepolymerizationinitiater initiater, and (E2) polar organic solvent is a feature.
6. the compositions of 5 records as described, wherein, (E2) for being selected from more than a kind of methyl alcohol, ethanol, Virahol and propyl carbinol.
7. the compositions of 5 or 6 records as described, wherein, (A2), (B2) and (C2) all have a hydrophobicity.
8. the composition of each record in 5 to 7 as described, wherein, contain 1～50 mass parts (A2) and (B2), 5～95 mass parts (C2), 0.1～20 mass parts (D2), 0.5～10 mass parts (E2).
9. tackiness agent is characterized in that, is formed by the composition of each record in described 1 to 8.
10. the method for temporarily fixing of member, it is characterized in that, utilize the bonding working fastening member of composition of each record in described 1 to 8, process after the member of this working fastening, in the warm water below 90 ℃, flood this member that processes, remove the cured body of described composition.
11. composition (claim example III) is characterized in that, contains following (A3), (B3) and (D3).
(A3) urethanum (methyl) acrylate,
(B3) by being selected from monomeric (methyl) acrylic acid derivative monomer formed more than a kind or 2 kinds of (methyl) acrylic acid derivative shown in n-(methyl) acryloyloxyalkyl hexahydrophthalic phthalimide, carboxylic (methyl) acrylate and the general formula (C3).
General formula (C3): Z-O-(R
2O)
P-R
1
(in the formula, Z represents (methyl) acryl, R
1Expression phenyl or have the phenyl of carbon number 1～3 alkyl.R
2Expression-C
2H
4-,-C
3H
6-,-CH
2CH (CH
3)-,-CH
2CH (OH) CH
2-,-C
4H
8-or-C
6H
12, PThe integer of expression 1～10.)
(D3) Photoepolymerizationinitiater initiater.
12. as described 11 the record compositions, wherein, urethanum (A3) (methyl) acrylate is water-soluble.
13. tackiness agent is characterized in that, is formed by described 11 or 12 compositions of putting down in writing.
14. the method for temporarily fixing of member, it is characterized in that: utilize and contact the tackiness agent adhesive member that can reduce bond strength with water, cured adhesive and working fastening are processed after the member of this working fastening, this member that processes be impregnated in the water, remove the tackiness agent that is cured.
15. the method for temporarily fixing of member, it is characterized in that, utilization contacts the tackiness agent adhesive member that can reduce bond strength with water, cured adhesive carries out working fastening, process after the member of this working fastening, this member that processes be impregnated in the water, remove film like solidified tackiness agent after the swelling.
16. the method for temporarily fixing of member is characterized in that, utilizes the described tackiness agent adhesive member of claim 13, cured adhesive carries out working fastening, process after the member of this working fastening, this member that processes be impregnated in the water, remove with film like solidified tackiness agent after the swelling.
Composition of the present invention has light solidified because of it combines, and can be cured by visible light or ultraviolet ray.Therefore, compare with existing hot melt adhesive, bonding process is simple, saves energy, has superiority aspect shortening the activity duration.And used influences such as cutting fluid when its cured body can not be subject to processing demonstrate high bond strength, so are difficult for producing skew during tool member, have the effect that is easy to make the good member of dimensional precision.And, this cured body, also has following feature, promptly and water, be preferably the warm water more than 30 ℃, particularly during the contact of the warm water below 90 ℃, bond strength reduces, between the member or member and anchor clamps between bonding force reduce, thereby be easy to reclaim member, compare with existing tackiness agent to have and need not use the price height, ignition quality is strong or produces the peculiar effect of the organic solvent of harmful gas.Have, for the composition of specific preferred compositing range, its cured body contacts with warm water below 90 ℃ can swelling, can reclaim from member with film like, thereby obtain superior operation effectiveness again.
The method of temporarily fixing utilization of member of the present invention as mentioned above, with water, when warm water below 90 ℃ contacts, reduce the composition of its bond strength or the tackiness agent that forms by said composition, therefore only have by contact the feature that can easily reclaim member with warm water, compare with existing tackiness agent to have and need not use price height, ignition quality by force or produce the peculiar effect of the organic solvent of harmful gas.
The best mode that carries out an invention
The present invention has best example (I) as described below, example (II), example (III).
Example (I)
End of (A1) molecule that this example (I) uses or side chain have (methyl) acryl more than 1; molecular weight is that (methyl) acrylate more than 500 exemplifies 1; 2-polyhutadiene terminal amino group ethyl formate (methyl) acrylate (for example; the system TE-2000 of Japan Cao Da society; TEA-1000); described hydride (as; the system TEAI-1000 of Japan Cao Da society); 1; 4-polyhutadiene terminal amino group ethyl formate (methyl) acrylate (for example; the system BAC-45 of Osaka organic chemistry society); polyisoprene end (methyl) acrylate; polyester urethanum (methyl) acrylate; polyethers urethanum (methyl) acrylate; polyester (methyl) acrylate; bisphenol type epoxy (methyl) acrylate (as, the system PVC ス コ of Osaka organic chemistry society-ト #540; the system PVC ス コ of clear and polymer society-ト VR-77) equimolecular quantity be more than 500 oligomer/polymer endways or (methyl) acrylate of side chain (methyl) propylene acidylate more than.
Be preferably for (A1) and be selected from polyhutadiene, polyisoprene, and aforementioned both more than a kind of arbitrary hydride, because help promoting when in the warm water during dip composition cured body, the character that helps promoting this cured body to peel off from adherend (hereinafter to be referred as, separability).
Among the present invention, the addition of (methyl) acrylate (A1) is, (A1) in 100 mass parts of (B1) and total amount (C1), and preferably 5～80 mass parts, especially preferably 5～60 mass parts.Addition is 5 mass parts when above, and separability is good, and guarantees that the cured body of composition peels off with film like.Also have, when 80 mass parts were following, viscosity was higher, thereby operation is good.
(A1) (methyl) acrylate, preferably hydrophobic.Because when water-soluble, the cured body swelling of composition or part dissolving in the time of may having machining cause that the position skew makes the problem of working accuracy poor quality, and be therefore unsatisfactory.But, even wetting ability, if the cured body of its composition can not use because of water swelling or part dissolving yet.
(B1) multifunctional (methyl) acrylate, be that 2 officials can exemplify 1 during (methyl) acrylate, 3-butyleneglycol two (methyl) acrylate, 1,4-butyleneglycol two (methyl) acrylate, 1,6 hexylene glycol two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, two (methyl) vinylformic acid dicyclo pentyl ester, 2-ethyl-2-butyl-propylene glycol (methyl) acrylate, neopentyl glycol modification TriMethylolPropane(TMP) two (methyl) acrylate, stearic acid modified pentaerythritol diacrylate, polypropylene glycol two (methyl) acrylate, 2,2-two (4-(methyl) acryloxy diethoxy phenyl propane, 2,2-two (4-(methyl) acryloxy propoxy-phenyl-propane, 2,2-two (4-(methyl) acryloxy tetraethoxy phenyl) propane etc.Be that 3 officials can exemplify trimethylolpropane tris (methyl) acrylate, three ((methyl) acryloxy ethyl) isocyanuric acid ester etc. during (methyl) acrylate.4 officials can be above (methyl) acrylate the time can exemplify dihydroxy methylpropane four (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, tetramethylolmethane oxyethyl group four (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, Dipentaerythritol six (methyl) acrylate etc.
The addition of multifunctional (methyl) acrylate (B1) is, (A1) (B1) and in 100 mass parts of total amount (C1), 1～50 mass parts preferably, 5～30 mass parts especially preferably, addition is that 1 mass parts is when above, separability is good, and can guarantee that the cured body of composition peels off with film like.Also have, when 50 mass parts are following, can not reduce the binding property at initial stage.
(B1) multifunctional (methyl) acrylate, preferably hydrophobic equally with (A1), because when water-soluble, may exist in the cutting process, the occurrence positions skew makes the problem of working accuracy poor quality owing to the cured body swelling of resin combination, and is therefore undesirable.Even wetting ability, if but the cured body of its composition can not use because of water swelling or a part of dissolving yet.
