WO2011033844A1 - Adhesive agent composition - Google Patents
Adhesive agent composition Download PDFInfo
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- WO2011033844A1 WO2011033844A1 PCT/JP2010/061579 JP2010061579W WO2011033844A1 WO 2011033844 A1 WO2011033844 A1 WO 2011033844A1 JP 2010061579 W JP2010061579 W JP 2010061579W WO 2011033844 A1 WO2011033844 A1 WO 2011033844A1
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- sensitive adhesive
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- 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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/625—Polymers of alpha-beta ethylenically unsaturated carboxylic acids; hydrolyzed polymers of esters of these acids
- C08G18/6254—Polymers of alpha-beta ethylenically unsaturated carboxylic acids and of esters of these acids containing hydroxy groups
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- 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
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
Definitions
- the present invention relates to a pressure-sensitive adhesive composition. More specifically, the present invention has a sufficient pressure-sensitive adhesive performance while using a polymer having a relatively small molecular weight, and can reduce the use amount of a volatile solvent and reduce the burden on the environment.
- the present invention relates to an adhesive composition.
- the pressure-sensitive adhesive it is effective to reduce the weight average molecular weight (Mw) of the polymer constituting the pressure-sensitive adhesive in order to increase the active ingredient ratio while maintaining good coating suitability.
- Mw weight average molecular weight
- the pressure-sensitive adhesive thus obtained has a lower viscosity than a high-molecular-weight polymer and can be adjusted to a viscosity that can be applied with relatively little solvent dilution, so that the amount of volatile solvent used can be greatly reduced. , Environmental burdens (solvent usage, CO 2 emissions during transportation, fuel usage), raw material costs during production, and the like can be reduced.
- the pressure-sensitive adhesive is composed of a polymer having a small Mw according to the conventional technique, there is a problem that a product that can withstand practical use cannot be obtained. That is, in order to impart practically cohesive strength to the pressure-sensitive adhesive while using a polymer having a small Mw as described above, it is necessary to blend a large amount of a crosslinking agent in the polymer. Since the ratio is too large, the pressure-sensitive adhesive layer becomes hard, the stringing phenomenon peculiar to the pressure-sensitive adhesive hardly occurs, and there is a problem that the adhesive strength to a curved adherend surface is remarkably reduced.
- Patent Document 1 describes a pressure-sensitive adhesive containing an acrylic acid alkyl ester monomer, a carboxyl group-containing monomer, and a polymerizable acid anhydride monomer as essential components.
- the polymer Mw is 40. It has been described that it is preferable to use a polymer with a small Mw. In fact, it is said that the tack force is large at 400,000 or less, the peel force immediately after pasting is large, and the re-tensioning property may be inferior. Indicates that there is no practicality.
- the present invention has been intensively studied on a copolymer used in an acrylic pressure-sensitive adhesive and a blend thereof.
- a polymer used in the pressure-sensitive adhesive a polymer having a heterogeneous sea-island structure is used. By using it, it was found that an adhesive having a low molecular weight and excellent adhesive properties was obtained, and the present invention was completed.
- the present invention provides the following components (A) and (B)
- Mw weight average molecular weight
- the present invention also provides the following components (A-1), (A-2) and (B) (A-1) First polymer having a weight average molecular weight (Mw) of 350,000 or less obtained by copolymerizing monomers (a′-1) to (a′-2) (a′-1) All monomer components (Meth) acrylic acid alkyl ester in an amount corresponding to 60 to 96 mass% (a′-2) hydroxy (meth) acrylic acid in an amount corresponding to 0.01 to 5 mass% with respect to all monomer components Alkyl ester (A-2) Second polymer (a′-3) having a weight average molecular weight (Mw) of 50,000 or less obtained by copolymerizing monomers (a′-3) to (a′-4) Carbonic acid vinyl ester in an amount corresponding to 3 to 30% by mass with respect to the monomer component (a'-4) Vinyl group-containing acid anhydride in an amount corresponding to 0.1 to 10% by mass with respect to the total monomer component (B) Including isocyanate crosslinking agent
- the present invention uses (meth) acrylic acid alkyl ester and carboxylic acid vinyl ester or vinyl group-containing acid anhydride which are poorly compatible with this as a monomer for copolymerization, these phases are used in the reaction system.
- a low molecular weight body in which only a monomer having poor solubility is copolymerized is produced, and a sea-island structure is formed in which the alkyl acrylate ester polymer is the sea and the carboxylic acid vinyl ester polymer is the island.
- a copolymer of a carboxylic acid vinyl ester and a vinyl group-containing acid anhydride is blended with an acrylic acid alkyl ester polymer.
- the pressure-sensitive adhesive composition of the present invention has such a sea structure in which mainly (meth) acrylic acid alkyl ester and hydroxy (meth) acrylic acid alkyl ester are copolymerized, and mainly carboxylic acid vinyl ester and vinyl group-containing acid. Since the polymer having an island structure copolymerized with an anhydride is used after cross-linking with an isocyanate, the cross-linking structure of the sea structure portion having a hydroxyl group highly reactive with the isocyanate group becomes dense, and conversely, the island structure portion is a cross-linking structure. Becomes sparse.
