JP4314444B2 - Cleaning film, cleaning member, and cleaning method - Google Patents

Description

The present invention relates to a cleaning film and a cleaning member which can clean a portion to be cleaned well due to its self-adhesiveness and which are excellent in flexibility, strength, peelability and heat resistance. More specifically, a cleaning film , a cleaning member , and the like used to remove impurities, dirt, and the like attached to or formed on the surface (including convex portions, side surfaces, etc.) of the electronic component and its inspection equipment (inspection component) The present invention relates to a cleaning method .

In the manufacturing process of a semiconductor device using a semiconductor wafer, for example, after the manufacturing process of the semiconductor wafer is completed and before being cut into individual chips, the performance test of the wafer is usually performed with a probe card, and the function is It is evaluated whether it is normal. This performance test is performed by bringing a plurality of probes arranged on the probe card into contact with a predetermined portion (measurement unit) of the wafer, and an electrical characteristic, an operation state, and the like are evaluated. However, when this performance test is performed over a long period of time, impurities such as fine particles made of metal, oxide, etc. adhere to the tip of the probe. If the amount of adhering impurities increases, the accuracy of the performance test decreases and the quality of the final product is affected. Therefore, it is necessary to remove impurities attached to the tip of the probe after using the probe card a certain number of times.
In addition, even when fine cutting chips or the like are accumulated on the surface of the cut chip, the quality of the final product is affected. Therefore, a process for cleaning the surface of the chip may be required.
Furthermore, depending on the manufacturing process of various products, heat treatment may be required, heat may be generated, etc., and the parts to be cleaned (including the surface to be cleaned) should be cleaned in a high temperature state, that is, not necessarily a room temperature ambient temperature. There is a case where it is required.
Therefore, in order to remove impurities, dirt, and the like attached to or formed on the surface of the electronic component and its inspection device (inspection component), a method using an adhesive material, a cleaning method using a cleaning liquid, and the like are performed.

As long as a pressure-sensitive adhesive sheet containing a pressure-sensitive adhesive is used as the pressure-sensitive adhesive material, for example, after removing impurities adhering to the tip of the probe, it may be unavoidable that the pressure-sensitive adhesive remains at the tip. .
Further, when cleaning is performed with a cleaning liquid or the like, a new process for completely removing the used cleaning liquid is required, resulting in an increase in cost.
The object of the present invention is to clean the parts to be cleaned (including the surface to be cleaned) satisfactorily due to its self-adhesiveness without using an adhesive, and is excellent in flexibility, strength, peelability and heat resistance. Another object of the present invention is to provide a cleaning film , a cleaning member , and a cleaning method .

The present invention is shown below.
1. Inspection comprising an elastomer composition containing at least one polymer selected from hydrogenated diene block polymers and polar group-modified olefin polymers, and used for performance evaluation of electronic components and their electrodes or terminals and electronic components A cleaning film that is used to remove impurities or dirt from a cleaning part by contacting it with a probe or stylus of a device or a part to be cleaned of a magnetic disk .
2. The hydrogenated product of the diene block polymer is at least one selected from a hydrogenated product of a block polymer of a conjugated diene and a hydrogenated product of a block copolymer comprising a conjugated diene and an aromatic vinyl compound. The cleaning film as described in.
3. The hydrogenated diene block polymer has a mass ratio of the butadiene polymer block (I) having a vinyl bond content of less than 25%, the conjugated diene unit (a1) and the other monomer unit (a2). Diene having (a1) / (a2) = (100-50) / (0-50) and at least one polymer block (II) having a vinyl bond content of 25-95% in the molecule. 3. The cleaning film according to 1 or 2 above, wherein the olefinically unsaturated bond in the system block polymer is hydrogenated.
4). The polar group-modified olefin polymer is at least one selected from a polar group-modified ethylene / α-olefin copolymer and a polar group-modified ethylene / α-olefin / non-conjugated diene copolymer, and the elastomer. 2. The cleaning film according to 1 above, wherein the composition contains metal ions and / or metal compounds.
5. 5. The cleaning film according to 4 above, wherein the polar group is selected from a carboxyl group, a hydroxyl group, an epoxy group, an amino group, an alkoxysilyl group, a sulfonic acid group, and a nitrile group.
6). The said elastomer composition contains a liquid material, The content of this liquid material is 50-5000 mass parts with respect to a total of 100 mass parts of a polymer component, The cleaning film in any one of said 1 thru | or 5 .
7). 7. The cleaning film as described in any one of 1 to 6 above, wherein at least a part of the elastomer composition is crosslinked.
8). 8. The cleaning film as described in any one of 1 to 7 above, further containing abrasive particles.
9. 9. The cleaning film as described in any one of 1 to 8 above, which has a thickness of 0.1 to 2000 μm.
10. 10. The cleaning film according to any one of 1 to 9 above, wherein at least one surface of the cleaning film is provided with a portion selected from a convex portion, a concave portion, a groove portion, and a cut portion.
11. 11. The cleaning film according to any one of 1 to 10 above, wherein a protective film is provided on at least one surface of the cleaning film.
12 12. The cleaning film as described in any one of 1 to 11 above, which is used for cleaning the probe of the probe guard.
13 . 13. A cleaning member comprising the cleaning film according to any one of 1 to 12 above disposed on a support layer.
14 The cleaning film according to any one of 1 to 12 or the cleaning film of the cleaning member according to 13 above, an electronic component and an electrode or a terminal thereof, a probe or a stylus of an inspection device used for performance evaluation of various electronic components, Alternatively, a cleaning method of removing the impurities or dirt of the cleaned portion by contacting the cleaned portion with the cleaning film by contacting the cleaned portion of the magnetic disk.
15. A probe card probe is inserted or pressed against the cleaning film according to any one of 1 to 12 or the cleaning member according to 13 above, and the probe and the cleaning film are brought into contact with each other. A probe card probe cleaning method for removing impurities or dirt on the probe surface by adhering to the cleaning film.

According to the cleaning film of the present invention, due to its self-adhesiveness, the portion to be cleaned (including the surface to be cleaned) can be cleaned well without using an adhesive.
When this cleaning film is a film formed by crosslinking a specific polymer, it is particularly excellent in flexibility, strength, peelability and the like.
In addition, when the present cleaning film contains abrasive particles, it is possible to remove the dirt and the like firmly adhered by the abrasive particles and at the same time adsorb and remove the dirt residue by the adhesive force of the film.
Furthermore, when the portion to be cleaned has a complicated shape such as a needle shape, it can be efficiently cleaned by using a cleaning film having a portion selected from a convex portion, a concave portion, a groove portion and a cut portion.
According to the cleaning member of the present invention, the portion to be cleaned can be cleaned well by the self-adhesive cleaning film.

Hereinafter, the present invention will be described in detail.
The cleaning film of the present invention is characterized by comprising an elastomer composition containing at least one polymer selected from a hydrogenated diene block polymer and a polar group-modified olefin polymer.

First, the hydrogenated product of the diene block polymer will be described.
The hydrogenated product of the diene block polymer is not particularly limited as long as it is a hydrogenated product of a diene block polymer. The diene block polymer may be a block copolymer of a conjugated diene or a block copolymer composed of a conjugated diene and one or more other monomers. Therefore, examples of the block structure of the diene block polymer include (AB) _mA , (BA) _m B, (ABA) _m , and (BABB) _m. are _{further, (a-B) m X} , (B-a) m X, (a-B-a) m X, as such _{(B-a-B) m} X, coupling agent residue X The polymer molecular chain may be extended or branched via In each general formula, “A” is a block mainly composed of conjugated diene units, “B” is a block mainly composed of other conjugated diene units or other monomer units, and m is an integer of 1 or more.

Examples of the conjugated diene include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4, Examples include 5-diethyl-1,3-octadiene and chloroprene. Of these, 1,3-butadiene, isoprene and 1,3-pentadiene are preferable, and 1,3-butadiene and isoprene are particularly preferable. In addition, the compound illustrated above can be used individually by 1 type or in combination of 2 or more types.
Examples of the block copolymer using these conjugated dienes include polybutadiene having two or more butadiene polymer blocks, polyisoprene having two or more isoprene polymer blocks, and the like.