(C1) described (A1), (B1) (methyl) acrylate in addition, (methyl) vinylformic acid formicester, (methyl) vinylformic acid is fat, (methyl) vinylformic acid third fat, (methyl) Butyl acrylate, the own fat of (methyl) vinylformic acid 2-ethyl, (methyl) vinylformic acid isooctyl, (methyl) isodecyl acrylate, (methyl) lauryl acrylate, (methyl) octadecyl acrylate, (methyl) phenyl acrylate, (methyl) vinylformic acid cyclohexanol, (methyl) vinylformic acid dicyclo pentyl ester, (methyl) vinylformic acid double cyclopentenyl ester, (methyl) isobornyl acrylate, methoxy ring triolefin in the last of the ten Heavenly stems (methyl) acrylate, (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid 3-hydroxypropyl acrylate, (methyl) vinylformic acid 4-hydroxy butyl ester, (methyl) tetrahydrofurfuryl acrylate, 2-hydroxyl-3-phenoxy propyl (methyl) acrylate, (methyl) glycidyl acrylate, caprolactone modification (methyl) tetrahydrofurfuryl acrylate, 3-chloro-2-hydroxypropyl (methyl) acrylate, N, N-dimethyl aminoethyl (methyl) acrylate, N, N-diethylamino ethyl (methyl) acrylate, t-butyl amino-ethyl (methyl) acrylate, ethoxy carbonyl methyl (methyl) acrylate, phenol ring oxidative ethane modification acrylate, phenol (2 moles of modifications of oxyethane) acrylate, phenol (4 moles of modifications of oxyethane) acrylate, p-isopropyl phenol ethylene oxide modification acrylate, nonylphenol oxyethane modification acrylate, nonylphenol (4 moles of modifications of oxyethane) acrylate, nonylphenol (8 moles of modifications of oxyethane) acrylate, nonylphenol (2.5 moles of modifications of propylene oxide) acrylate, 2-ethylhexyl Trivalin SF acrylate, oxyethane modification phthalic acid (methyl) acrylate, oxyethane modification Succinic Acid (methyl) acrylate, (methyl) vinylformic acid trifluoro ethyl ester, vinylformic acid, methacrylic acid, maleic acid, fumaroyl, ω-carboxyl-polycaprolactone one (methyl) acrylate, phthalic acid one hydroxyethyl (methyl) acrylate, (methyl) vinylformic acid dimeracid, β-(methyl) acrylyl oxy-ethyl succinate, n-(methyl) acryloyloxyalkyl hexahydrophthalic phthalimide.
The addition of (methyl) acrylate (C1) is, (A1), (B1) and (C1) in total amount 100 mass parts, preferably 5～80 mass parts are preferably 10～80 mass parts especially.Addition is that 5 mass parts can not reduce the binding property at initial stage when above, when 80 mass parts are following, can guarantee separability, and the cured body of composition is peeled off with film like.
(C1) (methyl) acrylate is preferably hydrophobic as (A1), (B1).Be more preferably (A1), (B1) and (C1) all be hydrophobicity.Because when water-soluble, the cured body swelling of composition in the time of may having machining and cause that position skew makes the problem of working accuracy poor quality, and can guarantee to prevent described problem during for hydrophobicity.Also have, even wetting ability, if but the cured body of its composition can not use because of water swelling or part dissolving yet.
Re-use the phosphoric acid ester that (methyl) acrylyl oxy-ethyl acid phosphoric acid ester, dibutyl 2-(methyl) acrylyl oxy-ethyl acid phosphoric acid ester, dioctyl 2-(methyl) acrylyl oxy-ethyl phosphoric acid ester, phenylbenzene 2-(methyl) acrylyl oxy-ethyl phosphoric acid ester, (methyl) acrylyl oxy-ethyl polyoxyethylene glycol acid phosphoric acid ester etc. contain vinyl or (methyl) propenyl in described (A1), (B1) and the blend compositions (C1), with the adhesivity of further raising for metal covering.
(D1) interpolation of Photoepolymerizationinitiater initiater be for, promoted after the sensitization photocuring of resin combination can use known various Photoepolymerizationinitiater initiater by visible rays or ultraviolet active ray.Can exemplify benzophenone and derivative thereof specifically; benzil and derivative thereof; anthraquinone and derivative thereof; bitter almond oil camphor; benzoin methylether; ethoxybenzoin; the bitter almond oil camphor propyl ether; the bitter almond oil camphor ethyl isobutyl ether; benzoin derivatives such as benzoin dimethylether; diethoxy acetophenone; acetophenone derivs such as 4-t-butyl Trichloroacetophenon; 2-dimethyl aminoethyl benzoic ether; p-dimethyl aminoethyl benzoic ether; diphenyl disulfide; thioxanthone and derivative thereof; camphorquinone; 7; 7-dimethyl-2; 3-dioxo two ring (2.2.1) heptane-1-carboxylic acids; 7; 7-dimethyl-2; 3-dioxo two ring (2.2.1) heptane-1-carboxyl-2-bromo ethyl esters; 7; 7-dimethyl-2; 3-dioxo two ring (2.2.1) heptane-1-carboxyl-2-methyl esters; 7; 7-dimethyl-2; 3-dioxo two ring (2.2.1) heptane-camphorquinone derivatives such as 1-carboxylic acid chloride; 2-methyl isophthalic acid-(4-(methylthio group) phenyl)-2-morpholino propane-1-ketone; 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-benzophenone derivatives such as alpha-aminoalkyl such as butanone-1 grade; the benzoyl diphenyl phosphine oxide; 2; 4; 6-Three methyl Benzene formyl diphenyl phosphine oxide; benzoyl diethoxy phosphine oxide; 2; 4; 6-Three methyl Benzene formyl Dimethoxyphenyl phosphine oxide; 2; 4, acylphosphine oxide derivatives such as 6-Three methyl Benzene formyl diethoxy phenyl phosphine oxide.Photoepolymerizationinitiater initiater can use and above-mentionedly be used in combination more than a kind or 2 kinds.
The addition of Photoepolymerizationinitiater initiater (D1) is with respect to (A1), (B1) and 100 mass parts of total (C1), to be preferably 0.1～20 mass parts.Being more preferably is 3～20 mass parts.0.1 when mass parts is above, can guarantee to promote the solidified effect, when 20 mass parts are following, can obtain sufficient curing speed.As better example, add (D1) 3 mass parts when above, have and can not rely on the rayed amount and can be cured, improve the degree of crosslinking of composition cured body more, can not be offset by occurrence positions during machining, and advantage such as separability raising.
Composition of the present invention in order to improve stability in storage, can use a small amount of polymerization retarder.As polymerization retarder, can exemplify, toluhydroquinone, quinhydrones, 2,2-methylene radical-two (4-methyl-6-tert butyl phenol), catechol, hydroquinone monomethyl ether, single tertiary butylated hydroquinone, 2,5-di-tert-butyl hydroquinone, p-benzoquinones, 2,5-phenylbenzene-p-benzoquinones, 2,5 di-t-butyls-p-benzoquinones, picric acid, citric acid, thiodiphenylamine, tert-butyl catechol, 2-butyl-4-hydroxyanisol and 2,6-di-t-butyl-p-cresols etc.
The usage quantity of above-mentioned polymerization retarder adds up to 100 mass parts with respect to (A1), (B1) and (methyl) acrylate (C1), 0.001～3 mass parts preferably, and being more preferably is 0.01～2 mass parts.0.001 guarantee stability in storage when mass parts is above, when 3 mass parts are following, have good binding property, avoid taking place uncured phenomenon.
Composition of the present invention, within the scope that does not influence the object of the invention, can use various elastomericss (elastomer) such as acrylic rubber, urethanes, vinyl cyanide one divinyl one styrenerubber, additives such as mineral filler (filler), solvent, extender, strongthener, softening agent, tackifier, dyestuff, pigment, fire retardant, organosilane coupler and tensio-active agent.
Method of temporarily fixing of the present invention is, utilizes the above-mentioned composition adhesive member, and curing composition carries out working fastening, processes after the member of this working fastening, this tool member be impregnated in the member method of temporarily fixing of removing cured compositions in the warm water.By this, do not need with an organic solvent, can high manufacturing accuracy ground processing optical with various members such as members.
According to best example of the present invention, when removing composition, cured body contacts after the also swelling with warm water below 90 ℃, reclaims with film like from member, thereby realizes superior operation.
Method of temporarily fixing of the present invention, the tackiness agent that utilizes described composition of the present invention to form can be guaranteed the effect of described invention.
In the present invention, utilize the warm water below the mildly heating to 90 ℃, just can realize at short notice peeling off, help productivity.Temperature for described warm water is 30 ℃～80 ℃, preferably 40 ℃～80 ℃, utilize the above-mentioned warm water cured body of swelling composition at short notice, thereby the residual deformation stress that is produced when composition solidifies simultaneously is released bond strength to be reduced, and can remove the cured body of composition with film like.Also have, for the method that cured body contacts with warm water, the method that links fit dipping together in warm water is comparatively easy, therefore can be recommended.
