JP2017105931A - Adhesive for fixing abrasive member and adhesive sheet for fixing abrasive member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive for fixing an abrasive member capable of enhancing coagulation power of an adhesive layer than conventional ones by exhibiting excellent adhesiveness to the abrasive member, having no generation of floating or peeling even under high temperature environment and excellent in acid resistance and alkali resistance.SOLUTION: It is solved by an adhesive for fixing an abrasive member containing an acrylic copolymer (A), a tackifier resin and (C) an isocyanate curing agent, where the acrylic copolymer (A) is a copolymer of monomers containing a carboxyl group-containing monomer and a hydroxyl group-containing monomer, the isocyanate curing agent (C) is a compound by modifying 10 to 40 mol% of isocyanate groups in a tolylene diisocyanate compound with monofunctional alcohol having 1 to 25 carbon atoms, content of the tackifier resin (B) is 5 to 60 pts.wt. based on 100 pts.wt. of the acrylic copolymer (A).SELECTED DRAWING: Figure 1

Description

  The present invention relates to an adhesive for fixing an abrasive member that can be suitably used for fixing an abrasive member to a polishing machine. More specifically, the present invention relates to a pressure-sensitive adhesive that can form a pressure-sensitive adhesive layer that does not float or peel even under a high-temperature environment in order to exhibit excellent adhesion to a polishing member.

  Conventionally, liquid crystal glass, hard disk substrates, optical lenses, silicon wafers, integrated circuits, and the like have been polished using a polishing member or the like. For fixing the polishing member, for example, after attaching an adhesive tape to the polishing member A polishing member with an adhesive tape is used by bonding it to a surface plate of a polishing machine. In the polishing process, a strong shearing force is applied to the pressure-sensitive adhesive layer, and it may become high temperature due to frictional heat during polishing. Therefore, cohesive force that can withstand strong shearing force and heat resistance that can withstand high temperature are required. . In addition, since an acidic or alkaline slurry may be used in the polishing step, acid resistance and alkali resistance are also required.

  As described above, various performances are required for the adhesive for fixing the polishing member. For example, Patent Document 1 and Patent Document 2 describe that terpene resin or coumarone resin is used for the polishing member. The improvement of the adhesion to the abrasive member due to the crosslinking of the polymer used is not taken into consideration, and it is not sufficient because it is inferior to the required performance required in recent years. That is, no pressure-sensitive adhesive for fixing a polishing member has been found that enables polishing for a longer time than before and is also suitable for polishing glass having a higher hardness than conventional glass.

JP 2010-194700 A JP 2011-122069 A

  The present invention makes it possible to increase the cohesive force of the pressure-sensitive adhesive layer than before by exhibiting excellent adhesion to the abrasive member, and does not cause floating or peeling even in a high temperature environment, and is acid resistant. Another object of the present invention is to provide a pressure-sensitive adhesive for fixing an abrasive member that is also excellent in alkali resistance.

  As a result of intensive studies to solve the above problems, the present inventors have used a specific acrylic copolymer (A) and a specific isocyanate curing agent (C), and a specific amount of tackifying. It has been found that the above problems can be solved by containing the resin (B), and the present invention has been achieved.

  That is, the present invention is an adhesive for fixing an abrasive member containing an acrylic copolymer (A), a tackifier resin (B), and an isocyanate curing agent (C), the acrylic copolymer (A ) Is a copolymer of a monomer containing a carboxyl group-containing monomer and a hydroxyl group-containing monomer, and the isocyanate curing agent (C) contains 10 to 40 mol% of the isocyanate groups in the tolylene diisocyanate compound. It is a compound formed by modification with 1 to 25 monofunctional alcohol, and the content of the tackifying resin (B) is 5 to 60 parts by weight with respect to 100 parts by weight of the acrylic copolymer (A). The present invention relates to a characteristic adhesive for fixing an abrasive member.

Moreover, this invention relates to the said adhesive for fixing a polishing member whose softening point of the said tackifying resin (B) is 80-150 degreeC.
The present invention also relates to the above adhesive for fixing an abrasive member, wherein the tackifier resin (B) contains at least one of a terpene phenol resin and a coumarone resin.
The present invention also relates to the abrasive member fixing adhesive, wherein the abrasive member is urethane-based.
The present invention also relates to a polishing member fixing pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer formed on the base material from the polishing member fixing pressure-sensitive adhesive.

  According to the present invention, excellent adhesion to an abrasive member can be expressed, the cohesive force of the pressure-sensitive adhesive layer can be increased, and acid resistance and resistance can be prevented without being lifted or peeled off even in a high temperature environment. Excellent alkalinity. Further, it is possible to polish for a longer time than before, and further, it is possible to supply an adhesive for fixing a polishing member suitable for polishing glass having a hardness higher than that of conventional glass.

Explanatory drawing of tensile shear force measurement.

