TW200808933A - Pressure sensitive adhesive layer for cleaning, process for producing the same, cleaning sheet, delivery member with cleaning function, and method of cleaning off foreign matter - Google Patents

Abstract

A pressure sensitive adhesive layer for cleaning that excels in both of the capabilities of delivery within substrate treating apparatus and removal of foreign matter adhering in the apparatus and thus is suitable for use in a cleaning sheet; a process for producing the same; a cleaning sheet; a delivery member with cleaning function; and a method of cleaning off foreign matter. There is provided a pressure sensitive adhesive layer for cleaning having a planar surface and used to remove any foreign matter from a treatment object, the layer consisting of a product of hardening of a radiating hardening or thermosetting acrylic pressure sensitive adhesive containing an acrylic polymer, characterized in that the surface of the pressure sensitive adhesive layer has discontinuous open depressions, and that the average diameter of openings is smaller than the average size of foreign matter.

Description

200808933 IX. OBJECTS OF THE INVENTION: 1. Field of the Invention The present invention relates to a foreign matter cleaning method using an adhesive layer having a fine, 'unconventional non-conformal concave portion on the surface. ^ ^ ^ Further, regarding a cleaning adhesive sheet having a special discontinuous concave surface and a manufacturing method thereof, and further relates to a cleaning adhesive layer having the above-mentioned cleaning adhesive layer, and further relates to a cleaning sheet The cleaning function of the cleaning function, the dry cleaning, and the cleaning method using the substrate processing device of the crucible. The foreign matter cleaning method of the present invention can be used for various purposes, and the cleaning layer is composed of the above-mentioned adhesive layer having a concave portion on the surface. The surface adhesion and the foreign matter trapping property can be controlled, so that the 髀士士&m# is well suited for the cleaning of various substrate processing apparatuses. For example, the foreign matter cleaning method of the present invention can be used for cleaning semi-conducting =, flat panel display, A substrate processing apparatus that avoids foreign matter such as a manufacturing apparatus or an inspection apparatus such as a printed board. The cleaning sheet of the present invention (adhesive for cleaning) can be used for various purposes. The above-mentioned adhesive layer having a concave portion on the surface is controllable, and the surface 4 is abrupt. And foreign matter trapping property, so it can be used as a cleaning substrate which is not attached to various substrate clothing itself but has foreign matter trapping properties. Garment facing / "Rabbit sheet. For example, the cleaning sheet of the present invention can be used as a cleaning sheet for a substrate processing apparatus which avoids foreign matter such as a semiconductor or a flat panel, a manufacturing apparatus such as a printed board, or an inspection apparatus. [Prior Art] A manufacturing apparatus such as a semi-conductor, a flat panel display, a printed circuit board, or the like, and various substrate surfaces physically contact each of the transport systems and the substrate, and the surface is moved. At this time, if foreign matter adheres to the substrate or the transport system, 120368.doc 200808933 will successively contaminate the subsequent substrate. Therefore, a ▲ must be continued to remove the foreign matter. Therefore, the device is used for the problem of 'workforce'. The second turn of the cleaning: the lowering: the problem that the foreign matter is attached to other parts, and there is a problem that the substrate is fixed by the transfer, and the substrate is fixed by the processing device. A method of removing foreign matter attached to the back surface of the substrate by a method of transferring a foreign material to a substrate (patent document 1) or a method of transporting a plate-shaped member (Patent Document 2).

The method disclosed in the patent document is an effective method for overcoming the above problems. However, in this method, the contact portion between the adhesive substance and the device is too strongly connected to cause a problem, and the substrate cannot be reliably conveyed or the transfer device is defective. Further, the adhesive substance adhering to the substrate transfer device contaminates the substrate. Further, the method disclosed in Patent Document 2 can be carried out without any problem, but there is a problem that the primary dust removal property is poor. χ, the substrate to which the adhesive substances are fixed is usually protected by a release film which is usually coated with a release agent such as a decane, before the use. However, in this method, there is a problem that the release agent component is transferred to the surface of the cleaning layer, and the transfer agent component contaminates the substrate contact portion of the transfer device. Further, a cleaning tape having a porous cleaning layer such as a woven fabric on the surface of the adhesive layer is proposed (Patent Document 3), and a cleaning sheet in which a porous non-adhesive layer is used as a cleaning layer (Patent Document 4, Patent Document 5) ). However, these cleaning sheets satisfy the conveyance property in the substrate processing apparatus and the foreign matter removal property adhering to the apparatus to some extent, but are not sufficiently satisfied. Further, it is proposed that the tensile modulus of the cleaning layer is set to 0.98 to 4900 N/mm 2 120368.doc 200808933 (〇·98 to 4900 MPa) (Patent Document 6) 'If the tensile modulus decreases, there is a generation On the other hand, if the tensile modulus increases, the ability to trap foreign matter tends to decrease. [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei No. Hei 11-87458 (Patent Document No. Hei. No. Hei. No. Hei. Patent Document 5: Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. 2001-198075. SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION In view of the above facts, the object of the present invention The present invention provides a cleaning adhesive layer which is excellent in both the transportability in the substrate processing apparatus and the foreign matter removal property adhering to the apparatus, and is suitable for use in a cleaning sheet. Further, it is an object of the present invention to provide a cleaning member using the above-described cleaning adhesive layer, a cleaning member using the cleaning sheet, and a cleaning method using the substrate processing apparatus. The present inventors have actively studied the above-mentioned objects, and as a result, found a cleaning adhesive layer (cleaning layer) and a method for producing the same, and a cleaning/decomposing sheet (adhesive sheet for α) The conveying member having the cleaning function and the foreign matter cleaning method do not cause the above-described conveyance problem, and the foreign matter can be easily and reliably removed and removed, thereby completing the present invention. 120368.doc 200808933 The present invention relates to a cleaning adhesive layer which is formed of a cured product of a radiation curable or thermosetting acrylic adhesive containing an acrylic polymer, and The surface having a flat surface for removing foreign matter from the object to be processed has a concave portion having a discontinuous opening on the surface of the adhesive layer, and the average opening diameter of the opening is smaller than the average foreign matter size. In the above adhesive layer, it is preferable that the foreign matter contains a foreign matter having a size of 10 μm or less. In the above adhesive layer, it is preferred that the average opening diameter of the opening portion is smaller than the average foreign matter size of the foreign matter having a foreign matter size of 10 μm or less. Preferably, in the adhesive layer, the ratio of the projected area of the discontinuous concave portion to the total projected area of the surface of the adhesive layer is 3% to 80% 〇 in the adhesive layer, preferably It is the elastic modulus of the surface of the upper adhesive layer (outside the concave portion) of the upper J 为 is 10 MPa or more. In the above adhesive layer, a ratio (h/H) of the depth (h) of the concave portion to the thickness (H) of the above-mentioned viscous (four) layer is preferably ^. In the above-mentioned adhesive layer, the opening of the concave portion is preferably circular, and the average opening diameter is (U~3 j μΠ1, and the standard deviation of the opening diameter is 〇·7 μηη or less, The opening of the opening portion <the standard deviation of the center distance between the knife cloth and the adjacent opening portion is 1 μm or less. In the above adhesive layer, it is preferable that the projected area of the discontinuous concave portion is relative to the above adhesive layer Table ', 15~80%. "The ratio of the area of the shirt is 120368.doc 200808933. In the upper (four) layer, the ratio of the depth (h) of the above recess to the thickness (H) of the above adhesive layer is preferred. h/H) is 〇〇ι~〇.]. In the above-mentioned adhesive layer, it is preferred that the center line average roughness (Ra) of the planar surface other than the above-mentioned concave portion is 〇〇1 to 〇3 μιη. In the adhesive layer, it is preferred that the ratio of the projected area of the discontinuous concave portion to the total projected area of the surface of the layer of the above-mentioned 荽 荽 y y ! 为 为 为 为 为 为 为 为 为 于 于 于 于In the above adhesive layer, it is preferable that the opening portion of the concave portion is substantially rounded. The average opening diameter is 〇Μ (4). In the above adhesive layer, it is preferred that the ratio (h) of the depth (h) of the concave portion to the thickness (H) of the adhesive layer is GG ^.9. In the above adhesive layer, it is preferred that the above-mentioned adhesive layer has a tensile modulus of elasticity of from 0.98 MPa to 500 MPa. Among the above adhesive layers, a radiation curable or thermosetting acrylic adhesive is preferably contained. The acrylic polymer and the polymerizable unsaturated compound 0 In the cleaning sheet of the present invention, it is preferred that the cleaning adhesive layer is provided on at least one side of the support so that the discontinuous concave portion becomes a surface. In the cleaning sheet of the present invention, it is preferred that the cleaning adhesive layer is provided on the one surface of the support as a cleaning layer on the other side in such a manner that the discontinuous concave portion becomes a surface. In the conveying member having the cleaning function of the present invention, it is preferable that the cleaning sheet is provided on the conveying member via the fixing adhesive layer. 120368.doc 200808933 The cleaning adhesive of the present invention The manufacturing method is the method for producing the above-mentioned cleaning adhesive layer, preferably comprising the step (1) of forming an adhesive composition layer by applying a solution of the adhesive composition onto a substrate. The adhesive composition solution is an adhesive composition of a compound containing a radiation-curable or thermosetting acrylic acid-based adhesive containing an acrylic polymer, and further containing the above-mentioned acrylic polymer-incompatible compound, In a mixed solvent comprising a solvent (A) which dissolves the above-mentioned propylene (tetra) polymer and a compatible solvent (B) which is compatible with both the above-mentioned propionic acid-based polymer and the above-mentioned incompatible compound, v (2), irradiating or heating the adhesive composition 曰' to cause the acrylic adhesive to harden and form an adhesive layer precursor 'the adhesive layer precursor and hardened, the above A phase separation structure of the compatible compound; and a step (3) of removing the incompatible compound from the obtained binder layer precursor. In the method for producing the cleaning adhesive layer of the present invention, it is preferred that the above acrylic polymer is compatible with the above incompatible compound = (8), and the compatibility parameter is particularly high, relative to the acrylic acid. The polymer is •, and is 0.5 to 3 relative to the incompatible compound. In the method for producing a cleaning adhesive layer, it is preferred that the ruthenium::: ruthenium compound has a ruthenium parameter of 7 or more with respect to the acrylic polymer, and has a boiling point of 19 Å. 〇 Above. In the manufacture of the adhesive layer of the present invention, the adhesive composition solution a is as good as the green on the sputum: the sentence state 'but for the compatible solvent (8) (B) 0 " phase separation The solvent (A) and the compatible solvent are selected. 120368.doc -11-200808933 In the method for producing a cleaning adhesive layer of the present invention, it is preferred that the compatible solvent (B) is an alcohol solvent.

The method for producing a cleaning adhesive layer of the present invention is the method for producing the above-mentioned cleaning adhesive layer, preferably comprising the step (1) of preparing a radiation curable or thermosetting acrylic adhesive. An adhesive composition of a compound which is incompatible with the above acrylic adhesive is applied to a substrate to form an adhesive composition layer; and step (2) has a center line average roughness (Ra) of 〇·〇 a cover film of the surface of the adhesive composition layer covering the surface of the adhesive composition layer in such a manner that the surface of the film having the average thickness (Ra) of the center line of the cover film is on the surface side of the adhesive composition layer In this state, the acrylic adhesive is hardened and the adhesive layer precursor is formed by radiation irradiation or heating, and the adhesive layer precursor has a phase separation structure of the cured product and the incompatible compound; and a step (3) removing incompatible compounds from the obtained adhesive layer precursor. In the method for producing a cleaning adhesive layer of the present invention, it is preferred that in the above step (1), as an adhesive composition, an adhesive composition solution in which an organic solvent capable of dissolving the adhesive composition is applied is applied. The substrate is further dried to form an adhesive composition layer. Preferably, in the method for producing the cleaning adhesive layer of the present invention, the step (3) removes the incompatibility from the adhesive layer precursor by heating: the cleaning adhesive step of the present invention is described. (3) From the compound by solvent extraction. In the method of producing the layer, it is preferred to remove the incompatible material in the precursor of the upper adhesive layer. 120368.doc 12-200808933 The solvent for solvent extraction in the cleaning adhesive layer of the present invention is liquefied vaporized carbon. In the production method, it is preferred that the carbon dioxide or the supercritical state is used in the method for producing the cleaning adhesive layer of the present invention, and it is preferred that the above-mentioned v (2) is covered with a coating film. The surface of the composition layer is irradiated or heated by radiation. #于=Invented foreign matter cleaning method, it is better to include the above cleaning