  As other monomers in the case of a copolymer, styrene, t-butylstyrene, α-methylstyrene, α-chlorostyrene, p-methylstyrene, divinylbenzene, N, N-diethyl-p- Examples thereof include aromatic vinyl compounds such as aminostyrene; vinyl cyanide compounds such as (meth) acrylonitrile; nitrogen atom-containing vinyl compounds such as vinylpyridine. Of these, aromatic vinyl compounds are preferable, and styrene and α-methylstyrene are particularly preferable. In addition, the compound illustrated above can be used individually by 1 type or in combination of 2 or more types. When the diene block polymer is a block copolymer composed of a conjugated diene and another monomer, the conjugated diene unit is random and tapered (the ratio of the conjugated diene unit increases or decreases along the molecular chain). And a distribution selected from some blocks.

  Examples of block copolymers comprising conjugated dienes and one or more other monomers include styrene / butadiene block copolymers, styrene / isoprene block copolymers, isobutylene / isoprene block copolymers, acrylonitrile / Examples thereof include a butadiene block copolymer, a styrene / butadiene / styrene block copolymer, and a styrene / isoprene / styrene block copolymer.

  As the diene block polymer to be a hydrogenated diene block polymer according to the present invention, a butadiene polymer block (I) having a vinyl bond content of less than 25%, a conjugated diene unit (a1), and Polymer block (II) in which the mass proportion of other monomer units (a2) is (a1) / (a2) = (100-50) / (0-50) and the vinyl bond content is 25-95% ) Is preferably a diene block polymer (hereinafter referred to as “polymer (P)”).

  In the butadiene polymer block (I), the content of vinyl bonds (1,2-vinyl bonds) is preferably less than 25%, more preferably 5 to 20%, still more preferably 7 to 19%. Therefore, the butadiene polymer block (I) becomes a crystalline block showing a structure similar to an ethylene / butene copolymer by hydrogenation. By setting the vinyl bond content within the above range, the mechanical properties and shape retention of the molded product can be improved.

The polymer block (II) may be a block composed only of a conjugated diene unit, or may be a block composed of a conjugated diene unit (a1) and another monomer unit (a2). . The mass ratio (a1) / (a2) of the conjugated diene unit (a1) and the other monomer unit (a2) is preferably (100-50) / (0-50), more preferably (100- 70) / (0-30), more preferably (100-90) / (0-10). By setting it as such a range, the molded object excellent in viscoelasticity can be obtained.
In the polymer block (II), the content of vinyl bonds (1,2-vinyl bond and 3,4-vinyl bond) is preferably 25 to 95%, more preferably 25 to 90%, Preferably it is 30 to 85%.

Therefore, when the polymer block (I) is “A ¹ ” and the polymer block (II) is “B ¹ ”, the polymer (P) is (A ¹ -B ¹ ) _m1 , (A ¹ -B ¹⁾ _m2 -A ^1, it is possible to use those represented by _{^{(B 1 -A 1) m3 -B}} 1 or the like. In each general formula, m1 to m3 represent an integer of 1 or more.
Moreover, if the said polymer (P) is a copolymer which has a block more than a triblock, when it is made into a hydrogenated substance, the molded object which is excellent in shape retention property and a mechanical property can be obtained. Therefore, in the above general formula, m1 is preferably an integer of 2 or more.

  The polymer (P) may have at least one of the butadiene polymer block (I) and the polymer block (II) in the molecule, and in addition to these, other blocks such as Further, it may be a polymer having a block composed of a monomer unit other than the conjugated diene unit.

  The content ratio (I) / (II) of the butadiene polymer block (I) and the polymer block (II) constituting the polymer (P) is preferably (70-10) / (30-90). More preferably, (50 to 10) / (50 to 90), still more preferably (40 to 15) / (60 to 85). By setting the content ratio of each of the blocks in the above range, a molded product particularly excellent in shape retention and mechanical properties can be obtained.

Also in the polymer _{^{(P), (A 1 -B}} 1) n X, (B 1 -A 1) n X, (A 1 -B 1 -A 1) n X, (B 1 -A 1 -B ¹⁾ as such n _X, or it may be via a coupling agent residue X which polymer molecular chain is extended or branched. In each general formula, n represents an integer of 2 or more. Moreover, in said each general formula, when n is three or more, the molded object excellent in shape retainability, hot-melt viscosity, and adhesiveness can be obtained.
As the coupling agent, 1,2-dibromoethane, methyldichlorosilane, trichlorosilane, methyltrichlorosilane, tetrachlorosilane, tetramethoxysilane, divinylbenzene, diethyl adipate, dioctyl adipate, benzene-1,2,4 -Triisocyanate, tolylene diisocyanate, epoxidized 1,2-polybutadiene, epoxidized linseed oil, tetrachlorogermanium, tetrachlorotin, butyltrichlorotin, butyltrichlorosilane, dimethylchlorosilane, 1,4-chloromethylbenzene, Bis (trichlorosilyl) ethane and the like can be mentioned.

  In the formation of the hydrogenated product of the polymer (P), it can be obtained by the method disclosed in JP-A-2-133406, JP-A-3-128957, JP-A-5-170844 and the like. . The hydrogenation rate of the obtained hydrogenated product is preferably 80% or more, more preferably 85% or more, and particularly preferably 90% or more. The higher the hydrogenation rate, the better the shape retention and mechanical properties when formed into a molded body.

  When the elastomer composition is mainly a hydrogenated diene block copolymer, it may contain other polymers as long as it does not affect the flexibility of the molded product. The other polymer may be a resin or an elastomer (including rubber). Furthermore, you may combine resin and an elastomer. Other polymers are not hydrogenated polymers, that is, non-hydrogenated diene polymers, acrylic polymers, urethane polymers, polyamide polymers, polyester polymers, vinyl chloride polymers. , Fluorine-based polymers, silicone-based polymers, and the like. These can be used alone or in combination of two or more.

  Examples of the diene polymer include polybutadiene, polyisoprene, styrene / butadiene copolymer, styrene / isoprene copolymer, isobutylene / isoprene copolymer, acrylonitrile / butadiene copolymer, styrene / butadiene / styrene block copolymer. Examples thereof include polymers and styrene / isoprene / styrene block copolymers. These can be used alone or in combination of two or more.

  The above-mentioned isobutylene / isoprene copolymer is generally known as “butyl rubber (IIR)”. However, isobutylene and isoprene and other monomers such as a compound having a polar group (hereinafter referred to as “polar group”). Or a partially cross-linked copolymer thereof.

As the polar group-containing compound, an organic compound having at least one selected from a hydroxyl group, an epoxy group, an amino group, a carboxyl group, an alkoxysilyl group, a nitrile group, and the like can be used.
The partially cross-linked copolymer can be obtained by copolymerizing a compound having a polyfunctional unsaturated bond with these polar group-containing compounds. ) Acrylate compounds, divinyl compounds, bismaleimide compounds, dioxime compounds and the like.

  The butyl rubber may be a chlorinated isobutylene / isoprene copolymer, a brominated isobutylene / isoprene copolymer or the like in which an isobutylene / isoprene copolymer or the like is halogenated.

Examples of the acrylic polymer include a polymer obtained from a monomer containing an alkyl acrylate ester.
Examples of the acrylic acid alkyl ester include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-methylpentyl acrylate, and n-octyl acrylate. 2-ethylhexyl acrylate, n-decyl acrylate, n-dodecyl acrylate, n-octadecyl acrylate, cyanomethyl acrylate, 1-cyanoethyl acrylate, 2-cyanoethyl acrylate, 1-cyanopropyl acrylate, 2-cyanopropyl acrylate, 3-cyano Propyl acrylate, 4-cyanobutyl acrylate, 6-cyanohexyl acrylate, 2-ethyl-6-cyano Hexyl acrylate, 8-cyano-octyl acrylate. These can be used alone or in combination of two or more.