- the amount of solvent used in the production of the pressure-sensitive adhesive is reduced, and the proportion of non-volatile content in the pressure-sensitive adhesive is increased. Amount, CO 2 emission amount during transportation, fuel consumption amount) and manufacturing cost can be reduced.
- a polymer having a sea-island structure is used as a polymer to be used as an adhesive component, and there are two methods for forming such a polymer.
- the method is (A) The following monomers (a-1) to (a-4) (A-1) (Meth) acrylic acid alkyl ester 60 to 96% by mass (A-2) Hydroxy (meth) acrylic acid alkyl ester 0.01 to 5% by mass (A-3) Carboxylic acid vinyl ester 3 to 30% by mass (A-4) Vinyl group-containing acid anhydride 0.1 to 10% by mass And a method for obtaining an acrylic polymer having a weight average molecular weight (Mw) of 350,000 or less and (b) monomers (a′-1) and (a′-2) (A′-1) (meth) acrylic acid alkyl ester in an amount corresponding to 60 to 96% by mass relative to all monomer components (a′-2) corresponding to 0.01 to 5% by mass relative to all monomer components A first polymer (component (A-1)) having a weight average molecular weight (Mw) of 350,000 or less obtained by copolymerizing an amount of hydroxy (meth) acrylic acid alkyl ester Mono
- the preparation of the polymer by the method (a) is performed by polymerizing the monomers (a-1) to (a-4) and, if necessary, a monomer polymerizable with them in the same reaction vessel.
- the component (a-1) used is preferably a linear or branched (meth) acrylic acid alkyl ester having 1 to 18 carbon atoms in the alkyl group, specifically, methyl (meth) acrylate, (Meth) ethyl acrylate, (meth) propyl acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, ( Examples include 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, and lauryl (meth) acrylate. Of these, butyl acrylate and 2-ethylhexyl acrylate are preferably used because the glass transition temperature
- Component (a-2) includes 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.
- the monomer of component (a-3) includes vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, cyclohexanecarboxylic acid.
- vinyl esters such as vinyl, vinyl pivalate, vinyl octylate, vinyl monochloroacetate, vinyl methacrylate, vinyl crotonate, vinyl sorbate, vinyl benzoate, and vinyl cinnamate.
- Vinyl acetate is preferably used from the viewpoint of dispersibility, polymerizability, and availability.
- examples of the component (a-4) include vinyl group-containing acid anhydrides such as maleic anhydride, itaconic anhydride, and tetrahydrophthalic anhydride.
- (meth) of (a-1) Maleic anhydride is preferably used because it has a good balance in the difference in compatibility with the alkyl acrylate ester and easily forms a sea-island structure.
- component (a-1) is 60 to 96% by mass (hereinafter referred to as “%”) in all monomer components
- component (a-2) is 0.01 to 5%
- component (a-3) is 3 to 30%
- component (a-4) is 0.1 to 10%.
- the monomer polymerization reaction itself can be carried out by a conventionally known method. However, if the Mw of the obtained polymer exceeds 350,000, the amount of solvent used in the production of the pressure-sensitive adhesive can be reduced, as in the prior art. Therefore, it is necessary to establish appropriate polymerization conditions experimentally and to set Mw to 350,000 or less.
- a polymerization reaction is controlled using a chain transfer agent such as normal dodecyl mercaptan, or a solvent such as methyl ethyl ketone having a large chain transfer constant is used as a polymerization solvent.
- a chain transfer agent such as normal dodecyl mercaptan
- a solvent such as methyl ethyl ketone having a large chain transfer constant is used as a polymerization solvent.
- polymerizing etc. is mentioned.
- the polymer prepared by the above method (a) is composed of a monomer (a-1) (meth) acrylic acid alkyl ester and a (a-2) hydroxy (meth) acrylic acid alkyl ester, and a monomer (a- 3) Since the compatibility with the carboxylic acid vinyl ester and (a-4) vinyl group-containing acid anhydride is poor, the polymer formed mainly of the monomers (a-1) and (a-2) is a sea component, A sea-island structure having a polymer formed mainly of monomers (a-3) and (a-4) as island components is obtained.
- Whether the polymer obtained by the above method has a sea-island structure is determined by, for example, separating a component having an Mw of 50,000 or less from this polymer by GPC or the like, and then analyzing the component by GC-MS or the like. It can confirm that the content rate of the carboxylic acid vinyl ester in a component is 70% or more.
- the preparation of the polymer by the method (b) requires the monomers (a′-1) and (a′-2) and the monomers (a′-3) and (a′-4) separately.
- a polymerizable monomer to polymerize a first polymer having an Mw of 350,000 or less and a second polymer having an Mw of 50,000 or less, and then blending them.