The cleaning layer of the adhesive layer is applied to the processing target body to which the foreign matter adheres, and the foreign matter is removed from the processing target body. In the foreign matter cleaning method of the present invention, it is preferred to use the above cleaning sheet. Preferably, the above-described conveying member having the function of cleaning the foreign matter cleaning method of the present invention is used. In the above-described cleaning method of the foreign matter cleaning method of the present invention, it is preferable that the cleaning sheet or the conveying member having the cleaning function is conveyed into the substrate processing apparatus. Advantageous Effects of Invention The cleaning adhesive layer (cleaning y) for removing foreign matter of the present invention has a concave portion having a discontinuous opening on the surface thereof, and therefore the adhesive surface of the adhesive surface is not smooth. The next layer of the layer is relatively low. The adhesive layer is formed by substantially setting the adhesive force to a concave portion to a low design without causing a transport problem. On the other hand, the adhesive layer (cleaning layer) is trapped with a concave portion. Foreign matter of various sizes can be reliably removed without having to let it go. That is, the adhesive layer has a fine 120368.doc • 13 - 200808933 concave bitter P, and the surface of the 'J J K shell is relatively flat, so the contact with the foreign matter is extremely close, and all or part of the foreign matter By entering the concave portion, the effect of reliably collecting the foreign matter is exhibited. The adhesive layer can be designed to control surface adhesion and foreign matter trapping of foreign materials of various sizes by the size and proportion of the concave portion of the surface. In particular, the cleaning adhesive layer of the present invention is designed such that the opening of the opening portion (hereinafter, the average opening diameter means the same as the average diameter) is smaller than the average foreign matter size, and can be effectively trapped. Remove foreign matter from the object to be treated. In particular, the cleaning adhesive layer of the present invention is effective when a small foreign matter having a foreign matter size of 1 〇 or less is used as the t-shaped shape of the object to be treated, and the average opening of the opening of the concave portion of the cleaning layer is 彡In addition, it is smaller than the foreign matter size, and the average foreign matter size of the foreign matter of 10 μπι or less is used to remove foreign matter even for small foreign matter. "Effectively collecting" self-processing object: In the cleaning adhesive layer of the present invention, the average opening diameter of the concave portion is fine, and the standard deviation of the opening diameter is 〇·1~3 ", Λ, ' 0,7 μηι or less 'there is no unevenness in the opening diameter, and the mouth does not have the characteristic 兀 caused by the difference in the surface of the adhesive layer, and the unevenness of the characteristics can exert the above effects, so it is preferable. It is preferable that the opening of the concave portion on the surface of the layer surface and the adjacent opening portion exerts the above-described effects in this respect. Further, the center line of the planar surface of the above-mentioned clear "& In addition to the above-mentioned recesses of the layer um, the 隹μ* = the degree of flux (Ra) is controlled to be 0.01 to 0.3 μm, and the foreign matter collecting property and the transport property are good. 120368.doc -14. 200808933 According to the adhesive layer having the cleaning adhesive layer as a cleaning layer), and further, the cleaning function of the cleaning sheet is used: the adhesiveness of the cleaning layer is substantially lower than that of the smoothing layer. In the case of the adhesive layer on the surface, the adhesion inside the concave portion is the same as that of the adhesive having a smooth surface. Therefore, when the cleaning sheet or the following conveying member is conveyed, it is not in contact with the device. The portion is reliably conveyed in the substrate processing apparatus in a strong state, and the fine foreign matter adhered to the inside of the apparatus is collected, and can be easily and surely removed without dropping it. The cleaning adhesive layer is formed of a radiation curable or thermosetting acrylic adhesive as a method for producing the same, and can be carried out, for example, by carrying out the above steps (1) to (3). Further, the method of forming the uneven structure on the fine surface of the grade is exemplified by a transfer method, a use of a phase separation phenomenon, an ink jet technique, and a laser processing. For example, as a method of forming a concavo-convex structure by a phase separation phenomenon, Japanese Laid-Open Patent Publication No. Hei. No. 3,26832 discloses a method of evaporating a mixed solvent as an anti-glare hard coating, and using a curable transparent resin and a residue. A phase separation and a peeling phenomenon between the solvents are formed on the substrate to form a hardened material containing a hardened transparent resin as a hard coat layer. Alternatively, it is disclosed in Japanese Patent Laid-Open No. Hei. No. 3,277,534. For the correction glue ▼, the 'evaporation mixed solvent' is used to form the adhesive on the substrate by using the phase difference and peeling phenomenon between the adhesive and the adhesive; Χ, in Japanese Patent Special 2_ JP-A-151642 discloses a method for forming a layer, which is characterized in that an anti-glare imparting group 120368.doc -15-200808933 containing a fine uneven structure is formed on a transparent substrate. The ink droplets were opened on the surface of the substrate by 70% of the fine concavo-convex structure. However, the structures obtained by the methods were all protrusion-shaped, and the adhesive layer was not formed by these methods. In the field, the dog-like structure is opened, so that the force is greatly reduced. Even if the adhesive layer is formed, the foreign matter collection property cannot be ensured. Moreover, these sentences are difficult to implement on a large scale. In the foreign matter cleaning method of the present invention, the cleaning adhesive layer is used as an average opening of the opening portion, and the foreign matter is removed in an average foreign matter size. "Effective collection" self-processing object [Embodiment], the cleaning adhesive layer (cleaning layer) of the present invention, a manufacturing method thereof, a cleaning sheet (clearing sheet), a cleaning member having a cleaning function, and a foreign matter cleaning The embodiment will be described in detail. The cleaning adhesive layer (cleaning layer) of the present invention will be described with reference to the drawings: Fig. i is a perspective view of the cleaning adhesive layer of the present invention. 1. As shown in Fig. 2, the cleaning adhesive layer of the present invention has a flat surface 8 having a non-recessed portion a on the surface 8. The surface 8 is a flat surface and represents a cleaning adhesive. The thickness (8) of the layers is substantially equal (the difference between the maximum thickness and the minimum thickness is about ±10%). (1) Cleaning layer (average opening diameter: 10 μηι or less) The cleaning adhesive layer of the present invention (in the surface s of the cleaning layer) The ratio of the concave portion & (presence ratio) is preferably such that the ratio of the projected area of the concave portion a to the total projected area of the surface 120368.doc • 16 - 200808933 s is 3% to 8〇%. /〇~观' is better 10%~5〇%, more preferably 1〇%~4〇%.,: The above-mentioned projected area refers to the case where the concave portion 3 of the adhesive layer (cleaning layer) is observed from the surface by a microscope. Observing the area ratio of the concave portion. When the projected area of the concave portion a is too small, the adhesion force of the adhesive layer is not lowered, and the base material for the cleaning layer cannot be sufficiently expressed (4) When the area of a shadow is too large, there is a clean two: (the cleaning layer) the adhesion is significantly reduced, the desired foreign matter is not captured, the ί月幵/X, and the cleaning adhesive layer (cleaning layer) The frictional resistance of the surface is too low, and the structure of the concave portion is broken, and the substrate is reversely contaminated during transportation. The shape of the opening of the concave portion a is not particularly limited, and as shown, it is easy to control the adhesion force. In terms of aspects and ease of formation, it is preferably a slightly round shape. The term "slightly circular" means a circle or an elliptical shape having a major axis length not exceeding 2 times the length of the minor axis. Honeycomb shape or square shape, no Problem. In addition, a portion of the recessed opening section, according to adhere to the body of the processed iso

Adjust the size of the object appropriately. Specifically, the adjustment is such that the average opening diameter of the opening portion I is smaller than the average foreign matter size. Further, the foreign matter size means the maximum length of each foreign matter. The foreign matter which is the object of the cleaning method using the cleaning adhesive layer (cleaning layer) of the present invention is suitable for the case where the foreign matter size is 1 〇 or less. If the foreign matter contains a foreign matter size of 10 (four) or less, it may also contain 120368.doc -17 * 200808933 Foreign matter size exceeding 1〇 4111. As the foreign matter, it is preferably used as a ratio of the number of foreign matters, and a foreign matter having a foreign matter size of 1 〇 μπ or less is contained in a ratio of 8 〇 % or more and further % % of the total foreign matter. Further, the size of the opening of the concave portion of the cleaning adhesive layer (cleaning layer) is controlled such that the average opening diameter (average diameter) (rl) thereof is smaller than the average foreign matter size (r2) of the foreign matter to be cleaned. The diameter of the opening means a large diameter of each of the openings, and the average opening diameter (9) is an average value of the maximum diameters of the respective openings obtained by image analysis as shown in the embodiment. # As described above, by controlling the average opening diameter (9) of the opening to be smaller than the average foreign matter size (9), the opening having a diameter relative to each other smaller than the foreign matter size is present, and therefore, it is possible to effectively collect even small foreign matter. The relationship between the average opening diameter (8) of the opening portion and the average foreign matter size (r2) satisfies the relationship between the average opening diameter (8) of the opening portion and the average foreign matter size (9), but it is preferable in terms of the collection effect of the minute foreign matter. It is the average opening diameter (Γΐ) + 〇.5 μιη < average foreign matter size (r2), more preferably full; i average opening diameter (1)) +1 μηη < average size (r2). / In the case where the foreign matter contains a foreign matter having a foreign matter size of 1 〇 μηη, it is preferable to control the sentence to be smaller than the foreign matter having a foreign matter size of 1 〇 _ or less (r21). The average foreign matter size (r21) is an average value of the foreign matter having a foreign matter size of μπι or less. In terms of the trapping effect of tiny foreign matter, the relationship between the average opening (rl) of the opening and the average foreign matter size (r21), 120368.doc •18-200808933 is preferably the full 3 Μ size (9)), the right to open The average opening diameter (8) + 〇.1 μιη <the average difference is better than the average opening diameter of the opening portion 5 and the foreign matter size (1*21). The average opening diameter (rl) of the opening portion is preferably in the range of 〇1 to 10 μηι, more preferably ～8 0 spot. It is particularly preferable to include a small foreign matter having a foreign matter size of 10 (four) or less. Further, the cross-sectional shape of the concave portion a is not particularly limited, and the size of the concave portion is produced, and the mouth is good in a hemispherical shape. However, when the cross-sectional shape is not hemispherical, the desired foreign matter trapping property can be ensured. Figure: Table = The case where the shape of the part a is hemispherical. In addition, when the surface of the adhesive layer becomes a non-continuous concave portion and becomes a protrusion (convex portion), there is a possibility that the following area may be greatly reduced, and the object collection cannot be obtained. Sexuality, or even if foreign matter is trapped, it is difficult to completely maintain the smear-like μ. The foreign matter is detached from the cleaning layer during the transfer step. 22, the depth of the part & (h) is relative to the cleaning adhesive layer (cleaning "to (H) ratio (h/H), preferably 〇〇ι~〇·9 = green _ The thickness (Η) and the depth of the concave portion a (=: average value. When the cross-sectional shape is hemispherical, the depth of the concave (h. In the case of the upper _ super-object, ί % recess a is too deep) The strength of the wall surface of the recess is insufficient. Γ)Γ°·01, or less than or equal to °·1, the necessary foreign matter is insufficient. The above ratio (h/H) is preferably set to 〇. 〇ι~〇5, more preferably 0.02~0.2, more preferably 〇.〇2~〇1. Further 120368.doc •19- 200808933, the above-mentioned adhesive layer (cleaning layer), It is preferable to set the elastic modulus of the surface (outside the concave portion) to 1 〇 Mpa.

Ayrri has a right elastic modulus of less than 1 ο a ', even if the above-mentioned concave is formed on the surface of the cleaning adhesive layer (cleaning layer)

In order to reduce the adhesion, the part is also increased in size, and when the apparatus is transported, it may cause a malfunction due to a conveyance roller or a suction stage, or a bad substrate. On the other hand, the elastic modulus of the surface of the above-mentioned cleaning adhesive layer (cleaning enamel) (other than the concave portion) is preferably 岐500 MPa or less. If the upper elastic modulus exceeds _ Mpa, there is a cleaning adhesive layer (cleaning layer): the adhesion is lowered, and the foreign matter trapping function cannot be exhibited even if the concave portion is formed. The elastic modulus of the surface of the cleaning adhesive layer (other than the concave portion) is preferably 1 G MPa to Mpa, more preferably the tensile modulus of the adhesive layer of the pressure-sensitive layer (10) MPa, according to the above-mentioned C The composition of the dilute acid-based adhesive 纟 'Example #acrylic acid-based compound and the amount of the polymerizable unsaturated compound (monomer component, polymer component) are appropriately set. The cleaning adhesive layer (cleaning layer) of the present invention is attached to the mirror surface of the Shixi wafer with a width of 10 _, and is measured at a tensile speed of 300 mm/min at room temperature (23 ° C).矽 卯 矽 卯. The peeling force is preferably 〇·3 N/10 mm or less. When the above-mentioned adhesive force is 〇·3 n/i 〇 mm or less, _ is the transportability on the babe. Further, since the cleaning adhesive layer (cleaning layer) of the present invention has a concave portion on the surface, it is possible to remove foreign matter in the concave portion even if the adhesive adhesion force of the raw material is reduced. In addition, the cleaning adhesive layer (cleaning layer) is attached to the mirror surface of the tantalum wafer with a width of 5 〇mni, and a weight of 2 kg is placed thereon, and a measuring terminal of φ 5 〇 mm is placed at room temperature (23. Under the squatting speed of 3 (10) mm / min vertical 120368.doc 200808933, the adhesion between the sub-cleaning adhesive layer (cleaning layer), preferably 疋 0 2G N. If it is within this range, it is considered In the present invention, the foreign matter collecting property is maintained, and the transport property is substantially obtained. The cleaning adhesive layer (cleaning layer) of the present invention has a structure having the above-described concave portion and has adhesiveness, and can be reduced by the formation of the concave portion. In addition, it is easy to control the adhesive force in the above range, and therefore, it is possible to use a cured product of a radiation curable or thermosetting curcumescent acid-based adhesive. Hereinafter, a radiation curable or thermosetting acrylic adhesive is described. _ The radiation-curable or thermosetting propylene (IV) adhesive can be used without any particular limitation, such as a radiation curable or thermosetting functional group having a carbon/carbon double bond, and exhibiting adhesiveness. The group preferably has a (meth) acrylonitrile group. The so-called (meth) acryl fluorenyl group means an acryl fluorenyl group and/or a methacryl fluorenyl group. Hereinafter, the (fluorenyl group) has the same meaning. Radiation hardening if

The number of carbons of the base, the eleventh burn, especially the carbon number of 4 to 18 or more, which is used as a monomer component, is 1 to 12, linear or branched. A type or two kinds of chain alkyl esters, etc. 120368.doc 21 200808933 Acrylic polymer or the like. The acryl-based polymer is intended to be modified by cohesive force, heat resistance, etc., and may contain other monomer components compatible with the above-mentioned (meth)acrylic acid alkyl hydrazine/, χκ a as needed. Unit. Examples of such a monomer-forming tool include acrylic acid, methacrylic acid, (meth)acrylic acid carboxyethyl sulfonium (methyl) decyl methacrylate, methylene succinic acid, maleic acid. a carboxyl group-containing monomer such as fumaric acid or crotonic acid; an acid anhydride monomer such as maleic anhydride or methylene succinic anhydride; (meth)acrylic acid 2-hydroxyethyl hydrazine or (meth)acrylic acid 2-hydroxypropyl ester, hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 1 〇 hydroxy hydroxy (meth) acrylate, ( Methyl)acrylic acid 12-hydroxylauryl vinegar, (meth)acrylic acid (4-hydroxymethylcyclohexyl) decyl ester and other hydroxyl-containing monomers; styrene sulfonic acid, allyl sulfonic acid, 2-(methyl) A sulfonic acid group such as acrylamide, 2, methyl propane sulfonic acid, (meth) acrylamide, sulfopropyl (meth) acrylate, (meth) propylene phthaloxy naphthalene sulfonic acid, etc. Monomer; phosphate-containing monomer such as 2-hydroxyethyl acryloyl phosphate; glycidyl (meth)acrylate, (mercapto) acrylamide, (mercapto)acrylic acid N- Hydroxymethyl decylamine, alkyl aminoalkyl (meth) acrylate (for example: dimethylaminoethyl methacrylate, tert-butylaminoethyl methacrylate, etc.), N-vinylpyrrolidone, propylene oxime Base morpholine, vinyl acetate, vinyl propionate, styrene, acrylonitrile; cycloalkyl (meth)acrylate (eg cyclodecyl ester, cyclohexyl ester, etc.). These copolymerizable monomer components may be used alone or in combination of two or more. The amount of the copolymerizable monomer used is preferably 70% by weight or less of the total monomer component. More preferably, it is 4% by weight or less. 0 120368.doc -22- 200808933 Further, the above acrylic polymer, In order to carry out the reaction, "a polyfunctional monomer or the like is used as a monomer for copolymerization to form such a polyfunctional monomer, and examples thereof include a sulfonate, a (poly) ethyl ketone. Monoalcohol (meth) propyl methacrylate, enoic acid _, (poly) propylene glycol di (meth) acrylate, neopentyl glycol bis ((methyl Ψ 土) propylene decyl ester, pentaerythritol di (indenyl) ) propylene decyl ester, trishydroxy fluorenyl 1 decyl acrylate, quaternary diol di(meth) acrylate, dipentaerythritol, tiangan, ^ y / yl acrylate, (T base) )Acrylic epoxy ester, Ju cool f

(Methyl) acetoacetate, urethane (meth) acrylate, and the like. It is also possible to use one or more of these types of sapphire saplings: in terms of characteristics, etc., the amount of the polyfunctional monomer used is preferably 70% by weight or less of the total steroid component. More preferably, the amount of the above-mentioned acrylic polymer is obtained by polymerizing a single monomer or a mixture of two or more kinds of monomers. The polymerization may be solution polymerization, emulsion polymerization, bulk polymerization, or suspension. The polymerization is carried out in any manner. The weight average molecular weight (Mw) of the acrylic acid polymerization is preferably from 500,000 to 150,000, more preferably from 80,000 to 1,200,000. Further, the degree of dispersion (Mw/Mn) of the weight average molecular weight (Mw) and the number average molecular weight (?η) is preferably 6 to 1 Torr. The weight average molecular weight means a value converted from standard polystyrene by the GPC method. As the GPC body, the product was manufactured by Tosoh Corporation using 2ΗΙχ_812 (^ρ(:, column temperature 40 °C, pump flow rate 5·5 ml/min, data processing using detector RI'). Calibration curve (corrected by molecular weight 500~20.6 million), molecular weight calculated according to converted molecular weight 0 120368.doc -23- 200808933 Using column: TSKgel GMH-H(S)x2 (made by Tosoh Corporation) Mobile phase· · tetrahydrofuran injection amount: 100 μΐ sample concentration · 1.0 g / ι (tetrahydrofuran solution) heterogeneous dispersion ' as the ratio of the weight average molecular weight to the number average molecular weight. The same as the determination of the average molecular weight of the heavy enthalpy The method performs a determination of the number average molecular weight.