The acrylic polymer may be a copolymer of an acrylic acrylic ester and another monomer, for example, an acrylic rubber. In that case, an acrylic acid alkoxyalkyl ester, an ethylenically unsaturated compound, Crosslinkable compounds and the like can be used as other monomers.
Examples of the alkoxyalkyl ester of acrylic acid include 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2- (n-propoxy) ethyl acrylate, 2- (n-butoxy) ethyl acrylate, 3-methoxypropyl acrylate, 3-ethoxy Examples include propyl acrylate, 2- (n-propoxy) propyl acrylate, and 2- (n-butoxy) propyl acrylate.

  Examples of the ethylenically unsaturated compounds include compounds having a carboxyl group such as acrylic acid, methacrylic acid, crotonic acid, 2-pentenoic acid, maleic acid, fumaric acid, and itaconic acid; 1,1-dihydroperfluoroethyl (meth) acrylate 1,1-dihydroperfluoropropyl (meth) acrylate, 1,1,5-trihydroperfluorohexyl (meth) acrylate, 1,1,2,2-tetrahydroperfluoropropyl (meth) acrylate, 1,1,7- Fluorinated acrylates such as trihydroperfluoroheptyl (meth) acrylate, 1,1-dihydroperfluorooctyl (meth) acrylate, 1,1-dihydroperfluorodecyl (meth) acrylate; 1-hydroxypropyl (meth) acrylate, 2 -Hydro Compounds having a hydroxyl group such as cypropyl (meth) acrylate and hydroxyethyl (meth) acrylate; Monomers having a tertiary amino group such as diethylaminoethyl (meth) acrylate and dibutylaminoethyl (meth) acrylate; methyl methacrylate; Methacrylic acid esters such as octyl methacrylate; Alkyl vinyl ketones such as methyl vinyl ketone; Vinyl and allyl ethers such as vinyl ethyl ether and allyl methyl ether; Vinyl aromatic compounds such as styrene, α-methyl styrene, chlorostyrene and vinyl toluene; Vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; ethylene, propylene, butene, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, vinyl acetate, propionic acid Examples include vinyl and alkyl fumarate.

  Examples of the crosslinkable compound include a diene compound, a (meth) acrylic acid ester having a dihydrodicyclopentadienyl group, an ethylenically unsaturated compound having an epoxy group, an active halogen-containing ethylenically unsaturated compound, and a carboxyl group. Examples thereof include an ethylenically unsaturated compound and an ethylenically unsaturated compound having an active hydrogen group.

Examples of the urethane polymer include those obtained by reacting an organic diisocyanate, a polymer diol, and a chain extender.
Examples of the organic diisocyanate include 4,4′-diphenylmethane diisocyanate, tolylene diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate, phenylene diisocyanate, and 3,3′-dichloro-4,4′-diphenylmethane diisocyanate. Aliphatic or alicyclic diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate and hydrogenated xylylene diisocyanate. These organic diisocyanates can be used alone or in combination of two or more.

Examples of the polymer diol include polyester diol, polyether diol, polycarbonate diol, polyester polycarbonate diol, and polyester polyether diol.
Among these, as polyester diol, aliphatic polyester diol obtained by reaction of aliphatic diol and aliphatic dicarboxylic acid or their ester-forming derivatives, aliphatic diol and aromatic dicarboxylic acid or their ester-forming derivatives Aromatic polyester diol obtained by the above reaction. Examples of the polyether diol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, or block copolymers thereof. Further, examples of the polycarbonate diol include polycarbonate diol obtained by reaction of an aliphatic diol and a carbonate compound, polycarbonate diol obtained by reaction of an aromatic diol such as bisphenol A and a carbonate compound, and the like. These polymer diols can be used singly or in combination of two or more.

  As the chain extender, a conventionally known chain extender can be used, and a low molecular weight compound having a molecular weight of 300 or less having two or more active hydrogen atoms capable of reacting with an isocyanate group in the molecule, such as ethylene glycol, Propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-bis (β-hydroxyethoxy) benzene, 1,4-cyclohexanediol, bis- (β-hydroxyethyl) terephthalate, xylylene glycol Diols such as hydrazine, ethylenediamine, propylenediamine, xylylenediamine, isophoronediamine, piperazine and derivatives thereof, diamines such as phenylenediamine, tolylenediamine, xylenediamine, adipic acid dihydrazine, and isophthalic acid dihydrazine, aminoethyl And amino alcohols such as alcohol and aminopropyl alcohol. These can be used alone or in combination of two or more.

  Examples of the polyamide polymer include a copolymer composed of a hard segment made of polyamide and a soft segment made of polyester, polyether, polyester / polyether or the like.

  The polyamide segment has carbon numbers such as ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopergonic acid, ω-aminocapric acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, etc. Segments derived from 6 or more aminocarboxylic acids; segments derived from lactams such as caprolactam and laurylactam; ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 1,4-butanediamine, 1 , 5-pentanediamine, 3-methyl-1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 2-methyl-1,8-octanediamine, , 9-nonanediamine, 1,10-decanediamine, 1,11-undeca Diamine components such as diamine, 1,12-dodecanediamine, cyclohexanediamine, and glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, orthophthalic acid, naphthalene- Examples thereof include segments derived from dicarboxylic acid components such as 2,6-dicarboxylic acid, diphenyl-4,4′-dicarboxylic acid and diphenoxyethanedicarboxylic acid.

  Examples of the polyester segment include a segment derived from a hydroxycarboxylic acid such as ω-oxycaproic acid; a segment derived from a lactone such as ε-caprolactone; glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacin Dicarboxylic acid components such as acid, dodecanedioic acid, terephthalic acid, isophthalic acid, orthophthalic acid, naphthalene-2,6-dicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, diphenoxyethanedicarboxylic acid, ethylene glycol, diethylene glycol , Triethylene glycol, tetraethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, Examples thereof include segments derived from diol components such as 1,10-decanediol, cyclohexanedimethanol and cyclohexanediol.

  Examples of the polyether segment include segments such as polymethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and polyhexamethylene glycol.

  Furthermore, as the polyester polyether segment, a segment derived from the dicarboxylic acid component of the above-described polyester segment and a diol component such as polymethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, etc. Is mentioned.

  Examples of the polyester polymer include polyesters such as polybutylene terephthalate as hard segments and polyesters such as polytetramethylene glycol ether (PTMG) and PTMEG (condensate of PTMG and terephthalic acid) as soft segments. Polyether type polymer; polyester / polyester type polymer having a polyester as a hard segment and an aliphatic polyester such as polycaprolactone as a soft segment.

Examples of the fluorine-based polymer include polymers obtained from monomers containing vinylidene fluoride. Examples of other monomers include perfluorovinyl ether, tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, ethylene, propylene, and a crosslinkable compound.
In addition to the above, polymers such as an ethylene / vinyl acetate copolymer, a styrene polymer, a polycarbonate, a polyacetal, and an epoxy polymer can also be used.

  The content in the case of using these other polymers is preferably 1 to 100 parts by mass, more preferably 1 to 90 parts by mass, and still more preferably 1 to 100 parts by mass of the hydrogenated product of the diene block polymer. ~ 80 parts by mass.

  When the cleaning film of the present invention is composed of an elastomer composition mainly composed of the hydrogenated product of the diene block copolymer, the polymer containing the hydrogenated product of the diene block copolymer is crosslinked. It may or may not be. Examples of the method for crosslinking include a method using a known crosslinking agent, a method by irradiation with radiation such as ultraviolet rays and electron beams, and the like.

When using a crosslinking agent, an organic peroxide, sulfur, a sulfur containing compound, etc. can be used, for example.
Organic peroxides include t-butyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, p-menthane hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5 -Dimethylhexane-2,5-dihydroperoxide, 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, di-t-butyl peroxide, t-butylcumyl peroxide, dic Milperoxide, 1,1-bis (t-butylperoxy) cyclododecane, 2,2-bis (t-butylperoxy) octane, 1,1-di-t-butylperoxycyclohexane, 2,5- Dimethyl-2,5-di- (t-butylperoxy) hexane, 2,5-dimethyl 2,5-di- (t-butylperoxy) hexyne, 1,3-bis (t-butylperoxy-isopropyl) benzene, 2,5-dimethyl-2,5-di- (benzoylperoxy) Hexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-bis (t-butylperoxy) valerate, bazoyl peroxide, m-toluyl Peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, t-butylperoxyisobutyrate, t-butylperoxy-2-ethylhexanoate, t-butylperoxybenzoate, t- Examples thereof include butyl peroxy-isopropyl carbonate and t-butyl peroxyallyl carbonate. These can be used alone or in combination of two or more.

