Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/15—Heterocyclic compounds having oxygen in the ring
  • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
  • C08K5/1515—Three-membered rings
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/06—Non-macromolecular additives organic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
  • C09J133/04—Homopolymers or copolymers of esters
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
  • C09J183/10—Block or graft copolymers containing polysiloxane sequences
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J201/00—Adhesives based on unspecified macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
  • C09J7/38—Pressure-sensitive adhesives [PSA]
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2301/00—Additional features of adhesives in the form of films or foils
  • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
  • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

Definitions

• the present invention relates to an adhesive tape.
• an adhesive tape is used to facilitate handling during processing of a wafer or a semiconductor chip and to prevent breakage. For example, when a thick film wafer cut out from a high-purity silicon single crystal or the like is ground to a predetermined thickness to form a thin film wafer, grinding is performed after an adhesive tape is bonded to the thick film wafer.
• Such an adhesive tape has a high adhesive enough to firmly fix an adherend such as a wafer or a semiconductor chip during a processing process, and without damaging the adherend such as a wafer or a semiconductor chip after the process is completed. It must be peelable (hereinafter also referred to as “high adhesion easy peeling”).
• Patent Document 1 discloses a pressure-sensitive adhesive tape using a photo-curing pressure-sensitive adhesive that is cured by irradiating light such as ultraviolet rays to reduce the adhesive force. By using a photo-curing pressure-sensitive adhesive as the pressure-sensitive adhesive, the adherend can be reliably fixed during the processing step, and can be easily peeled off by irradiation with ultraviolet rays or the like.
• An object of this invention is to provide the adhesive tape which can be used also for the material which can reduce the enhancement of adhesion
• the present invention is a pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer, and the pressure-sensitive adhesive layer has a shear storage elastic modulus at 25 ° C. evaluated by dynamic viscoelasticity measurement of 4.0 ⁇ 10 4 to 2.0 ⁇ 10 6.
• the pressure-sensitive adhesive layer is Pa, and the pressure-sensitive adhesive layer has a water contact angle of 80 ° or more after the pressure-sensitive adhesive layer side of the pressure-sensitive adhesive tape is attached to glass and heated at 220 ° C. for 120 minutes and peeled off. It is.
• the present invention is described in detail below.
• the adhesive tape which is one embodiment of this invention has an adhesive layer.
• the adhesive tape which is one embodiment of the present invention may have other layers as long as it has an adhesive layer.
• the support tape which has a base material may be sufficient as the adhesive tape which is one embodiment of this invention, and the non-support type which does not have a base material may be sufficient as it.
• the pressure-sensitive adhesive tape according to one embodiment of the present invention has a base material, it is sufficient that it has a pressure-sensitive adhesive layer on at least one side of the base material, and it may be a single-sided pressure-sensitive adhesive tape or a double-sided pressure-sensitive adhesive tape. .
• the pressure-sensitive adhesive layer has a shear storage modulus at 25 ° C. evaluated by dynamic viscoelasticity measurement of 4.0 ⁇ 10 4 to 2.0 ⁇ 10 6 Pa. It can be set as the adhesive layer of the hardness suitable for an adhesive tape because the shear storage elastic modulus of an adhesive layer is 4.0 * 10 ⁇ 4 > Pa or more. Moreover, when the shear storage elastic modulus of the pressure-sensitive adhesive layer is 2.0 ⁇ 10 6 Pa or less, the pressure-sensitive adhesive layer does not become too hard, and adhesion of the pressure-sensitive adhesive tape can be prevented to suppress adhesive residue. From the same viewpoint as described above, a preferable lower limit of the shear storage elastic modulus is 8.0 ⁇ 10 4 Pa, and a more preferable lower limit is 1.0 ⁇ 10 5 Pa.
• the upper limit of the above-described elastic storage modulus is preferably 1.5 ⁇ 10 6 Pa, more preferably 1.3 ⁇ 10 6 Pa, still more preferably 1.0 ⁇ 10 6 Pa, and particularly preferably 7.0 ⁇ 10 6 Pa. 5 Pa, the most preferred upper limit is 2.0 ⁇ 10 5 Pa.