Further, the polymerizable unsaturated compound is a radiation curable or thermosetting monomer component or an oligomer component, and is a compound in which one or more unsaturated double bonds are contained in a knife which is hardened by an active energy source such as radiation or heat. Preferred are compounds containing two or more and double bonds. The hardening component is suitable for &<><>> used to transport 8 keeper so that the cleaning adhesive layer (cleaning layer) is not clear with the mouth: M (strongly followed by force, χ, by adding the monomer components The nutrient-forming knife can reduce the viscosity of the system, so that the effect of forming the concave structure more uniformly during phase separation can also be expected. As the above polymerizable unsaturated compound, it is preferably non-volatile and has a weight average molecular weight of 1〇. _ below the low molecular weight body, particularly preferably having a molecular weight of = 5 Å or less, and m for the cleaning adhesive which is effective for hardening as 4, such polymerization and sufficiency «, : Π Phenoxy polyethylene glycol (methyl) propylene fluorene (meth) acrylate, polyethylene glycol bis (methyl S 曰, polypropylene glycol di (meth) acrylate, 1,4-butyl Diol diol (methyl methacrylate vinegar, "1) _ brewed, W hexane diol (methyl) propyl - methacrylic trimethyl (meth) acrylate vinegar, tetramethyl methacrylate 120368 .doc -24- 200808933 Tetrakis(meth)acrylate, quaternary tetraol tri(meth)acrylate, pentaerythritol tetrakis(methyl) Esterified ester of (meth)acrylic acid and polyhydric alcohol such as acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, diquaternic pentaerythritol hexa(meth)acrylate, neodecanediol di(meth)acrylate And a urethane (meth) acrylate, a (meth) acrylate epoxy ester, an oligoester (meth) acrylate, etc., and one type or two or more types can be used.

In the preparation of the above polymerizable unsaturated compound (monomer component, oligomer component), it is preferably 3 to 10 〇 heavy blind, more preferably 5 to 8 with respect to 100 parts by weight of the acrylic polymer. The parts by weight, more preferably the parts by weight, are more preferably 10 to 60 parts by weight. Further, as the radiation curable or thermosetting acrylic adhesive, in addition to the above-described additive type, the raw material polymer may be used in the side chain or main chain of the polymer or have carbon at the end of the main chain. The intrinsic type of carbon double bond. The intrinsic type curable adhesive does not need to contain a polymer component as a low molecular component, or is not contained in a large amount, so that the polymer component or the like is not moved to the sticky (four) towel, and a stable layer structure can be formed. Cleaning adhesive layer (cleaning layer). /, the raw material polymer having the above-mentioned bismuth-slave double bond, and a carbon "carbon double bond and having adhesiveness" can be used without particular limitation. As such a raw material polymer, it is preferred that the propylene-(tetra) compound is The basic skeleton of the acrylic polymer is exemplified as the above-mentioned exemplified acrylic polymer. The method of introducing a carbon-carbon double bond into the acrylic polymer is not particularly limited, and various methods can be employed. The carbon-carbon double bond leads to the polymer side 120368.doc -25·200808933 chain, which is easy to molecularly design. For example, a method of copolymerizing a monomer having a functional group with an acrylic polymer in advance is exemplified. A compound having a functional group capable of reacting with the functional group and a carbon-carbon double bond is subjected to condensation or addition while maintaining the radiation hardenability of the carbon-carbon double bond. As an example of the combination of the functional groups Examples thereof include a decanoic acid group and an epoxy group, a carboxylic acid group and an aziridine group, a hydroxyl group and an isocyanate group, etc. Among the combinations of the functional groups, in terms of ease of reaction tracking, a hydroxyl group 2 is preferred. different Further, if a combination of an acrylic polymer having the above carbon-carbon double bond is formed by a group of such functional groups, a functional group may be present in the acrylic polymer and the above In any one of the above compounds, in the above preferred combination, it is preferred that the acrylic polymer has a hydroxyl group and the above compound has an isocyanate group. In this case, as an isocyanate compound having a carbon-carbon double bond, For example, methacrylic acid methyl methacrylate, 2-methyl propylene methoxyethyl isocyanate, iso-isopropenyl-α, α-dimethyl hydrazine, etc. As the acrylic acid polymer, a hydroxyl group-containing monomer or 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, a compound, etc., which are exemplified above, can be used. The above-mentioned intrinsic type of curable adhesive may be a raw material polymer (acrylic polymer) having the above carbon-carbon double bond, or may be blended to such an extent that the properties are not deteriorated. A curable monomer component or oligomer component. In the case of an intrinsic type of curable adhesive, it is preferred to contain more than 5% by weight, more preferably 5% by weight or more of the base polymer having the above carbon-carbon double bond 120368.doc -26 - 200808933 Further, in order to promote crosslinking of the acrylic polymer as the raw material, it is also possible to appropriately add an external crosslinking agent to the above-mentioned adhesive. For example, it is preferably a polyfunctional compound which is not reactive with the functional group with respect to an acrylic polymer having a carboxyl group or a hydroxyl group. For example, it may be listed as I, 夭_-addition of diphenylnonane diisocyanate and曱Benzene diisocyanate, etc. ^ 昱 # # ^ octa cyanide, epoxy compounds, aziridine compounds, tri-polyamide crosslinkers, start + receive ^

^ The amount of the recombining agent (polyfunctional compound) used for the reaction of the so-called cross-linking agent such as the poly-compound, the anhydrous amine, the polyamine, the carboxyl group-containing poly-amp; The acrylic polymer is preferably blended in an amount of 20 parts by weight or less with respect to 100 parts by weight of the acrylic polymer in an amount of 〇01 to 2 parts by weight and 〇〇1 to 1 part by weight. These cross-linking agents have no problem even if they are used in combination of two or more kinds. In the above-mentioned curable acrylic pressure-sensitive adhesive, an initiator may be contained depending on the curing method. When the curable adhesive is cured by ultraviolet rays or the like, a photopolymerization initiator is contained. Examples of the photopolymerization initiator include 4-(2-hydroxyethoxy)phenylhydroxy-2-propyl) ketone, hydroxy-α, α-methylacetophenone, and 2-methyl- An α-keto alcohol compound such as 2-hydroxypropiophenone or i-hydroxycyclohexyl phenyl ketone; methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2- Acetophenone-based compound such as diethoxyacetophenone or 2-methyl(methylthio)-phenyl]-2-morpholinyl-1-propanone; benzoin ethyl ether, benzoin isopropyl ether, fennel A benzoin ether compound such as indoline ether; a ketal compound such as benzyl dimethyl ketal; an aromatic solvent such as 2-naphthalene sulfonate 120368.doc • 27- 200808933 Μ醯 糸 compound quot · 酮 · 丙 丙Photoactive lanthanide compounds such as ketone oxime; ^ carbonyl-based) L-methoxy-benzolone, benzoic benzoic acid, ^diphenyl ketone compound such as guanidine, 嗣L plugin, "base: (4) C (tetra) ketone, 2, dichloro: Ethylene sylvestre _, different s gan ~ 2,4-ethyl thioxanthin 1, 2 4 _ one: base "ketone and other sinotic ketones combined brain" : = scales thiophosphoric acid _ etc. Preparation of photopolymerization initiator: phase = 〇 heavy injury The raw material polymer such as the two olefinic polymer constituting the adhesive is, for example, about 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight. The adhesion is described, in addition to the above ingredients, ί: Additives such as various adhesion-imparting agents, aging-preventing agents, coloring agents, chain transfer agents, plasticizers, etc., such as the description, the formation of the cleaning adhesive layer (cleaning layer) of the present invention (The production of the adhesive layer of the second Jr having a non-continuous recess on the surface is not particularly limited, for example, by performing the following steps: 仃Step (1), which will be radiation hardening or heat hardening An adhesive composition for dissolving the chelate incompatible with the above-mentioned acrylic adhesive is applied to a substrate to form an adhesive composition genus; step (7), The adhesive composition layer is irradiated with radiation or/and the acrylic adhesive is cured, and the adhesive layer precursor is formed. The adhesive layer precursor has phase separation of the cured product from the incompatible compound. Structure; and σ y (3 Removing the incompatible 120368.doc -28- 200808933 from the obtained adhesive layer precursor. In the step (i), it is to be in a radiation curable or thermosetting acrylic adhesive, and further An adhesive composition formulated to be compounded with the above-mentioned acrylic adhesive is applied to a support to form an adhesive combination: a layer. The above incompatible compound is used for cleaning an adhesive layer. The surface is formed with a concave portion which is compatible with the acrylic adhesive. The above incompatible compound may be mixed with the above propylene (4) adhesive and may be formed in the formation of the adhesive composition layer. There is no particular limitation on the phase separation. Usually, the adhesive composition is used as a solution, and therefore it is preferred to apply the dosing composition to the substrate and then dispense (iv) away from the solvent during the solvent removal process. As the degree of phase separation of the above incompatible compound, it is preferred to adhere to the acrylic state in the liquid state. The liquid phase is formed into a liquid phase separation. The preparation of the composition of the composition can be carried out by combining the above-mentioned incompatible compounding agent with the above-mentioned acrylic acid-based adhesive. For the solvent, an organic solvent can be used. As an organic solvent, in terms of film stability at the time of film formation, the composition of the composition can be used as a < For example, Dingyuan, cadaveric scorpion*, o-toluene, m-xylene, p-f-benzene, cyclohexanone, ethanol, isopropanol, di-tergin, s pentyl hexanol, 2-methylcyclohexyl, propyl ether, dibutyl M ^ ketone, methyl ethyl net, methyl m - hydrazine, tetra..., bis-butanone, hydrazine, earth " butyl Ketone, 2_heptanone (methyl amyl ketone), bismuth, acid pentane _ (cyclohexyl, A_e), methylcyclohexamine, cyclopentate M, acetic acid, propyl acetate , acetic acid = 120368.doc -29· 200808933 ester, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methylpyrrolidone, 2-methoxy Ethyl alcohol, 2. ethoxyethanol, 2-butoxyethanol, etc. The organic solvent is preferably ethyl acetate, toluene or xylene. Further, it is preferably dissolved in the above organic solvent. And methanol and the like It is a mixture of the adhesive-incompatible compounds. The solvent composition is usually adjusted to have a solid content concentration of 5 to 50% by weight, preferably 5 to 3 % by weight, more preferably. It is a solution of 10 to 25% by weight. Examples of the above incompatible compound include, for example, ethylene glycol, ethylene glycol glycol, polyethylene glycol, propylene glycol, dipropylene glycol propanol, and *propanol. And an ethylene glycol-based compound such as a single-terminal or two-terminal methyl block, a single-end or a two-terminal (meth) acrylate block, as an example, one or more of which may be selected. In the case of the addition of the curable acrylic adhesive, it is preferably 3 parts by weight based on 1 part by weight of the total of the acrylic polymer and the polymerizable unsaturated compound. The amount of the above-mentioned preparation is preferably 100 parts by weight or less, more preferably 5 parts by weight or less, in order to optimize the size of the formed concave portion. On the other hand, it is preferable to achieve phase separation to the extent that the concave portion is expressed. Is 5 heavy Applying the above-mentioned adhesive (tetra) compound to the support Zhao to form an adhesive (four) person == the formation method can be carried out by various methods. For example, in the case of using a joint to form an adhesive composition layer, For example, the adhesive composition (solution) can be supplied in the following manner, and the adhesive composition (solution) can be sprayed from the die attached to the front end of the package 120368.doc -30- 200808933, and formed as a ,tf I, to the base. Extrusion into a thin layer on the material. Method 2:::: The method of the layer can be listed on the batch substrate, using a batcher, or a coating agent on the M (solution is in the method) Thus, the thin layered 3-stick is formed by heating the film forming machine to remove the layer on the support, and the above-mentioned incompatible compound is caused by drying the solvent. The acrylic adhesive layer has a very fine concave and non-glutinized phase separation, and the temperature is i UP to dry the mixed solvent, and is particularly limited, and is preferably about 50 to 60 tons. The thickness of the adhesive composition layer is not particularly limited, and is usually preferably about 5 to 100 μmη, more preferably _. Thinner than the above range, the shape of the cleaning adhesive layer (cleaning layer)

Drop, the situation in which the foreign matter is trapped. Moreover, if it is more than this range, J may be too thick and it is difficult to operate. The above substrate may also be used as a support for a cleaning sheet (adhesive sheet for cleaning) in which the obtained cleaning adhesive layer cleaning layer is provided. The base material which can be used as the support is not particularly limited, and examples thereof include a polyolefin resin such as polyethylene or polypropylene, and a polyethylene resin such as polyethylene terephthalate. A cellulose resin such as a cellulose resin, a polycarbonate resin, a polyamide resin, a polyimide resin, a polycarbodiimide resin, a plastic sheet such as a chlorinated resin, or the like. The thickness of the substrate is usually preferably about 10 to 300 μηι. In terms of operation, it is better to be 3〇~2〇〇 ^^2 right. Further, when a radiation curable adhesive is used for forming an adhesive layer, a plastic sheet that transmits light such as ultraviolet rays is used. Also, for the base 120368.doc -31- 200808933, metal boxes can be used depending on the situation. Various surface treatments can also be carried out on the surface of the substrates. Then, in the step (2), the adhesive composition layer is irradiated or heated by radiation to harden the acrylic adhesive, and an adhesive layer precursor is formed, the adhesive layer precursor having the cured product and the above Phase separation structure of non-phase compound.