In the present invention, without particular limitation for the material of working fastening member, when using the ultraviolet hardening tackiness agent, preferably can see through the member that ultraviolet material forms.Described material, for example, quartzy member, glass component, plastic member etc.Method of temporarily fixing of the present invention is applicable to the processing of quartz crystal, glass mirror, glass lens and CD etc.
Using method about the tackiness agent of method of temporarily fixing, when supposing as tackiness agent use light solidified tackiness agent, can exemplify, employing is an amount of coating binder on the bonding plane of member of need fixed or supporting substrates, follow superimposed another member method or, in advance a plurality of member laminations that need working fastening, coating binder makes after the coating binders such as method of its infiltration to its gap, to irradiation visible light or ultraviolet ray on this member, thereby make the light solidified adhesive solidification carry out each member of working fastening.
Secondly, the member of working fastening cuts off, grinds and cut, after the processing such as grinding, perforate, by this member of dipping in the warm water, peel off the cured article of resin combination from member according to required shape.
Example (II):
Be used in the end of (A2) molecule of this example (II) or side chain and have (methyl) acryl more than 1; molecular weight is (methyl) acrylate more than 500; can use the compound that employed composition (A1) exemplified in the above-mentioned example (I), therefore omit for example at this.
Be preferably about (A2), be selected from polyhutadiene, polyisoprene and the above two arbitrary hydride more than a kind, because can promote that the cured body of its composition impregnated in warm water the time, the separability of this cured body from being peeled off by thing.
The present invention, the addition of (methyl) acrylate (A2) is, (A2), in (B2) and 100 mass parts of total amount (C2), be preferably 1～50 mass parts, is preferably 5～45 mass parts especially.Addition is 1 mass parts when above, and its separability is good, guarantees that the cured body of composition is peeled off with film like.And, when 50 mass parts are following, can not reduce the binding property at initial stage.
(A2) (methyl) acrylate is preferably hydrophobic, because when water-soluble, and the cured body swelling of composition or part dissolving and cause that the position skew makes the relatively poor problem of working accuracy in the time of may having machining, thereby undesirable.But, even wetting ability, if the cured body of its composition can not use because of bigger swelling or part dissolving take place water yet
(B2) multifunctional (methyl) acrylate, the cited compound of composition (B1) as above-mentioned example (I) use, promptly, during 2 officials energy (methyl) acrylate, during 3 officials energy (methyl) acrylate, 4 officials can be above (methyl) acrylate the time, each compound that exemplifies all can use.Therefore, exemplify in this omission.
The addition of multifunctional (methyl) acrylate (B2) is, (A2), in (B2) and 100 mass parts of total amount (C2), be preferably 1～50 mass parts, is preferably 5～40 mass parts especially.Addition is 1 mass parts when above, and separability is good, guarantees that the cured body of composition is peeled off with film like.And, when 50 mass parts are following, also can not reduce the binding property at initial stage.
(B2) multifunctional (methyl) acrylate, hydrophobic preferable as (A2), because when water-soluble, the cured body swelling of composition in the time of may having machining and cause that the position skew makes the problem of working accuracy poor quality, thereby undesirable.Even wetting ability, if but the cured body of its composition can not use because of bigger swelling or part dissolving take place water yet.
(C2) (methyl) acrylate monomer can use the compound that employed composition (C1) exemplified in the described example (I).Therefore, exemplify in this omission.
The addition of (methyl) acrylate (C2) is, (A2), in (B2) and 100 mass parts of total amount (C2), be preferably 5～95 mass parts, is preferably 10～80 mass parts especially.Addition is 5 mass parts when above, can not reduce the binding property at initial stage; When 95 mass parts are following, can guarantee separability, the cured body of composition is peeled off with film like.
(C2) (methyl) acrylate, hydrophobic preferable as (A2), (B2), particularly (A2), (B2) and (C2) better when being hydrophobicity.Because water miscible, the cured body swelling with composition in the time of may existing in machining causes that the position skew makes the relatively poor problem of working accuracy, therefore hydrophobicly guarantees not take place above-described problem.Also have, even wetting ability, if the cured body of said composition can not use because of swelling or part dissolving take place water yet.
And, can in (A2) of the present invention, (B2) and blend compositions (C2), re-use the phosphoric acid ester that (methyl) acrylyl oxy-ethyl acid phosphoric acid ester, dibutyl 2-(methyl) acrylyl oxy-ethyl acid phosphoric acid ester, dioctyl 2-(methyl) acrylyl oxy-ethyl acid phosphoric acid ester, phenylbenzene 2-(methyl) acrylyl oxy-ethyl acid phosphoric acid ester, (methyl) acrylyl oxy-ethyl polyoxyethylene glycol acid phosphoric acid ester etc. have vinyl or (methyl) propenyl, further improve adhesivity for the metallic surface.
The interpolation of Photoepolymerizationinitiater initiater (D2) be for, promoted the photocuring of resin combination after the sensitization by visible rays or ultraviolet active ray.Can use known various Photoepolymerizationinitiater initiater.For example concrete, can use all cpds that Photoepolymerizationinitiater initiater exemplified as (D1) that in above-mentioned example (I), use.Therefore, exemplify in this omission.Photoepolymerizationinitiater initiater can use more than a kind or a kind and be used in combination.
The addition of Photoepolymerizationinitiater initiater (D2) is, with respect to (A2), (B2) and 100 mass parts of total (C2), preferably 0.1～20 mass parts.Being more preferably is 3～20 mass parts.0.1 when mass parts is above, guarantee to solidify promoted effect; When 20 mass parts are following, can obtain sufficient curing speed.The example that is more preferably is, add 3 mass parts above (D2), be not cured with can relying on the rayed amount like this, improve the degree of crosslinking of the cured body of composition more, when machining, can not cause the position skew, and its separability increases also.
One of the present invention is characterised in that, polar organic solvent (E2) with (A2), (B2) and (C2) the common use, thereby easy swelling and reduce the phenomenon of bond strength can guarantee that cured composition takes place to be contacted with warm water the time.
For the polar solvent of (E2), its boiling point is preferably more than 50 ℃ below 130 ℃.When selecting the polar organic solvent in the described boiling spread, guarantee further to take place that cured composition contacts with warm water and the phenomenon that makes the bond strength reduction.Described polar solvent, for example alcohol, ketone, ester etc., according to inventor's result of study, preferred alcohols wherein.
Can exemplify methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol, Pentyl alcohol, primary isoamyl alcohol, 2-ethyl butanol etc. as alcohol.In described alcohol, be preferably methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol of boiling point below 120 ℃.Wherein be more preferably methyl alcohol, ethanol, Virahol, propyl carbinol.
(E2) the polar organic solvent addition is, with respect to (A2), (B2) and (C2) total amount 100 mass parts, preferably 0.5～10 mass parts.0.5 when mass parts is above, can guarantee separability; When 10 mass parts are following, can not reduce the binding property at initial stage, and the cured body of composition is peeled off with film like.
The present composition in order to improve stability in storage, can use a small amount of polymerization retarder.The concrete example of polymerization retarder is as all cpds that polymerization retarder exemplified as use in the above-mentioned example (I).Therefore, exemplify in this omission.
The usage quantity of described polymerization retarder is, with respect to (A2), (B2) and 100 mass parts of total amount (C2), and 0.001～3 mass parts preferably, being more preferably is 0.01～2 mass parts.0.001 can guarantee its stability in storage when mass parts is above, can obtain good binding property when 3 mass parts are following, uncured problem can not take place.
Composition of the present invention, within the scope that does not influence the object of the invention, can use various synthetic rubber such as acrylic rubber commonly used, urethanes, vinyl cyanide one divinyl one styrenerubber, additives such as mineral filler, solvent, extender, strongthener, softening agent, tackifier, dyestuff, pigment, fire retardant, organosilane coupler and tensio-active agent.
Secondly, the present invention is, utilize and to contact with warm water below 90 ℃ and reduce the composition adhesive member of bond strength, curing composition, carry out working fastening, process after the member of this working fastening, this member that processes be impregnated in the member method of temporarily fixing of removing cured compositions in the warm water.Thereby, do not need with an organic solvent, can high manufacturing accuracy ground processing optical with various members such as members.
In addition, according to best example of the present invention, when removing the cured body of composition, cured body contacts and swelling with warm water below 90 ℃, reclaims with film like from member, thereby can realize superior operation.
Method of temporarily fixing of the present invention, the tackiness agent that utilizes composition of the present invention to form can guarantee to obtain the effect of described invention.