• the shear storage modulus is measured using a dynamic viscoelasticity measuring device (for example, DVA-200, manufactured by IT Measurement Control Co., Ltd.) in a shear mode of dynamic viscoelasticity measurement, at an angular frequency of 10 Hz and a temperature increase rate of 5 ° C./min. Of the measured values obtained by measuring from ⁇ 50 ° C. to 200 ° C., it can be obtained as the value of the storage elastic modulus at 25 ° C.
• the said shear storage elastic modulus has a small fluctuation
• the pressure-sensitive adhesive layer is formed by attaching the pressure-sensitive adhesive layer side of the pressure-sensitive adhesive tape to glass, heating at 220 ° C. for 120 minutes, and peeling off (hereinafter, simply referred to as the water-contact angle after heating). Is 80 ° or more. Adhesive tape is attached to glass, heated, and the adhesive layer after peeling has a water contact angle in the above range, making the surface hydrophobic and less likely to interact with the adherend. Therefore, adhesion enhancement due to heating can be reduced. From the same viewpoint, the preferable lower limit of the contact angle with water after heating is 81 °, the more preferable lower limit is 81.5 °, and the still more preferable lower limit is 82 °.
• the preferable upper limit of the contact angle with water after heating is 110 °, the more preferable upper limit is 105 °, the still more preferable upper limit is 103 °, the still more preferable upper limit is 100 °, the particularly preferable upper limit is 97 °, and the particularly preferable upper limit is 95 °.
• a very preferable upper limit is 92 °, and a preferable upper limit is 91 °.
• the contact angle with water after the heating can be measured by a method based on JIS R 3257: 1999, and specifically by the following method. Cut the adhesive tape to a width of 25 mm. The cut adhesive tape is applied to a glass adherend (for example, Matsunami Glass Industrial Co., Ltd., large slide glass white edge polish No. 2) at room temperature of 23 ° C. and relative humidity of 50% using a 2 kg pressure-bonded rubber roller and 10 mm / SEC. Paste at the speed of. Next, heat treatment is performed at 220 ° C. for 120 minutes.
• a glass adherend for example, Matsunami Glass Industrial Co., Ltd., large slide glass white edge polish No.
• the pressure-sensitive adhesive tape After cooling, the pressure-sensitive adhesive tape is peeled off from the glass adherend, and the water contact angle of the pressure-sensitive adhesive layer is measured using a contact angle measurement device (for example, KSV, CAM 200) according to JIS R 3257: 1999.
• a contact angle measurement device for example, KSV, CAM 200
• JIS R 3257 1999.
• 2 ⁇ L of water drops are dropped onto the surface of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape placed horizontally in an environment of room temperature of 25 ° C. and humidity of 40%.
• the angle formed between the pure water and the pressure-sensitive adhesive layer surface after 5 seconds from the dropping is defined as the contact angle with water.
• the pressure-sensitive adhesive tape according to one embodiment of the present invention preferably has a water contact angle at 25 ° C. of the pressure-sensitive adhesive layer of 103 ° or less.
• the adhesive layer has a contact angle with water at 25 ° C. of 103 ° or less, it can be attached to the adherend with a more appropriate adhesive force (initial adhesive force).
• the more preferable upper limit of the contact angle with water at 25 ° C. of the pressure-sensitive adhesive layer is 102 °, and the more preferable upper limit is 100 °.
• the lower limit of the water contact angle at 25 ° C. of the pressure-sensitive adhesive layer is not particularly limited, but is preferably 80 °.
• the water contact angle at 25 ° C. of the pressure-sensitive adhesive layer can be measured by the same method as that for the water contact angle after the heating except that heat treatment is not performed.
• the pressure-sensitive adhesive layer can be cross-linked by reacting with a pressure-sensitive adhesive having a crosslinkable functional group, a silicone-based graft copolymer having a crosslinkable functional group, and the pressure-sensitive adhesive and the silicone-based graft copolymer. It is preferable to contain a crosslinking agent. When the pressure-sensitive adhesive layer contains a cross-linking agent, the pressure-sensitive adhesive can be cross-linked and the shear storage modulus can be easily adjusted to the above range. In addition, when the pressure-sensitive adhesive layer contains a silicone-based graft copolymer, the surface of the pressure-sensitive adhesive layer becomes hydrophobic because the silicone-based graft copolymer bleeds out to the surface of the pressure-sensitive adhesive layer by heating.