When the adhesive composition layer on the substrate is irradiated or heated, the acrylic adhesive is cured to suppress the cross-linked oxygen, and the flat surface on which the concave portion is formed is further prevented. For smoothing, it is preferred that the surface of the adhesive composition layer is subjected to a hardening treatment in a state covered with a cover film. Therefore, it is possible to suppress the degree of hardening caused by the oxygen barrier during curing of the acrylic acid-based adhesive, and the degree of crosslinking is lowered, and when the convex portion is formed on the surface which is separated by using the cover film, The effect of flattening the portion thereof is not particularly limited as a cover film, and examples thereof include polyethylene, polypropylene polyethylene terephthalate, acetonitrile cellulose, polycarbonate, polyamide, and carbonization. Plastic film such as diimine. The thickness is usually preferably about 10 to 1 GG μηι. When a radiation curable adhesive is used to form a cleaning adhesive layer (cleaning layer), a plastic film having a high transparency through ultraviolet light is selected. As the cover film, various treatments can be carried out on the surface facing the adhesive, and the release film can be directly produced. The above propylene I (10) agent is irradiated or heated according to its hardenability. Examples of the radiation include ultraviolet rays, electron beams, and the like. As a method of hardening 120368.doc -32- 200808933, ultraviolet light hardening is preferred in terms of its steps. By this, the concave structure formed on the substrate is fixed. Further, when curing, the acrylic adhesive and the incompatible compound may be phase-separated by reaction-induced phase separation to enlarge the concave structure. Further, in the hardening process of the acrylic adhesive, even incompatible compounds There is no problem in partial crosslinking with an acrylic adhesive (acrylic polymer or polymerizable unsaturated compound).

Further, in the method for forming the cleaning adhesive layer (cleaning layer) of the present invention, the following step may be carried out as the step (1) instead of the above step (1): in the radiation curable or thermosetting acrylic adhesive Further, an adhesive composition solution capable of dissolving an organic solvent containing an adhesive group a compound which is incompatible with the above-mentioned acrylic adhesive, is applied onto a substrate, and further dried to form an adhesive composition. The material layer is dried by the organic solvent to form an adhesive layer precursor having a phase separation structure of the acrylic adhesive and the incompatible compound. In the step, the viscosity of the adhesive composition solution can be adjusted by using an organic solvent, and the viscosity can be easily applied to the substrate. Examples of the organic solvent include aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol and ethanol, methyl ethyl steel, and the like, and two: vinegar and acetic acid, and the like, and the above-mentioned adhesive can be dissolved. The solvent of the composition. The amount of organic solvent used is relative to 1 〇〇 ... 着 composition, usually 1 〇〇 ~ 1 〇〇〇 weight 八? The good thing is 200~9〇〇. If the amount of the organic solvent used is less than the above range, there is a case where p: the viscosity of the solution of the adhesive composition rises 'cannot be obtained = two 120368.doc -33 - 200808933 =_ the effect of easy coating. Further, in the above range, there are the following cases: • Adhesive combination: = too low, the coating thickness of the adhesive composition solution is thinned, and there is no: obtaining a cleaning adhesive layer having a desired thickness (2) In the step (1)), the adhesive composition layer is formed by the adhesive composition, and the adhesive is formed by drying it overnight, and the body is ... Γ from the solution before the adhesive layer of the structure: go = coating Adhesive composition on the above substrate

The method of using the common heating device core L:r agent can dry η & , , , , σ,,,, and the device, for example, heat convection type: thermal cycle dryer, vacuum dryer, floating oven, etc. . The temperature is such that the organic solvent is easily volatilized, and the above incompatible compound does not have a temperature, usually 20 to war, preferably 3 to 6 Torr. . Vanity = set according to the above incompatible compounds. In addition to this aspect, step (1) proceeds to the same operation as step (1). When the above step (n) is employed, as step (2), the above-mentioned adhesive composition layer is irradiated or heated to harden the upper acrylic adhesive, and the hardened material is cured. The adhesive layer precursor of the phase-separated structure of the above incompatible compound is immobilized. Step (2) is carried out in the same manner as in step (2). Hereinafter, step (3) is carried out. ', in step (3) Removing the non-phase compound from the obtained adhesive layer precursor. For example, as step (3), the incompatible compound may be removed from the adhesive layer precursor by heating. Further, the solvent may be removed by the solvent. Extracting and removing incompatible compounds from the adhesive layer precursor. Thereby, a recess can be formed on the surface of the cleaning adhesive layer (cleaning layer). 120368.doc -34· 200808933 As incompatibility is removed by heating The method of the compound can be applied to a common heating device 'such as 'publishing a heat convection dryer, a heat cycle dryer, a vacuum dryer or a floating oven, a hot air circulation oven, etc. As a heating temperature, considering the phase difference When the base material or the cleaning adhesive layer (cleaning layer) which produces a recessed part is not deformed by heat, the boiling point and the scattering temperature of the compound are not particularly limited, and it is usually preferable in terms of effective removal. It is 50~2〇0. (: Left and right, better is 1〇〇~2〇η: the range around.

Further, in the case where the solvent is extracted from the adhesive layer precursor to remove the incompatible compound, the solvent for extracting the incompatible compound is formed according to the formation of the acrylic adhesive layer (cleaning layer), Flexible use of compatible compounds. It is often used as an organic solvent which extracts incompatible compounds from the above-mentioned cleaning adhesive layer (cleaning layer). Examples of the solvent include decene, ethyl acetate and the like. Further, instead of the organic solvent, carbon dioxide which is a non-toxic, non-hazardous substance or a carbon dioxide in a supercritical state may be used. As a container for removing incompatible compounds by using carbon dioxide, if it is a container which can be extracted and removed under pressure, there is no particular limitation, and the batch type pressure pen can be stretched with pressure resistance. Any one of a sheet, a winding device, and the like. As a supply mechanism of the above-mentioned carbon dioxide of the raw material and the fluid, it can be composed of a fruit, a pipe, and a concrete. ΜYou use the adhesive layer (clear layer), as shown in Figure 3, the discontinuous recess can be the surface, and the formula can be placed on at least one side of the support 2 as a cleaning sheet (cleaning sheet). The substrate in the above manufacturing method is used as the support 2 120368.doc •35· 200808933 The 'offer can be pre-set on the surface of the cleaning adhesive layer (cleaning layer) ι. It is used as a label sheet. In the case of using the above-mentioned cleaning sheet, 'as shown in Fig. 4', the other side of the support body 2 provided with the cleaning adhesive layer (cleaning layer) having the above-mentioned concave portion can be provided for fixing. For the adhesive agent, a separator may be provided on the surface of the adhesive layer 3. The adhesive layer 3' is used as long as it satisfies the ordinary adhesive function, and the material is: Ordinary adhesive (for example, enamel, rubber, etc.). Double-sided tape can also be used for the adhesive layer 3. The adhesive layer 3 can attach the cleaning sheet to various substrates or other tapes and sheets, etc. The conveying member with the cleaning function is transported into the device The cleaning part is cleaned by contact with the cleaning part. The fixing member is attached to the conveying member to which the cleaning sheet is attached, and the substrate for a flat panel display such as a semiconductor wafer, an LCD, or a PDP is not particularly limited, and the substrate of the optical disk or the magnetoresistive head is used. In the case of the agent layer 3, in order to reuse the transport member such as the above substrate, it is preferable to shed the substrate from the adhesive sound 3 4 丨 5 a 4 layer 3 after/after freezing. The agent layer 3 can be easily peeled off from the substrate, and the contact force of the adhesive layer 3 is 180, which is 180 with respect to the silicon wafer (mirror surface). The peeling w5N/1〇mm/l force GNmmm, especially It is preferable that the left and right sides of the county can not be peeled off during transportation and can be easily peeled off after cleaning. It is preferable that the conveying member having a cleaning function after the month is preferably smaller than the shape of the conveying member. The cleaning sheet is larger than the end portion of the conveying member Lm. When the shape is 6-shaped, sometimes the cleaning sheet 120368.doc -36 - 200808933 is attached to the skirt, or stuck in the conveying system, so that the shelf is beneficial. The normal operation of the method. For the conveying member with the cleaning function as described above The manufacturing method is not particularly limited. For example, the cleaning sheet can be attached to a conveying member such as a substrate to produce a cleaning conveying member. The 愔mi* is m in the following manner: after attaching a cleaning sheet larger than the conveying member, The shape of the member is cut (hereinafter, referred to as a direct cutting method); or the pre-cut processing is performed: the cleaning label sheet of the member member is attached to the conveying member and the cleaning member (hereinafter referred to as a pre-cutting member) Cutting method). month (7) cleaning layer (average opening diameter: 0.1 to 3 μηι) Further, the ratio of the concave portion a in the surface S of the cleaning adhesive layer (cleaning layer) 1 of the present invention (there is a 屮, , , , w 5 A concave main rate, it is preferable that the projected area of the concave portion a is relative to the total projection surface of the surface S, and is 15% to 90% to 15% to 90%. The above ratio is better. More preferably 20% to 70%. In addition, the product is referred to as a cleaning adhesive layer (cleaning layer) when the projection surface concave portion a is formed by a microscopic transcript. The area ratio of the portion which is the concave portion a after 邙a. In the case where the area of the concave-concave is too small, there is a solid layer (cleaning layer) which is required to fully exhibit the projection surface of the clean layer when the adhesive layer is used. The situation. On the other hand, the adhesion force in the concave portion a is remarkably lowered, and I... is formed by an adhesive layer (cleaning layer). In addition, the law of the 获 ... method is limited by the fact that the foreign object is trapped by the servant, and the ruin of the recess (4) U layer) is the friction of the surface. The shape of the opening portion of ° a is the same as the case of the above (1) cleaning layer (average opening 120368.doc -37 - 200808933 diameter: 10 μmη or less). The opening portion of the concave portion & preferably has an average opening diameter of equal to two: a fine opening smaller than the average foreign matter size. The opening portion = the opening diameter is preferably 〇ι 2 2 μιη. If the opening of the recessed portion & is larger than the size of the object and the number of X' is too large, the trapping effect of the foreign matter is remarkable. * As described above, by setting the fine π', it is possible to capture a wide range of sizes. For example, when the opening diameter of the opening is about 1 〇 (four), the concave portion P or the flat portion can be recessed to collect a foreign matter having a diameter of 10 μm or more and it is difficult to trap a small diameter (four) μηι. On the other hand, as in the case of the present invention, the average opening diameter of the opening of the concave & the concave opening & is set to a micro-portion such as _, and the foreign matter of the size larger than the opening diameter can be trapped. The range of the grain shuttle due to the foreign matter of the 卞 变 is widened. The opening diameter of the opening means the maximum diameter, and the average opening diameter is, as in the embodiment, the average value of the maximum diameters of the respective opening portions obtained by the θ analysis. Further, the standard deviation of the above-mentioned opening diameter is preferably G.7 _ or less, and the opening control of the upper 卩 is controlled to have the same size. The standard deviation I of the above-mentioned opening shuttle is preferably G.6 μηη or less. It is preferable that the opening portion of the concave portion of the surface of the cleaning adhesive layer (cleaning layer) is a standard deviation from the center of the adjacent opening portion, and the dispersion of the second portion is uniform. The above-mentioned center distance standard is 疋 μΠ1 or less. Further, the above-mentioned "adjacent opening 1" means the length of the opening portion where the center distance is the smallest, and the "center distance" to the center point of the opening portion. The cross-sectional shape of the concave portion a is not particularly limited, and the controllability of the concave portion size 120368.doc -38 - 200808933 is preferably hemispherical, and the above (i) cleaning layer (average opening diameter: 10 μπι or less) the same. Further, the ratio (h/H) of the depth (h) of the concave portion a to the thickness (H) of the cleaning adhesive layer (cleaning layer) 1 is preferably from 0. 01 to 0.1. The thickness (H) of the cleaning adhesive layer (cleaning layer) 1 and the depth (h) of the above-mentioned concave portion a are their respective average values. The size of the concave portion a is determined by the depth (h) of the concave portion a when the cross-sectional shape is hemispherical. When the above ratio (h/H) exceeds 〇1,

When the concave portion a is too deep, the strength of the wall surface of the concave portion is insufficient. Further, when the above ratio (h/H) is less than 〇·01 or less than or equal to 〇〇1, there is a case where the necessary foreign matter collection property is insufficient. The above ratio (h/H) is preferably in the range of from 0. 01 to 0.05. In the present invention, by forming the cleaning adhesive layer (cleaning layer) having the concave structure as described above, the adhesion area of the surface of the cleaning adhesive layer (cleaning layer) and the adhering body can be reduced, and, on the other hand, #由为细的凹: The structure, because the foreign matter is larger than the opening diameter of the concave portion, and then the area is increased, so that the foreign matter can be reliably collected. χ, the opening diameter of the concave portion is not uneven, and the concave portion is uniformly dispersed to the surface of the cleaning adhesive layer (cleaning layer), whereby unevenness in characteristics can be suppressed. The above-mentioned cleaning adhesive layer (cleaning layer) has a tensile modulus of elasticity of preferably θ 2 Mpa to 500 Mpa. If the anti-tensioning of the cleaning adhesive layer (cleaning layer): (4) exceeds 500 Mpa, the adhesion of the surface of the cleaning adhesive layer (cleaning layer) is reduced, and the force is reduced even in the cleaning adhesive layer (cleaning layer) Forming a concave:: It is also impossible to express the foreign matter trapping function. In addition, when it is less than MPa, even if a concave portion is formed on the surface of the cleaning adhesive layer (cleaning layer), the surface structure is deformed, resulting in the deformation of the surface structure. The transport device is inline [J ϊ ϊ, t > ° *. The above-mentioned adhesive layer (cleaning layer) has a good tensile modulus of 9 杈 〇 MPa 〜 3 (10) MPa, more preferably 1 〜 〜 200 MPa. The tensile elasticity of the cleaning adhesive layer (cleaning layer) may be based on the composition of the above acrylic adhesive, for example, an acrylic polymer and a polymerizable unsaturated compound (monomer component, polymer blending amount, etc.) _ In addition, the cleaning adhesive layer (cleaning layer) of the present invention is used as the π 4 layer of the cooling sheet with respect to the 矽 wafer. The peeling force is the same as (1) above. The same is true for the cleaning layer (average opening diameter: 10 μηι or less). When the monthly cleaning adhesive layer (cleaning layer) is used as the cleaning layer of the cleaning sheet, the diameter is 2 kg. The 5G mm metal piece is placed on the cleaning layer for 3 minutes, and the force (vertical peeling force) is applied when the metal piece is lifted vertically at a stretching speed of 1 〇〇mm/knife at room temperature 23, c. In the present invention, it is considered that not only the foreign matter collecting property but also the transport property is obtained in the present invention. The cleaning adhesive layer (cleaning layer) of the present invention has the above-mentioned If the structure of the recess is sticky and the material is The quality, structure, and the like are not particularly limited to the same as in the case of the above (1) cleaning layer (average opening diameter: 1 Torr or less). The above-mentioned radiation curable or thermosetting acrylic adhesive, weight average molecular weight, and external crosslinking The agent, the initiator, and other additives are also the same as the above (1) cleaning layer (average opening diameter: 1 〇μπι or less). As for the cleaning adhesive layer (cleaning layer) of the present invention, for example, 120368. Doc 200808933, the method for forming a cleaning adhesive layer (cleaning layer) having a discontinuous concave portion on the surface is not particularly limited, and may be performed by radiation hardening containing the above acrylic polymer or The thermosetting acrylic adhesive is carried out by performing the above steps (1) to (3). In the step (1), the adhesive composition solution is applied onto a substrate and dried to form an adhesive composition layer. The adhesive composition (4) liquid system is further blended with the above-mentioned acrylic resin in a radiation curable or thermosetting acrylic adhesive containing an acrylic polymer. An adhesive composition of a compound incompatible compound, dissolved in a solvent (4) containing the above-mentioned acrylic acid-based polymer, and a compatible solvent compatible with both the above-mentioned propylene-based polymer and the above-mentioned non-phase compound The mixed solvent of (B) is the same. The above-mentioned incompatible compounds are used for the adhesive layer for cleaning (cleaning layer: the compatibility of the surface forming concave portion with the acrylic acid adhesive: Γ The compatible composition can be phase-separated if it is miscible with the above-mentioned acrylic adhesive and forms a layer of the adhesive composition. The above adhesive composition is used as a solution, so the two temples涂布 After the adhesive composition is applied to the substrate, the phase separation is removed in the solvent. The ratio of phase separation of the non-phase compound is better than that of ^μ, +, T 4 + ^ θ, In the state of liquid, it is the same as that of women. (4) The bismuth-based adhesive G-liquid) forms a liquid phase separation. The above-mentioned non-phase-valer compound ' can be used as a phase of an acrylic-based adhesive: human: low' and has a degree of non-volatility when the solvent is dried. For example, when the number of dots is 7 or more, the acrylic acid polymer is easily separated from the acrylic adhesive, and the phase separation structure is formed in the form of 120368.doc -41 - 200808933. If the χ parameter is 7 or less, phase separation is difficult to occur, and small changes in composition affect phase separation. Therefore, it is easy to be affected by the drying conditions of the solvent, and it is difficult to form a structure stably. Further, the above enthalpy parameter is preferably at least 7.5, more preferably at least 8. χ parameters can be based on