In the present invention, utilize the warm water of mildly heating, be specially the warm water below 90 ℃, can realize at short notice peeling off, very desirable aspect productivity.Temperature for described warm water is 30 ℃～90 ℃, preferably 40 ℃～90 ℃, because use described warm water to get final product the cured body of swelling composition at short notice, thereby the residual deformation stress that produces of doing when composition solidifies simultaneously is released the bond strength reduction, the vapour pressure of (E2) polar organic solvent that adds can be used as the reactive force of peeling off of member and composition cured body, thereby can remove the composition of the tackiness agent on the clung body with film like.Also have, for the method that cured body contacts with warm water, the method that connects fit dipping together in warm water is comparatively easy, therefore can be recommended.
In the present invention, without particular limitation for the material of working fastening member, when using the ultraviolet hardening tackiness agent, preferably select to see through the member that ultraviolet material forms.Described material, for example, quartzy member, glass component, plastic member etc.Method of temporarily fixing of the present invention is applicable to the processing of quartz crystal, glass mirror, glass lens and CD etc.
Using method about tackiness agent in the method for temporarily fixing, can exemplify following method when supposing: adopt for example an amount of coating binder on the bonding plane of member of need fixed or supporting substrates as tackiness agent use light solidified tackiness agent, then the method for superimposed another member or, at first a plurality of member laminations that need working fastening, tackiness agent is coated with in its gap, make after the coating binders such as method of its infiltration, to irradiation visible light or ultraviolet ray on this member, thereby make the method for light solidified adhesive solidification working fastening member.
Then, the member of working fastening according to required shape cut off, grind cut, after the processing such as grinding, perforate, by at water, this member of dipping in the preferred warm water is peeled off the cured article of its tackiness agent from member.
Example (III)
Example (III), one of its composition uses (A3) urethanum (methyl) acrylate.(A3) urethanum (methyl) acrylate that the present invention uses is to make by polyisocyanates, polyvalent alcohol and (methyl) vinylformic acid are reacted.
Polyisocyanates can exemplify 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4 '-diphenylmethanediisocyanate, m-benzene diisocyanate, benzene diformazan subunit vulcabond, tetramethylene diisocyanate, 1, hexamethylene-diisocyanate, lysinediisocyanate 1,4 cyclohexalene diisocyanate, 4,4 '-dicyclohexyl methane diisocyanate, 3,3 '-dimethyl-4,4 '-biphenylene vulcabond etc.Such can separately or mix more than 2 kinds and use.
Can exemplify polyester glycol, polyether glycol, polycaprolactone glycol, polycarbonate diol etc. as polyvalent alcohol.
(A3) addition of urethanum (methyl) acrylate is, (A3), in total amount 100 mass parts of (B3), and preferably 5～80 mass parts, especially preferably 5～50 mass parts.Preferable binding property can be guaranteed when described addition 5 mass parts are above, the too high reduction operation of viscosity can be prevented below 80 mass parts.
The present invention, (B3) use is selected from monomeric at least a above (methyl) acrylic acid derivative monomer of (methyl) acrylic acid derivative shown in n-(methyl) acryloyloxyalkyl hexahydrophthalic phthalimide, carboxylic (methyl) acrylate and the general formula (C3).
General formula (C3): Z-O-(R
2O)
P-R
1
[in the formula, Z represents (methyl) acryl, and R represents phenyl or contains the phenyl of the alkyl of carbonatoms 1～3.R
2Expression-C
2H
4-,-C
3H
6-,-CH
2CH (CH
3)-,-CH
2CH (OH) CH
2-,-C
4H
8-or-C
6H
12, p represents 1～10 integer.)
In the present invention, use by (B3) and described (A3) are common, provide to possess to have strong bonding force, its cured body reduces the characteristic tackiness agent of bonding force in water.
N-(methyl) acryloyloxyalkyl hexahydrophthalic phthalimide can exemplify n-(methyl) acrylyl oxy-ethyl hexahydrophthalic phthalimide, n-(methyl) acryloyl-oxy propyl group hexahydrophthalic phthalimide.N-(methyl) acryloyl-oxy butyl hexahydrophthalic phthalimide etc.
When composition (B3) was selected n-(methyl) acryloyloxyalkyl hexahydrophthalic phthalimide, its content was in (A3), (B3) total amount 100 mass parts, preferably 10～60 mass parts, especially preferably 20～60 mass parts.Described addition is 10 mass parts when above, guarantees the abundant bonding force of adhesive member, when 60 mass parts are following, guarantees the separability when cured body is in water.
And composition among the present invention (B3) can also select to contain (methyl) acrylate of carboxyl.
Carboxylic (methyl) acrylate is vinylformic acid, methacrylic acid, maleic acid, fumaroyl, ω-carboxyl-polycaprolactone one (methyl) acrylate, phthalic acid one hydroxyethyl (methyl) acrylate, (methyl) vinylformic acid dimeracid, β-(methyl) acrylyl oxy-ethyl succinate.
When using carboxylic (methyl) acrylate, its addition is, (A3), in (B3) total amount 100 mass parts, and preferably 1～50 mass parts, especially preferably 5～40 mass parts.Described addition is 1 mass parts when above, guarantees sufficient binding property, when 50 mass parts are following, guarantees the separability in the water.
In addition, also can select to have (methyl) acrylic acid derivative monomer of general formula (C3) structure as (B3) of the present invention composition.
General formula (C3): Z-O-(R
2O)
P-R
1
(in the formula, Z represents (methyl) acryl, and R represents phenyl or contains the phenyl of the alkyl of carbonatoms 1～3.R
2Expression-C
2H
4-,-C
3H
6-,-CH
2CH (CH
3)-,-CH
2CH (OH) CH
2-,-C
4H
8-or-C
6H
12-, p represents 1～10 integer.〕
(methyl) acrylic acid derivative monomer with general formula (C3) structure can exemplify, phenoxy group ethyl (methyl) acrylate, phenoxy group Diethylene Glycol (methyl) acrylate, phenoxy group polyoxyethylene glycol (methyl) acrylate, phenoxy propyl (methyl) acrylate, 2-hydroxyl-3-phenoxy propyl (methyl) acrylate, phenoxy propandiol (methyl) acrylate and phenoxy group polypropylene glycol (methyl) acrylate etc.
The monomeric addition of (methyl) acrylic acid derivative with general formula (C3) structure is, (A3), in total amount 100 mass parts of (B3), and preferably 10～80 mass parts, especially preferably 10～70 mass parts.Described addition is that 10 mass parts can be guaranteed strong binding property when above, when 80 mass parts are following, can guarantee the separability in water.
And, can also in containing described (A3) and composition (B3), re-use the phosphoric acid ester that (methyl) acrylyl oxy-ethyl acid phosphoric acid ester, dibutyl 2-(methyl) acrylyl oxy-ethyl acid phosphoric acid ester, dioctyl 2-(methyl) acrylyl oxy-ethyl phosphoric acid ester, phenylbenzene 2-(methyl) acrylyl oxy-ethyl phosphoric acid ester, (methyl) acryloyl ethyl polyoxyethylene glycol acid phosphoric acid ester etc. contain vinyl or (methyl) propenyl, improve adhesivity thus for metal covering.
The present invention, described composition (A3) and (B3) in, add (D3) Photoepolymerizationinitiater initiater.
(D3) interpolation of Photoepolymerizationinitiater initiater be for, promoted the photocuring of resin combination after the sensitization by visible rays or ultraviolet active ray.Can use known various Photoepolymerizationinitiater initiater.For example concrete, can use all cpds that exemplifies as (D1) Photoepolymerizationinitiater initiater that uses in the described example (I).Therefore, exemplify in this omission.Photoepolymerizationinitiater initiater can use more than a kind or a kind and be used in combination.
(D3) addition of Photoepolymerizationinitiater initiater is, total 100 mass parts with respect to (A3), (B3) are preferably 0.1～20 mass parts.Be more preferably 0.5～15 mass parts.Described addition is 0.1 mass parts when above, guarantees to promote solidification effect; When 20 mass parts are following, can reach sufficient curing speed.
Composition of the present invention in order to improve its stability in storage, can use a small amount of polymerization retarder.Specifically exemplifying of polymerization retarder, use in the example (I) as described as all cpds that polymerization retarder exemplified.Therefore, exemplify in this omission.
The usage quantity of described polymerization retarder is, with respect to (A3) and (B3) (methyl) total 100 mass parts, and 0.001～3 mass parts preferably, being more preferably is 0.01～2 mass parts.0.001 when mass parts is above, guarantee stability in storage; When 3 mass parts are following, have good binding property, uncured phenomenon can not take place.
Composition of the present invention, within the scope that does not influence the object of the invention, can use various elastomericss (elastomer) such as acrylic rubber, urethanes, vinyl cyanide one divinyl one styrenerubber, the additive that mineral filler, solvent, extender, strongthener, softening agent, tackifier, dyestuff, pigment, fire retardant, organosilane coupler and tensio-active agent etc. are commonly used.