• the water contact angle can be easily adjusted within the above range. Further, since the surface of the pressure-sensitive adhesive layer becomes hydrophobic, it becomes difficult for the pressure-sensitive adhesive layer and the adherend to interact with each other, and the adhesive force is reduced, so that the adhesion enhancement can be reduced. Furthermore, since the silicone-based graft copolymer has a crosslinkable functional group, the silicone-based graft copolymer can be bonded to the pressure-sensitive adhesive via a crosslinking agent, so that contamination of the adherend can be suppressed.
• the pressure-sensitive adhesive is not particularly limited, and may be curable or non-curable.
• a cured adhesive is one that has a polymerizable functional group such as a double bond, for example, and is cured by a stimulus such as heat or light, and a non-curable adhesive substantially contains a polymerizable functional group. It does not have.
• the pressure-sensitive adhesive is preferably a non-curable pressure-sensitive adhesive because the manufacturing process can be simplified and it can be used for an opaque material that cannot be photocured. Examples of the non-curable adhesive include a non-photo curable adhesive, a non-thermo curable adhesive, and a non-energy curable adhesive.
• the pressure sensitive adhesive examples include acrylic pressure sensitive adhesive, silicone pressure sensitive adhesive, urethane pressure sensitive adhesive, and rubber pressure sensitive adhesive. Especially, since it is easy to adjust the water contact angle after the said heating and the said shear storage elastic modulus, a non-silicone adhesive is preferable and it is more preferable that it is an acrylic adhesive.
• Examples of the crosslinkable functional group present in the pressure-sensitive adhesive and the silicone-based graft copolymer independently include a carboxyl group, a hydroxyl group, a glycidyl group, an amino group, an amide group, and a nitrile group.
• a carboxyl group is preferable because it can be easily adjusted to the range of the shear storage modulus.
• the pressure-sensitive adhesive is preferably an acrylic polymer having a molecular weight distribution (Mw / Mn) of 1.05 to 2.5, and a molecular weight distribution (Mw / Mn) of 1.05 to 2.5 obtained by living radical polymerization.
• the polymer is an acrylic polymer (hereinafter also simply referred to as “living radical polymerization acrylic polymer”).
• the living radical polymerization acrylic polymer is obtained by living radical polymerization using an acrylic monomer such as (meth) acrylic acid ester or (meth) acrylic acid as a raw material, preferably living radical polymerization using an organic tellurium polymerization initiator. Acrylic polymer.
• Living radical polymerization is polymerization in which molecular chains grow without the polymerization reaction being hindered by side reactions such as termination reactions or chain transfer reactions.
• living radical polymerization for example, a polymer having a more uniform molecular weight and composition than that of free radical polymerization can be obtained and generation of low molecular weight components can be suppressed. Even glue residue can be suppressed.
• the shear storage elastic modulus can be easily adjusted to the above range. From the viewpoint of further suppressing the adhesive residue, the more preferable lower limit of the molecular weight distribution of the living radical polymerization acrylic polymer is 1.1, and the more preferable upper limit is 2.0.
• living radical polymerization various polymerization methods may be employed. For example, iron, ruthenium, a copper catalyst, and a halogen-based initiator may be used (ATRP), TEMPO may be used, and an organic tellurium polymerization initiator may be used. Among these, it is preferable to use an organic tellurium polymerization initiator. Unlike other living radical polymerizations, living radical polymerization using an organic tellurium polymerization initiator is the same initiator without protecting any radically polymerizable monomer having a polar functional group such as a hydroxyl group or a carboxyl group. To obtain a polymer having a uniform molecular weight and composition. For this reason, the radically polymerizable monomer having a polar functional group can be easily copolymerized.
• the organic tellurium polymerization initiator is not particularly limited as long as it is generally used for living radical polymerization, and examples thereof include organic tellurium compounds and organic telluride compounds.