The interaction constant of Flory-Huggins theory is defined as % parameter ^(νΜΊχδγδΟ2. V!: molar volume, R • gas constant, τ: absolute temperature, δ: solubility parameter. Also, near 5〇~6(rc Dry the above mix

In the case of a solvent, if a boiling point of 19 or more is used as the above-mentioned incompatible compound, the solvent does not volatilize when dried, and a phase separation structure can be formed. The boiling point of the above incompatible compound is preferably 2〇. 〇〇c or more, more preferably 200 to 300 ° C. The above-mentioned incompatible compound and its blending amount are the same as those in the above (丨) clean layer (average opening diameter: 10 μΓη or less). The preparation of the solution can be carried out by mixing the incompatible opening 'with a solvent with the acrylic adhesive. The solvent can be used to contain the C: strontium used in the above acrylic adhesive. a solvent in which the polymer is dissolved (Α) and a mixed solvent of a compatible solvent (Β) which is compatible with one of the above-mentioned acrylic polymer W phase glutenated σ. ^ Solvent (4), depending on the type of the acrylic polymer, It is preferable to dissolve the acrylic polymer in the following two sentences. If the solvent (4) is used as the solubility index, it is preferable to use the ruthenium parameter of 3 with respect to the ruthenium acrylate. % In the case where the number exceeds 3, the case where the acrylic polymer is stored in the solution and the glutinous solution (2) 屯. The above χ parameter is preferably 120368, doc - 42 - 200808933 〇 · 34 ～ 2.8. As the above solvent (4), for example Listed: butadiene, hexane, g-burn, toluene, o-toluene, m-xylene, p-xylene, cyclohexyl, diethylene isopropyl isopropyl ether, dibenzyl ether, tetrahydrofuran, acetone, methyl ethyl Ketone, methyl isobutyl ketone, + Π 2-heptanone (methyl amyl ketone), diisobutyl ketone, cyclohexyl _ (cyclohexa a, an〇ne), methylcyclohexanone, Cyclopentanone, acetic acid vinegar, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, hydrazine, hydrazine-dimercaptomethylamine (DMF), hydrazine, hydrazine-dimethylacetamide (DMAc) And the above-mentioned organic solvent is preferably ethyl acetate, toluene, xylene or the like. On the other hand, the compatible solvent (Β) is the above-mentioned acrylic polymer and the above It is compatible with one of the gluten-free δ materials, and can be used with a solvent (Α). Compatible solvent (Β), preferably using χ parameters relative to acrylic polymer Preferably, G.5~3, more preferably G.5~2, is preferably 0.5~3 relative to the incompatible compound, more preferably it is ~. If compatible solvent (b) When the above enthalpy parameter is out of the above range, there is a case where the acrylic adhesive and the above-mentioned incompatible compound are uniformly dispersed in the solution as the adhesive composition solution. The above compatible solvent (Β) 'according to the acrylic type' The type of the polymer, the incompatible compound, and the solvent are appropriately selected. The above-mentioned compatible solvent is, for example, preferably an alcohol solvent. Examples of the alcohol solvent include methanol 'ethanol, isopropyl alcohol, and 1 - decyl alcohol, cyclohexanol, 2-methylcyclohexane: 2-methoxyethanol, 2-ethoxyethanol, 2-butanylethanol, and the like. Among these, a suitable mixing ratio of the above solvent (A) and the compatible solvent (B) is decyl alcohol and ethylene glycol (120368.doc -43-200808933), and if the acrylic polymer is uniformly mixed, the polymerization property is not The saturated compound and the incompatible compound are not particularly limited, and usually the solvent (A) / compatible solvent (B) = 1 / 3 to 3 / 1 (weight ratio) is preferred. If solvent (A) / compatible solvent

In the following (4) or more, there is a case where the mixture cannot be uniformly mixed, and the second embodiment is that the cleaning adhesive layer (cleaning layer) cannot form a uniform concave portion. Further, with the above mixed solvent, the adhesive composition is usually adjusted to a solid content of preferably 5 to 50% by weight, more preferably 5 to 3 % by weight, still more preferably 10 to 25% by weight. Solution. The above-mentioned adhesive composition solution is in a homogenous state by using a mixed solvent of the solvent (A) and the compatible solvent (8), and it is preferred that the phase separation occurs in the absence of the compatible solvent (8). In the step (7), it is preferred to form an acrylic acid-based adhesive =: a phase-separated structure of a chemical substance. The above adhesive composition solution is applied onto a support and dried to form an adhesive composition layer. As the method of the above-mentioned type, the above (1) cleaning layer (average diameter: 1 to Å;; thickness or substrate of the adhesive composition layer, and the above (1) / (sentence opening diameter: 10 μιη or less) The same is true. The same as in the case of the above (1) cleaning layer (below 1 〇 μηη), or the following: or the following: The adhesive composition layer on the substrate is irradiated with radiation. It is also the same as the above (1) cleaning layer (average opening diameter: 1 〇qing) 120368.doc -44- 200808933. As a cover film, and helmet county - 乂..., especially limited, with the above (1) cleaning layer (The average opening diameter: 10 Å or less) is the same. The above-mentioned acrylic viscous | | , , β β β β 放射 放射 放射 放射 放射 放射 放射 放射 放射 放射 放射 放射 放射 放射 放射 放射 放射 放射 放射 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸In terms of the steps, it is preferred that the ultraviolet curing is carried out, whereby the concave shape formed on the substrate is concave, and the crucible is fixed. Further, when hardened, the acrylic adhesive is not Compatible person 4 1 ν " Phase separation is carried out by reaction-induced phase separation, and the concave structure is enlarged, but it is preferable that the opening of the concave portion is substantially circular, and the average opening is 〇. 1~3 μχη, the standard deviation of the above opening diameter 0.7 μιη or less 〇 'The distribution of the opening is controlled so that the rod + deviation from the center of the adjacent opening becomes 1 or less. In addition, during the hardening of the acrylic adhesive, the incompatible compound is even There is no problem in performing partial crosslinking with an acrylic adhesive (acrylic polymer or polymerizable unsaturated compound). Then, in the step (3, Φ, && said from the obtained adhesive layer precursor In the case of removing the incompatible compound, the same as in the case of the above (1) cleaning layer (average opening of 10 μπι or less), the removal method is also the same. Further, the extraction of the precursor from the adhesive layer is removed. The case of the content of the compound is also the same as the case of the above (1) the Uyue/糸 layer of the Uygur (the average permeation diameter: 1 〇μιη or less). The liquefied carbon dioxide of the mother non-hazardous substance or the carbon dioxide in the supercritical state replaces the organic solvent, and in this case, it is also the same as the above (1) clean layer (average opening J, the same diameter, less than 10 arrays). -45- 200808933 Layer) ι, the cleaning agent used for the main invention on the plate (cleaning as in 03, layer (average opening diameter: 10 _ or less),

H does not have a non-continuous concave portion as a surface, and at least one surface of the j holding body 2 is provided as a cleaning sheet (an adhesive sheet for cleaning). The substrate in the above-described chemical conversion method can be used as the support 2 as it is. Further, a separator may be provided in advance on the surface of the adhesive layer (cleaning layer) 1. The cleaning agent layer (cleaning) 1 and the above (1) cleaning layer of the present invention obtained in the above manner are obtained. (Average opening diameter: 1 inch or less) Similarly, as shown in FIG. 3, the discontinuous concave portion may be provided as a surface, and may be provided on at least one surface of the support body 2 as a cleaning sheet (a cleaning adhesive sheet). The substrate in the above-described production method is used as the support 2. The separator can be provided in advance on the surface of the adhesive layer 3. The fixing adhesive layer 3 and the above (1) cleaning layer (average opening diameter· The transfer member to which the cleaning sheet is attached is not particularly limited, and is the same as the case of the above (1) cleaning layer (average opening diameter: 1 〇 or less). The adhesive layer 3 is When the substrate is transported from the adhesive layer 3 after cleaning, it is preferable that the adhesive layer 3 can be easily peeled off from the substrate, and the adhesive force of the adhesive layer 3 is the same as above (1). ) clean layer (average opening The same applies to the conveying member having a cleaning function and the method for producing the same, and is the same as the above (1) cleaning layer (average opening diameter: 10 μπι or less). (3) Cleaning Layer (Ra ··0·01~0.3 μπι) 120368.doc -46- 200808933 Further, the cleaning adhesive layer of the present invention (the ratio of the concave portion a of the surface s (the ratio), or the opening of the concave portion a) The shape is the same as the above-mentioned (1) cleaning layer (average opening diameter: 10 μm or less). : 'The opening of the concave portion a can be appropriately smeared according to the size of the foreign matter, and the opening size (average opening diameter) of the concave portion a is adjusted to When the amount is larger than the average foreign matter size, if the number is too large, the trapping effect of the foreign matter may be reduced. For example, when the foreign matter ruler is a particle of about 1 to _ (four), usually The mouth portion of the concave portion (10) preferably has a mean opening diameter of about 1 to about 1, more preferably a fine concave structure of ~ μηη, and the size of the opening (average opening diameter) of the concave portion & Sexually 'The diameter (average opening diameter) which is smaller than the size of the foreign matter to be removed can be used. Further, the cross-sectional shape of the concave portion a is not particularly limited, but the controllability of the size of the Jingyou concave portion is preferably hemispherical. The same as (1) the cleaning layer (average opening diameter: 10 μπι or less). The ratio of the depth of the concave portion a (... to the thickness (H) of the cleaning adhesive layer (cleaning layer) 1 (h/H) It is the same as the above (1) cleaning layer (average opening: :: 10 μηη or less). Further, in the above surface s, the center line average roughness (Ra) of the planar surface b other than the concave portion a is preferably bG1 to G3. _. More preferably μιη. If the average thickness of the centerline (4) is less than 〇〇ι, then the transportability is not good. Further, when the average center line thickness (Ra) of the center line exceeds 〇 3 μm, it is less desirable in terms of foreign matter collection property. · The above-mentioned cleaning agent layer (cleaning layer) is preferably a tensile modulus of elasticity 120368.doc •47- 200808933 ^ Screening Mpa~500 Mpa. If the adhesion coefficient of the cleaning adhesive layer (cleaning layer) is 5 GG MPa, there is a cleaning adhesive layer (cleaning layer), and the squeezing force is lowered. Even in the cleaning adhesive layer (cleaning layer) The formation of the concave portion 2 also does not indicate the foreign matter trapping function. In addition, when the surface of the cleaning adhesive layer (cleaning layer) is formed on the surface of the cleaning adhesive layer (cleaning layer), the surface structure is deformed when it is less than 10 MPa (9), and the surface structure is deformed. Hey. The above-mentioned cleaning adhesive layer (clearing 3) preferably has a tensile modulus of 1 〇 to 3 〇〇 Mpa, more preferably MPa 200 MPa. The tensile modulus of the cleaning adhesive layer (cleaning layer) may be based on the composition of the above acrylic adhesive, such as an acrylonitrile-based polymer and a polymerizable unsaturated salt. The amount of the component, the oligomer component, and the like are appropriately set. Regarding the cleaning adhesive layer (cleaning layer) of the present invention, it is 9 相对 with respect to the ruthenium wafer when it is used as the π filter layer of the /month/'I sheet. The peeling adhesion force or its material or structure is also the same as the above (1) cleaning layer (average opening diameter: 10 μηι or less). Further, the radiation curable or thermosetting acrylic adhesive, the weight average molecular weight, the external crosslinking agent, the initiator, and the other additives are also the same as the above (1) cleaning layer (average opening diameter: 10 μηι or less). The method for forming the cleaning adhesive layer (cleaning layer) of the present invention is not particularly limited as long as it is a method of forming a cleaning adhesive layer (cleaning layer) having a discontinuous concave portion on the surface as described above. This is carried out by carrying out the above steps (1) to (3). In the step (1), an adhesive composition of a compound which is incompatible with the above-mentioned acrylic adhesive is prepared in a radiation curable or thermosetting acrylic 120368.doc • 48-200808933 adhesive, and is coated. On the support, a layer of the adhesive composition is formed. The above incompatible compound is an additive which is less compatible with an acrylic adhesive which forms a concave portion on the surface of the cleaning adhesive layer (= cleansing layer). The above-mentioned incompatible compound is not particularly limited as long as it can be combined with the above-mentioned propylene glycol-based adhesive and can be phase-separated when the adhesive composition layer is formed. Usually, the adhesive composition is used as a solution, and therefore it is preferred to apply the adhesive composition to the substrate and perform phase separation during solvent removal. As the degree of phase separation of the above incompatible compound, it is more suitable for the liquid form and the state of the acrylic adhesive (solution). The preparation of the above adhesive composition, the above-mentioned incompatible compound and its formulation, the thickness of the above-mentioned adhesive composition layer, and the above-mentioned substrate are also the same as the domain (1) cleaning layer (average opening diameter: 1 Å or less). ▲In the step (2), the above-mentioned adhesive composition layer is irradiated with radiation or heated to harden the acrylic adhesive, and an adhesive layer having a phase separation structure of the above-mentioned incompatible compound is formed. Moon 焉 物. The adhesive composition layer is irradiated with radiation to perform hardening of the propylene (tetra) adhesive, inhibiting the cross-linked oxygen person's screen and recognizing, and the ten-face is more slippery', and the adhesive group is two or two; In the state of covering, 'hardening treatment is performed. The hardening caused by the oxygen barrier during the hardening of the adhesive is reduced. Further, as the cover film, it is preferred to use a surface having a mean thickness (Ra) of 368·〇ι~〇·3 in the range of 120368.doc •49-200808933 to cover the film having the above-mentioned centerline average The surface of the thickness (Ra) is covered by the surface side of the above-mentioned adhesive composition layer. By using the cover film, the surface of the center line average roughness (Ra) can be transferred onto the surface of the cleaning adhesive layer (cleaning layer), and the cleaning adhesive layer (cleaning layer) other than the phase-separated concave portion can be removed. The surface control is the center line average roughness ^ hook is 〇〇1~〇3 pm. The cover film is not particularly limited, and is the same as the case of the above (1) cleaning layer (average opening diameter: 10 μm or less). The propylene (tetra) adhesive is subjected to radiation irradiation or heating 1 according to the curability thereof, and is irradiated and cured in the same manner as in the above (1) cleaning layer (average opening m _ or less), and in the case of hardening, the acrylic adhesive is not in phase. The bulk compound can also be subjected to phase separation by reaction-induced phase separation to expand the concave structure. Further, in the hardening process of the acrylic adhesive 2, the incompatible compound is not problematic even if it is partially crosslinked with an acrylic adhesive (acrylic polymer or polymerizable unsaturated compound). Capacitor: The method for forming the cleaning adhesive layer (cleaning layer) of the present invention can be carried out as a step (Γ-^ for the above step (1) ··will be radiation==sexual or thermosetting _ Adhesively bonding, and then formulating an adhesive composition solution for dissolving 2" of the above-mentioned acrylic acid-based adhesive-incompatible compound, onto the substrate, and applying: Solvent 1: 烨== combination of agents The layer 'and the phase separation by the above organic-capacity compound: the dimercapto-acid-based dot-donating agent does not correspond to the above-mentioned "from the "adhesive layer precursor" by using an organic solvent - (1) The viscosity of the solution of the adhesive composition for 5 weeks is 120368.doc -50-200808933 degree' can be set to be easy to apply on the substrate. The use of the above-mentioned organic solvent and its organic solvent is used to clean the layer ( Average - diameter: ... shouted) the same. In the above (1) in step (r), by the adhesive agent composition layer, and the shape = dry, forming a precursor, specifically, if =The structure of the adhesive sword layer solution can be removed from the organic solvent The agent composition