- Monomer (a′-1), monomer (a′-2), monomer (a′-3) and (a′-4) used in method (b) are the monomers used in method (a), respectively. These are the same corresponding to (a-1), monomer (a-2), monomers (a-3) and (a-4).
- the polymerization reaction itself for obtaining the first polymer and the second polymer can be carried out by a conventionally known method, but it is necessary to make Mw 350,000 or less and 50,000 or less, respectively. It is necessary to establish proper polymerization conditions.
- the polymerization reaction is controlled using a chain transfer agent such as normal dodecyl mercaptan, or a solvent such as methyl ethyl ketone having a large chain transfer constant is used as a polymerization solvent.
- a chain transfer agent such as normal dodecyl mercaptan
- a solvent such as methyl ethyl ketone having a large chain transfer constant
- examples thereof include a polymerization method.
- the first polymer and the second polymer thus obtained are then blended according to a conventional method to form a pressure-sensitive adhesive polymer.
- the polymer obtained by the above method (a) or method (b) can be further crosslinked with an isocyanate-based crosslinking agent as component (B) to obtain a pressure-sensitive adhesive composition.
- isocyanate-based crosslinking agent for component (B) used for this crosslinking examples include tolylene diisocyanate, chlorophenylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, water Isocyanate monomers such as diphenylmethane diisocyanate added and isocyanate compounds, isocyanurate compounds, burette type compounds obtained by adding these isocyanate monomers with trimethylolpropane, etc., as well as polyether polyols, polyester polyols, acrylic polyols, polybutadiene polyols, polyisoprene polyols Urethane prepolymer-type isocyanate produced by addition reaction Etc. The.
- the amount of component (B) used is about 0.5 to 5 parts by weight, preferably 1.0 to 3.0 parts by weight, based on 100 parts by weight of the solid content of the polymer. It is.
- the pressure-sensitive adhesive composition of the present invention includes a tackifier resin, an antioxidant, an ultraviolet absorber, a plasticizer, an antistatic agent, a flame retardant, and a filler as necessary within the range that does not impair the effects of the present invention. You may mix
- the reason why the polymer used as a pressure-sensitive adhesive has a sufficient adhesion performance even though the Mw of the polymer is smaller than that of a conventional polymer is that it has a sea-island structure, and the sea component and the island component have different functions.
- the sea component is mainly composed of an acrylic acid alkyl ester polymer, but by incorporating a hydroxy (meth) acrylic acid alkyl ester into this, a hydroxyl group as a crosslinking point is introduced.
- the island component is mainly composed of a carboxylic acid vinyl ester polymer. By incorporating maleic anhydride into this, a carboxyl group as a crosslinking point is introduced.
- the crosslinking ratio is estimated to be in the relationship of sea component> island component.
- the sea component is a low-molecular-high bridge and has a strong and cohesive property
- the island component is an ultra-low molecule-low-crosslink and has a flexible and stringing property. It is considered that the sea part and the island part have the characteristics that the toughness and the flexibility are contradictory, so that the adhesive part has excellent adhesive performance even though the Mw is small.
- Example 1 In a reactor equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube, 40 parts by weight of butyl acrylate (BA), 49 parts by weight of 2-ethylhexyl acrylate (2EHA), 2-hydroxyethyl acrylate (2HEA) 0.5 parts by weight, vinyl acetate (VAc) 10 parts by weight, maleic anhydride (MM) 1 part by weight, chain transfer agent normal dodecyl mercaptan (NDM) 0.025 part by weight and methyl ethyl ketone (MEK) 50 parts by weight The air in the reaction vessel was replaced with nitrogen gas.
- BA butyl acrylate
- EHA 2-ethylhexyl acrylate
- 2HEA 2-hydroxyethyl acrylate
- VAc vinyl acetate
- MM maleic anhydride
- NDM chain transfer agent normal dodecyl mercaptan
- MEK methyl ethyl
- a polymerized rosin ester resin DP2669 (manufactured by Rika Finetech Co., Ltd.), which is a tackifier resin, is an isocyanate-based crosslinking agent with respect to 100 parts by weight of the solid content of the obtained acrylic polymer (1) solution.
- Coronate L (manufactured by Nippon Polyurethane Industry Co., Ltd.) was added so that the active ingredient was 1.4 parts by weight to obtain a pressure-sensitive adhesive composition.
- the obtained pressure-sensitive adhesive composition was coated on a paper separator so that the thickness after drying was 65 ⁇ m, dried at 80 ° C. for 2 minutes, transferred to both surfaces of the nonwoven fabric, and 23 ° C., 65%. Was aged for 7 days to obtain a nonwoven fabric double-sided PSA sheet having a tape thickness of 145 ⁇ m.
- Examples 2 to 8 and Comparative Examples 1 to 9 According to the composition shown in Table 1, the pressure-sensitive adhesive compositions of Examples 2 to 8 and Comparative Examples 1 to 9 were obtained according to Example 1. This was made into the nonwoven fabric double-sided adhesive sheet by the method described in Example 1.