• examples of the organic tellurium compounds include (methylterranyl-methyl) benzene, (1-methylterranyl-ethyl) benzene, (2-methylterranyl-propyl) benzene, 1-chloro-4- (methylterranyl-methyl) benzene, 1-hydroxy- 4- (methylterranyl-methyl) benzene, 1-methoxy-4- (methylterranyl-methyl) benzene, 1-amino-4- (methylterranyl-methyl) benzene, 1-nitro-4- (methylterranyl-methyl) benzene, 1- Cyano-4- (methylterranyl-methyl) benzene, 1-methylcarbonyl-4- (methylterranyl-methyl) benzene, 1-phenylcarbonyl-4- (methylterran
• the methyl terranyl group in these organic tellurium compounds may be an ethyl terranyl group, n-propyl terranyl group, isopropyl terranyl group, n-butyl terranyl group, isobutyl terranyl group, t-butyl terranyl group, phenyl terranyl group, etc.
• These organic tellurium compounds may be used alone or in combination of two or more.
• organic telluride compound examples include dimethyl ditelluride, diethyl ditelluride, di-n-propyl ditelluride, diisopropyl ditelluride, dicyclopropyl ditelluride, di-n-butyl ditelluride, di-sec-butyl ditelluride.
• These organic telluride compounds may be used alone or in combination of two or more. Of these, dimethyl ditelluride, diethyl ditelluride, di-n-propyl ditelluride, di-n-butyl ditelluride and diphenyl ditelluride are preferable.
• an azo compound as a polymerization initiator for the purpose of acceleration
• the azo compound is not particularly limited as long as it is generally used for radical polymerization.
• 2,2′-azobis isobutyronitrile
• a monomer having a crosslinkable functional group is blended in the living radical polymerization acrylic polymer as a monomer to be polymerized.
• the crosslinkable functional group is a carboxyl group
• examples of the monomer having a carboxyl group include (meth) acrylic acid.
• examples of the monomer having a hydroxyl group include (meth) acrylic acid esters having a hydroxyl group such as 4-hydroxybutyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate. It is done.
• examples of the monomer having a glycidyl group include glycidyl (meth) acrylate.
• examples of the monomer having an amide group include hydroxyethyl acrylamide, isopropyl acrylamide, and dimethylaminopropyl acrylamide.
• examples of the monomer having a nitrile group include acrylonitrile.
• the content thereof is not particularly limited, but the preferable lower limit in the radical polymerizable monomer polymerized in the living radical polymerization is 0.1% by weight, and the preferable upper limit is 10% by weight. is there.
• the content is 0.1% by weight or more, the living radical polymerization acrylic polymer can be sufficiently bonded to the silicone graft copolymer via the crosslinking agent, thereby reducing the contamination of the adherend. Can do.
• the content is 10% by weight or less, the pressure-sensitive adhesive does not become too hard, and adhesive residue of the pressure-sensitive adhesive tape can be suppressed.
• the content is not particularly limited, but a preferable upper limit in the radical polymerizable monomer to be polymerized in the living radical polymerization is 30% by weight. When the content is 30% by weight or less, the heat-resistant adhesiveness of the pressure-sensitive adhesive can be further improved.
• acrylic monomer that is polymerized in the living radical polymerization other radical polymerizable monomers other than the acrylic monomer having a crosslinkable functional group may be used.
• other (meth) acrylic acid ester is mentioned, for example.
• acrylic monomers having other polar functional groups such as amino groups, amide groups, and nitrile groups can also be used.
• a vinyl compound may be used as a monomer.
• the other (meth) acrylic acid esters are not particularly limited, and are methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2 (Meth) acrylic acid alkyl esters such as ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isomyristyl (meth) acrylate, stearyl (meth) acrylate, Cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, gly
• the vinyl compound is not particularly limited, and examples thereof include (meth) acrylamide compounds such as N, N-dimethylacrylamide, N, N-diethylacrylamide, N-isopropylacrylamide, N-hydroxyethylacrylamide, and acrylamide, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylacetamide, N-acryloylmorpholine, acrylonitrile, styrene, vinyl acetate and the like can be mentioned. These vinyl compounds may be used alone or in combination of two or more.
• a dispersion stabilizer may be used.
• the dispersion stabilizer include polyvinyl pyrrolidone, polyvinyl alcohol, methyl cellulose, ethyl cellulose, poly (meth) acrylic acid, poly (meth) acrylic acid ester, and polyethylene glycol.