A common heating device can be applied. As a method of adding, 4m & U, for example, a heat convection type "machine, a heat cycle dryer, vacuum drying, etc.. The heating temperature is organic (4) is easy to volatilize, and the above (4) capacity = non-volatile The temperature ' is usually preferably from 20 to 1 Torr (r, more preferably from 30 to 60 C, and is set according to the above incompatible compound. Step (1 ') is the same as step (1) except for this aspect. In the case of the above step (1'), as the step (2), the acrylic adhesive is cured by radiation irradiation or heating of the above-mentioned adhesive composition layer, and the cured adhesive is cured. The adhesive layer precursor of the phase separation structure of the above incompatible compound is immobilized. Step (2) is carried out in the same manner as in the step (2). Hereinafter, the step (3) is carried out. Then, in the step (3), The incompatible compound is removed from the obtained adhesive layer precursor. For example, as step (3), the incompatible compound may be removed from the adhesive layer precursor by heating. Further, by solvent extraction, Self-adhesive layer The incompatible compound is removed from the extrudate, whereby a recess can be formed on the surface of the cleaning adhesive layer (cleaning layer). As a method of removing the incompatible compound by heating, ordinary 120368.doc -51-200808933 can be applied. The heating device is the same as the above (1) clearing layer (average opening diameter · 1 〇 or less). Further, the solvent is extracted from the adhesive layer precursor to remove the incompatible compound, and the above (1) The cleaning layer (average opening diameter · 1 〇μπι or less) is the same, and liquefied carbon dioxide as a non-toxic, non-hazardous substance or carbon dioxide in a supercritical state can be used instead of the organic solvent, and in this case, also with the above (1) The cleaning layer (average opening diameter · 10 μm or less) is the same.

The cleaning adhesive layer of the present invention obtained in the above manner (cleaning layer 同样 is the same as the above (1) cleaning layer (average opening diameter: 1 〇 μηη or less) = as shown in Fig. 3, the discontinuous concave portion can be The surface is provided on at least one side of the support 2 as a cleaning sheet (an adhesive sheet for cleaning), and the substrate in the above manufacturing method can be directly used as the support 2. Further, the cleaning adhesive layer (cleaning layer) The separator may be provided in advance on the surface of the mouth. "Also, with the above 0" cleaning layer (average opening diameter: 1 〇 μηη or less), the above cleaning sheet can also be used as a label sheet. 4, a fixing adhesive may be provided on the other surface provided with the above-mentioned concave support layer (four) support body 2. Further, a separator may be provided on the surface of the adhesive layer 3. The fixing adhesive layer 3 is the same as the above-mentioned (1) cleaning layer (average. 10 μm or less). h · There is no special conveying member to which the cleaning sheet is attached. (1) Cleaning layer (average opening diameter: 10 or less) The same situation. 'In order to reuse the above-mentioned substrate or the like, the above-mentioned #-patent layer 3 is better than 120368.doc -52-200808933. When the substrate is peeled off from the adhesive layer 3 after cleaning, the adhesive layer 3 can be easily applied from the substrate. The peeling force of the adhesive layer 3 is the same as that of the above-mentioned cleaning layer (average opening diameter: 10 μπι or less). There is no particular limitation on the conveying member having a cleaning function and the manufacturing method thereof, and the above (1) cleaning layer (The average opening diameter: 1 〇μχη or less) is the same as in the following. - EXAMPLES Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. Further, the following is a part by weight. %〜 represents a weight average molecular weight, Μη represents a number average molecular weight, and Mw/Mn represents a dispersion degree of a polymer molecular weight. (1) Cleaning layer (average opening diameter: 1 〇μηχ or less) Example 1-1 (ultraviolet curable acrylic acid) Preparation of an adhesive) as a raw material from a monomer mixture containing 70 parts of butyl acrylate, 30 parts of acrylic acid, 1 part of acrylic acid, and 5 parts of 2-hydroxyethyl acrylate 100 parts of an acrylic polymer (Mw of about 850,000, Mw/Mn of 9), and 40 parts of polyfunctional urethane acrylate (manufactured by Nippon Synthetic Chemical Co., Ltd., trade name: UV1700B) As a polymerizable unsaturated compound, 2 parts of a polyisocyanate compound (manufactured by Nippon Polyamide Co., Ltd., trade name: Coronate L) and 1 part of a polyepoxide (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name: Tetrad) C) As a crosslinking agent, 3 parts of a photopolymerization initiator (lrgacure 651, manufactured by Ciba Specialty Chemicals Co., Ltd.) was further added, and then ethyl acetate was uniformly mixed to prepare a concentration adjustment of 120368.doc -53-200808933. A solution of a UV curable acrylic adhesive. (Preparation of ultraviolet curable acrylic pressure-sensitive adhesive composition) In the above adhesive solution, a total of 1 part (solid content) of the acrylic polymer and the polymerizable unsaturated compound contained in the (four) solution is uniformly mixed. A 1,3-propanediol (manufactured by Kishida Chemical Co., Ltd.) was used as an incompatible compound for phase separation to prepare a solution of an ultraviolet curable acrylic adhesive composition. (Preparation of cleaning sheet) The above-mentioned adhesive composition solution was applied to one side of a polyester film for a support having a width of 2 guaguas and a thickness of 50 μm, and the thickness after drying was 35 μm. It was dried at room temperature for 4 minutes to form a layer of an adhesive composition in which a concave portion was formed with hydrazine and 3-propylene glycol. Then, a polyester-based release film having a thickness of 50 μm is attached to the surface of the 6-adhesive composition layer, followed by ultraviolet irradiation to harden the acrylic adhesive, and the structure of the concave portion is fixed to form an adhesive layer having a phase-separated structure. Precursor. Thereafter, the poly-free film was removed and heated at 15 CTC for 10 minutes to remove the propylene glycol which formed the concave portion, thereby obtaining an adhesive sheet. The adhesive sheet was held at 5 Torr for 72 hours, and an adhesive layer (cleaning layer) for etching was etched. The main adhesive sheet is used as a cleaning sheet. Further, the adhesive solution was applied to the side of the support film of the cleaning sheet on the side where the adhesive layer (cleaning layer) was not provided, and the thickness after drying was 20 μm, and a fixing adhesive layer was provided to be formed on the surface. A cleaning sheet with a polyester release film attached thereto. Further, the fixing adhesive layer was heated at 50 ° C for 72 hours to etch the adhesive layer. Further, the fixing adhesive solution was prepared by the following method. Into a three-necked flask type reactor having a capacity of 120368.doc -54·200808933 /jiil, a mixer, a nitrogen inlet tube and a reflux cooling tube, the content of 73 parts of 2-ethylhexyl acrylate was adjusted. 10 parts of n-butyl acrylate, 15 parts of N,n-didecyl acrylamide and 5 parts of acrylic acid, as a polymerization initiator, 15 parts of 2,2-azobisisobutyronitrile, 100 parts The ethyl acetate was adjusted to 2 〇〇g in total, and nitrogen gas was introduced for about 1 hour while stirring, and the inside air was replaced with nitrogen. Thereafter, the internal temperature was set to 58 ° C, and polymerization was carried out for about 4 hours in this state to obtain an acrylic polymer solution. To the 00 parts of the acrylic acid polymer solution, 3 parts of a polyisocyanate compound (trade name: Coronate L, manufactured by Japan Polyurethane Industry Co., Ltd.) was uniformly mixed to obtain a fixing adhesive solution. Example 1 - 2 (Preparation of ultraviolet curable acrylic adhesive) Relative to self-contained 70 parts of butyl acrylate, 30 parts of ethyl acrylate, 1 part of acrylic acid, and 5 parts of 2-hydroxyethyl acrylate 100 parts of an acrylic polymer (Mw of about 850,000, Mw/Mn of 9) obtained as a raw material polymer, and 30 parts of polyfunctional urethane acrylate (sodium complex) Chemical company: trade name: UV1700B) As a polymerizable unsaturated compound, 2 parts of a polyisocyanate compound (manufactured by Japan Polyurethane Industry Co., Ltd., trade name: Coronate L) and 1 part of a polyepoxide (Mitsubishi Gas Chemical Co., Ltd.) , product name: Tetrad C), as a parent agent, and further added 3 parts of photopolymerization initiator (Irgacure 65 1, manufactured by Ciba Specialty Chemicals Co., Ltd.), and then uniformly mixed with ethyl acetate to prepare a concentration adjusted to 18% by weight. A solution of an ultraviolet curable acrylic adhesive. 120368.doc -55-200808933 (Preparation of ultraviolet curable acrylic adhesive composition) In the above adhesive solution, a total of 1 part of the acrylic polymer and the polymerizable unsaturated compound contained in the solution (Solid form), 25 parts of 1,3-propanediol (manufactured by Kishida Chemical Co., Ltd.) was uniformly mixed, and as an incompatible compound for phase separation, a solution of an ultraviolet curable acrylic pressure-sensitive adhesive composition was prepared. Next, a cleaning sheet was produced in the same manner as in Example 1-1 except that the above-prepared adhesive composition solution was used.