- AA Acrylic acid DP2669: Polymerized rosin ester resin (manufactured by Rika Finetech Co., Ltd.)
- TR-105 Terpene resin (YS resin TR-105; manufactured by Yasuhara Chemical Co., Ltd.)
- SEA-100 Rosin ester resin (Superester A-100; Arakawa Chemical Industries, Ltd.)
- CL Isocyanate-based crosslinking agent (Coronate L; manufactured by Nippon Polyurethane Co., Ltd.)
- TX Epoxy crosslinking agent (Tetrad X; manufactured by Mitsubishi Gas Chemical Co., Inc.)
- MA Metal chelate crosslinking agent (Narsem Aluminum; Nippon Chemical Industry Co., Ltd.) Made)
- Test example 1 The nonwoven fabric double-sided PSA sheets prepared in Examples 1 to 8 and Comparative Examples 1 to 9 were tested for adhesive strength, holding power and constant load by the following methods. The results are shown in Table 2.
- Adhesive force The paper separator on one side of the obtained double-sided pressure-sensitive adhesive sheet was peeled off, and a 25 ⁇ m-released polyethylene terephthalate film was bonded to the peeled pressure-sensitive adhesive layer to obtain a pressure-sensitive adhesive sheet.
- the obtained adhesive sheet was cut into a size of 25 mm ⁇ 150 mm to obtain a test piece.
- the paper separator was peeled off from this test piece, bonded to a SUS plate and a PP plate, respectively, and reciprocally pressed with a 2 kg roller, and allowed to stand in an environment of 23 ° C. and 65% for 20 minutes. 180 degree peel strength (g / 25 mm) was measured in min.
- a pressure-sensitive adhesive sheet was prepared in the same manner as described above, and cut into a width of 20 mm to prepare a test piece.
- the paper separator is peeled off from this test piece and attached to a SUS plate so that an area of 20 mm ⁇ 20 mm is in contact, and the size (mm) or drop when left for 60 minutes at a temperature of 80 ° C. and a load of 1 kg. The time until was measured ( ⁇ in the table means falling).
- a pressure-sensitive adhesive sheet was prepared in the same manner as described above, and cut into a size of 20 ⁇ 50 mm to prepare a test piece.
- the paper separator is peeled off from this test piece and bonded to an SUS plate and a PP plate, respectively, and a load of 200 g is applied in the direction of 90 ° at a temperature of 80 ° C., and the peeling distance (mm) when left for 60 minutes or until dropping. Time was measured ( ⁇ in the table means falling).
- the viscosity of the pressure-sensitive adhesive composition is measured with a B-type viscometer. When the viscosity is less than 200 poise (25 ° C.), the coating property is good ( ⁇ ), and the viscosity is 200 poise (25 ° C.) or more. Evaluated as defective (x).
- CO 2 emissions (kg) fuel consumption (L) x CO 2 emission factor CO 2 emission factor: 2.62 Fuel consumption: 3.5km / L
- the (meth) acrylic acid alkyl ester as the component (a-1) of the present invention of Examples 1 to 8, the hydroxy (meth) acrylic acid alkyl ester as the component (a-2), the component (a- 3) A pressure-sensitive adhesive composition obtained by crosslinking a low molecular weight acrylic polymer obtained by copolymerizing a predetermined amount of a carboxylic acid vinyl ester (3) and a vinyl group-containing acid anhydride (a-4) with an isocyanate crosslinking agent.
- the product was found to be a pressure-sensitive adhesive composition having a low molecular weight and good adhesive performance, and further reducing the load on the environment due to the small amount of solvent used.
- Comparative Example 1 in which the carboxylic acid vinyl ester of component (a-3) was not copolymerized was insufficient in formation of the sea-island structure, so that sufficient adhesion performance could not be exhibited, and the holding power The pressure-sensitive adhesive composition was inferior in constant load peelability.
- Comparative Example 2 where the vinyl group-containing acid anhydride of component (a-4) was not copolymerized, the sea-island structure was formed, but the functional group serving as a cross-linking point was substantially present in the island-structured polymer. For this reason, the obtained pressure-sensitive adhesive composition was inferior in constant load peelability.
- Comparative Example 3 in which the hydroxy (meth) acrylic acid alkyl ester of component (a-2) was not copolymerized, the polymer that forms the sea part of the sea-island structure has almost no functional group serving as a crosslinking point. Even when the isocyanate-based crosslinking agent (B) was added, sufficient cohesive force could not be imparted, and the pressure-sensitive adhesive composition was inferior in both holding power and constant load peelability. Further, in Comparative Examples 5 and 6 using an epoxy crosslinking agent and a metal chelate crosslinking agent in place of the isocyanate crosslinking agent of component (B), there is a difference in crosslinking density between the sea part and the island part of the sea-island structure. Therefore, the toughness derived from the sea part and the flexibility derived from the island part cannot be achieved, and the pressure-sensitive adhesive composition is inferior in the constant load peelability.