• the living radical polymerization method conventionally known methods are used, and examples thereof include solution polymerization (boiling point polymerization or constant temperature polymerization), emulsion polymerization, suspension polymerization, bulk polymerization and the like.
• the polymerization solvent is not particularly limited.
• polymerization solvent examples include nonpolar solvents such as hexane, cyclohexane, octane, toluene, xylene, water, methanol, ethanol, propanol, butanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, dioxane, N, N—
• a highly polar solvent such as dimethylformamide can be used.
• These polymerization solvents may be used alone or in combination of two or more.
• the polymerization temperature is preferably 0 to 110 ° C. from the viewpoint of the polymerization rate.
• the living radical polymerization acrylic polymer has a molecular weight with a preferred lower limit of 500,000, a more preferred lower limit of 800,000, a preferred upper limit of 1.5 million, and a more preferred upper limit of 1,200,000.
• the molecular weight of the living radical polymerization acrylic polymer is in the above range, the contact angle with water and the shear storage modulus after the heating can be easily adjusted to the above range.
• the silicone-based graft copolymer is not particularly limited as long as it has a crosslinkable functional group.
• the crosslinkable functional group may be present in the graft chain, may be present in the main chain, or may be present in the graft chain and the main chain.
• the silicone-based graft copolymer preferably contains a polar functional group-containing monomer and a structural unit derived from a silicone macromonomer.
• the silicone-based graft copolymer is preferably a graft copolymer having a side chain having silicone.
• the polar functional group-containing monomer include a hydroxyl group-containing monomer, an amino group-containing monomer, and a hydroxyl group-containing monomer. Of these, the polar functional group-containing monomer is preferably a carboxyl group-containing monomer from the viewpoint of easily controlling the adhesive force.
• the silicone-based graft copolymer is preferably 0.1% by weight or more from the viewpoint of further improving the initial adhesive force and the adhesive force after heating. It is preferable to copolymerize a mixed monomer containing 90% by weight or less of a carboxyl group-containing monomer.
• the content of the carboxyl group-containing monomer is more preferably 0.5% by weight or more, and still more preferably 1% by weight or more.
• the content of the carboxyl group-containing monomer is more preferably 80% by weight or less, still more preferably 70% by weight or less, still more preferably 60% by weight or less, particularly preferably 50% by weight or less, particularly preferably. It is 40% by weight or less, particularly preferably 30% by weight or less, and very preferably 20% by weight or less.
• the silicone-based graft copolymer is a mixture containing 0.1 to 2.5% by weight of a carboxyl group-containing monomer (carboxylic acid-containing monomer) and 1 to 90% by weight of a silicone macromonomer. It is preferable that the monomer is copolymerized.
• the carboxyl group-containing monomer is a source of the crosslinkable functional group of the silicone-based graft copolymer, and is blended in a content within the above range, thereby allowing the silicone-based graft copolymer and the pressure-sensitive adhesive via the crosslinking agent. And contamination of the adherend can be suppressed.
• the silicone macromonomer imparts the performance as a bleed agent to the silicone-based graft copolymer, and the adhesion enhancement due to high temperature can be reduced by blending in a content within the above range.
• the above-mentioned pressure-sensitive adhesive, the above-mentioned crosslinking agent, and a silicone-based graft copolymer obtained by copolymerizing the above mixed monomer it is possible to further reduce the increase in adhesion due to high temperatures and suppress the contamination of the adherend. can do.
• the content of the carboxyl group-containing monomer is particularly important.
• the resulting silicone-based graft copolymer can be sufficiently bonded to the pressure-sensitive adhesive.
• the carboxyl group-containing monomer is 2.5% by weight or less, the surface of the pressure-sensitive adhesive layer can be prevented from becoming hydrophilic due to a decrease in carboxyl groups that are not used for bonding with the pressure-sensitive adhesive. It is easy to adjust the subsequent water contact angle within the above range, and the adhesion enhancement can be reduced.
• the more preferable lower limit of the content of the carboxyl group-containing monomer is 1.0% by weight
• the still more preferable lower limit is 1.5% by weight
• the more preferable upper limit is 2.0% by weight
• the still more preferable upper limit is 1.7%. % By weight.
• a more preferable lower limit of the content of the silicone macromonomer is 2% by weight.