  When the hydrogenated product of the diene block copolymer is cross-linked, at least a part of the elastomer composition forms a three-dimensional skeleton due to the cross-linked structure, so that flexibility, strength, peelability and heat resistance are increased. A molded article having excellent properties can be formed, and the portion to be cleaned can be cleaned well without containing an adhesive.

  Next, the polar group-modified olefin polymer will be described. Examples of the polar group-modified olefin polymer include those having a polar group in polyethylene, polypropylene, polybutene, ethylene / α-olefin copolymer, ethylene / α-olefin / non-conjugated diene copolymer, and the like. These can be used alone or in combination of two or more. Examples of the polar group include a carboxyl group, a hydroxyl group, an epoxy group, an amino group, an alkoxysilyl group, a sulfonic acid group, and a nitrile group. These polar groups may have only one type per molecule, or may have two or more types.

The α-olefin in the ethylene / α-olefin copolymer and the ethylene / α-olefin / non-conjugated diene copolymer is an α-olefin excluding ethylene. Examples of the α-olefin include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, and 3-ethyl-1. -Pentene, 1-octene, 1-decene, 1-undecene and the like can be mentioned, and α-olefins having 3 to 12 carbon atoms are preferable, and propylene and 1-butene are particularly preferable. In addition, the alpha-olefin illustrated above can be used individually by 1 type or in combination of 2 or more types.
Examples of the ethylene / α-olefin copolymer include ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / 1-pentene copolymer, ethylene / 3-methyl-1-butene copolymer, ethylene 1-hexene copolymer, ethylene-3-methyl-1-pentene copolymer, ethylene / 4-methyl-1-pentene copolymer, ethylene-3-ethyl-1-pentene copolymer, ethylene / 1 -An octene copolymer, an ethylene / 1-decene copolymer, an ethylene / 1-undecene copolymer, etc. are mentioned. Of these, ethylene / propylene copolymers and ethylene / 1-butene copolymers are preferred. The ethylene / α-olefin copolymers exemplified above can be used singly or in combination of two or more.

In addition, as the non-conjugated diene in the case of the ethylene / α-olefin / non-conjugated diene copolymer, 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,7-octadiene, 1, 9-decadiene, 3,6-dimethyl-1,7-octadiene, 4,5-dimethyl-1,7-octadiene, 5-methyl-1,8-nonadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 2,5-norbornadiene and the like can be mentioned. These can be used alone or in combination of two or more.
Examples of the ethylene / α-olefin / non-conjugated diene copolymer include ethylene / propylene / dicyclopentadiene copolymer, ethylene / propylene / 5-ethylidene-2-norbornene copolymer, ethylene / 1-butene / dicyclopentadiene. And a copolymer, an ethylene / 1-butene / 5-ethylidene-2-norbornene copolymer, and the like. These can be used alone or in combination of two or more.

  In order to make the ethylene / α-olefin copolymer and the ethylene / α-olefin / non-conjugated diene copolymer have the polar group, in the formation of each polymer, the ethylene / α-olefin copolymer has the polar group. An unsaturated compound may be used as a monomer. Such unsaturated compounds can be used singly or in combination of two or more. The amount of the unsaturated compound used is preferably 0.01 to 10 mol%, more preferably 0.1 to 5 mol%, based on the total amount of monomers.

（上記一般式（１）において、Ｒ^１は、水素原子又は炭素数１〜１０の炭化水素基であり、Ｙ^１、Ｙ^２及びＹ^３は、それぞれ独立して、水素原子、炭素数１〜１０の炭化水素基又は−ＣＯＯＨであり、Ｙ^１、Ｙ^２及びＹ^３のうち少なくとも１つは−ＣＯＯＨであり、また、Ｙ^１、Ｙ^２及びＹ^３のうち２つ以上が−ＣＯＯＨである場合は、それらは互いに連結して形成された酸無水物（−ＣＯ−（Ｏ）−ＣＯ−）であってもよい。ｐは０〜２の整数であり、ｑは０〜５の整数である。） As an unsaturated compound having a carboxyl group, maleic anhydride, (meth) acrylic acid, a cyclic compound represented by the following general formula (1), or the like can be used.

In (the above general formula (1), ^{R 1} is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon ^atoms, Y 1, ^{Y 2} and ^{Y 3} are each independently a hydrogen atom, 1 to carbon atoms 10 hydrocarbon groups or —COOH, at least one of Y ¹ , Y ² and Y ³ is —COOH, and two or more of Y ¹ , Y ² and Y ³ are —COOH. In the case, they may be acid anhydrides (—CO— (O) —CO—) formed by linking each other, p is an integer of 0-2, and q is an integer of 0-5. is there.)

Examples of the cyclic compound include 5,6-dimethyl-5,6-dicarboxy-bicyclo [2.2.1] -2-heptene, 5,6-diethyl-5,6-dicarboxy-bicyclo [2. 2.1] -2-heptene, 5,6-dimethyl-5,6-bis (carboxymethyl) -bicyclo [2.2.1] -2-heptene, 5,6-diethyl-5,6-bis ( Carboxymethyl) -bicyclo [2.2.1] -2-heptene, 5-methyl-5-carboxy-bicyclo [2.2.1] -2-heptene, 5-ethyl-5-carboxy-bicyclo [2. 2.1] -2-heptene, 5-carboxy-5-carboxymethyl-bicyclo [2.2.1] -2-heptene, 5-methyl-5-carboxymethyl-bicyclo [2.2.1] -2 -Heptene, 5-ethyl-5-carboxy Chill - bicyclo [2.2.1] -2-heptene, 8,9-dimethyl-8,9-dicarboxy - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] -3-dodecene, 8,9-diethyl-8,9-dicarboxy-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-methyl-8-carboxy-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-ethyl-8-carboxy-tetracyclo [4.4.0.1 ^2,5 . ^{17, 10} ] -3-dodecene and the like. These can be used alone or in combination of two or more.

The amount of the compound represented by the general formula (1) used is preferably 0.01 to 5 mol%, more preferably 0.01 to 4 mol%, based on the total amount of the monomers. .
The polar group-modified ethylene / α-olefin copolymer or the polar group-modified ethylene / α-olefin / non-conjugated diene copolymer obtained by copolymerizing the compound represented by the general formula (1) is randomly selected. A copolymer is preferred. Further, the weight average molecular weight Mw in terms of polystyrene by GPC of these random copolymers is preferably 1,000 to 3,000,000, more preferably 3,000 to 1,000,000, still more preferably 5. , 000-700,000.

When the elastomer composition is mainly composed of a polar group-modified olefin polymer, it may contain other polymers as long as it does not affect the flexibility of the molded product. The other polymer may be a resin or an elastomer (including rubber). Furthermore, you may combine resin and an elastomer. As other polymers, those exemplified above can be used.
The content in the case of using these other polymers is preferably 1 to 100 parts by mass, more preferably 1 to 90 parts by mass, and still more preferably 1 to 80 parts by mass with respect to 100 parts by mass of the polar group-modified olefin polymer. Part by mass.

  When the cleaning film of the present invention is composed of an elastomer composition mainly composed of the polar group-modified olefin polymer, the polar group-modified olefin polymer is preferably crosslinked.

  In the case where a copolymer obtained by using the cyclic compound represented by the general formula (1) is formed with a chemically crosslinked structure or a structure having a constraint point similar thereto, a metal ion, a metal compound, etc. Can be used. This metal ion also means an ion of an element exemplified below and an ion of a metal compound containing this element. Examples of the metal include lithium, sodium, potassium, aluminum, magnesium, calcium, barium, cesium, strontium, rubidium, titanium, zinc, copper, iron, tin, lead, zirconium, etc. Can be mentioned. The ions containing these elements can also form a crosslinked structure between the copolymers by ionic bonding or electrostatic bonding to the functional group in the random copolymer obtained above. In addition, as a substance for making the ion of the above metal compound, each metal oxide, hydroxide, salt, complex (metal carboxylate, metal acetylacetonate, etc.), an organic compound containing a metal element (having a carbon number) Alkoxides selected from 1 to 8 and containing a metal element).