Secondly, the present invention is, the water that utilizes, particularly the tackiness agent adhesive member of reduction bond strength when warm water more than 30 ℃ contact, cured adhesive, carry out working fastening, process after the member of this working fastening, this member that processes be impregnated in the member method of temporarily fixing of removing the solidified tackiness agent in the water.Thereby, do not need with an organic solvent, can improve working accuracy ground processing optical with various members such as members.
According to best example of the present invention, when removing tackiness agent, cured body contacts and swelling with water, reclaims with film like from member, therefore can realize superior operation.
Method of temporarily fixing of the present invention, the tackiness agent that utilizes described composition of the present invention to form can be guaranteed the effect of described invention.
In the present invention, the temperature of water can be general room temperature, but when utilizing the warm water of mildly heating, can realize in the short period of time peeling off in water, and its productivity aspect is preferable.The temperature of described warm water is 30 ℃～90 ℃, and preferred 40 ℃～80 ℃ warm water because the warm water that uses the said temperature scope cured body of swelling tackiness agent at short notice reduces bond strength, is removed composition with film like.Also have, for the method that cured body contacts with warm water, the method that connects fit dipping together in water is comparatively easy, therefore can be recommended.
In the present invention, without particular limitation for the material of working fastening member, when using the ultraviolet hardening tackiness agent, preferably can see through the member that ultraviolet material is formed.Described material, as, quartzy member, peeling member, plastic member etc.Fixing means of the present invention is applicable to, the processing of quartz crystal, glass mirror, glass lens and CD etc.
Using method about the tackiness agent in the method for temporarily fixing exemplifies following method, when supposing to use the light solidified tackiness agent: after an amount of coating binder on the bonding plane that needs member of fixed or supporting substrates, the method of superimposed another member or, at first a plurality of member laminations that need working fastening, make after the coating binders such as method of its infiltration in its gap of coating binder, to irradiation visible light or ultraviolet ray on this member, make the light solidified adhesive solidification, thus the method for working fastening member.
Then, the member of working fastening cuts off, grinds and cut, after the processing such as grinding, perforate, by this member of dipping in the warm water, peel off the cured article of its tackiness agent from member according to required shape.
Embodiment
Below, by embodiment and comparative example the present invention is described in more details, but the present invention is not limited to the embodiment that is exemplified, also have, the evaluation method of using among the embodiment is as described below.
Evaluation method
Tensile shear bond strength: measure according to JIS K 6850.Specifically be, as being glued material, use pyrex (pyrex) (registered trademark of Corning society thermal glass) glass (long 25mm * wide 25mm * thick 2.0mm), the diameter at bonding position is 8mm, bonding two pyrex glass of the composition that utilization is made, and utilize the solidification equipment of the use electrodeless discharge lamp that Fusion society makes, at the accumulation light quantity 2000mJ/cm of 365nm wavelength
2Condition under be cured, make tensile shear adhesion test sheet.The test film of gained by universal testing machine, 23 ℃ of temperature, under the condition of humidity 50%, is measured the tensile shear bond strength with draw speed 10mm/min.
Stripping test: the composition of coating preparation on described pyrex glass, the blue or green sheet glass (long 150mm * wide 150mm * thick 1.7mm) that is in as supporter is gone up outside the stickup, with above-mentioned same condition curing composition, make the stripping test body.Gained test body impregnated in 80 ℃ of warm water, measures the splitting time of pyrex glass, and observes the state of peeling off.
Embodiment 1-1
At (methyl) acryl that has as the end of (A1) molecule or side chain more than 1; molecular weight is (methyl) acrylate more than 5 00; 1; 2-polyhutadiene terminal amino group ethyl formate acrylate (the Japanese Cao Da system TE-2000 of society; hereinafter to be referred as " TE-2000 ") 20 mass parts; diacrylate dicyclo pentyl ester (the Japanese chemical drug system KAYARAD R-684 of society as (B1) multifunctional (methyl) acrylate; hereinafter to be referred as " R-684 ") 15 mass parts; remove (A1) as (C1); (B1) the n-acrylyl oxy-ethyl hexahydrophthalic phthalimide of Wai (methyl) acrylate (the system TO-1429 of the synthetic society in East Asia; hereinafter to be referred as " TO-1429 ") 40 mass parts; benzene oxygen ethyl propylene acid esters (the system light of chemistry society of common prosperity society acrylate PO-A; hereinafter to be referred as " PO-A ") in total 100 mass parts of 25 mass parts; add (D1) Photoepolymerizationinitiater initiater benzoin dimethylether (hereinafter to be referred as " BDK ") 10 mass parts; as 2 of polymerization retarder; 2-methylene radical-two (4-methyl-6-tert butyl phenol (hereinafter to be referred as " MDP ") 0.1 mass parts, preparation composition.And utilize the composition of described preparation, carry out the mensuration and the stripping test of tensile shear bond strength.It the results are shown in table 1-1.
Table 1-1
| Embodiment No. | 1-1 | 1-2 | 1-3 | 1-4 | 1-5 | 1-6 | 1-7 | 1-8 | 1-9 | 1-10 | 1-11 |
| (A1) composition (mass parts) TE-2000 TEA-1000 | 20 | 20 | 20 | 35 | 20 | 50 | 20 | 20 | 20 | 20 | 20 |
| (B1) composition (mass parts) R-684 TMPTA NPA | 15 | 15 | 15 | 15 | 15 | 5 | 15 | 15 | 15 | 15 | 15 |
| (C1) composition (mass parts) TO-1429 PO-A M-101A | 40 25 | 40 25 | 40 25 | 25 25 | 40 25 | 25 10 | 40 25 | 40 25 | 40 25 | 40 25 | 40 25 |
| (D1) Photoepolymerizationinitiater initiater (mass parts) BDK TPO I-907 | 10 | 5 | 1.5 | 10 | 10 | 10 | 10 | 10 | 2 | 2 | 6 |
| Polymerization retarder (mass parts) MDP | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| Bond strength (MPa) | 11.7 | 12.6 | 12.4 | 11.8 | 10.1 | 15.1 | 9.0 | 9.8 | 13.3 | 9.8 | 11.3 |
| 80 ℃ of warm water splitting times (branch) | 30 | 30 | 153 | 20 | 34 | 97 | 41 | 30 | 166 | 131 | 41 |
| Peel off state *) | Film like | Film like | Film like | Film like | Film like | Film like | Film like | Film like | Film like | Film like | Film like |
*) film like: the cured body of resin combination is peeled off with film like from the surface of glass, does not stay residue embodiment 1-2～1-11
Except that the starting material of kind shown in the table 1-1 are formed the use according to shown in the table 1-1, as embodiment 1 preparation resin combination.For the resin combination that makes,, carry out the mensuration and the stripping test of tensile shear bond strength as embodiment 1-1.It the results are shown in table 1-1.
Materials used
TEA-1000:1,2-polyhutadiene terminal amino group ethyl formate acrylate (the Japanese Cao Da system TEA-1000 of society)
TMPTA: Viscoat 295 (the Japanese chemical drug system KAYARAD TMPTA of society)
NPA: neopentylglycol diacrylate (the system light of chemistry society of common prosperity society acrylate NP-A)
M-101A: 2 moles of modification acrylates of phenol ring oxidative ethane (the system ア ロ two Star Network ス M-101A of the synthetic society in East Asia)
TPO:2,4,6-Three methyl Benzene formyl diphenyl phosphine oxide (the system Le シ リ of BASF society Application TPO)
The I-907:2-methyl isophthalic acid-[4-(methylthio group) phenyl)-2-morpholine propane-1-ketone (the system IRGACURE907 of Ciba.Speciality.Chemicals society)
Comparative example 1-1～1-4
Except that the starting material of showing kind shown in the 1-2 use according to the composition shown in the table 1-2, prepare resin combination as embodiment 1-1.For the composition that makes, carry out the mensuration and the stripping test of tensile shear bond strength as embodiment 1-1.It the results are shown in table 1-2.