  The pressure-sensitive adhesive for fixing a polishing member disk according to the present invention is a pressure-sensitive adhesive for fixing a polishing member containing an acrylic copolymer (A), a tackifier resin (B), and an isocyanate curing agent (C). The copolymer (A) is a copolymer of a monomer containing a carboxyl group-containing monomer and a hydroxyl group-containing monomer, and the isocyanate curing agent (C) is 10 to 40 of isocyanate groups in the tolylene diisocyanate compound. The mol% is a compound formed by modification with a monofunctional alcohol having 1 to 25 carbon atoms, and the content of the tackifier resin (B) is 5 to 60 with respect to 100 parts by weight of the acrylic copolymer (A). It is a weight part.

The pressure-sensitive adhesive for fixing an abrasive member of the present invention can be used as a pressure-sensitive adhesive sheet provided with a base material by coating to form a pressure-sensitive adhesive layer.
That is, in the present invention, the adhesive for fixing an abrasive member is an adhesive that can form an adhesive sheet used for fixing an abrasive member such as a polishing pad used for polishing to a polishing machine. It is. In addition, a conventionally well-known adhesive can be used for the adhesive of the surface plate side, and you may use the adhesive for polishing member board fixation of this invention.
Moreover, an adhesive sheet, an adhesive tape, and an adhesive film are synonymous with this invention.

  In the present invention, examples of the polishing member include a urethane-based polishing pad, a nonwoven fabric-based polishing pad, a suede-based polishing pad, and the like. It is not limited. Among them, the adhesive for fixing an abrasive member of the present invention contains more urethane bonds and the like than conventional adhesives and has an effect of excellent adhesion to urethane-based materials. It can be used suitably.

《Abrasive material panel fixing adhesive》
<Acrylic copolymer (A)>
An acrylic copolymer is a (meth) acrylic polymer that can be synthesized using an acrylic monomer having an ethylenically unsaturated bond. The acrylic copolymer (A) of the present invention is a copolymer of a monomer containing a carboxyl group-containing monomer and a hydroxyl group-containing monomer, that is, an acrylic copolymer having a carboxyl group and a hydroxyl group.

As the carboxyl group-containing monomer, any monomer having a carboxyl group may be used, and examples thereof include (meth) acrylic acid, itaconic acid, maleic acid, and the like, but are not limited thereto and may be used alone. And two or more kinds may be used in combination.
Among these, (meth) acrylic acid is preferable.

  When the acrylic copolymer contains a carboxyl group, it is easy to control the crosslinking density with the curing agent, and it becomes easy to obtain a balance between the adhesion to the polishing member and the cohesive force of the pressure-sensitive adhesive layer. The sticking layer is unlikely to float or peel off. From the above viewpoint, it is preferable to use 0.1 to 10.0 parts by weight of the carboxyl group-containing monomer in 100 parts by weight of the total amount of monomers constituting the acrylic copolymer (A), and 0.5 to 8.0. Part by weight is more preferred.

Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycidyl (meth) acrylate, N-methylolacrylamide, and hydroxypropyl (meth). An acrylate etc. are mentioned, However, It is not limited to this, You may use individually and may be used in combination of 2 or more type.
Among these, a hydroxyl group-containing monomer having an alkylene group having 1 to 3 carbon atoms is preferable from the viewpoint of appropriate crosslinkability with a curing agent because adhesion and cohesion can be further improved.
Among these, 2-hydroxyethyl (meth) acrylate is more preferable.

  By using a hydroxyl group-containing monomer, it is easy to control the cross-linking density between the acrylic copolymer (A) and the curing agent, and it is easy to obtain a balance between the adhesion to the polishing member and the cohesive force of the pressure-sensitive adhesive layer. It is difficult for the abrasive member and the adhesive layer to float or peel off. From the above viewpoint, it is preferable to use 0.01 to 1.5 parts by weight of the hydroxyl group-containing monomer in 100 parts by weight of the total amount of monomers constituting the acrylic copolymer (A), and 0.05 to 1.0 Part by weight is more preferred.

Moreover, as a monomer for constituting the acrylic copolymer (A) of the present invention, a monomer other than the carboxyl group-containing monomer and the hydroxyl group-containing monomer may be contained.
Examples of other acrylic monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, propyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, (Meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid octyl, (meth) acrylic acid nonyl, (meth) acrylic acid decyl, (meth) acrylic acid dodecyl, (meth) acrylic acid lauryl, (meth) acrylamide, acetic acid Examples thereof include vinyl and acrylonitrile, but the present invention is not limited to these, and may be used alone or in combination of two or more.

  In the synthesis, a polymerization method such as solution polymerization, emulsion polymerization, bulk polymerization, or polymerization by ultraviolet irradiation can be employed. In the present invention, it is preferable to use solution polymerization that allows easy reaction control and physical property control.

  For the copolymerization, conventionally known polymerization initiators such as peroxide polymerization initiators and azobis polymerization initiators can be used. Examples of the organic peroxide polymerization initiator include benzoyl peroxide, di-t-butyl peroxide, cumene hydroperoxide, t-butyl peroxybenzoate, t-butyl peroxyneodecanoate, and t-butyl. Peroxy 2-ethylhexanoate and the like. As the azo polymerization initiator, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2 , 2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis (2-methylpropionamidine) disulfate, 2,2′-azobis ( N, N′-dimethyleneisobutylamidine) and the like, but these polymerization initiators may be used alone or in combination of two or more. It may be used in combination.