• the more preferable lower limit of the content of the silicone macromonomer is 2.5% by weight, the still more preferable lower limit is 3% by weight, the particularly preferable lower limit is 3.5% by weight, the particularly preferable lower limit is 4% by weight, and the very preferable lower limit is 4.5 wt%, the most preferred lower limit is 5 wt%.
• a more preferable upper limit of the content of the silicone macromonomer is 80% by weight, a still more preferable upper limit is 60% by weight, an even more preferable upper limit is 50% by weight, a particularly preferable upper limit is 40% by weight, and a particularly preferable upper limit is 30% by weight.
• a preferred upper limit is 25% by weight, and a most preferred upper limit is 20% by weight.
• the silicone-based graft copolymer is obtained by copolymerizing a mixed monomer containing a (meth) acrylic acid ester in addition to the polar functional group-containing monomer and the silicone macromonomer. May be.
• the (meth) acrylic acid ester is not particularly limited.
• (meth) acrylic acid esters may be used alone or in combination of two or more.
• content of (meth) acrylic acid ester becomes like this.
• it is 1 weight% or more, Preferably it is 99 weight% or less.
• the content of the (meth) acrylic acid ester is more preferably 5% by weight or more, further preferably 7.5% by weight or more, still more preferably 10% by weight or more, more preferably 95% by weight or less, Preferably it is 90 weight% or less, More preferably, it is 80 weight% or less.
• crosslinkable functional group of the silicone-based graft copolymer the same crosslinkable functional group as that of the pressure-sensitive adhesive can be used.
• the crosslinkable functional group of the silicone-based graft copolymer may be the same as or different from the crosslinkable functional group of the pressure-sensitive adhesive.
• the silicone macromonomer preferably has a weight average molecular weight of 500 or more, more preferably 1000 or more.
• the weight average molecular weight of the silicone macromonomer is equal to or more than the above lower limit, the hydrophobic surface layer formed by the silicone-based graft copolymer becomes thick, so that adhesion enhancement can be further reduced.
• the more preferable upper limit of the weight average molecular weight of the silicone macromonomer is 50000, and usually 20000 or less.
• the silicone-based graft copolymer has an acid value of preferably 0.5 mgKOH / g or more, more preferably 1 mgKOH / g or more, from the viewpoint of controlling contamination of the adherend, initial adhesive force and post-heating adhesive force. More preferably, it is 3 mgKOH / g or more, Most preferably, it is 5 mgKOH / g or more, Most preferably, it is 10 mgKOH / g or more.
• the oxidation is preferably 22 mgKOH / g or less, more preferably 20 mgKOH / g or less, and still more preferably 19 mgKOH / g or less.
• silicone macromonomer what is necessary is just a monomer which has a siloxane bond containing group in a side chain, for example, a silicone group containing acrylic monomer, a siloxane bond containing styrene monomer, etc. are mentioned. Especially, since it is excellent in heat resistance and a weather resistance, a siloxane bond containing acrylic monomer is preferable.
• siloxane bond containing acrylic monomer the monomer which has structural formula like following General formula (1) or General formula (2) is mentioned, for example.
• R represents a (meth) acryloyl group-containing functional group
• X and Y each independently represent an integer of 0 or more, usually 5000 or less, particularly 500 or less.
• the content of the silicone macromonomer in the raw material monomer of the silicone-based graft copolymer of the present invention is preferably 1% by weight or more and 90% by weight or less.
• adhesion enhancement at high temperatures can be further suppressed.
• the more preferred lower limit of the silicone macromonomer content is 5% by weight
• the still more preferred lower limit is 10% by weight
• the more preferred upper limit is 80% by weight
• the still more preferred upper limit is 60% by weight. %.
• monomers other than the carboxyl group-containing monomer and the silicone macromonomer include (meth) acrylic acid esters.
• acrylic monomers having other polar functional groups such as a hydroxyl group, an amino group, an amide group, and a nitrile group can also be used.
• a vinyl compound may be used as a monomer.
• the silicone-based graft copolymer preferably has a weight average molecular weight of 400,000 or less.
• the silicone-based graft copolymer easily collects on the surface of the pressure-sensitive adhesive layer because it easily moves in the pressure-sensitive adhesive layer, thereby further reducing the increase in adhesion. can do.