- Comparative Examples 7 and 8 using a polymer having an Mw of 500,000 the amount of solvent used is increased in Comparative Example 7 in which the solvent is diluted to the extent that coating is possible and the solid content concentration is 45%.
- the amount of CO 2 emission and the amount of fuel used increase, resulting in a high environmental load.
- Comparative Example 8 in which the solid content concentration is 70% in order to reduce the amount of solvent used the workability is high because the viscosity is too high. It was bad and it became an adhesive composition which had a problem in coating property, such as film thickness becoming non-uniform
- Example 9 A reactor equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube was charged with 45 parts by weight of butyl acrylate (BA), 55 parts by weight of 2-ethylhexyl acrylate (2EHA), and 2-hydroxyethyl acrylate. (2HEA) 0.5 parts by weight, normal transfer decyl mercaptan (NDM) 0.040 parts by weight and methyl ethyl ketone (MEK) 50 parts by weight were charged, and the air in the reaction vessel was replaced with nitrogen gas.
- BA butyl acrylate
- 2EHA 2-ethylhexyl acrylate
- 2-hydroxyethyl acrylate 2-hydroxyethyl acrylate
- 2HEA normal transfer decyl mercaptan
- MEK methyl ethyl ketone
- reaction vessel was raised to 70 ° C.
- 0.1 part by weight of initiator azobisisobutyronitrile (AIBN) was added, and the mixture was reacted for 1 hour.
- AIBN initiator azobisisobutyronitrile
- 0.1 part by weight of AIBN was added and reacted for 2 hours while raising the reaction temperature to 80 ° C.
- 0.2 part by weight of AIBN was added, and the reaction was carried out for 3 hours while maintaining the reaction temperature at 80 ° C.
- the temperature of the reaction vessel was raised to 70 ° C., 0.2 part by weight of an initiator azobisisobutyronitrile (AIBN) was added, and the mixture was reacted for 1 hour. Thereafter, 0.2 part by weight of AIBN was added, and the reaction was carried out for 2 hours while raising the reaction temperature to 80 ° C. Further, 0.4 part by weight of AIBN was added and reacted for 3 hours while maintaining the reaction temperature at 80 ° C. to obtain an acrylic polymer solution (3) having a weight average molecular weight of 35,000.
- AIBN initiator azobisisobutyronitrile
- the obtained pressure-sensitive adhesive composition was made into a nonwoven fabric double-sided pressure-sensitive adhesive sheet by the method described in Example 1, and evaluated by the method described in Test Examples. The results are shown in Table 3.
- the polymer obtained by the blending method from polymer 1 (component (A-1)) and polymer 2 (component (A-2)) has the same characteristics as the polymer having a sea-island structure obtained by copolymerization. It became clear that the adhesive composition which has this was obtained.
- the present invention it is possible to obtain a pressure-sensitive adhesive composition having no problem with the adhesiveness even if the polymer Mw constituting the pressure-sensitive adhesive is smaller than the conventional one. And since Mw of a polymer component is small, the solvent amount at the time of preparing an adhesive composition can be reduced, and the effect excellent in the environmental aspect and the cost side can be acquired.
- the pressure-sensitive adhesive composition of the present invention can be widely used in place of the conventional pressure-sensitive adhesive composition as having excellent environmental properties and economy.
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Abstract
Disclosed is an adhesive agent composition which has a satisfactory level of adhesion performance even though a polymer having a relatively small molecular weight is used, and in which the amount of a volatile solvent used can be reduced. The adhesive agent composition is characterized by comprising the following components (A) and (B).
(A) An acrylic polymer which is produced by the copolymerization of the monomers (a-1) to (a-4) mentioned below and has a weight average molecular weight (Mw) of 350,000 or less: (a-1) 60 to 96 mass% of a (meth)acrylic acid alkyl ester; (a-2) 0.01 to 5 mass% of a hydroxy(meth)acrylic acid alkyl ester; (a-3) 3 to 30 mass% of a carboxylic acid vinyl ester; and (a-4) 0.1 to 10 mass% of an acid anhydride containing a vinyl group.
(B) An isocyanate-type cross-linking agent.
Description
本発明は粘着剤組成物に関し、更に詳細には、比較的分子量の小さいポリマーを用いながら十分な粘着性能を有し、揮発性溶剤の使用量を減少させ環境への負荷を低減することのできる粘着剤組成物に関する。
The present invention relates to a pressure-sensitive adhesive composition. More specifically, the present invention has a sufficient pressure-sensitive adhesive performance while using a polymer having a relatively small molecular weight, and can reduce the use amount of a volatile solvent and reduce the burden on the environment. The present invention relates to an adhesive composition.