In the present invention, the weight average molecular weight of the acrylic copolymer (A) is preferably 300,000 to 1,500,000, more preferably 500,000 to 1,200,000. By setting it as the said range, since it is easy to obtain the balance of the adhesiveness to an abrasive | polishing member and the cohesive force of an adhesive layer, a floating or peeling of an abrasive member and an adhesive layer is hard to generate | occur | produce in a grinding | polishing process.
In addition, in this invention, the weight average molecular weight of resin is the weight average molecular weight of polystyrene conversion calculated | required by GPC measurement.

<Tackifying resin (B)>
The pressure-sensitive adhesive of the present invention contains a tackifier resin (B) having a function as a tackifier resin.
The content of the tackifying resin (B) is 5 to 60 parts by weight with respect to 100 parts by weight of the acrylic copolymer (A). By setting it as the said range, the balance of the adhesiveness with respect to an abrasive | polishing member and the cohesion force of an adhesive layer is obtained. From the above viewpoint, 15 to 50 parts by weight are more preferable.

The tackifying resin (B) is preferably a tackifying resin having a softening point of 80 to 150 ° C.
By setting the softening point of the tackifying resin within the above range, adhesion to the polishing member and heat resistance can be imparted in a balanced manner. From the above viewpoint, the softening point is more preferably 95 to 135 ° C.

  Examples of the tackifier resin (B) include rosin esters, polymerized rosins, hydrogenated rosins, disproportionated rosins, maleic acid-modified rosins, fumaric acid-modified rosins, rosin phenol resins and the like; and α-pinene resins , Terpene resins such as β-pinene resin, dipentene resin, aromatic modified terpene resin, hydrogenated terpene resin, terpene phenol resin, acid modified terpene resin, styrenated terpene resin, alkylphenol resin, coumarone resin, styrene resin, Examples include petroleum resins or copolymers thereof, but are not limited to these, and such tackifying resins can be used as needed within a range that does not impair the required performance. A combination of the above may also be used.

Among these, terpene phenol resin or coumarone resin is preferable.
The terpene phenol resin and the coumarone resin are excellent in compatibility with the acrylic copolymer (A). Adhesion is further improved. In addition, since the compatibility between the terpene phenol resin and the coumarone resin is also good, even when the terpene phenol resin and the coumarone resin are used in combination, the cohesive force of the pressure-sensitive adhesive layer is not reduced due to the tackifying resin. It is possible to improve the adhesion to a polishing member or the like.

  Specific examples of the terpene phenol resin include YS Polystar U130 (manufactured by Yashara Chemical Co., softening point 130 ± 5 ° C.), YS Polystar U115 (manufactured by Yashara Chemical Co., softening point 115 ± 5 ° C.), YS Polystar T145 (manufactured by Yashara Chemical Co., Ltd.). , Softening point 145 ± 5 ° C.), YS polystar T130 (manufactured by Yasuhara Chemical Co., softening point 130 ± 5 ° C.), YS polystar T115 (manufactured by Yashara Chemical Co., softening point 115 ± 5 ° C.), YS polystar T100 (manufactured by Yashara Chemical Co., softening) 100 ± 5 ° C.), YS Polystar T80 (Yasuhara Chemical Co., softening point 80 ± 5 ° C.), YS Polystar S145 (Yasuhara Chemical Co., softening point 145 ± 5 ° C.), YS Polystar G125 (Yasuhara Chemical Co., softening point 125) ± 5 ° C), YS polystar N1 25 (Yasuhara Chemical Co., softening point 125 ± 5 ° C), YS Polystar K140 (Yasuhara Chemical Co., softening point 140 ± 5 ° C), YS Polystar K125 (Yasuhara Chemical Co., softening point 125 ± 5 ° C), YS Polystar TH130 ( Yashara Chemical Co., Ltd., softening point 130 ± 5 ° C.) can be exemplified.

  As the coumarone resin, for example, coumarone G-90 (manufactured by Nikkaku Chemical Co., Ltd., softening point 90 ± 5 ° C.), coumarone V-120 (manufactured by Nikko Chemical Co., Ltd., softening point 120 ± 5 ° C.), Nikkan Chemicals, softening point 120 ± 5 ° C.) can be exemplified.

  Note that the terpene phenol resin and the coumarone resin are not limited to these, and such a tackifier resin may be used in combination of two or more kinds as necessary as long as the required performance is not impaired. good.

<Isocyanate curing agent (C)>
The pressure-sensitive adhesive of the present invention contains an isocyanate curing agent (C). The isocyanate curing agent (C) is a compound obtained by modifying 10 to 40 mol% of the isocyanate group in the tolylene diisocyanate compound with a monofunctional alcohol having 1 to 25 carbon atoms.