  The amount of the substance used for forming the ion is 1 equivalent of a unit formed from the cyclic compound constituting the copolymer obtained by using the cyclic compound represented by the general formula (1). , Preferably 0.01 to 50 equivalents, more preferably 0.05 to 10 equivalents, particularly preferably 0.05 to 5 equivalents. If the amount of the substance used for forming the ions is too small, the resulting molded product has a low crosslink density or a constrained point density and tends to be inferior in mechanical strength and heat resistance. On the other hand, when the amount used is too large, the resulting molded article has a high crosslinking density or a constrained point density, and the hardness may be too high and become brittle.

Furthermore, in order to improve the miscibility of the substance for forming the above ions and the heat resistance of the resulting molded body with respect to the copolymer obtained by using the cyclic compound represented by the general formula (1), In addition to the substance for making the ions, a metal salt of an organic acid such as a carboxylic acid may be added as an activator. As the metal salt of the carboxylic acid, a metal salt of a monovalent or divalent carboxylic acid having 3 to 23 carbon atoms is preferably used.
Further, the metal element in the metal salt used as the activator may be selected from the metal elements constituting the substance for forming the ion, but the same kind of element as the metal element constituting the substance for forming the ion It is preferable to use a metal salt containing.

When using the above-mentioned polar group-modified olefin polymer, in addition to cross-linking with metal ions, metal compounds, etc., cross-linking by covalent bonds is also formed by methods such as irradiation with ultraviolet rays and electron beams, methods using organic peroxides, etc. You may let them.
When the polar group-modified olefin polymer is crosslinked, at least a part of the elastomer composition forms a three-dimensional skeleton due to the crosslinked structure, and is excellent in flexibility, strength, peelability and heat resistance. A molded body can be formed, and the portion to be cleaned can be cleaned well without containing an adhesive.

  The elastomer composition according to the present invention constitutes an elastomer composition both in the case of mainly a hydrogenated diene block copolymer and in the case of mainly a polar group-modified olefin polymer. By changing the content ratio with other components (softener, metal ion, etc.), the flexibility and self-adhesiveness of the resulting cleaning film can be adjusted.

In the present invention, it is preferable that the elastomer composition contains a liquid material in order to obtain a molded body with improved flexibility. This not as the liquid material is particularly limited, preferably has a kinematic viscosity at 40 ° C. is ^{500mm 2 / s (1mm 2 /} s = 1cSt) below. More preferred kinematic viscosity 400 mm ² / s or less, more preferably 0.1 to 100 mm ² / s. As such a liquid material, a softener, a plasticizer, a lubricant, a liquid polymer, or the like can be suitably used.

Examples of the softener include petroleum-based softeners such as paraffinic oil, mineral oil, ethylene / α-olefin oligomers, mineral oil-based softeners such as gilsonite, and fatty acids such as oleic acid and ricinoleic acid.
Plasticizers include various fatty acids such as phthalic acid derivatives, isophthalic acid derivatives, tetrahydrophthalic acid derivatives, adipic acid derivatives, sebacic acid derivatives, fumaric acid derivatives, citric acid derivatives, azelaic acid derivatives, phosphoric acid derivatives, maleic acid derivatives, etc. Derivatives and the like.
Examples of the lubricant include paraffin-based lubricant, hydrocarbon-based lubricant, and metal soap.
Examples of the liquid polymer include liquid rubber such as liquid polybutadiene and liquid styrene / butadiene rubber, polyisobutylene, and silicone oil.
The liquid materials exemplified above can be used singly or in combination of two or more. These liquid materials can be formed into a molded body having particularly excellent flexibility when the elastomer composition is mainly a hydrogenated diene block copolymer.

  The amount of the liquid material used is preferably 50 to 5000 parts by mass, more preferably 50 to 4000 parts by mass, and more preferably 50 to 4000 parts by mass when the total amount of the polymer contained in the elastomer composition is 100 parts by mass. Preferably it is 50-3000 mass parts, Most preferably, it is 50-2000 mass parts. When the blending amount of the liquid material is less than 50 parts by mass, a molded article having a desired elastic modulus may not be obtained. On the other hand, when the blending amount of the liquid material exceeds 5000 parts by mass, the liquid material may ooze from the molded body.

The elastomer composition according to the present invention may contain various additives as long as the mechanical properties and shape retention of the film formed thereby are not impaired.
These additives include antioxidants, anti-aging agents, UV absorbers, plasticizers, lubricants, flame retardants, heat stabilizers, antibacterial agents, fungicides, weathering agents, tackifiers, nucleating agents, fillers , Abrasive particles, silane coupling agents, titanium coupling agents, colorants (pigments, dyes) and the like.

  Examples of the anti-aging agent include naphthylamine, diphenylamine, p-phenylenediamine, quinoline, hydroquinone derivative, mono, bis, tris, polyphenol, thiobisphenol, hindered phenol, and phosphite. , Imidazole, nickel dithiocarbamate, phosphoric acid anti-aging agent and the like. These can be used alone or in combination of two or more.

  Examples of the ultraviolet absorber include benzophenones, benzotriazoles, salicylic acid esters, metal complex salts and the like. These can be used alone or in combination of two or more.

As the abrasive particles, inorganic particles, organic particles, and organic / inorganic composite particles can be used singly or in combination of two or more.
As inorganic particles, diamond powder, metals such as Si, carbides such as SiC, oxides containing at least one element selected from Si, Al, Ti, Ce, Cr, Mn, Fe, Zr, etc., Si, Al It is possible to use nitrides containing at least one element selected from Ti, etc., carbonates such as BaCO _{3, and the} like.
Organic particles include polyvinyl chloride, polystyrene, styrene copolymer, polyacetal, saturated polyester, polyamide, polycarbonate, polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene and other polyolefins, olefins Crosslinks obtained by copolymerizing thermoplastic resins such as (meth) acrylic resins such as methacrylic copolymers, phenoxy resins, and polymethyl methacrylate, styrene, methyl methacrylate, etc. with divinylbenzene, ethylene glycol dimethacrylate, etc. A copolymer resin having a structure, and further a thermosetting resin such as a phenol resin, a urea resin, a melamine resin, an epoxy resin, an alkyd resin, and an unsaturated polyester resin can be used.

The organic / inorganic composite particles need only be integrated so that the inorganic particles and the organic particles are not easily separated during polishing. For example, in the presence of polymer particles such as polystyrene and polymethylmethacrylate, Silane, aluminum alkoxide, titanium alkoxide, etc. can be polycondensed, and at least the surface of the polymer particles can be combined with polysiloxane or the like. The produced polycondensate may be directly bonded to the functional group of the polymer particles, or may be bonded via a silane coupling agent or the like.
As the organic / inorganic composite particles, those obtained by attaching inorganic fine particles such as silica and alumina to the surface of organic particles such as polymer particles can also be used. These may be held electrostatically or may be chemically bonded to organic particles by a functional group such as a hydroxyl group possessed by inorganic fine particles and a silane coupling agent.
As the organic / inorganic composite particles, an aqueous dispersion containing organic particles having different zeta potentials and inorganic particles having different signs can be used in which these particles are combined by electrostatic force.
Moreover, as said abrasive | polishing particle | grains, what grind | pulverized natural garnet (garnet), emery, flint (silica stone), etc. can also be used.