粘着剤において、良好な塗工適性を維持しつつ有効成分比率をアップさせるには、粘着剤を構成するポリマーの重量平均分子量(Mw)を小さくすることが有効である。そして、このようにして得られた粘着剤は、高分子量ポリマーに比べて粘度が低く比較的少ない溶剤希釈で塗工可能な粘度に調整できるため揮発性溶剤の使用量を大幅に減らすことができ、環境への負荷(溶剤使用量、輸送時のCO2排出量、燃料使用量)や、製造時の原料コスト等を低減することができる。
In the pressure-sensitive adhesive, it is effective to reduce the weight average molecular weight (Mw) of the polymer constituting the pressure-sensitive adhesive in order to increase the active ingredient ratio while maintaining good coating suitability. The pressure-sensitive adhesive thus obtained has a lower viscosity than a high-molecular-weight polymer and can be adjusted to a viscosity that can be applied with relatively little solvent dilution, so that the amount of volatile solvent used can be greatly reduced. , Environmental burdens (solvent usage, CO 2 emissions during transportation, fuel usage), raw material costs during production, and the like can be reduced.
しかしながら、従来技術によりMwの小さいポリマーで粘着剤を構成した場合、実用に耐えるものが得られないという問題があった。すなわち、上記したようなMwの小さいポリマーを使用しながら粘着剤に実用に耐えうる凝集力を付与するには、ポリマー中に架橋剤を多量に配合することが必要であるが、その場合、架橋割合が多くなりすぎるため、粘着剤層が硬くなり、粘着剤特有の糸引き現象が生じ難く、曲面のある被着面に対しての接着強度が著しく低下してしまうという問題があった。
However, when the pressure-sensitive adhesive is composed of a polymer having a small Mw according to the conventional technique, there is a problem that a product that can withstand practical use cannot be obtained. That is, in order to impart practically cohesive strength to the pressure-sensitive adhesive while using a polymer having a small Mw as described above, it is necessary to blend a large amount of a crosslinking agent in the polymer. Since the ratio is too large, the pressure-sensitive adhesive layer becomes hard, the stringing phenomenon peculiar to the pressure-sensitive adhesive hardly occurs, and there is a problem that the adhesive strength to a curved adherend surface is remarkably reduced.
このため、理論的にはMwの小さいポリマーの利用が好ましいものの、このようなものを用いた粘着剤は提供されていないのが実情である。例えば、特許文献1には、アクリル酸アルキルエステルモノマー、カルボキシル基含有モノマーおよび重合性酸無水物モノマーを必須成分とする粘着剤が記載されているが、この文献中には、ポリマーのMwは40万以上が好ましいと記載しており、40万以下ではタック力が大きくなり、貼り付け直後の剥離力が大きくなり張り直し性に劣る場合があるとされており、事実上Mwの小さいポリマーの利用は実用性がないことを示している。
For this reason, although it is theoretically preferable to use a polymer having a small Mw, the actual situation is that an adhesive using such a polymer is not provided. For example, Patent Document 1 describes a pressure-sensitive adhesive containing an acrylic acid alkyl ester monomer, a carboxyl group-containing monomer, and a polymerizable acid anhydride monomer as essential components. In this document, the polymer Mw is 40. It has been described that it is preferable to use a polymer with a small Mw. In fact, it is said that the tack force is large at 400,000 or less, the peel force immediately after pasting is large, and the re-tensioning property may be inferior. Indicates that there is no practicality.
従って、比較的分子量の小さいポリマーを用いながら十分な粘着性能を有し、揮発性溶剤の使用量を減少させることのできる粘着剤組成物が求められており、本発明の課題は、このような組成物を提供することである。
Accordingly, there is a need for a pressure-sensitive adhesive composition that has sufficient adhesive performance while using a polymer having a relatively low molecular weight and that can reduce the amount of volatile solvent used. It is to provide a composition.
本発明は、上記課題を解決すべく、アクリル系粘着剤で用いる共重合体や、そのブレンドに関し、鋭意検討を行っていたところ、粘着剤で用いるポリマーとして不均一系の海島構造を有するものを利用することにより、低分子量でありながら、粘着物性に優れた粘着剤が得られることを見出し、本発明を完成した。
In order to solve the above problems, the present invention has been intensively studied on a copolymer used in an acrylic pressure-sensitive adhesive and a blend thereof. As a polymer used in the pressure-sensitive adhesive, a polymer having a heterogeneous sea-island structure is used. By using it, it was found that an adhesive having a low molecular weight and excellent adhesive properties was obtained, and the present invention was completed.