  The total content of the isocyanate curing agent (C) is preferably 2.0 to 15.0 parts by weight with respect to 100 parts by weight of the acrylic copolymer (A). By setting it in the above range, it is easy to control the crosslinking density between the acrylic copolymer (A) and the curing agent, and it is easy to obtain a balance between the adhesion to the polishing member and the cohesive force of the pressure-sensitive adhesive layer. It is difficult for the member and the adhesive layer to float or peel off. From said viewpoint, 3.0-12.0 weight part is more preferable.

  The tolylene diisocyanate compound includes not only tolylene diisocyanate but also its burette, isocyanurate, and derivatives such as adducts with alcohols. The tolylene diisocyanate compound is preferably a trimethylolpropane adduct of tolylene diisocyanate.

  The isocyanate curing agent (C) of the present invention is a compound obtained by modifying a part of the isocyanate group of the tolylene diisocyanate compound with a monohydric alcohol. In addition, the modification | denaturation here means reacting an isocyanate group and a hydroxyl group specifically, and producing | generating a urethane bond. In the modification of the isocyanate curing agent (C), 10 to 40 mol% of the isocyanate group is modified, whereby a certain amount of urethane bonds are contained in the isocyanate curing agent, and the acrylic copolymer (A) is further added. By forming a urethane bond by reaction with the contained hydroxyl group, the proportion of the urethane bond in the pressure-sensitive adhesive coating film increases, and the adhesion to an abrasive member, particularly a urethane-based abrasive member, is improved. When there are few urethane bonds, adhesiveness cannot be improved, and when there are many urethane bonds, since an adhesive coating film becomes too hard, adhesiveness falls. From the above viewpoint, it is more preferable that 15 to 35 mol% of the isocyanate group is modified.

  The monohydric alcohol which modifies a part of the isocyanate group of the tolylene diisocyanate compound in the isocyanate curing agent (C) is a monofunctional alcohol having 1 to 25 carbon atoms. By using a monohydric alcohol having 1 to 25 carbon atoms, the compatibility between the isocyanate curing agent and the acrylic copolymer (A) can be improved. From the above viewpoint, it is more preferable to use a monohydric alcohol having 3 to 20 carbon atoms.

Examples of such monofunctional alcohols having 1 to 25 carbon atoms include aliphatic alcohols, aromatic alcohols, alcohols having an ether skeleton, an ester skeleton, and a carbonate skeleton. Specifically, for example, methanol, ethanol, propanol, butanol, hexanol, dodecyl alcohol, misty alcohol, cetyl alcohol, oleyl alcohol, isopropyl alcohol, isooctyl alcohol, isostearyl alcohol, butyl decanol, hexyl decanol, decyl tetradecanol, Octyldodecyl alcohol, and the like. These monofunctional alcohols can be used alone or in combination.
Among these, it is preferable to use an aliphatic alcohol.

  In the presence of the acrylic copolymer (A) having a carboxyl group and a hydroxyl group, the isocyanate curing agent (C) crosslinks with the hydroxyl group to form a urethane bond, and also self-crosslinks through water in the atmosphere. Thus, a urea bond having a rigid skeleton can be formed, and the adhesion to the polishing member and the cohesive force of the pressure-sensitive adhesive layer can be maintained in a balanced manner.

  Furthermore, other isocyanate compounds, aziridine compounds, metal chelate compounds, epoxy compounds, and the like can be used as necessary as long as the required performance is not impaired.

  Examples of the isocyanate compound include hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenyl. Polyisocyanate compounds such as isocyanate, adducts and burettes of these isocyanate compounds and polyol compounds such as trimethylolpropane, isocyanurates, and also these isocyanate compounds and known polyether polyols, polyester polyols, acrylic polyols, Polybutadiene polyol, Adducts and the like of the polyisoprene polyol and the like.

  As the metal chelate compound, for example, a metal complex compound can be used. Examples of the metal include nickel, aluminum, chromium, iron, titanium, zinc, cobalt, manganese, copper, tin, and zirconium. Examples of the metal chelate compound include ferric trisacetylacetonate, aluminum trisacetylacetonate, aluminum monoacetylacetonate bis (ethylacetoacetate), aluminum tris (ethylacetoacetate), and the like. Aluminum trisacetylacetonate is more preferred.

  Examples of the aziridine compound include N, N′-hexamethylene-1,6-bis (1-aziridinecarboxamide, trimethylolpropane-tri-β-aziridinylpropionate, N, N′-diphenylmethane 4, 4′-bis (1-aziridinecarboxamide), trimethylolpropane-tri-β- (2-methylaziridine) propionate and the like can be mentioned.

  Examples of the epoxy compound include bisphenol A, epichlorohydrin type epoxy resin, ethylene glycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol glycidyl ether, trimethylolpropane tri Examples include glycidyl ether, diglycidyl aniline, diamine glycidyl amine, N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N′-diamine glycidylaminomethyl) cyclohexane, and the like. It is done.

  These curing agents may be used alone or in combination of two or more.

<Other additives>
In the pressure-sensitive adhesive of the present invention, fillers, pigments, dyes, diluents, anti-aging agents, polymerization inhibitors, UV absorbers, UV stabilizers, coupling agents, etc., which are blended with known pressure-sensitive adhesives as necessary. Various additives may be included, and two or more types may be used. Moreover, the addition amount of an additive should just be taken as the quantity from which a required physical property is obtained, and is not specifically limited.