The average particle diameter of the abrasive particles is preferably 0.05 to 10 μm, more preferably 0.1 to 10 μm, and still more preferably 0.1 to 5 μm.
What is necessary is just to select the kind (a constituent material, an average particle diameter, etc.) of this abrasive particle according to the objective and a use.
When the cleaning film contains the abrasive particles, the volume ratio of the abrasive particles to the cleaning film is preferably 1 to 80%, more preferably 1 to 70%, and still more preferably 10 to 70% by mass.
When the cleaning film contains abrasive particles, the exposure rate of the abrasive particles on the film surface is preferably 80% or less, more preferably 70% or less, and still more preferably 50% or less. When the exposure rate of the abrasive particles is too high, the abrasive particles may be detached and adhere to the cleaned portion when the cleaning film is used, or the cleaned portion may be damaged. On the other hand, if the exposure rate of the abrasive particles is too low, the dirt stuck to the cleaned part may not be sufficiently removed.

  Using the above elastomer composition, injection molding, extrusion molding, hollow molding, compression molding, vacuum molding, laminate molding, calendar molding, cast molding, coater molding, roll molding, T-die coater, T-die extrusion molding, injection molding, etc. A molded body (cleaning film) having a desired shape can be obtained by a known method.

A schematic view of the cleaning film of the present invention is shown in FIG. The cleaning film 1 shown in FIG. 1 is a film having a uniform thickness and a flat surface.
In addition, the cleaning film of the present invention can have various surface structures or cross-sectional structures depending on the purpose and application. For example, at least one surface of the present cleaning film may be provided with a portion such as a convex portion, a concave portion, a groove portion, and a cut portion, either singly or in combination of two or more. The shape of each of these parts is not particularly limited, and in the case of a convex part and a concave part, it can be a circle, a square (polygon such as a triangle or a quadrangle), a star, or a random shape. There are no particular limitations on the length of the opening (maximum length or the like) in the case of these shapes, the height in the case of a convex portion, the depth or the like in the case of a concave portion. Moreover, in the case of a groove part, it can be set as the shape arbitrarily selected or combined from linear form, curvilinear form, etc. The cross-sectional shape of the groove portion can also be a shape corresponding to the purpose and application, such as a square shape, a U-shape. Further, the width and depth of the groove are not particularly limited.
In the case of the cut portion, it may be a point or a line (straight line, curved line, cross shape, etc.). Further, the cut may be perpendicular to the film body or oblique.
In addition, also when providing the said site | part with two or more, the shape, size, etc. of each site | part may be the same, and the combination of a different thing may be sufficient. Furthermore, the interval between adjacent portions is not particularly limited.

  The cleaning film provided with the said site | part is illustrated with sectional drawing (FIGS. 2-6). The cleaning film 1 in FIG. 2 is a schematic view showing an aspect having a flat surface in which one surface is wavy. FIG. 3 is a schematic view showing a cleaning film having one surface having a zigzag plane. FIG. 4 is a schematic view showing a cleaning film having a plurality of convex portions 11 on one surface. FIG. 5 is a schematic view showing a cleaning film having a plurality of recesses (or grooves) 12 on one surface. FIG. 6 is a schematic view showing a cleaning film having a plurality of cut portions 13 on one surface.

The cleaning film of the present invention has excellent strength and flexibility, and the shear storage modulus (G ′) obtained by dynamic viscoelasticity measurement at 30 ° C. and 1 Hz is preferably 1 to ^{10 10} dyn. / cm ^2, more preferably ^{1~5 × 10 9 dyn / cm 2} , more preferably be a 1~10 ⁹ dyn / cm ^2.
The cleaning film of the present invention is also excellent in heat resistance, and preferably has flexibility and shape retention at −80 to 100 ° C., more preferably at −50 to 70 ° C.
Therefore, the cleaning film of the present invention is suitable not only for use at room temperature but also for use at a low temperature of 0 ° C. or lower.

  The cleaning film of the present invention preferably has a low concentration of metal components (including ions), anions and the like contained in the film in order to prevent contamination of the cleaned portion. Examples of the metal component include cations such as sodium ions. Moreover, a chlorine ion etc. are mentioned as an anion. These concentrations are preferably 1000 ppm or less, more preferably 50 ppm or less, and still more preferably 20 ppm or less. However, as in the case of using a crosslinked elastomer composition, metal ions and the like blended for the purpose of crosslinking are not included in the above concentration.

The thickness of the cleaning film of the present invention is preferably 0.1 to 2000 μm, more preferably 1 to 1000 μm, and particularly preferably 5 to 600 μm.
Since the cleaning film of the present invention is excellent in flexibility, strength, and heat resistance, the portion to be cleaned can be cleaned well by utilizing its own self-adhesiveness.
In addition, the self-adhesive property of this cleaning film can be easily maintained while maintaining its shape (deformation) after adhering to a general object made of inorganic materials (metals, alloys, ceramics, etc.), organic materials, etc. The adhesive remains in the contacted part when it is removed from contact with an object or after cleaning the cleaned part. Etc. does not occur at all.

The cleaning film of the present invention can be provided with a protective film on at least one surface thereof. That is, a protective film may be provided on one side or both sides. This protective film is provided for peeling off during use. The constituent material of this protective film is not particularly limited. For example, α-olefin such as polyethylene, polypropylene, ethylene / propylene copolymer, polybutene, ethylene / vinyl acetate copolymer, ethylene / ethyl acrylate copolymer, ionomer, etc. Homopolymers or copolymers, polyesters such as polyethylene terephthalate and polyethylene naphthalate, thermoplastic elastomers, and the like.
The contact surface of the protective film with the cleaning film may be subjected to chemical treatment such as corona treatment, plasma treatment, and primer treatment. Further, in order to facilitate peeling, a silicone-based or fluorine-based release coating layer may be provided. Moreover, you may have an unevenness | corrugation.
The protective film may be a single layer or a multilayer. Moreover, the thickness of this protective film is 10-3000 micrometers normally, Preferably it is 10-2000 micrometers, More preferably, it is 10-500 micrometers.

  The shape of the cleaning film of the present invention is not particularly limited, and may be a long shape, a roll shape, a circle, a square (polygon such as a triangle or a quadrangle), a star, or a random shape. It may be adjusted to a predetermined shape.

The cleaning member of the present invention is characterized in that the cleaning film is disposed on a support layer. A schematic view of the cleaning member is illustrated with the cross-sectional view of FIG. The cleaning member 2 in FIG. 7 has a structure in which a cleaning film 1 a is disposed on one surface of a support layer 21.
As shown in FIG. 8, the cleaning member 2 a of the present invention may have a cleaning film 1 b adjusted to a predetermined shape disposed on the surface of the support layer 21.

  The support layer may be composed of any material, may be an inorganic material (mainly metal, alloy, ceramic, etc.), or is an organic material (paper, cloth, resin composition). Etc.). Further, depending on the purpose and application, the constituent material of the support layer may be selected in consideration of the adhesive force between the cleaning film and the support layer. A preferred material is an organic material (made of paper, cloth, resin composition, etc.), and a film made of resin composition is particularly preferred.

The support layer may be a solid body made of the above constituent material, or may be a foam.
The support layer may be a single layer or a multilayer. The thickness of the support layer is preferably 10 to 1000 μm, more preferably 10 to 500 μm.

  The cleaning film and the cleaning member of the present invention include a substrate such as a semiconductor wafer, a wiring portion formed on the surface of the substrate, a non-wiring portion after formation, a mounting component (chip or the like) disposed on the substrate, etc. Of electronic parts and their electrodes or terminals, surfaces of inspection equipment (inspection parts) used for performance evaluation of various electronic parts (probes such as probes, tips of styluses, convex parts, concave parts, side faces, etc.), magnetic disks It can be suitably used for removing impurities or dirt adhered or formed on the surface or the like, and wiping.

The cleaning film and the cleaning member of the present invention can be used by themselves or can be used by being disposed in an apparatus.
As a cleaning method using the cleaning film and the cleaning member of the present invention, it may be brought into contact with a portion (or surface) to which dirt or the like is attached. The degree of contact may be in consideration of the amount of dirt, the degree of fixation, etc., and examples thereof include a method of pressing and holding for a certain period of time, and a method of heating to the extent that the film does not deform, deteriorate or melt. Further, when the cleaning film contains abrasive particles, the dirt can be removed by the abrasive particles. Further, when the portion to be cleaned has a symmetrical shape, a dynamic method such as rotating the portion to be cleaned or the object having the portion to be cleaned, or rotating the cleaning film or the cleaning member can be used.