Table 1-2
| Comparative example No. | 1-1 | 1-2 | 1-3 | 1-4 |
| (A1) composition (mass parts) TE-2000 | 20 | 0 | ||
| (B1) composition (mass parts) R-684 | 0 | 0 | ||
| (C1) composition (mass parts) TO-1429 PO-A | 40 40 | 60 40 | ||
| Other composition (mass parts) MTEGMA acryloyl morpholine | 100 | 70 30 | ||
| (D1) Photoepolymerizationinitiater initiater (mass parts) BDK TPO | 10 | 10 | 1.5 | 2.0 |
| Polymerization retarder (mass parts) MDP | 0.1 | 0.1 | 0.1 | 0.1 |
| Bond strength (Mpa) | 18.6 | 9.8 | 2.0 | 8.4 |
| 80 ℃ of warm water splitting times (branch) | Nothing is peeled off | Nothing is peeled off | 30 | 60 |
| Peel off state **) | Residual | Residual |
*) residual: glass can be peeled off, but the cured body of resin combination residues in glass surface
Materials used
MTEGMA: methoxyl group TEG monomethyl acrylate (the system NK of Xin Zhong village chemistry society ester M-90G)
Embodiment 1-12
Use embodiment 1-1, each different resin combination of (D1) Photoepolymerizationinitiater initiater amount of 1-2 and 1-11, the solidification equipment of the use electrodeless discharge lamp of making by Fusion society is at accumulation light quantity 200,500,1000, the 4000mJ/cm of 365nm wavelength
2Each condition under curable resin composition, preparation stripping test body outside the preparation tensile shear adhesion test sheet, carries out the mensuration and the stripping test of tensile shear bond strength as embodiment 1-1.Its result has all kept bond strength under each accumulation light quantity, demonstrate good separability.It the results are shown in table 1-3.
Table 1-3
| Cumulative exposure (mJ/cm 2) | Embodiment No. | 1-1 | 1-2 | 1-11 |
| 200 | Bond strength (MPa) | 9.8 | 10.5 | 9.8 |
| Splitting time (branch) | 73 | 79 | 45 | |
| 500 | Bond strength (MPa) | 11.3 | 13.7 | 11.3 |
| Splitting time (branch) | 76 | 130 | 35 | |
| 1000 | Bond strength (MPa) | 13.6 | 14.6 | 11.3 |
| Splitting time (branch) | 53 | 150 | 25 | |
| 4000 | Bond strength (MPa) | 10.9 | 10.0 | 10.6 |
| Splitting time (branch) | 35 | 88 | 66 |
Embodiment 1-13
Utilize the composition of embodiment 1-1 preparation, the blue or green sheet glass that uses among the pyrex glass of long 150mm * horizontal 150mm * thick 2mm and the embodiment 1 carries out bonding curing as sample glass as embodiment 1.Only the heat-resisting pyrex glass part with this adhesive test body cuts into 10mm four directions type by cutting unit.Pyrex glass not comes off or breakage during cutting, and cutting processing is good.When the bond test body that has only cut the pyrex part is immersed in 80 ℃ of warm water, peeled off fully in 120 minutes.
Embodiment 2-1
The end or the side chain that add as (A2) molecule have (methyl) acrylate more than 1, molecular weight is that the TE-2000 of (methyl) acrylate more than 500 is 20 mass parts, R-684 as (B2) multifunctional (methyl) acrylate is 15 mass parts, remove (A1) as (C2), (B1) TO-1429 of Wai simple function (methyl) acrylate is 40 mass parts, M-101A is 25 mass parts, add up to 100 mass parts, and (E2) the polar organic solvent Virahol (hereinafter to be referred as " IPA " 2 mass parts, as (D2) Photoepolymerizationinitiater initiater BDK10 mass parts, as MDP 0.1 mass parts of polymerization retarder, the preparation composition.The composition that use makes carries out the mensuration and the stripping test of tensile shear bond strength, and it the results are shown in 2-1.
Table 2-1
| Embodiment No | 2-1 | 2-2 | 2-3 | 2-4 | 2-5 | 2-6 | 2-7 | 2-8 | 2-9 | 2-10 | 2-11 |
| (A2) composition (mass parts) TE-2000 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 |
| (B2) composition (mass parts) R-684 | 15 | 15 | 15 | 15 | 15 | 15 | 15 | 15 | 15 | 15 | 15 |
| (C2) composition (mass parts) TO-1429 M-101A | 40 25 | 40 25 | 40 25 | 40 25 | 40 25 | 40 25 | 40 25 | 40 25 | 40 25 | 40 25 | 40 25 |
| (E2) composition IPA (82 ℃ of boiling points) ethanol (78 ℃ of boiling points) methyl alcohol (65 ℃ of boiling points) propyl carbinol (83～118 ℃ of boiling points) | 2 | 2 | 2 | 2 | 0.5 | 4 | 6 | 2 | 2 | 2 | 2 |
| (D2) Photoepolymerizationinitiater initiater (mass parts) BDK TPO 1-907 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 5 | 15 | 2 | 2 |
| Polymerization retarder (mass parts) MDP | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| Bond strength (MPa) | 116 | 112 | 120 | 98 | 140 | 10.6 | 9.6 | 13.3 | 117 | 124 | 102 |
| 80 ℃ of warm water splitting times (branch) | 20 | 25 | 22 | 32 | 44 | 16 | 10 | 44 | 79 | 48 | 75 |
| Peel off state *) | Film like | Film like | Film like | Film like | Film like | Film like | Film like | Film like | Film like | Film like | Film like |
*) film like: the solidified adhesive compound does not residue in glass surface and peels off with film like.
Embodiment 2-2～2-21
Form the use shown in table 2-1, table 2-2 except that the starting material of showing kind shown in 2-1, the table 2-2, prepare composition as embodiment 2-1.The composition that makes carries out the tensile shear bond strength as embodiment 2-1 to be measured and stripping test, and it the results are shown in table 2-1, table 2-2.
Table 2-2
| Embodiment No | 2-12 | 2-13 | 2-14 | 2-15 | 2-16 | 2-17 | 2-18 | 2-19 | 2-20 | 2-21 |
| (A2) composition (mass parts) TE-2000 | 20 | 20 | 20 | 20 | 10 | 10 | 0 | 0 | 20 | 35 |
| (B2) composition (mass parts) R-684 | 15 | 15 | 15 | 5 | 25 | 5 | 25 | 5 | 15 | 35 |
| (C2) composition (mass parts) TO-1429 QM M-101A BZ IBX | 40 25 | 40 25 | 40 25 | 40 35 | 40 25 | 40 45 | 40 35 | 40 55 | 40 25 | 15 15 |
| (E2) composition (mass parts) IPA (82 ℃ of boiling points) | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 12 | 2 |
| (D2) Photoepolymerizationinitiater initiater (mass parts) BDK | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 10 | 10 |
| Polymerization retarder (mass parts) MDP | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| Bond strength (MPa) | 13.9 | 108 | 98 | 163 | 10.7 | 21.2 | 128 | 9.5 | 3.7 | 2.8 |
| 80 ℃ of warm water splitting times (branch) | 20 | 152 | 283 | 22 | 26 | 81 | 140 | 290 | 5 | 12 |
| Peel off state *) | Film like | Film like | Film like | Film like | Film like | Film like | Film like | Film like |
*) film like: the solidified adhesive compound does not residue in glass surface and peels off with film like.
Materials used
QM: methacrylic acid dicyclopentadiene oxygen base ethyl ester (ロ-ム ﹠amp; Ha-system the QM-657 of ス society)
BZ: benzyl methacrylate (the system light of chemistry society of common prosperity society ester BZ)
IBX: isobornyl methacrylate (the system light of chemistry society of common prosperity society ester IBX)
Comparative example 2-1～2-5
Form the use shown in table 2-3 except that the starting material of kind shown in the table 2-3, prepare composition as embodiment 2-1.The composition that makes carries out the tensile shear bond strength as embodiment 2-1 and measures and stripping test, and it the results are shown in table 2-3.
Table 2-3
| Comparative example No. | 2-1 | 2-2 | 2-3 | 2-4 | 2-5 |
| (A2) composition (mass parts) TE-2000 | |||||
| (B2) composition (mass parts) R-684 | |||||
| (C2) composition (mass parts) TO-1429 M-101A BZ IBX | 40 60 | 30 | |||
| (E2) composition (mass parts) IPA | 2 | ||||
| Other composition (mass parts) 2-HEMA MTEGMA acryloyl morpholine | 100 | 100 | 70 30 | 70 | |
| (D2) Photoepolymerizationinitiater initiater (mass parts) BDK TPO | 5 | 1.5 | 1.5 | 2.0 | 2.0 |
| Polymerization retarder (mass parts) MDP | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| Bond strength (Mpa) | 10.5 | 2.0 | 2.0 | 8.4 | 12.3 |
| 80 ℃ of warm water splitting times (branch) | Nothing is peeled off | 30 | 30 | 60 | Nothing is peeled off |
| Peel off state **) | Residual | Residual | Residual |
*) residual: glass is peelable, but the solidified adhesive compound residues in glass surface
Materials used
2-HEMA: methacrylic acid 2-hydroxyl ethyl ester
Embodiment 2-22, comparative example 2-6
Remove each composition that utilizes embodiment 2-1 and comparative example 2-5, utilize the solidification equipment of the use electrodeless discharge lamp of Fusion society manufacturing, at accumulation light quantity 500,1000,2000, the 4000mJ/cm of 365nm wavelength
2Each condition under curable resin composition, make outside stripping test body, the tensile shear adhesion test sheet, carry out the mensuration and the stripping test of tensile shear bond strength as embodiment 2-1.It the results are shown in table 2-4.