《Abrasive member fixing adhesive sheet》
The pressure-sensitive adhesive sheet for fixing a polishing member of the present invention is a pressure-sensitive adhesive sheet used for fixing a polishing member such as a polishing pad used for polishing to a polishing machine, and has a pressure-sensitive adhesive layer on both surfaces of a substrate. The pressure-sensitive adhesive sheet has a pressure-sensitive adhesive layer formed by using the pressure-sensitive adhesive for fixing a polishing member of the present invention at least on the side of the polishing member. The pressure-sensitive adhesive layer on the surface plate side may be a pressure-sensitive adhesive layer formed using a conventionally known pressure-sensitive adhesive, or may be a pressure-sensitive adhesive layer formed using the polishing member disk fixing pressure-sensitive adhesive of the present invention.

  When it is set as an adhesive sheet, 10-150 micrometers is preferable and, as for the thickness of an adhesive layer, 30-120 micrometers is more preferable. By setting the pressure-sensitive adhesive layer in the above range, a pressure-sensitive adhesive tape excellent in fixing the polishing member can be obtained.

  For the application of the pressure-sensitive adhesive, known methods such as a roll coater method, a comma coater method, a lip coater method, a die coater method, a reverse coater method, a silk screen method, and a gravure coater method can be used. After coating, it can be dried with a hot air oven, an infrared heater or the like.

  As the base material for preparing the pressure-sensitive adhesive sheet, a member that can be used as a base material for the pressure-sensitive adhesive, such as non-woven fabric, paper, plastic film, and synthetic paper, can be used. When using as a base material (core material) of an adhesive sheet, a nonwoven fabric and a plastic film are preferable. Examples of the plastic film include films made of polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate, PPS (polyphenylene sulfide), nylon, triacetyl cellulose, cycloolefin, polyimide and polyamide.

The substrate may be an optical member such as an antireflection (AR) film, a polarizing plate, or a retardation plate, which is obtained by applying a desired coating solution to the plastic film. In addition, the base material may be subjected to an easy adhesion treatment in order to improve the adhesion with the pressure-sensitive adhesive layer. For the easy adhesion treatment, a known method such as a dry method for performing corona discharge and a wet method for coating with an anchor coating agent can be used. Moreover, the base material may be provided with the antistatic layer. Further, an antistatic layer may be provided. The antistatic layer is formed of a composition in which at least one of conductive carbon particles, conductive metal particles, and conductive polymer is blended with a resin as necessary, in addition to the antistatic agent described above. It is preferable to become. Alternatively, the antistatic layer can be formed by metal deposition or metal plating on the substrate.
Among the substrates, it is more preferable to use a film having an easy adhesion treatment surface. By using a film having an easy adhesion treatment surface, it is difficult for the adhesive component to migrate to a polishing member, a polishing machine or the like.

  Although the thickness in particular of a base material is not restrict | limited, 5-300 micrometers is preferable.

  The release liner for producing the pressure-sensitive adhesive sheet has a release layer formed by applying a release agent to a substrate such as paper, plastic film, or synthetic paper. Examples of the release agent include silicone, alkyd resin, melamine resin, fluororesin, and acrylic resin. The re-peelable pressure-sensitive adhesive of the present invention has an effect that the peel force hardly depends on the type of the release agent. The thickness of the release liner is not particularly limited, but is about 10 to 200 μm.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples. In the examples, “part” means “part by weight”, and “%” means “% by weight”.

  Moreover, the measuring method of the weight average molecular weight of resin, the softening point of tackifying resin, the isocyanate group amount of a hardening | curing agent, and the modification rate (mol%) of an isocyanate group (NCO group) is as follows.

(Weight average molecular weight of resin)
The weight average molecular weight of the resin is the polystyrene equivalent weight average molecular weight determined by GPC measurement, and the GPC measurement conditions are as follows. Apparatus: SHIMADZU Prominence (manufactured by Shimadzu Corporation) Column: TOSOH TSK-GEL GMHXL (manufactured by Tosoh Corporation) is used. Solvent: tetrahydrofuran, flow rate: 0.5 ml / min, temperature: 40 ° C., sample concentration: 0.1 wt%, sample injection amount: 100 μl.

(Softening point of tackifying resin)
It measured according to JISK5902 and JISK2207.

(Isocyanate group (NCO group) amount)
It measured according to JIS K1603-1.

(Modification rate of the isocyanate group (NCO group) in the tolylene diisocyanate compound (mol%))
It calculated | required by the following formula.
NCO group modification mol% =
(Mol number of NCO groups before modification−mol number of NCO groups after modification) ÷ mol number of NCO groups before modification × 100

  Then, the acrylic copolymer (A) used by the Example and the comparative example and the manufacturing method of an adhesive are demonstrated.