Although the usage method of the cleaning film of this invention is illustrated, a usage method is not limited to these.
(1) When dirt is attached to a needle-like probe arranged on an inspection device, etc. A probe card used for a performance test of a semiconductor wafer or the like is placed on the probe card when the number of times and time have accumulated. Impurities adhere to the tip of the provided probe. In order to remove this impurity, for example, a cleaning film 1 having a recess 12 as shown in FIG. 9 is used. The probe 3 is inserted into the recess 12 of the cleaning film 1, held for a certain time, and then pulled up to remove impurities attached to the probe 3. When impurities are stuck, a method of rotating the probe 3 in the recess 12 can be applied. In this case, not only the tip part of the probe 3 but also the side part can be cleaned.
If the degree of impurity adhesion is small, the probe 3 may be pressed against a flat surface having no recesses.

(2) When dirt is attached to the surface of a planar electronic component or the like When there is dirt on the surface of the wiring board on which no mounting component is disposed, for example, an apparatus as shown in FIG. 10 is used. Dirt can be removed. The cleaning device of FIG. 10 includes a rotating support 4 and a cleaning film 1c disposed on the outer periphery thereof. The wiring board 3a is sent in the direction of the arrow in FIG. 10 by a conveyor or the like, and removes dirt by contacting the surface of the wiring board 3a with the cleaning film 1c. A pressure may be applied between the wiring board 3a and the cleaning film 1c.

Hereinafter, the present invention will be specifically described with reference to examples. In addition, this invention is not restrict | limited at all by these Examples. Further, “%” and “part” in the examples are based on mass unless otherwise specified.
1. Preparation of Elastomer Composition Elastomer compositions (i) to (ix) were prepared by mixing the polymers and liquid materials shown below at the ratios shown in Table 1.
1-1. Polymer (1) Hydrogenated Diene Block Copolymer (A1)
25 kg of cyclohexane, 1 g of tetrahydrofuran, 1500 g of 1,3-butadiene and 3.9 g of n-butyllithium were charged into a reaction vessel having an internal volume of 50 liters purged with nitrogen, and polymerization was started at 70 ° C. After completion of the reaction, the temperature of the reaction solution was set to 40 ° C., 100 g of tetrahydrofuran was added, and then 3500 g of 1,3-butadiene was added for further adiabatic polymerization. After 30 minutes, 2.7 g of methyldichlorosilane was added and reacted for 15 minutes to complete the reaction.
Next, hydrogen gas was supplied at a pressure of 0.4 MPa-G, and while the reaction solution was stirred, it was reacted with living polymer terminal lithium as a living anion for 20 minutes to obtain hydrogenated lithium. Thereafter, the reaction solution was brought to 80 ° C., titanocene dichloride as a hydrogenation catalyst was added, and the mixture was reacted for 2 hours while maintaining the hydrogen gas pressure at 1.0 MPa. After the reaction, the reaction solution was returned to room temperature and normal pressure and extracted from the reaction vessel. Next, the reaction solution was stirred into water and the solvent was removed by steam distillation to obtain the target diene block copolymer hydrogenated product A1. The hydrogenation rate of the hydrogenated product A1 of the obtained diene block copolymer was 99%, the weight average molecular weight by GPC was 340,000, and the vinyl bond content of the first butadiene polymer block of the polymer before hydrogenation was 14 %, The vinyl bond content of the second butadiene polymer block of the polymer before hydrogenation was 49%.

(2) Hydrogenated product of diene block copolymer (A2)
25 kg of cyclohexane, 1 g of tetrahydrofuran, 1500 g of 1,3-butadiene and 4.1 g of n-butyllithium were charged into a reaction vessel having an internal volume of 50 liters purged with nitrogen, and polymerization was started at 70 ° C. After the completion of the reaction, the temperature of the reaction solution was set to 35 ° C., 27 g of tetrahydrofuran and then 3500 g of 1,3-butadiene were added to further carry out adiabatic polymerization. After 30 minutes, 2.9 g of methyldichlorosilane was added and reacted for 15 minutes to complete the reaction.
Next, hydrogen gas was supplied at a pressure of 0.4 MPa-G, and while the reaction solution was stirred, it was reacted with living polymer terminal lithium as a living anion for 20 minutes to obtain hydrogenated lithium. Thereafter, the reaction solution was brought to 80 ° C., titanocene dichloride as a hydrogenation catalyst was added, and the mixture was reacted for 2 hours while maintaining the hydrogen gas pressure at 1.0 MPa. After the reaction, the reaction solution was returned to room temperature and normal pressure and extracted from the reaction vessel. Next, the reaction solution was stirred into water and the solvent was removed by steam distillation to obtain the target diene block copolymer hydrogenated product A2. The hydrogenation rate of the hydrogenated product A2 of the resulting diene block copolymer was 98%, the weight average molecular weight by GPC was 290,000, and the vinyl bond content of the first butadiene polymer block of the polymer before hydrogenation was 14 %, The vinyl bond content of the second stage butadiene polymer block of the polymer before hydrogenation was 35%.

(3) Hydrogenated product of diene block copolymer (A3)
25 kg of cyclohexane, 1 g of tetrahydrofuran, 1500 g of 1,3-butadiene and 4.1 g of n-butyllithium were added to a reaction vessel having an internal volume of 50 liters purged with nitrogen, and polymerization was started at 70 ° C. After completion of the reaction, the temperature of the reaction solution was set to 35 ° C., 350 g of tetrahydrofuran, and then 3500 g of 1,3-butadiene were added for further adiabatic polymerization. After 30 minutes, 2.9 g of methyldichlorosilane was added and reacted for 15 minutes to complete the reaction.
Next, hydrogen gas was supplied at a pressure of 0.4 MPa-G, and while the reaction solution was stirred, it was reacted with the polymer terminal lithium alive as a living anion for 20 minutes to obtain hydrogenated lithium. Thereafter, the reaction solution was brought to 80 ° C., titanocene dichloride as a hydrogenation catalyst was added, and the mixture was reacted for 2 hours while maintaining the hydrogen gas pressure at 1.0 MPa. After the reaction, the reaction solution was returned to room temperature and normal pressure and extracted from the reaction vessel. Next, the reaction solution was stirred into water and the solvent was removed by steam distillation to obtain the target diene block copolymer hydrogenated product A3. The hydrogenation rate of the hydrogenated product A3 of the obtained diene block copolymer was 99%, the weight average molecular weight by GPC was 300,000, and the vinyl bond content of the first butadiene polymer block of the polymer before hydrogenation was 14 %, The vinyl bond content of the second stage butadiene polymer block of the polymer before hydrogenation was 78%.

(4) Polar group-modified olefin polymer (A4)
75.1 mol% of structural units derived from ethylene, 22.8 mol% of structural units derived from propylene, 1.8 mol% of structural units derived from 5-ethylidene-2-norbornene, and 8-methyl- 8-carboxytetracyclo [4.4.0.1 ^2,5 . 100 parts of a functional group-containing olefin copolymer containing 0.3 mol% of a structural unit derived from 1 ^7,10 ] -3-dodecene and having a weight average molecular weight (Mw) of 16.0 × 10 ⁴ Then, 0.25 mol% of zirconium (IV) butoxide (85% 1-butanol solution (Wako Pure Chemical Industries, Ltd.) is used with respect to 1 mol% of the functional group in the functional group-containing olefin copolymer. Product) was used, and toluene was removed by drying to obtain a polar group-modified olefin polymer A4.
(5) Thermoplastic polyurethane elastomer (A5)
For comparison, a thermoplastic polyurethane elastomer (manufactured by Kuraray Co., Ltd., trade name “Clamiron U1190”) was used.

1-2. Liquid material “B1”: a mineral oil-based softener (trade name “PW-32” manufactured by Idemitsu Kosan Co., Ltd.) having a kinematic viscosity at 40 ° C. of 30.85 mm ² / s.
“B2”: a mineral oil softener (trade name “PW-90” manufactured by Idemitsu Kosan Co., Ltd.) having a kinematic viscosity at 40 ° C. of 95.54 mm ² / s.
“B3”: a mineral oil softener (trade name “PW-380” manufactured by Idemitsu Kosan Co., Ltd.) having a kinematic viscosity at 40 ° C. of 381.6 mm ² / s.
1-3. Crosslinking agent “C1”; organic peroxide (manufactured by NOF Corporation, trade name “Perhexa 3M”).