Table 2-4
| Resin combination No. | Accumulation light quantity (mJ/cm 2) | 500 | 1000 | 2000 | 4000 | |
| Embodiment 2-22 | Embodiment 2-1 | Bond strength (MPa) | 10.2 | 10.5 | 11.6 | 10.3 |
| Splitting time (branch) | 16 | 15 | 20 | 10 | ||
| Comparative example 2-6 | Comparative example 2-5 | Bond strength (MPa) | 0 | 0 | 12.3 | 9.8 |
| Splitting time (branch) | - | - | Nothing is peeled off | Nothing is peeled off |
Embodiment 2-23,2-24
Use the composition of embodiment 2-1 and 2-6, prepare the stripping test body, in temperature respectively is 40 ℃, 50 ℃, 60 ℃, 70 ℃ warm water, carry out stripping test as embodiment 2-1.It the results are shown in table 2-5.As a result, all has separability at arbitrary temp.
Table 2-5
| Resin combination No. | Warm water temperature (℃) | 40 | 50 | 60 | 70 | |
| Embodiment 2-23 | Embodiment 2-1 | Splitting time (branch) | 353 | 267 | 185 | 84 |
| Embodiment 2-24 | Embodiment 2-6 | Splitting time (branch) | 192 | 143 | 99 | 70 |
Embodiment 2-25
Utilize embodiment 2-1 composition, the blue or green sheet glass that uses among the pyrex glass of 150mm * 150mm * 2mmt and the embodiment 1 carries out bonding curing as sample glass as embodiment 2-1.The pyrex glass part of this adhesive test body cuts into 10mm four directions type by cutting unit.Pyrex glass does not come off or is damaged in cutting, and processibility is good.The bond test body that has only cut the pyrex glass part is immersed in 80 ℃ of warm water, peeled off fully in 60 minutes.And the cut-out test film of peeling off from this its takes out 10 arbitrarily, and each cuts off the medial surface (carrying out the face of working fastening with composition) of test film to utilize observation by light microscope, measures the maximum amplitude at glass shortcoming place, asks its mean value and standard deviation.It the results are shown in 2-6.
Table 2-6
| 10 maximum amplitudes (μ m) of cutting off the medial surface shortcoming of test film | ||||||||||||
| Cut off test film No. | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | On average | Standard deviation |
| Embodiment 2-25 | 54 | 44 | 45 | 41 | 52 | 56 | 39 | 45 | 47 | 46 | 46.9 | 5.2 |
| Comparative example 2-7 | 44 | 51 | 70 | 52 | 47 | 42 | 49 | 50 | 59 | 51 | 51.5 | 7.6 |
| Comparative example 2-8 | 80 | 93 | 75 | 103 | 84 | 92 | 76 | 99 | 109 | 118 | 92.9 | 13.7 |
Comparative example 2-7
(the system ア of daily use chemicals Seiko society De Off ィ Star Network ス A) is heated to 90 ℃ of fusions with hot melt adhesive, the blue or green sheet glass that uses among the pyrex glass of bonding 150mm * 150mm * 2mmt and the embodiment 1, only the pyrex glass with this adhesive test body partly utilizes cutting unit to cut into 10mm four directions type.Coming off of pyrex glass do not taken place in the cutting process, has good processibility.This test film flooded 1 day in N-Methyl pyrrolidone solution, reclaim and cut off after the test film, 10 cut-out test films of peeling off are taken out in operation arbitrarily similarly to Example 25, medial surface (with the face of hot melt adhesive working fastening) to this cut-out test film is observed by opticmicroscope, measure the maximum amplitude at glass shortcoming place, obtain its mean value and standard deviation.It the results are shown in table 2-6.
Comparative example 2-8
Use the pyrex glass of the bonding 150mm * 150mm of UV curing PET adhesive tape * 2mm.Only the pyrex part with this adherence test body cuts into 10mm four directions type by cutting unit.By the part of the adhesive tape of this test film is reduced after the clinging power by irradiation ultraviolet radiation, reclaimed this cut-out test film.This cut-out test film takes out 10 cut-out test films of peeling off arbitrarily as embodiment 25, cut off the medial surface (with the face of adhesive tape working fastening) of test film observes by opticmicroscope this each, measure the maximum amplitude at glass shortcoming place, obtain its mean value and standard deviation.It the results are shown in table 2-6.
Embodiment 2-26, comparative example 2-9,2-10
Utilizing the resin combination of embodiment 2-1 and comparative example 2-5,2-6, utilize the solidification equipment of the use electrodeless discharge lamp of Fusion society system, is 4000mJ/cm in the accumulation light quantity of the wavelength of 365nm
2Under the condition, make resin combination be solidified into 30mm * 10mm * 1mm shape.Measure after the initial weight of this cured body, dipping was measured the weight of this cured article in 24 hours in 25 ℃ water.The swelling capacity of each resin combination is by swelling capacity (%)=(dipping after fixing thing weight-initial solidification thing weight)/initial solidification thing weight * 100 are calculated the results are shown in of gained and shown 2-7.Consequently, compare with the resin combination of use wetting ability (methyl) acrylate of comparative example, low even the resin combination of embodiment 2-1 impregnated in 25 ℃ of water its swelling capacity, the influences of using when therefore being difficult to be subject to processing such as cutting fluid.
Table 2-7
| Resin combination No. | Swelling capacity (%) | |
| Embodiment 2-26 | Embodiment 2-1 | 0.8 |
| Comparative example 2-9 | Comparative example 2-5 | 100 |
| Comparative example 2-10 | Comparative example 2-6 | Because dissolving can not be measured |
Embodiment 3-1
Add purple light UV-7000B as (A3) urethanum (methyl) acrylate (Japanese synthetic chemistry society system, hereinafter to be referred as UV-7000B) 35 mass parts, (B3) as the n-acrylyl oxy-ethyl hexahydrophthalic phthalimide of n-(methyl) acryloyloxyalkyl hexahydrophthalic phthalimide (the system TO-1429 of the synthetic society in East Asia, hereinafter to be referred as TO-1429) 40 mass parts, ω-carboxyl-polycaprolactone one (methyl) acrylate (system ア ロ two Star Network ス M-5300 of the synthetic society in East Asia as (methyl) acrylate that contains carboxyl, hereinafter to be referred as M-5300) 5 mass parts and as (the system light of the common prosperity society chemistry society acrylate PO-A of the monomeric phenoxyethyl acrylate of (methyl) acrylic acid derivative with general formula (C3) structure, hereinafter to be referred as PO-A) 20 mass parts, add up to totally 100 mass parts, reach (D3) Photoepolymerizationinitiater initiater BDK1.5 mass parts, polymerization retarder MDP0.1 mass parts prepares composition.The composition that use makes carries out the mensuration and the stripping test of tensile shear bond strength, and its result is shown in table 3-1.
Table 3-1
| Embodiment No. | 3-1 | 3-2 | 3-3 | 3-4 | 3-5 | 3-6 | 3-7 |
| (A3) composition (mass parts) UV-7000B worker ベ Network リ Le-2001 | 35 | 20 | 35 | 35 | 35 | 50 | 20 |
| (B3) composition (mass parts) TO-1429 M-5300 PO-A M-5700 | 40 5 20 | 55 5 20 | 40 5 20 | 40 5 20 | 25 20 20 | 25 5 20 | 55 5 20 |
| (D3) Photoepolymerizationinitiater initiater (mass parts) BDK TPO | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 |
| Polymerization retarder (mass parts) MDP | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | |
| Bond strength (Mpa) | 15.9 | 13.3 | 18.1 | 13.4 | 13.8 | 12.1 | 14.2 |
| 80 ℃ of warm water splitting times (branch) | 60 | 100 | 150 | 78 | 120 | 87 | 55 |
| Peel off state **) | Film like | Film like | Film like | Film like | Film like | Film like | Film like |
*) film like: the solidified adhesive compound does not residue in glass surface and peels off with film like
Form the use shown in table 3-1 except that the starting material of kind shown in the table 3-1, prepare composition as embodiment 3-1.Composition that makes such as embodiment 3-1 carry out the mensuration and the stripping test of tensile shear bond strength.It the results are shown in table 3-1.