<Acrylic copolymer (A)>
(Acrylic copolymer solution (A-1))
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser, dripping device, and nitrogen inlet tube, 23.5 parts by weight of butyl acrylate, 22.45 parts by weight of 2-ethylhexyl acrylate, and succin vinyl 2. 5 parts by weight, 1.5 parts by weight of acrylic acid, 0.05 parts by weight of 2-hydroxyethyl acrylate, ethyl acetate as a solvent, and azobisisobutyronitrile as an initiator were charged in appropriate amounts. Separately, in the dropping tube, 23.5 parts by weight of butyl acrylate, 22.45 parts by weight of 2-ethylhexyl acrylate, 2.5 parts by weight of succinvinyl, 1.5 parts by weight of acrylic acid, 0.05 parts by weight of 2-hydroxyethyl acrylate Then, an appropriate amount of ethyl acetate as a solvent and azobisisobutyronitrile as an initiator were charged. Next, the flask was gradually heated, and after confirming the start of the reaction, the solution was dropped from the dropping tube over 1 hour. Furthermore, the reaction was continued at an internal temperature of about 80 ° C. for 8 hours. After completion of the reaction, the mixture was cooled and diluted with ethyl acetate and toluene to obtain an acrylic polymer solution (A-1) having a nonvolatile content of 46.2%, a viscosity of 9100 mPa · s, and a weight average molecular weight of 780000.

(Acrylic copolymer solution (A-2 to 6))
Synthesis in the same manner as in the acrylic polymer solution (A-1), except that the type and blending amount (parts by weight) of the acrylic monomer in the production of the acrylic polymer solution (A-1) were changed as shown in Table 1. The acrylic copolymer solutions (A-2 to 6) of Examples 2 to 6 were obtained.

Abbreviations in Table 1 are described below.
BA: butyl acrylate 2EHA: 2-ethylhexyl acrylate VAC: succin vinyl (carboxyl group-containing monomer)
AA: Acrylic acid (hydroxyl group-containing monomer)
HEA: 2-hydroxyethyl acrylate

<Isocyanate curing agent (C)>
(Isocyanate curing agent solution (C-1))
After replacing the air in the reaction vessel of the reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping device, nitrogen introduction tube with nitrogen gas, coronate L (trimethylolpropane adduct body of tolylene diisocyanate, NCO% = 13.0%, non-volatile content = 75%, manufactured by Tosoh Corporation), 100 parts, and then Calcoal 200GD (octyldodecyl alcohol (carbon number 20), manufactured by Kao Corporation) 15.4 parts were charged in a nitrogen atmosphere with stirring. The solution was heated to 60 ° C. and reacted with octyldodecyl alcohol by reacting for 7 hours (NCO% = 9.39%, 16.7% modification of NCO group). By diluting with an appropriate amount of ethyl acetate, an isocyanate curing agent solution (C-1) having a nonvolatile content of 42.0% was obtained.

(Isocyanate curing agent solution (C-2 to 8))
In the production of the isocyanate curing agent (C-1), the isocyanate curing was carried out in the same manner as the isocyanate curing agent (C-1) except that the type of alcohol and the amount (parts by weight) were changed as shown in Table 2. An agent solution (C-2 to 8) was obtained.
Table 2 also shows the modification rate of the isocyanate group (NCO group) in the tolylene diisocyanate compound (NCO group modification mol%).

[Example 1]
(Preparation of adhesive)
30 weights of YS Polystar K125 (manufactured by Yashara Chemical Co., terpene phenol resin, softening point 125 ° C.) as a tackifying resin with respect to 100 parts by weight of the nonvolatile content of the acrylic polymer in the acrylic copolymer solution (A-1) Parts, isocyanate curing agent in isocyanate curing agent solution (C-1) (ethyl acetate solution having a nonvolatile content of 42.0% by weight), 9.5 parts by weight in terms of nonvolatile content, and an appropriate amount of ethyl acetate as a solvent, The pressure-sensitive adhesive 1 was obtained by stirring with a disper.

[Examples 2 to 20, Comparative Examples 1 to 6]
The pressure-sensitive adhesive 1 is the same as the pressure-sensitive adhesive 1 of Example 1 except that the acrylic copolymer, the tackifier resin, the type of the isocyanate curing agent, and the blending amount are changed as described in Tables 3 to 5. ~ 26 was obtained.

  Abbreviations in Tables 3 to 5 are as follows. Further, the blending amount (parts by weight) is an addition amount in terms of nonvolatile content relative to the solid content of the acrylic copolymer.

<Tackifying resin>
YS Polystar K125: (Yasuhara Chemical Co., Ltd., terpene phenol resin, softening point 125 ° C.)
YS Polystar N125: (Yasuhara Chemical Co., Ltd., terpene phenol resin, softening point 125 ° C.)
Coumarone V120: (manufactured by Nikko Chemical Co., Ltd., Coumarone resin, softening point 120 ° C.)
Coumaron G90: (manufactured by Nikkaku Chemical Co., Ltd., Coumarone resin, softening point 90 ° C.)
SYLVARES SA100: (Arizona Chemical Co., petroleum resin, softening point 100 ° C.)
Pencel D125: (Arakawa Chemical Industries, rosin resin, softening point 125 ° C.)
<Isocyanate curing agent>
TDI-TMP (unmodified): Trimethylolpropane adduct of tolylene diisocyanate

  A pressure-sensitive adhesive sheet was formed using the obtained pressure-sensitive adhesive, and the following physical properties were evaluated.