すなわち本発明は、下記成分(A)および(B)
(A)次のモノマー(a-1)ないし(a-4)を共重合させることにより得られる重
量平均分子量(Mw)35万以下のアクリル系ポリマー
(a-1)(メタ)アクリル酸アルキルエステル 60~96質量%
(a-2)ヒドロキシ(メタ)アクリル酸アルキルエステル
0.01~5質量%
(a-3)カルボン酸ビニルエステル 3~30質量%
(a-4)ビニル基含有酸無水物 0.1~10質量%
(B)イソシアネート系架橋剤
を含有する粘着剤組成物である。 That is, the present invention provides the following components (A) and (B)
(A) Acrylic polymer having a weight average molecular weight (Mw) of 350,000 or less obtained by copolymerizing the following monomers (a-1) to (a-4): (a-1) alkyl (meth) acrylate Esters 60-96 mass%
(A-2) Hydroxy (meth) acrylic acid alkyl ester 0.01 to 5% by mass
(A-3) Carboxylic acid vinyl ester 3 to 30% by mass
(A-4) Vinyl group-containing acid anhydride 0.1 to 10% by mass
(B) A pressure-sensitive adhesive composition containing an isocyanate-based crosslinking agent.
(A)次のモノマー(a-1)ないし(a-4)を共重合させることにより得られる重
量平均分子量(Mw)35万以下のアクリル系ポリマー
(a-1)(メタ)アクリル酸アルキルエステル 60~96質量%
(a-2)ヒドロキシ(メタ)アクリル酸アルキルエステル
0.01~5質量%
(a-3)カルボン酸ビニルエステル 3~30質量%
(a-4)ビニル基含有酸無水物 0.1~10質量%
(B)イソシアネート系架橋剤
を含有する粘着剤組成物である。 That is, the present invention provides the following components (A) and (B)
(A) Acrylic polymer having a weight average molecular weight (Mw) of 350,000 or less obtained by copolymerizing the following monomers (a-1) to (a-4): (a-1) alkyl (meth) acrylate Esters 60-96 mass%
(A-2) Hydroxy (meth) acrylic acid alkyl ester 0.01 to 5% by mass
(A-3) Carboxylic acid vinyl ester 3 to 30% by mass
(A-4) Vinyl group-containing acid anhydride 0.1 to 10% by mass
(B) A pressure-sensitive adhesive composition containing an isocyanate-based crosslinking agent.
また本発明は、下記成分(A-1)、(A-2)及び(B)
(A-1)モノマー(a'-1)ないし(a'-2)を共重合させることに
より得られる重量平均分子量(Mw)35万以下の第1ポリマー
(a'-1)全モノマー成分に対し、60~96質量%に該当する量の
(メタ)アクリル酸アルキルエステル
(a'-2)全モノマー成分に対し、0.01~5質量%に該当する量の
ヒドロキシ(メタ)アクリル酸アルキルエステル
(A-2)モノマー(a'-3)ないし(a'-4)を共重合させることに
より得られる重量平均分子量(Mw)5万以下の第2ポリマー
(a'―3)全モノマー成分に対し、3~30質量%に該当する量のカル
ボン酸ビニルエステル
(a'-4)全モノマー成分に対し、0.1~10質量%に該当する量の
ビニル基含有酸無水物
(B)イソシアネート系架橋剤
を含有する粘着剤組成物である。 The present invention also provides the following components (A-1), (A-2) and (B)
(A-1) First polymer having a weight average molecular weight (Mw) of 350,000 or less obtained by copolymerizing monomers (a′-1) to (a′-2) (a′-1) All monomer components (Meth) acrylic acid alkyl ester in an amount corresponding to 60 to 96 mass% (a′-2) hydroxy (meth) acrylic acid in an amount corresponding to 0.01 to 5 mass% with respect to all monomer components Alkyl ester (A-2) Second polymer (a′-3) having a weight average molecular weight (Mw) of 50,000 or less obtained by copolymerizing monomers (a′-3) to (a′-4) Carbonic acid vinyl ester in an amount corresponding to 3 to 30% by mass with respect to the monomer component (a'-4) Vinyl group-containing acid anhydride in an amount corresponding to 0.1 to 10% by mass with respect to the total monomer component (B) Including isocyanate crosslinking agent A pressure-sensitive adhesive composition.
(A-1)モノマー(a'-1)ないし(a'-2)を共重合させることに
より得られる重量平均分子量(Mw)35万以下の第1ポリマー
(a'-1)全モノマー成分に対し、60~96質量%に該当する量の
(メタ)アクリル酸アルキルエステル
(a'-2)全モノマー成分に対し、0.01~5質量%に該当する量の
ヒドロキシ(メタ)アクリル酸アルキルエステル
(A-2)モノマー(a'-3)ないし(a'-4)を共重合させることに
より得られる重量平均分子量(Mw)5万以下の第2ポリマー
(a'―3)全モノマー成分に対し、3~30質量%に該当する量のカル
ボン酸ビニルエステル
(a'-4)全モノマー成分に対し、0.1~10質量%に該当する量の
ビニル基含有酸無水物
(B)イソシアネート系架橋剤
を含有する粘着剤組成物である。 The present invention also provides the following components (A-1), (A-2) and (B)
(A-1) First polymer having a weight average molecular weight (Mw) of 350,000 or less obtained by copolymerizing monomers (a′-1) to (a′-2) (a′-1) All monomer components (Meth) acrylic acid alkyl ester in an amount corresponding to 60 to 96 mass% (a′-2) hydroxy (meth) acrylic acid in an amount corresponding to 0.01 to 5 mass% with respect to all monomer components Alkyl ester (A-2) Second polymer (a′-3) having a weight average molecular weight (Mw) of 50,000 or less obtained by copolymerizing monomers (a′-3) to (a′-4) Carbonic acid vinyl ester in an amount corresponding to 3 to 30% by mass with respect to the monomer component (a'-4) Vinyl group-containing acid anhydride in an amount corresponding to 0.1 to 10% by mass with respect to the total monomer component (B) Including isocyanate crosslinking agent A pressure-sensitive adhesive composition.