• the upper limit of the polymerization average molecular weight of the silicone-based graft copolymer is more preferably 300,000, further more preferably 250,000, and particularly preferably 200,000, usually 10,000 or more.
• the content of the silicone-based graft copolymer is preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the pressure-sensitive adhesive. Adhesion enhancement can be further reduced when the content of the silicone-based graft copolymer is 0.1 parts by weight or more. When the content of the silicone-based graft copolymer is 30 parts by weight or less, the silicone-based graft copolymer can be sufficiently bonded to the pressure-sensitive adhesive, and contamination of the adherend can be further suppressed.
• the more preferred lower limit of the content of the silicone-based graft copolymer with respect to 100 parts by weight of the pressure-sensitive adhesive is 0.5 parts by weight
• the still more preferred lower limit is 1 part by weight
• the more preferred upper limit is 10 parts by weight.
• the upper limit is 5 parts by weight.
• the crosslinking agent can be appropriately selected from those capable of binding to the crosslinkable functional group of the pressure-sensitive adhesive and the silicone-based graft copolymer.
• an epoxy-type crosslinking agent, an isocyanate type crosslinking agent, etc. are mentioned, for example.
• an epoxy-based crosslinking agent is preferable because it is easy to adjust to the range of the shear storage modulus.
• the content of the crosslinking agent with respect to 100 parts by weight of the pressure-sensitive adhesive is such that a preferable lower limit is 0.5 parts by weight, a more preferable lower limit is 1 part by weight, a preferable upper limit is 5 parts by weight, and a more preferable upper limit is 3 parts by weight.
• a preferable lower limit is 0.5 parts by weight
• a more preferable lower limit is 1 part by weight
• a preferable upper limit is 5 parts by weight
• a more preferable upper limit is 3 parts by weight.
• the pressure-sensitive adhesive layer may contain known additives such as an inorganic filler such as fumed silica, a plasticizer, a resin, a surfactant, a wax, a fine particle filler, an antioxidant, and a gas generating agent.
• an inorganic filler such as fumed silica, a plasticizer, a resin, a surfactant, a wax, a fine particle filler, an antioxidant, and a gas generating agent.
• the thickness of the said adhesive layer is not specifically limited, It is preferable that a minimum is 5 micrometers and an upper limit is 100 micrometers. When the thickness of the pressure-sensitive adhesive layer is within the above range, it can be attached to the adherend with sufficient adhesive force, and adhesive residue at the time of peeling can be further suppressed.
• the minimum with more preferable thickness of the said adhesive layer is 10 micrometers, and a more preferable upper limit is 60 micrometers.
• the method for producing the pressure-sensitive adhesive tape according to one embodiment of the present invention is not particularly limited, and a conventionally known method can be used.
• it can be produced by coating and drying the solution of the above-mentioned pressure-sensitive adhesive component on a film subjected to a release treatment.
• the application of the pressure-sensitive adhesive tape according to one embodiment of the present invention is not particularly limited, and examples thereof include the manufacture of electronic components such as semiconductor chips and display devices (such as OLEDs and liquid crystal display devices). Since it can be reduced and can be applied to an opaque material, it can be particularly suitably used as a protective tape in the manufacture of electronic components such as semiconductor chips.
• the use of the above-mentioned pressure-sensitive adhesive tape in the manufacture of electronic components is also provided.
• the adhesive tape can be advantageously used as a protective tape in the manufacture of electronic components using opaque materials, such as semiconductor chips.
• the adhesive tape which can be used also for the material which does not permeate
• a living radical polymerized acrylic polymer (adhesive A) -containing solution was obtained.
• the obtained adhesive A-containing solution was diluted 50 times with tetrahydrofuran (THF).
• THF tetrahydrofuran
• the obtained diluted solution is filtered through a filter, the filtrate is supplied to a gel permeation chromatograph, GPC measurement is performed under the conditions of a sample flow rate of 1 ml / min and a column temperature of 40 ° C., and the polystyrene equivalent molecular weight of the adhesive A is determined.
• the weight average molecular weight (Mw) and the molecular weight distribution (Mw / Mn) were determined by measurement.
• 2690 Separations Model made from Waters was used for the gel permeation chromatograph.
• a filter made of polytetrafluoroethylene and having a pore diameter of 0.2 ⁇ m was used.