<Production of adhesive sheet>
As shown in Tables 6 to 8, using the obtained pressure-sensitive adhesive, coating (polishing member side pressure-sensitive adhesive layer) on a 25 μm PET film substrate so that the thickness after drying becomes 80 μm, and at 100 ° C. for 2 minutes. After drying, the release liner was bonded together, and then the resulting adhesive was coated on the release liner (surface plate side adhesive layer) so that the thickness after drying was 50 μm, and dried at 100 ° C. for 2 minutes. Then, it bonded together on the surface where the adhesive of PET film base material was not apply | coated, and it was left to stand at 23 degreeC-50% for 1 week, and obtained the adhesive sheet.
In Example 1-A, an adhesive sheet was obtained using the adhesive 1 on the polishing member side and the adhesive 26 on the surface plate side.

<Adhesive strength>
The release liner on the non-measured surface of the obtained pressure-sensitive adhesive sheet was peeled off, and a 25 μm PET film was bonded, and then prepared as a sample having a width of 25 mm and a length of 100 mm. Next, in a 23 ° C.-50% RH atmosphere, the release liner opposite to the 25 μm PET film was peeled off from the obtained sample, and the exposed adhesive layer was reciprocated once on a stainless steel plate with a 2 kg roller. After the pressure bonding and leaving for 20 minutes or 24 hours, the adhesive strength was measured using a tensile tester under the conditions of a peeling angle of 180 degrees and a peeling speed of 0.3 m / min. The adhesive strength on both sides was measured by the same method.

<Retention force>
The release liner on the non-measured surface of the obtained pressure-sensitive adhesive sheet was peeled off, and a 25 μm PET film was bonded, and then prepared as a sample having a width of 25 mm and a length of 100 mm. Next, in a 23 ° C.-50% RH atmosphere, the release liner opposite to the surface on which the 25 μm PET film was pasted from the obtained sample was peeled off 25 mm long × 25 mm wide, and pressed once on a stainless steel plate with a 2 kg roll, It was left for 20 minutes in an atmosphere of 23 ° C.-50%. Then, set a weight of 1kg under an atmosphere of 80 ° C so that force is applied in the direction of 180 degrees. After 24 hours, how many millimeters the adhesive sheet has been displaced from the adherend or the number of seconds that have completely dropped Was measured. The holding force on both sides was measured by the same method. The smaller the deviation, the higher the holding power.

<Abrasive member adhesive strength>
The release liner on the surface plate surface side of the obtained pressure-sensitive adhesive sheet was peeled off and a 25 μm PET film was bonded, and then prepared as a sample having a width of 25 mm and a length of 100 mm. Next, the release liner on the polishing member surface side of the adhesive sheet having a length of 10 mm and a width of 25 mm is peeled off in an atmosphere of 23 ° C. to 50%, and heat lamination is performed on the polishing member (general commercial hard urethane pad) (lamination speed: 1.0 m, Laminating temperature: 90 ° C., laminating pressure: 4.0 kg / cm ² ), and left in an atmosphere of 23 ° C.-50% for 24 hours. Thereafter, the adhesive strength was measured at a peeling angle of 180 degrees and a peeling speed of 300 mm / min using a tensile tester in an atmosphere of 23 ° C.-50% in accordance with the measurement method of JISZ1528 (Abrasive member adhesive strength 1). . The larger the value, the higher the adhesion and the better.

<Alkali resistance>
The release liner on the surface plate surface side of the obtained pressure-sensitive adhesive sheet was peeled off and a 25 μm PET film was bonded, and then prepared as a sample having a width of 25 mm and a length of 100 mm. Next, the release liner on the polishing member surface side of the adhesive sheet having a length of 10 mm and a width of 25 mm is peeled off in an atmosphere of 23 ° C. to 50%, and heat lamination is performed on the polishing member (general commercial hard urethane pad) (lamination speed: 1.0 m, Laminating temperature: 90 ° C., laminating pressure: 4.0 kg / cm ² ), and left in an atmosphere of 23 ° C.-50% for 24 hours. Then, it was immersed in an aqueous solution adjusted to pH 11.5 using sodium hydroxide, and left in a 40 ° C. environment for an additional 24 hours. Thereafter, a sample is taken out from the aqueous solution, washed with water, and left in an atmosphere of 23 ° C.-50% for 1 hour. Thereafter, the adhesive strength was measured at a peeling rate of 300 mm / min using a tensile test in accordance with the measurement method of JISZ1528 in an atmosphere of 23 ° C.-50%. The smaller the change with respect to the 180 ° adhesive strength (abrasive member adhesive strength 1), the better the alkali resistance.