Example 1-3 (Preparation of ultraviolet curable acrylic adhesive) Relative to self-containing 70 parts of butyl acrylate, 3 parts of ethyl acrylate, 1 acryl, and 5 parts of 2-hydroxyethyl acrylate An acrylic polymer (Mw of about 10,000, Mw/Mn of 9) obtained as a raw material polymer obtained by mixing a monomer, and a mixture of 4 parts of polyfunctional urethane acetate (manufactured by Nippon Synthetic Chemical Co., Ltd., trade name: as a polymerizable unsaturated compound' 2 parts of polyisocyanate compound (manufactured by Japan Polyamine Industrial Co., Ltd.), trade name: c〇r〇nate卩 and i parts Epoxy compound (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name: Tetrad®, as a crosslinking agent' and further added 3 parts of photopolymerization initiator (We 651, manufactured by Ciba Specialty Chemicals Co., Ltd.), using ethyl acetate and ethanol The mixed solvent is uniformly mixed to prepare a solution of the ultraviolet curable galena guar gum adhesive having a concentration adjusted to 18% by weight. (Preparation of ultraviolet curable acrylic adhesive composition) In the above adhesive solution, phase 斟T邗 for the side 100 parts of the acrylic acid-containing polycondensate 120368.doc • 56- 200808933 and a polymerizable unsaturated compound (solid content), uniformly mixed 10 parts of propylene glycol (manufactured by Kishida Chemical Co., Ltd.) for phase separation A solution of the ultraviolet curable acrylic pressure-sensitive adhesive composition was prepared as an incompatible compound. In the following, a cleaning sheet was produced in the same manner as in Example 1-1 except that the above-described adhesive composition solution was used. 1 - 4 (Preparation of ultraviolet curable acrylic adhesive) with respect to monomer containing 70 parts of butyl acrylate, 3 parts of ethyl acrylate, 1 part of acrylic acid, and 5 parts of 2-hydroxyethyl acrylate Acrylic polymer (Mw of about 850,000, ]^~/]^11 of 9) 100 parts obtained by mixing liquid, adding 35 parts of polyfunctional urethane acrylate (Japanese synthesis) Manufactured by a chemical company, trade name: UV1700B) As a polymerizable unsaturated compound, 2 parts of a polyisocyanate compound (manufactured by Japan Polyurethane Industry Co., Ltd., trade name: Coronate L) and 1 part of a polymer are added. Oxygen compound (trade name: Tetrad c, manufactured by Mitsubishi Gas Chemical Co., Ltd.), as a crosslinking agent, further added 3 parts of a photopolymerization initiator (Irgacure 651, manufactured by Ciba Specialty Chemicals Co., Ltd.), and further uniformly mixed with ethyl acetate. A solution of an ultraviolet curable acrylic adhesive having a concentration adjusted to 18% by weight is prepared. (Preparation of ultraviolet curable acrylic adhesive composition) Acrylic polymer and polymerization contained in the above adhesive solution A total of 1 part by weight of the unsaturated compound (solid content), uniformly mixed 10 parts of ethylene glycol (manufactured by Kishida Chemical Co., Ltd.), and used as an incompatible compound for phase separation to prepare an ultraviolet curable acrylic adhesive combination A solution of 120368.doc -57- 200808933. (Production of cleaning sheet) The above-mentioned adhesive composition solution was applied to one side of a poly-I film for a support having a width of 200 Å and a thickness of 50 μm, and the thickness after drying was 35 μm. It was dried under warm conditions for 4 minutes to form a layer of an adhesive composition in which a concave portion was formed with ethylene glycol. Then, the surface of the material composition layer is attached with a thickness of 5 μm 2 of a polyester peeling film, followed by ultraviolet irradiation, and the hard: acrylic adhesive fixes the structure of the concave portion to form a phase separation and structure. Sticky | agent layer precursor. Thereafter, the polyacetal release film was removed, and the undergarment was heated for 10 minutes to remove the ethylene glycol which formed the concave portion, and the adhesive sheet was obtained to adhere the sheet to 5 Å. . The adhesive layer (cleaning layer) for cleaning was etched for 72 hours. Hereinafter, a cleaning sheet was produced in the same manner as in Example 1 β1 except that the above-mentioned pressure-sensitive adhesive sheet was used. Example 1-5 An ultraviolet curable acrylic adhesive was prepared in the same manner as in Example ii except that in the Example 1-1, the polyfunctional amino phthalic acid ester acrylate was used in an amount of 10 parts in summer. . Thereafter, an ultraviolet curable acrylic pressure-sensitive adhesive composition was prepared in the same manner as in Example 1 and i, and then a cleaning sheet was prepared. Comparative Example 1-1 In the solution of the ultraviolet curable acrylic adhesive prepared in Example 1-4, the incompatible compound for phase separation was not added, and the ultraviolet curable acrylic adhesive was directly used. Except for this, a cleaning sheet was produced in the same manner as in Example 1-1 of 120368.doc -58 - 200808933. The cleaning adhesive layer (cleaning layer) obtained in the examples and the comparative examples was subjected to the following evaluation. The results are shown in Fig. 5 to Fig. 1 and Table 1. (Concave area of the concave portion) The surface of the cleaning adhesive layer (cleaning layer) was photographed by a scanning electron microscope (manufactured by Hitachi, Ltd., S570), and the concave portion of the surface of the cleaning adhesive layer (cleaning layer) was calculated by image analysis. (Average opening diameter (average diameter) of the opening of the concave portion) The image observed by the scanning electron microscope was subjected to image analysis by the image analysis software, and the average opening diameter (average diameter) of the concave portion was calculated. (Deep Depth) The concave portion of the cleaning adhesive layer (cleaning layer) was freeze-fractured by liquid sad nitrogen, and the cross section was observed by the above-described electron microscope to calculate h/H from the depth h of the concave portion of the cross section and the thickness of the cross section. Elastic modulus) Tribo Indenter manufactured by Hysitron Inc., an indenter of the analytical device, was used with a press-in speed of 50 nm/s and a maximum indentation load of 1 μμΝ to use a single press of the indenter Berkovich. Method, the elastic modulus is measured. The above-mentioned scanning microscope images of the cleaning adhesive layer (cleaning layer) obtained in Examples 1-1 to 1-5 correspond to FIG. 5, respectively. Fig. 9. Comparative Example corresponds to the image of the top surface of the self-cleaning layer in Fig. 6°. The black portion in the figure is a concave portion. From Fig. 5 to Fig. 9, it is known that the surface of the cleaning layer is planar, Further, as shown in Fig. 1A, the cleaning obtained in Comparative Example 1β1 120368.doc • 59- 200808933 layer 'apparently has no concave portion. 'The following evaluations were performed on the cleaning sheets obtained in the examples and comparative examples. The results are shown in Table 1. (Vertical adhesion force) After attaching the cleaning adhesive layer (cleaning layer) to the surface of the stone substrate with a width of 5 以 to increase the probe of 2 kg and then φ 50 mm, The tensile strength was measured at room temperature (23. Torr) at a tensile speed of 300 mm/min. The adhesion to the cleaning adhesive layer (cleaning layer) was 180. The peeling force was applied. (Transportability) Transfer to a substrate processing apparatus having a wafer platform (The name of the device: gr_3 000 'manufactured by Nitto Seiki Co., Ltd.) is evaluated according to the following criteria: x The case is attached to each part and platform, and the conveying device is stopped. △: Although it is attached to each part or platform, The case where the transport device has not stopped. It is attached to each part and platform, and the conveying device is not stopped. (Foreign material collection property) The foreign matter is simulated. The average foreign matter size of the simulated foreign matter is 8 μηι, and the foreign matter size is less than 10 μιη. The foreign matter size and the average foreign matter size were measured by a laser particle counter (manufactured by TENCOR, SURFSCAN 6200). The peeling film on the adhesive layer side of the β/ruthenium sheet was peeled off, and the hand roll was used. The adhesive layer is attached to the back surface (mirror surface) of the wafer of 8 ,, and the cleaning wafer for cleaning with a cleaning force b is prepared. Then, at the substrate with the wafer platform, 120368.doc 200808933 device (device name) : GR-3000, manufactured by Nitto Seiki Co., Ltd.) The wafer was placed several times on the platform to allow the simulation of foreign matter to adhere. In the initial contamination state evaluation, the 8 吋矽 wafer was transferred mirror-down to the substrate processing apparatus for initial contamination state evaluation, and the mirror surface was measured by a laser type foreign matter measuring device to measure the initial amount of foreign matter ( 8 吋 wafer size area). The cleaning wafer for cleaning is transferred to the substrate at the cleaning device with the cleaning surface facing down three times. The amount of the foreign matter after the transfer was measured by the above-described laser type foreign matter measuring device (laser particle counter), and the amount of the initial foreign matter amount - the amount of the foreign matter collected after the transfer was calculated. If the ratio is 3〇% or more, it is judged as "〇". The case of less than 30% is judged as "X". [Table 1] Projection area of the concave portion (%) Average opening diameter (μιη) of the opening portion of the cleaning adhesive portion [: depth ratio of the concave portion of the agent layer (h/H) elastic modulus (MPa) vertical adhesion force (N ) Evaluation of transporting foreign matter trapping examples Μ 4 1.72 0.105 20.8 0 〇〇Example 1-2 3.6 1.61 0.111 0.027 13.1 26.1 10 0 Example 1-3 41 076^^ —— _ 〇〇~~〇~ Example 1-4 20 2.16 0.100 20.5 0.1 〇〇 Example 1-5 24 2.2 0.119 1.35 8 Δ 〇 Comparative Example - - - - 28.0 12.6 X 〇 (2) Cleaning layer (average opening diameter: 〇1 to 3 μπ1) Example 2-1 (Preparation of ultraviolet curable acrylic adhesive) Relative to self-containing 70 parts of butyl acrylate, 3 parts of ethyl acrylate, 1 acryl, and 5 parts of 2-hydroxyethyl acrylate Acrylic polymer obtained as a raw material polymer obtained from a monomer mixture (Μλγ is about 850,000, 120368.doc -61 - 200808933

Mw/Mn was 9) 100 parts, and 40 parts of polyfunctional urethane acrylate (manufactured by Nippon Synthetic Chemical Co., Ltd., trade name: UV1700B) was added as a polymerizable unsaturated compound, and 2 parts of a polyisocyanate compound was added (Japan) Manufactured by Polyurethane Industry Co., Ltd., trade name: Coronate L) and 1 part of polyepoxide (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name: Tetrad C), as a crosslinking agent, and further added 3 parts of photopolymerization initiator (Irgacure 65) 1, manufactured by Ciba Specialty Chemicals Co., Ltd.) and then uniformly mixed with ethyl acrylate as solvent (A) (relative to the enthalpy parameter of the above acrylic polymer: 〇·53, relative to the polymerizable unsaturated compound) Parameters: 8.7) and methanol as a compatible solvent (Β) (relative to the above-mentioned acrylic polymer χ parameter ························ A solution of a UV-curable propionic acid-based adhesive having a concentration adjusted to 18% by weight was prepared in a mixed solvent in which the ratio of the solvent (Β) ==ΐ2/7 was adjusted. (Preparation of ultraviolet curable acrylic pressure-sensitive adhesive composition) In the above adhesive solution, 10 parts (solid content) of the acrylic polymer and the polymerizable unsaturated compound contained in the solution are uniformly mixed in 10 parts. Glycerol (parameter: 10, boiling point: 290 C with respect to the above acrylic polymer), as an incompatible compound for phase separation, a solution of an ultraviolet curable acrylic adhesive composition was prepared. (The production of cleaning tablets), the team to the side of the polyester film with a thickness of 50 μΐη and a thickness of 50 μΐη, so that the thickness after drying becomes 35 μΐη, at 55t: After drying for 4 minutes, a layer of an adhesive composition in which a concave portion was formed with glycerin was formed. Then, a polyester release film having a thickness of 50 μm was attached to the surface of the adhesive composition layer, followed by ultraviolet irradiation, and the acrylic adhesive was hardened to fix the structure of the concave portion to form a phase separation. Adhesive layer precursor of the structure. Thereafter, the polyester release film was removed, and the mixture was heated at 150 °C for 1 minute to remove the glycerin forming the concave portion to obtain an adhesive sheet. The above adhesive sheet was held at 5 (rc for 72 hours), and the cleaning adhesive layer (cleaning layer) was etched.

The main adhesive sheet is used as a cleaning sheet. Further, the adhesive solution is applied to the side of the support film of the cleaning sheet which is not provided with the cleaning adhesive layer (cleaning layer), and the thickness after drying is 2 μm, and the fixing adhesive layer is provided. A cleaning sheet having a polyester release film attached to its surface was prepared. Further, the fixing adhesive layer was heated at 5 {rc for 72 hours, and the adhesive layer was engraved. Further, the fixing adhesive solution was prepared in the same manner as in the case of the above (1) cleaning layer (average opening diameter: 10 μπι or less). Example 2-2 (Preparation of ultraviolet curable acrylic adhesive) / In the case of Example 2-W, a solvent (Α) / solvent (Β) = 7 / ΐ 2 ratio was used as a mixed solvent' A solution of an ultraviolet curable (tetra) acid-based adhesive was prepared in the same manner as in Example 2-i. (Preparation of ultraviolet curable acrylic adhesive composition) In the above adhesive solution, the total amount of the acrylic acid polymer and the polymerizable unsaturated compound contained in the solution (10) parts (solid content), Mix 1 part of glycerol (relative to μ, +, work aa /, the above propylene I 糸 polymer χ parameters: 10 'Hai Dianqing as an incompatible compound for phase separation, 120368.doc - 63-200808933 A solution of an ultraviolet curable acrylic adhesive composition was prepared. Hereinafter, a cleaning sheet was produced in the same manner as in Example 2-1 except that the above-described adhesive composition solution was used. 3 (Preparation of ultraviolet curable acrylic adhesive composition) In the adhesive solution prepared in Example 2_1, the total amount (10) parts of the acrylic polymer and the polymerizable unsaturated compound contained in the solution was Solid content), uniformly mixing 25 parts of H3. butyl triol (relative to the above-mentioned C: #% acid parameter: 8.8), as an incompatible compound for phase separation, preparing ultraviolet curable propylene The adhesive composition liquid was prepared in the same manner as in Example 2-1 except that the above-described adhesive composition solution was used. Comparative Example 2-1 (Ultraviolet curable acrylic adhesive) (Preparation) _ In the same manner as in Example 21, except that ethyl acetate was used as the solvent (Α) instead of the mixed solvent, and the concentration was adjusted to 18% by weight. A solution of an ultraviolet curable acrylic acid-based adhesive is prepared. (Preparation of an ultraviolet curable acrylic pressure-sensitive adhesive composition) In the above-mentioned adhesive, a solution of an acrylic acid-containing substance contained in the solution And a total of (10) parts of the polymerizable unsaturated compound (solid content), adding U-injured propanol (relative to the above-mentioned acrylic polymer: 〇 parameter: 1 〇, boiling point 290 〇, as phase separation for phase separation) In the case of a compound, 12036B.doc -64 - 200808933 phase separation was produced, and a homogeneous solution could not be prepared. As a result, a cleaning sheet could not be produced. Comparative Example 2-2 (Preparation of ultraviolet curable acrylic adhesive) In Example 2-1, the amount of the polyfunctional urethane acrylate (manufactured by Nippon Synthetic Chemical Co., Ltd., trade name: UV1700B) as a polymerizable unsaturated compound was changed to 8 parts, and only used as A solution of an ultraviolet curable acrylic adhesive was prepared in the same manner as in Example 2-1 except that the ethyl acetate of the solvent (A) was used instead of the mixed solvent, and the concentration was adjusted to 8% by weight. Preparation of Curable Acrylic Adhesive Composition) In the above adhesive solution, 10 parts are uniformly mixed with respect to the total amount of the acrylic polymer and the polymerizable unsaturated compound contained in the solution (solid content) The 1,3-propanediol (the enthalpy parameter relative to the above acrylic polymer: 5.6, the boiling point 214). Further, as an incompatible compound for phase separation, a solution of an ultraviolet curable acrylic adhesive composition is prepared. Next, a cleaning sheet was produced in the same manner as in Example 2-1, except that the above-described adhesive composition solution was used. The following evaluations were made for the shelling agent and the cleaning adhesive layer (cleaning layer) obtained in the example. The results of Example 2-^2-3 and Comparative Example 2-2 are shown in Figs. 11 to 14 and Table 2. (Average opening diameter and standard deviation of the opening of the concave portion) The image observed by the scanning electron microscope was subjected to image analysis by an image analysis software, and the average opening diameter (average diameter) of the concave portion was calculated. The standard of the opening diameter of 120368.doc -65. 200808933 is used as the average opening diameter. Poor. (Uniformity); The image observed by the bronzing electron microscope is image-analyzed by the image analysis software, and the distance from the center of the adjacent opening is calculated, and the standard deviation is calculated. The projected area of the concave portion and the concave collar. The 卩/木度 was evaluated in the same manner as described above.