The materials used name
ェ ベ Network リ Le 2001: water soluble amino ethyl formate acrylate (the system ェ ベ of ダ イ ゼ Le UCB society Network リ Le 2001)
M-5700: 2-hydroxyl-3-phenoxy propyl acrylate (the system ア ロ ニ of the synthetic society in East Asia Star Network ス M-5700)
Comparative example 3-1～3-5
Remove the starting material of kind shown in the table 3-2, shown in table 3-1, form outside the use, prepare composition as embodiment 3-1.The composition that makes carries out the tensile shear bond strength as embodiment 3-1 and measures and stripping test.It the results are shown in table 3-2.
Table 3-2
| Comparative example No. | 3-1 | 3-2 | 3-3 | 3-4 | 3-5 |
| (A3) composition (mass parts) UV-7000B | 25 | 5 | 5 | ||
| (B3) composition (mass parts) TO-1429 M-5300 PO-A MTEGMA | 10 55 10 | 70 5 20 | 5 5 85 | 70 | |
| Other composition acryloyl morpholine | 100 | 30 | |||
| (D3) Photoepolymerizationinitiater initiater (mass parts) BDK TPO | 1.5 | 1.5 | 1.5 | 1.5 | 2.5 |
| Polymerization retarder (mass parts) MDP | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| Bond strength (MPa) | 11.1 | 17.0 | 5.1 | 2.0 | 8.4 |
| 80 ℃ of warm water splitting times (branch) | Nothing is peeled off | Nothing is peeled off | Nothing is peeled off | 30 | 60 |
| Peel off state **) | - | - | - | Residual | Residual |
*) residual: glass is stripped from, but the solidified adhesive compound residues in glass surface.
Embodiment 3-8
Use the composition of embodiment 3-1, carry out bonding curing as sample glass as embodiment 3-1 with the blue or green sheet glass that uses among the pyrex glass of 150mm * 150mm * 2mmt and the embodiment 3-1.
Only the pyrex glass with described adhesive test body partly utilizes cutting unit to be cut into 10mm four directions type.Coming off or breakage of pyrex glass do not taken place in the cutting, and cutting processing is good.The adhesive test body of the pyrex glass part of only having cut be impregnated in 80 ℃ of warm water, and 120min all peels off.
Utilize possibility on the industry
Composition of the present invention because its composition has curing, is cured under visible light or ultraviolet ray, and its firming body is not affected by cutting fluid etc., can realize high bonding strength. Therefore be difficult for being offset during tool member, have the effect that is easy to make the good member of dimensional accuracy. And, reduce bonding strength by contacting with warm water, and between the reduction member or the adhesion of member and anchor clamps, thereby be easy to reclaim member based on this feature, thereby can be used as optical mirror slip, prism, array, silicon chip, semiconductor installation component etc. temporary fixedly stick with glue agent, be effectively applied to industry.
The method of temporarily fixing of member of the present invention, utilization has the composition of aforementioned feature, need not use in the prior art the organic solvent that must use, and be easy to from member, reclaim with film-form, therefore having good workability is feature, industrially very effective.
Also have, so far quote Japanese patent application 2005-110798 number that applied on April 7th, 2005, Japanese patent application 2005-110799 number of on April 7th, 2005 application, and the full content of scope, accompanying drawing and the summary of Japanese patent application 2005-78298 number specification sheets of on March 18th, 2005 application, claim, as the announcement of specification sheets of the present invention.
Claims (16)
1. composition; it is characterized in that; contain (A1): it is (methyl) acrylate more than 500 that the end of molecule or side chain have (methyl) acryl, molecular weight more than 1; (B1): multifunctional (methyl) acrylate; (C1): (methyl) acrylate outside described (A1), (B1), and (D1): Photoepolymerizationinitiater initiater.
2. composition as claimed in claim 1 is characterized in that, (A1) for being selected from polyhutadiene, polyisoprene and described both more than a kind of arbitrary hydride.
3. composition as claimed in claim 1 or 2 is characterized in that, (A1), (B1) and (C1) all have a hydrophobicity.
4. as each described composition in the claim 1 to 3, it is characterized in that, contain (A1) 5～80 mass parts, (B1) 1～50 mass parts, (C1) 5～80 mass parts, (D1) 0.1～20 mass parts.
5. composition; it is characterized in that; contain (A2): it is (methyl) acrylate more than 500 that the end of molecule or side chain have (methyl) acryl, molecular weight more than 1; (B2): multifunctional (methyl) acrylate; (C2): (methyl) acrylate outside described (A2), (B2); (D2): Photoepolymerizationinitiater initiater, and (E2) polar organic solvent.
6. composition as claimed in claim 5 is (E2) for being selected from more than a kind of methyl alcohol, ethanol, Virahol and propyl carbinol.
7. as claim 5 or 6 described compositions, it is characterized in that, (A2), (B2) and (C2) all have a hydrophobicity.
8. as each described composition in the claim 5 to 7, it is characterized in that, contain (A2) and (B2) 1～50 mass parts, (C2) 5～95 mass parts, (D2) 0.1～20 mass parts, (E2) 0.5～10 mass parts.
9. a tackiness agent is characterized in that, is formed by each described composition in the claim 1 to 8.
10. the method for temporarily fixing of a member, it is characterized in that, utilize the bonding working fastening member of each described composition in the claim 1 to 8, process after this member that is temporarily fixed, this member that processes be impregnated in the warm water below 90 ℃, remove the cured body of described resin combination.
11. a composition is characterized in that, contains following (A3), (B3) and (D3),
(A3): urethanum (methyl) acrylate,
(B3): by being selected from monomeric (methyl) acrylic acid derivative monomer formed more than a kind or 2 kinds of (methyl) acrylic acid derivative shown in n-(methyl) acryloxyalkyl hexahydrophthalic phthalimide, carboxylic (methyl) acrylate and the general formula (C3)
General formula (C3): Z-O-(R
2O)
P-R
1
In the formula, Z represents (methyl) acryl, R
1Expression phenyl or have the phenyl of the alkyl of 1～3 of carbon number, R
2Expression-C
2H
4-,-C
3H
6-,-CH
2CH (CH
3)-,-CH
2CH (OH) CH
2-,-C
4H
8-or-C
6H
12-, p represents 1～10 integer,
(D3): Photoepolymerizationinitiater initiater.
12. composition as claimed in claim 11 is characterized in that, urethanum (A3) (methyl) acrylate is water-soluble.
13. a tackiness agent is characterized in that, is formed by claim 11 or 12 described compositions.
14. the method for temporarily fixing of a member is characterized in that, utilization contacts the tackiness agent adhesive member that can reduce bond strength with water, cured adhesive carries out working fastening, process after the member of this working fastening, this member that processes be impregnated in the water, remove the solidified tackiness agent.
15. the method for temporarily fixing of a member, it is characterized in that, utilization contacts the tackiness agent adhesive member that can reduce bond strength with water, cured adhesive carries out working fastening, process after the member of this working fastening, this member that processes be impregnated in the water, remove with film like solidified tackiness agent after the swelling.
16. the method for temporarily fixing of a member is characterized in that, utilizes the described tackiness agent adhesive member of claim 13, cured adhesive carries out working fastening, process after this working fastening member, this member that processes be impregnated in the water, remove with film like solidified tackiness agent after the swelling.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP078298/2005 | 2005-03-18 | ||
| JP2005078298A JP4593328B2 (en) | 2005-03-18 | 2005-03-18 | Temporary fixing adhesive composition and temporary fixing method |
| JP110798/2005 | 2005-04-07 | ||
| JP2005110798A JP4749751B2 (en) | 2005-04-07 | 2005-04-07 | Temporary fixing method for members |
| JP2005110799 | 2005-04-07 | ||
| JP110799/2005 | 2005-04-07 | ||
| PCT/JP2005/010612 WO2006100788A1 (en) | 2005-03-18 | 2005-06-09 | Adherent composition and method of temporarily fixing member therewith |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110286355.8A Division CN102516893B (en) | 2005-03-18 | 2005-06-09 | Adherent composition and method of temporarily fixing member therewith |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101146837A true CN101146837A (en) | 2008-03-19 |
| CN101146837B CN101146837B (en) | 2012-06-27 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2005800491464A Active CN101146837B (en) | 2005-03-18 | 2005-06-09 | Adherent composition and method of temporarily fixing member therewith |
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|---|---|
| JP (1) | JP4593328B2 (en) |
| CN (1) | CN101146837B (en) |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN101146837B (en) | 2012-06-27 |
| JP4593328B2 (en) | 2010-12-08 |
| JP2006257312A (en) | 2006-09-28 |
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