2. Preparation and Evaluation of Cleaning Film Examples 1 to 8 and Comparative Example 1
Using the elastomer compositions (i) to (ix), a film having a thickness of 500 μm was produced by coater molding, and this was used as a cleaning film. This cleaning film was evaluated by the following method. The results are shown in Table 2.
(1) Viscoelasticity The shear storage elastic modulus (G ′) of the film (thickness: 500 μm) was measured under the conditions of a temperature of 30 ° C. and a frequency of 1 Hz using a dynamic viscoelasticity measuring device (Rheology, model “MR-500”) It was measured. A lower G ′ value is more flexible and does not damage the portion to be cleaned. In Table 2, “◯” indicates that the G ′ value was 2,000,000 dyn / cm ² or less, and “×” indicates that the G ′ value was greater than 3,000,000 dyn / cm ^2. Indicates.
(2) Strength Based on JIS K-7127, the tensile strength and tensile elongation of the film were measured at a tensile speed of 500 mm / min.
(3) using a heat-resistant the dynamic viscoelasticity measuring apparatus, the shear storage modulus of the film (thickness 500 [mu] m) at a temperature of 70 ° C. and a frequency 1Hz and temperature -50 ° C. and a frequency 1Hz were measured _{respectively, G 70} 'And G- ₅₀ ' were obtained. Then, a change amount δG ′ [log (G- ₅₀ ′ at −50 ° C./G ₇₀ ′ at 70 ° C.)] of G ′ at the measurement temperatures of 30 ° C. and 70 ° C. was calculated. The smaller this δG ′, the better the heat resistance. In Table 2, “◯” indicates that δG ′ is 3.5 or less, and “x” indicates that δG ′ is greater than 3.5.
(4) Ion concentration Using an inductively coupled plasma emission spectrometer (ICP-AES), the concentration of sodium ions and the concentration of chloride ions were measured by ion chromatography. In Table 2, “◯” indicates that all of these concentrations were 1000 ppm or less, and “x” indicates that at least one of the concentrations exceeded 1000 ppm.
(5) Adhesive residue As a performance test of the semiconductor wafer, an energization test using a probe card provided with a plurality of probes was performed. Thereafter, the tip of the probe was brought into contact with the cleaning film obtained above and immediately pulled up. The tip of the probe was visually observed to evaluate the presence or absence of adhesive residue. In Table 2, “◯” indicates that no adhesive residue was observed, and “x” indicates that adhesive residue was observed.

3. Evaluation Results From Table 2, since the cleaning film of Comparative Example 1 is not sufficiently flexible, it may damage the portion to be cleaned such as the tip of the probe. Since it is inferior in heat resistance (becomes hard at low temperatures), the parts to be cleaned are particularly damaged at low temperatures of 0 ° C. or lower. Further, since the concentration of sodium ions and the like is high, dirt may adhere to the portion to be cleaned by contact.
On the other hand, Examples 1 to 8 are excellent in flexibility, tensile strength and tensile elongation, and further, since the temperature change of the shear storage elastic modulus is small, the tip of the probe in a wide temperature range from low temperature to high temperature. The parts to be cleaned such as are not damaged. Further, since the concentration of sodium ions and the like is small and there is no adhesive residue, the occurrence of contamination due to cleaning is small.

  The cleaning film and cleaning member of the present invention include a substrate such as a semiconductor wafer, a wiring portion formed on the surface of the substrate, a non-wiring portion after formation, a mounting component (chip or the like) disposed on the substrate, etc. On the surface (such as the tip of a probe such as a probe, convex part, concave part, side face, etc.), magnetic disk surface, etc. It can be suitably used for removing adhered or formed impurities, dirt, and the like.

It is a schematic sectional drawing which shows an example of a cleaning film. It is a schematic sectional drawing which shows another example of a cleaning film. It is a schematic sectional drawing which shows another example of a cleaning film. It is a schematic sectional drawing which shows another example of a cleaning film. It is a schematic sectional drawing which shows another example of a cleaning film. It is a schematic sectional drawing which shows another example of a cleaning film. It is a schematic sectional drawing which shows an example of a cleaning member. It is a schematic perspective view which shows an example of a cleaning member. It is explanatory drawing which shows the method of removing the stain | pollution | contamination of a probe (to-be-cleaned part) with a cleaning film. It is explanatory drawing which shows the apparatus and removal method which remove the stain | pollution | contamination of a wiring board (surface to be cleaned) with a cleaning film.

Explanation of symbols

  1, 1a, 1b and 1c; cleaning film, 11; convex portion, 12; concave portion or groove portion, 13; cut portion, 2 and 2a; cleaning member, 21; support layer, 3; probe (cleaned portion), 3a Wiring board (surface to be cleaned), 4; rotating support.

Claims (15)

Inspection comprising an elastomer composition containing at least one polymer selected from hydrogenated diene block polymers and polar group-modified olefin polymers, and used for performance evaluation of electronic components and their electrodes or terminals and electronic components A cleaning film that is used to remove impurities or dirt by contacting a probe or stylus of an apparatus or a cleaned part of a magnetic disk to adhere to the cleaned part .   The hydrogenated product of the diene block polymer is at least one selected from a hydrogenated product of a block polymer of a conjugated diene and a hydrogenated product of a block copolymer comprising a conjugated diene and an aromatic vinyl compound. The cleaning film according to 1.   The hydrogenated diene block polymer has a mass ratio of the butadiene polymer block (I) having a vinyl bond content of less than 25%, the conjugated diene unit (a1) and the other monomer unit (a2). Diene having (a1) / (a2) = (100-50) / (0-50) and at least one polymer block (II) having a vinyl bond content of 25-95% in the molecule. The cleaning film according to claim 1 or 2, wherein the olefinically unsaturated bond in the system block polymer is hydrogenated.   The polar group-modified olefin polymer is at least one selected from a polar group-modified ethylene / α-olefin copolymer and a polar group-modified ethylene / α-olefin / non-conjugated diene copolymer, and the elastomer. The cleaning film according to claim 1, wherein the composition contains metal ions and / or metal compounds.   The cleaning film according to claim 4, wherein the polar group is selected from a carboxyl group, a hydroxyl group, an epoxy group, an amino group, an alkoxysilyl group, a sulfonic acid group, and a nitrile group.   The cleaning according to any one of claims 1 to 5, wherein the elastomer composition includes a liquid material, and the content of the liquid material is 50 to 5000 parts by mass with respect to 100 parts by mass in total of the polymer components. the film.   The cleaning film according to claim 1, wherein at least a part of the elastomer composition is crosslinked.   The cleaning film according to any one of claims 1 to 7, further comprising abrasive particles.   The cleaning film according to claim 1, which has a thickness of 0.1 to 2000 μm.   The cleaning film according to claim 1, further comprising a portion selected from a convex portion, a concave portion, a groove portion, and a cut portion on at least one surface of the cleaning film.   The cleaning film according to claim 1, further comprising a protective film on at least one surface of the cleaning film. The cleaning film according to claim 1, which is used for cleaning a probe of a probe guard. Cleaning member cleaning film according is disposed on the support layer to one of claims 1 to 12. The cleaning film according to any one of claims 1 to 12 or the cleaning film of the self-adhesive cleaning member according to claim 13 is used to detect an inspection device used for performance evaluation of an electronic component and its electrodes or terminals and various electronic components. A cleaning method for removing impurities or dirt from a cleaning part by contacting the cleaning film with a needle or a stylus, or a cleaning part of a magnetic disk. A probe card probe is inserted or pressed into the cleaning film according to any one of claims 1 to 12 or the cleaning member according to claim 13, and the probe and the cleaning film are brought into contact with each other. A method for cleaning a probe of a probe guard, which removes impurities or dirt on the probe surface by adhering to the cleaning film.

Images