The above-described scanning microscope images of the cleaning adhesive layers (cleaning layers) obtained in Examples 2-1 to 2-3 correspond to Figs. 11 to 14, respectively. Each of Figs. U to 14 (A) is an image observed from the upper surface of the surface of the self-cleaning adhesive layer (cleaning layer), and each (B) is a cross-sectional image. The black portion in the figure is a recess. It is understood from Fig. 14 to Fig. 14 that the surface of the cleaning adhesive layer (cleaning layer) is flat and has a concave portion. Further, the cleaning sheets obtained in the examples and the comparative examples were subjected to the following evaluations. The results are shown in Table 2. (Vertical peeling force) A metal piece having a diameter of 5 mm was adhered to the cleaning adhesive layer for 3 minutes with a weight of 2 kg, and measured at a stretching speed of 1 mm/min at room temperature of 23 ° C. The peeling force applied when lifting the metal sheet. The transportability and foreign matter trapping property were evaluated in the same manner as described above. 120368.doc • 66· 200808933 [Table 2] Evaluation of the vertical peeling force (Ν) of the concave portion of the concave portion of the recessed portion of the recessed portion of the recessed portion (μπι) Standard deviation (μπι) Standard deviation (μπι) Uniform projection area (%) Depth ratio _ 性 实施 Example 2-1 1.75 0.49 0.586 66.7 0.014 0 〇〇 Example 2-2 1.0 0.15 0.645 36 0.019 1.7 〇〇 Example 2-3 1.3 0.42 0.343 20 0.017 1.5 〇〇 Comparative Example 24 - - - - - 8.5 Δ 〇 Comparative Example 2-2 3.6 0.95 4.016 14 0.11 5 Δ 〇 (3) Cleaning layer (Ra: 0·01 to 0.3 μπι) Example 3-1 (Ultraviolet curable acrylic adhesive) Preparation of acrylic polymer as a base polymer obtained from a monomer mixture containing 30 parts of 2-ethylhexyl acrylate, 70 parts of decyl acrylate and 10 parts of acrylic acid (Mw: about 100,000 to 890,000, Mw/Mn: 7 to 9) 100 parts, 35 parts of polyethylene glycol 200 dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK Ester 4G) is added as a polymerizable unsaturated Compound, adding 3 parts of polyisocyanate compound (Japan Poly i manufactured by Industrial Co., Ltd., trade name · Coronate L) and 2 parts of polyepoxide (Mitsubishi Gas Chemical Co., Ltd., trade name: Tetrad C), as a crosslinking agent, and further added 3 parts of photopolymerization initiator ( Irgacure 651 (manufactured by Ciba Specialty Chemicals Co., Ltd.) was further uniformly mixed with ethyl acetate to prepare a solution of an ultraviolet curable acrylic adhesive having a concentration adjusted to 23% by weight. (Preparation of ultraviolet curable acrylic pressure-sensitive adhesive composition) In the above adhesive solution, 100 parts (solid content) of the acrylic polymer and the polymerizable unsaturated compound contained in the solution are uniformly mixed, and 120368 is uniformly mixed. Doc-67-200808933 A 10 part ethylene glycol (manufactured by Kishida Chemical Co., Ltd.) is used as a solution for preparing an ultraviolet curable acrylic pressure-sensitive adhesive composition as an incompatible compound for phase separation. (Support substrate) A polyester film for a support having a width of 200 mm and a thickness of 75 μm was used. The adhesive solution is applied to one surface of the polyester film for the support to have a thickness of 20 μm after drying, and a fixing adhesive layer is provided, and a polyester-based release film is attached to the surface thereof. The fixing adhesive layer was heated at 50 ° C for 7 hours, and the adhesive layer was left. Further, the fixing adhesive solution was prepared in the same manner as in the case of the above (1) cleaning layer (average opening diameter: 10 μm or less). (Production of Cleaning Sheet) The ultraviolet curable acrylic pressure-sensitive adhesive composition is applied to one surface of the support substrate on which the fixing adhesive layer is not provided, and the thickness after drying is 35 μm at room temperature. It was dried for 4 minutes to form a layer of an adhesive composition in which a concave portion was formed with ethylene glycol. Then, a polyolefin-based release film having a thickness of 60 Å 2 μηι having a center line average roughness of 〇 2 μηι was attached as a cover film on the surface of the adhesive composition layer. The cover film has the side having the above surface roughness as the side of the adhesive composition layer. Then, two rows of ultraviolet rays are irradiated, and the acrylic acid-based adhesive is hardened to solidify the structure of the concave portion to form an adhesive layer precursor having a phase-separated structure. Thereafter, the cover film was peeled off and heated under reading for 10 minutes to remove the ethylene glycol forming the concave portion. The polyacetal release film was attached again, and the adhesive layer (cleaning layer) for cleaning was etched at 5 (rc for 72 hours) to obtain an adhesive sheet. The adhesive sheet was used as a cleaning sheet of 120368.doc-68-200808933. 3-2 In the case of preparing the ultraviolet curable acrylic pressure-sensitive adhesive in Example 3-1, 'the amount of the polymerizable unsaturated compound used was 70 parts, and when the cleaning sheet was produced, the center line average roughness was used. A cleaning sheet was produced in the same manner as in the example except that a polyolefin-based release film having a thickness of 60 μm was used as a cover film of 〇〇2 μηι. Comparative Example 3-1 was carried out in Example 3-1. In the ultraviolet curable acrylic adhesive prepared in the solution, the incompatible compound for phase separation is not added, and the ultraviolet curable acrylic adhesive is used as it is, and in addition to Example 3 In the same manner as in the first embodiment, the cleaning sheet was produced. Comparative Example 3-2 In the case of preparing the ultraviolet curable acrylic pressure-sensitive adhesive in Example 3-1, the amount of the polymerizable unsaturated compound used was set to 7 parts, and Making cleaning In the same manner as in Example 3-1, except that a polyolefin-based release film having a thickness of 60 μηη with a center line average roughness of 〇〇〇6 μηΐ2 was used as a cover film. Cleaning sheet. The cleaning adhesive layer (cleaning layer) obtained in the examples and the comparative examples was subjected to the following evaluation. The results are shown in Fig. 15 and Table 3. The cleaning adhesive layer obtained in Example Hongsheng The scanning microscope image of the (cleaning layer) is as shown in Fig. 15. The black portion in the drawing is a concave portion. The projected area of the concave portion and the average opening diameter (average diameter) of the opening portion of the concave portion and the depth of the concave portion are the same as described above. The method is evaluated. 120368.doc -69- 200808933 (Center line average roughness (Ra) of the surface other than the concave portion) Measuring device: Scanning laser microscope LEXT-OLS3 000 (manufactured by Olympus Co., Ltd.) Viewing angle: 128x96 [μιη] Lens magnification: 1〇〇 Remarks: After correcting the inclination of the X-axis and the Υ axis, perform the coarseness analysis at 0.125 μηη. (Tensile elastic modulus) φ Apply the adhesive composition The PET film with a width of 200 mm and a thickness of 50 μm was subjected to drying and ultraviolet curing, and then peeled off from the PET film to a sample width of 10 mm, a chuck distance of 110 mm, and a tensile speed of 50. The tensile test was performed in mm/min, and the tensile modulus of elasticity was calculated from the stress at the time of measurement. The measurement was based on JIS K7127. Further, the cleaning sheets obtained in the examples and the comparative examples were subjected to the following evaluations. The vertical adhesion force, the conveyance property, and the foreign matter collection property were evaluated in the same manner as described above. [Table 3] The cleaning adhesive layer evaluated the depth ratio of the flat concave portion of the opening portion of the concave portion of the concave portion _ concave portion Surface flat tensile modulus (MPa), vertical stripping, foreign object area (%), average opening diameter (μιη), uniformity (Ra): (μιη), separation force (N), trapping example 3 1 27 2.3 0.05 0.023 70 2 〇75% or more Example 3-2 25 2.5 0.06 0.25 300 0.5 〇75% or more Comparative Example 3-1 - - 70 15 X Cannot be evaluated Comparative Example 3-2 24 2.5 0.06 0.006 300 2 〇 60 to 70% 120368.doc -70- 200808933 in Comparative Example 3·1 'Cannot be transported, so it cannot be evaluated. [Simplified description of the drawings] The stomach 1 is the cleaning adhesive of the present invention. FIG. 2 is the cleaning adhesive of the present invention. FIG. 3 is a section using the cleaning adhesive sheet of the present invention. An example of a diagram. An example of a cross-sectional view of a layer is an example of a cross-sectional view of a layer of a cleaning agent (a cleaning sheet is used in Fig. 4, which is a cleaning adhesive sheet of the present invention). Cleaning layer for the agent layer (for cleaning)

Figure 5 is a cross-sectional view of the cleaning image obtained in Example 1-1 with a coating layer. Figure 6 is a cleaning image obtained in Example 1 _2. The profile of the adhesive layer is a cross-sectional view of the adhesive layer. Figure 7 is a cleaning image obtained in Example 1-3. Figure 8 is a cross-sectional image of the cleaning adhesive layer obtained in Example 丨-4.

Figure 9 is a cross-sectional view of the cleaning adhesive layer obtained in Example 1-5. Fig. 10 is a cross-sectional view of the cleaning adhesive layer obtained in Comparative Example 1-1. Fig. 11A is a plan view of the cleaning adhesive layer obtained in Example 2-1. Figure 11B is a cross-sectional image of the cleaning adhesive layer obtained in Example 2-1. 0 120368.doc -71- 200808933 Figure 12A is a partial view of the cleaning adhesive layer obtained in Example 2-2. Fig. 12B is a 曰al|face image of the cleaning adhesive obtained in Example 2-2. Figure 13A is a top view of the cleaning adhesive layer obtained in Example 2-3. Figure 13B is a cross-sectional view of the cleaning adhesive layer obtained in Example 2-3.

Fig. 14A is a clear image obtained in the clear example of Example 2-2 obtained in Comparative Example 2-2 obtained in Comparative Example 2-2. >Top view of the adhesive layer. Cross-sectional view of the adhesive layer / Cross-sectional view of the adhesive layer [Main component symbol description]

2 Adhesive layer for cleaning with recesses Support (cleaning layer) 3 Adhesive layer for fixing S Surface a b Concave Cleaning for adhesions other than recesses Adhesive layer (cleaning layer) surface 120368.doc -72-

Claims (1)

200808933, Patent Application Range: A cleaning adhesive layer, which comprises a cured product of a radiation curable or thermosetting acrylic adhesive containing an acrylic polymer, and has a planar surface for When the foreign matter is removed from the object to be processed, the surface of the adhesive layer has a concave portion of the discontinuous opening portion, and the average opening diameter of the opening 卩 is smaller than the average foreign matter size. 2. The cleaning adhesive layer of claim 1 wherein the foreign matter contains a foreign matter having a size of 1 〇 μιη or less. In the cleaning adhesive layer of the first or second aspect, the average opening diameter of the opening in the crucible is smaller than the average apparent size of the foreign matter shouted by the foreign matter size of 10 μ. In the case of the above-mentioned discontinuous concave portion, the ratio of the two areas to the total projected area of the surface of the above adhesive layer is 3% to 8 Å/〇. 5. The elastic modulus of the cleaning of claim 1 (other than + on the surface of the (four) agent layer) is 10 MPa or more. 6. The cleaning adhesive layer of the cleaning adhesive of claim 1, wherein the opening of the concave portion is substantially circular, and the average opening 1 is 0.1 to 3, and the opening is The standard deviation of 仫 is 0.7 μm or less, and the variation of the distribution of the openings is 1 μϊη or less. The standard of the center distance of the phase mouth 120368.doc 200808933 l = ^ 7 of the cleaning adhesive layer 'the ratio of the above-mentioned discontinuous recess &amp; ® % relative to the total projected area of the surface of the above adhesive layer is 15~ 8〇%. 9. The cleaning adhesive layer according to Item 7 or 8, wherein the depth (h) of the concave portion is 〇·〇1 to 0·1 with respect to the thickness of the adhesive agent (8). </ RTI> 10] The cleaning adhesive layer of claim 1, wherein the recess is not flat The center line average roughness (Ra) of the planar surface is 0.01 to 0.3 μη. 11. The cleaning adhesive layer of claim 10, wherein a ratio of the area of the discontinuous concave portion to the total projected area of the surface of the adhesive layer is 3% to 8%. The cleaning adhesive layer according to claim 10 or 11, wherein the opening portion of the concave portion is substantially circular, and an average opening diameter is 〇 U0 μιη. 13· The cleaning adhesive layer according to claim 1, wherein the ratio (h/H) of the depth (匕) of the concave portion to the thickness (H) of the adhesive layer is 〇. 〇丨~〇.9 . The cleaning adhesive layer according to claim 10, wherein the adhesive layer has a tensile modulus of 0.98 MPa to 500 MPa. 15. The cleaning adhesive layer according to claim 1, wherein the radiation curable or thermosetting acrylic ruthenium adhesive contains an acrylic polymer and a polymerizable unsaturated compound. A cleaning sheet characterized in that the cleaning adhesive layer according to any one of claims 1 to 15 is provided on at least one side of the support as a surface in such a manner that the discontinuous concave portion thereof becomes a surface. Floor. A cleaning sheet characterized in that the cleaning adhesive layer '120368.doc 200808933 according to any one of claims 1 to 15 is provided on one side of the support with the discontinuous concave portion as a surface thereof. Clean the layer on the other mask/adhesive layer. A transporting member having a cleaning function, characterized in that the cleaning sheet of the request item 或 or 17 is placed on the conveying member via a fixing adhesive layer. Further, a method for producing a cleaning adhesive layer, which is characterized in that it is a cleaning adhesive layer according to any one of claims 7 to 9, which comprises, step (1), by using an adhesive The composition solution is applied to the substrate to carry out (4)' to form an adhesive composition layer, and the adhesive composition solution is further blended in a radiation curable or thermosetting acrylic adhesive containing an acrylic polymer. The adhesive composition of the compound in which the acrylic polymer is incompatible is dissolved in a solvent (A) containing the above-mentioned acrylic polymer, and a phase compatible with the above-mentioned non-phase compound a solvent (B) mixed solvent; step (2) 'radiating or heating the above-mentioned adhesive composition layer to harden the acrylic adhesive, and forming the cured product and the above incompatible compound The adhesive layer precursor of the phase separation structure; and the step (3), the incompatible compound is removed from the obtained adhesive layer precursor. 2. The method for producing a cleaning adhesive layer according to the item 19, wherein the compatibility of the above-mentioned two-dimensional polymer with the above-mentioned incompatible compound is compatible (B)' compatibility The parameter % parameter is 120368.doc 200808933 0·5~3 with respect to the acrylic polymer, and 〇·5~3 with respect to the incompatible compound. The method for producing a cleaning adhesive layer according to claim 19 or 20, wherein the X parameter of the above-mentioned incompatible compound with respect to the acrylic polymer is 7 or more and the boiling point is 190 ° C or higher. The manufacturing method, wherein the above-mentioned selective solvent (A) and the compatible solvent which are not present in the compatible solvent (B) are 22. The cleaning adhesive layer composition solution of claim 19 is in a uniform state. The way in which phase separation occurs, (B). 23. The method of producing a cleaning adhesive layer according to claim 19, wherein the above-mentioned compatible solvent (B) is an alcohol solvent. 〃 24. A method of producing a cleaning adhesive layer, characterized in that it comprises a cleaning adhesive layer according to claims 10 to 15, which comprises the step (1) 'to be radioactive or thermosetting. An adhesive composition in which an acrylic-based adhesive is further compounded with a compound which is incompatible with the above-mentioned acrylic adhesive, is applied to a substrate, and a coating composition layer is formed; (7) 'by having a center line average roughness (10)) a coating film on the surface of the surface of the adhesive composition layer in such a manner that the surface of the cover film having the average thickness (R:) of the center line becomes the surface side of the adhesive composition layer And performing radiation, radiation or heating in the state to harden the acrylic adhesive, and forming an adhesive layer precursor having a phase separation structure of the cured product and the incompatible compound; and step (3) And removing the incompatible compound from the obtained adhesive layer precursor. The method for producing the cleaning adhesive layer according to claim 24, wherein in the above step (1), In the adhesive composition, a solution of an adhesive composition prepared by dissolving an organic solvent capable of dissolving the adhesive composition is applied onto a substrate, followed by drying to form an adhesive composition layer. A method of producing an adhesive layer, wherein the step (3) removes an incompatible compound from the adhesive layer precursor by heating. 27. The method for producing a cleaning adhesive layer according to claim 19, wherein the above The step (3) removes the phase-incompatible compound from the adhesive layer precursor by solvent extraction. μ 28. The method for producing a cleaning adhesive layer according to claim 27, wherein the solvent used for the above-mentioned solvent extraction 1 is used The method for producing a cleaning adhesive layer according to claim 19, wherein in the step (2), the surface of the adhesive composition layer is covered with a cover film. Under the bear's radiation exposure or heating. 3〇· A method of cleaning foreign matter, characterized in that a cleaning layer containing a cleaning adhesive layer as claimed in claims -15 to 15 is applied. The processing target body to which the foreign matter adheres is removed, and the foreign matter is removed from the processing target body. The π-bleave method is characterized in that the cleaning sheet of claim 16 or 17 is used. 32. A cleaning method characterized by using the item 18 The cleaning method of the cleaning power. 33. - A cleaning method for a substrate processing apparatus, characterized in that it is a cleaning method of the method of claim 30368.doc 200808933, which is as claimed in claim 16 Or the cleaning sheet of 17 or the conveying member having the cleaning function of claim 18 is transported into the substrate processing apparatus. 120368.doc 200808933 VII. Designated representative map: (1) The representative representative of the case is: (1). (2) The symbol of the symbol of the representative figure is briefly described as follows: 1 The adhesive layer with a recess (cleaning layer) a The concave part % S Surface 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention. no) 120368.doc