• GPC KF-806L manufactured by Showa Denko
• a differential refractometer was used as the detector.
• bleed agent A which is a silicone-based graft copolymer
• Mw weight average molecular weight
• Mw / Mn molecular weight distribution
• the acid value was computed from the preparation amount of the monomer.
• Tg is the glass transition temperature (K) of the bleed agent A
• W1, W2,..., Wn are the weight fractions of each monomer
• Tg1, Tg2,..., Tgn are , The glass transition temperature of the homopolymer of each monomer.
• Example 1 Ethyl acetate is added to the resulting adhesive A-containing solution with respect to 100 parts by weight of the non-volatile content and stirred, and then the bleed agent A and the epoxy crosslinking agent are added in the types and blending amounts shown in Table 4.
• Table 4 An ethyl acetate solution of a pressure-sensitive adhesive composition having a nonvolatile content of 30% by weight.
• the coating solution was dried by heating at 110 ° C. for 5 minutes. Thereafter, static curing was performed at 40 ° C. for 3 days to obtain an adhesive tape.
• Mitsubishi Gas Chemical Co., Ltd. tetrad C was used as an epoxy type crosslinking agent.
• the contact angle with water was measured using a contact angle measuring device (CAM 200, manufactured by KSV). Specifically, the adhesive tape was cut into a width of 25 mm and used for measurement. 2 ⁇ L of water droplets (ultra pure water) were dropped onto the surface of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape placed horizontally in an environment of room temperature of 25 ° C. and humidity of 40%. The angle between the pure water and the pressure-sensitive adhesive layer surface after 5 seconds from the dropping was defined as the contact angle with water.
• CAM 200 manufactured by KSV
• the adhesive tape was cut to a width of 25 mm.
• the cut adhesive tape is applied to a glass adherend (manufactured by Matsunami Glass Industry Co., Ltd., large slide glass white edge polish No. 2) at a room temperature of 23 ° C. and a relative humidity of 50% using a 2 kg pressure rubber roller and a speed of 10 mm / SEC. Pasted with.
• the heat treatment at 220 ° C. for 120 minutes was performed once.
• the adhesive tape was peeled from the glass adherend, and the contact angle with water was measured using a contact angle measuring device (CAM 200, manufactured by KSV) in accordance with JIS R 3257: 1999.
• CAM 200 manufactured by KSV
• Examples 2 to 25, Comparative Examples 1 to 12 A pressure-sensitive adhesive tape was produced in the same manner as in Example 1 except that the types and amounts of the pressure-sensitive adhesive, bleed agent, and crosslinking agent used were as shown in Tables 4 to 6, and the water contact angle before heating and the water contact after heating. Angular and shear storage moduli were measured.
• the Tosoh company make and coronate L were used as an isocyanate type crosslinking agent.
• As the epoxy-modified silicone X-22-163C manufactured by Shin-Etsu Chemical Co., Ltd. was used.
• Nippon Polyurethane Industry Co., Ltd. coronate L45 was used as an isocyanate type crosslinking agent.
• the adhesive tape was cut to a width of 25 mm.
• the cut adhesive tape is applied to a glass adherend (manufactured by Matsunami Glass Industry Co., Ltd., large slide glass white edge polish No. 2) at a room temperature of 23 ° C. and a relative humidity of 50% using a 2 kg pressure-bonded rubber roller of 10 mm / SEC. Pasted at speed.
• the surface protective film was peeled off at a speed of 300 mm / min, and the 180-degree peel strength was measured.
• the adhesive tape was cut to a width of 25 mm.
• the cut adhesive tape is applied to a glass adherend (manufactured by Matsunami Glass Industry Co., Ltd., large slide glass white edge polish No. 2) at a room temperature of 23 ° C. and a relative humidity of 50% using a 2 kg pressure-bonded rubber roller of 10 mm / SEC. Pasted at speed.
• the heat treatment at 220 ° C. for 120 minutes was performed once.
• the surface protective film was peeled off at a rate of 300 mm / min, and the 180-degree peel strength was measured.
• the adhesive tape which can be used also for the material which does not permeate

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• 2019
  • 2019-05-27 JP JP2019534983A patent/JP7334117B2/ja active Active
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