<Acid resistance>
The release liner on the surface plate surface of the obtained pressure-sensitive adhesive sheet was peeled off, and a 25 μm PET film was bonded, and then prepared as a sample having a width of 25 mm and a length of 100 mm. Next, the release liner on the polishing member surface side of the adhesive sheet having a length of 10 mm and a width of 25 mm is peeled off in an atmosphere of 23 ° C. to 50%, and heat lamination is performed on the polishing member (general commercial hard urethane pad) (lamination speed: 1.0 m, Laminating temperature: 90 ° C., laminating pressure: 4.0 kg / cm ² ), and left in an atmosphere of 23 ° C.-50% for 24 hours. Then, it was immersed in an aqueous solution adjusted to pH 1.5 using sulfuric acid, and left in a 40 ° C. environment for another 24 hours. Thereafter, a sample is taken out from the aqueous solution, washed with water, and left in an atmosphere of 23 ° C.-50% for 1 hour. Thereafter, the adhesive strength was measured at a peeling rate of 300 mm / min using a tensile test in accordance with the measurement method of JISZ1528 in an atmosphere of 23 ° C.-50%. The smaller the change to the value of 180 degree adhesive strength (abrasive member adhesive strength 1), the better the acid resistance.

<Tensile shear force>
The release liner on the surface plate side of the obtained pressure-sensitive adhesive sheet was peeled off, and a 188 μm PET film (PET188) was bonded thereto, and then prepared as a sample having a width of 10 mm and a length of 100 mm. Next, peel off the release liner on the polishing member side of the adhesive sheet 10 mm long x 10 mm wide in an atmosphere of 23 ° C.-50%, press it once on a stainless steel plate with a 2 kg roller, and immediately put it in hot water at 50 ° C. Leave for 24 hours. After 24 hours, a sample was taken out of the water, washed with water, and left in an atmosphere of 23 ° C.-50% for 1 hour. Thereafter, both ends of the bonded sample were fixed to a tensile tester in an atmosphere of 23 ° C.-50%, and pulled at a peeling rate of 100 mm / min using a tensile test in the direction of 180 degrees, and the tensile shear force was measured. (FIG. 1). The higher the tensile shearing force, the better the shearing force and the longer the polishing.

From the results of Tables 6 to 8, the adhesive for fixing a polishing member of the present invention has a high adhesive force and a small deviation in evaluation of holding power, and exhibits excellent adhesion to the polishing member. But there was no lifting or peeling. Moreover, it has confirmed that it was an adhesive for fixing an abrasive member excellent in acid resistance and alkali resistance.
In particular, when the tackifier resin (B) is a terpene phenol resin or a coumarone resin, the cohesive force of the pressure-sensitive adhesive layer is higher, the adhesive force to the polishing member, and the deviation in the holding force evaluation are small, and the polishing member It was excellent in adhesiveness to etc.

  On the other hand, the pressure-sensitive adhesive sheet formed using the pressure-sensitive adhesive 21 containing no isocyanate curing agent (C) has a low adhesive strength, and particularly has a problem with the adhesive strength to the polishing member. Moreover, in the isocyanate curing agent (C), when the modification rate of the isocyanate group is too high, the holding force and the tensile shearing force are weak, resulting in poor adhesion, and even when the alcohol has too many carbon atoms, The tensile shear force was weak.

  In addition, the pressure-sensitive adhesive sheet formed using the pressure-sensitive adhesive 22 not containing the tackifier resin (B) has not only low adhesive strength, but also a large deviation in evaluation of holding power, and also has poor acid resistance and alkali resistance. there were. Moreover, even when there was too much content of tackifying resin (B), it was a result with small adhesive force.

  From these results, the adhesive tape for fixing an abrasive member formed using the adhesive for fixing an abrasive member of the present invention is not only excellent in adhesive force, but can be polished for a longer time than before, It is apparent that the present invention can be suitably used for polishing glass having higher hardness than conventional glass.

Claims (5)

Abrasive member fixing adhesive containing an acrylic copolymer (A), a tackifier resin (B), and an isocyanate curing agent (C),
The acrylic copolymer (A) is a copolymer of a monomer containing a carboxyl group-containing monomer and a hydroxyl group-containing monomer,
The isocyanate curing agent (C) is a compound in which 10 to 40 mol% of the isocyanate group in the tolylene diisocyanate compound is modified with a monofunctional alcohol having 1 to 25 carbon atoms,
The adhesive for fixing an abrasive member, wherein the content of the tackifying resin (B) is 5 to 60 parts by weight with respect to 100 parts by weight of the acrylic copolymer (A).   The pressure-sensitive adhesive for fixing an abrasive member according to claim 1, wherein the softening point of the tackifying resin (B) is 80 to 150 ° C.   The pressure-sensitive adhesive for fixing an abrasive member according to claim 1 or 2, wherein the tackifying resin (B) contains at least one of a terpene phenol resin and a coumarone resin.   The abrasive member fixing adhesive according to any one of claims 1 to 3, wherein the abrasive member is urethane-based.   An adhesive sheet for fixing an abrasive member, comprising an adhesive layer formed from the adhesive for fixing an abrasive member according to any one of claims 1 to 4 on a substrate.

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