本発明は、共重合させる際のモノマーとして、(メタ)アクリル酸アルキルエステルおよびこれと相溶性が悪いカルボン酸ビニルエステルやビニル基含有酸無水物を利用するため、反応系中において、これらの相溶性の悪いモノマーだけが共重合された低分子量体が生成され、アクリル酸アルキルエステル系ポリマーを海、カルボン酸ビニルエステル系ポリマーを島とする海島構造が形成される。このことは、カルボン酸ビニルエステルとビニル基含有酸無水物との共重合物をアクリル酸アルキルエステル系ポリマーにブレンドした場合も同様である。
Since the present invention uses (meth) acrylic acid alkyl ester and carboxylic acid vinyl ester or vinyl group-containing acid anhydride which are poorly compatible with this as a monomer for copolymerization, these phases are used in the reaction system. A low molecular weight body in which only a monomer having poor solubility is copolymerized is produced, and a sea-island structure is formed in which the alkyl acrylate ester polymer is the sea and the carboxylic acid vinyl ester polymer is the island. The same applies to the case where a copolymer of a carboxylic acid vinyl ester and a vinyl group-containing acid anhydride is blended with an acrylic acid alkyl ester polymer.
本発明の粘着剤組成物は、このような主に(メタ)アクリル酸アルキルエステルとヒドロキシ(メタ)アクリル酸アルキルエステルが共重合された海構造と、主にカルボン酸ビニルエステルとビニル基含有酸無水物とが共重合された島構造を有するポリマーをイソシアネート架橋して利用するため、イソシアネート基と反応性の高い水酸基を有する海構造部分の架橋構造が密となり、逆に島構造部分は架橋構造が疎となる。このように海島構造を有するポリマーに架橋構造の違いを持たせることで、従来の溶剤型アクリル系粘着剤においては困難であるとされていた、低分子量でありながら粘着物性に優れた粘着剤となるのである。
The pressure-sensitive adhesive composition of the present invention has such a sea structure in which mainly (meth) acrylic acid alkyl ester and hydroxy (meth) acrylic acid alkyl ester are copolymerized, and mainly carboxylic acid vinyl ester and vinyl group-containing acid. Since the polymer having an island structure copolymerized with an anhydride is used after cross-linking with an isocyanate, the cross-linking structure of the sea structure portion having a hydroxyl group highly reactive with the isocyanate group becomes dense, and conversely, the island structure portion is a cross-linking structure. Becomes sparse. Thus, by giving the polymer having a sea-island structure a difference in the cross-linking structure, it is said that it is difficult in the conventional solvent-type acrylic pressure-sensitive adhesive, and has a low molecular weight and excellent pressure-sensitive adhesive properties. It becomes.
そして本発明では、海島構造を有するMwの低いポリマーを利用する結果、粘着剤製造の際の溶剤の使用量を減らし、粘着剤中の不揮発分の割合が高まるため、環境への負荷(溶剤使用量、輸送時のCO2排出量、燃料使用量)を低減し、製造コストを下げることが可能となる。
And in the present invention, as a result of using a low Mw polymer having a sea-island structure, the amount of solvent used in the production of the pressure-sensitive adhesive is reduced, and the proportion of non-volatile content in the pressure-sensitive adhesive is increased. Amount, CO 2 emission amount during transportation, fuel consumption amount) and manufacturing cost can be reduced.
本発明においては、粘着剤成分として利用するポリマーとして海島構造を有するものを利用するが、このようなポリマーを形成させる方法として、2つの方法が挙げられる。
In the present invention, a polymer having a sea-island structure is used as a polymer to be used as an adhesive component, and there are two methods for forming such a polymer.
その方法は、
(イ)下記モノマー(a-1)ないし(a-4)
(a-1)(メタ)アクリル酸アルキルエステル 60~96質量%
(a-2)ヒドロキシ(メタ)アクリル酸アルキルエステル
0.01~5質量%
(a-3)カルボン酸ビニルエステル 3~30質量%
(a-4)ビニル基含有酸無水物 0.1~10質量%
を共重合させ、重量平均分子量(Mw)35万以下のアクリル系ポリマーを得る方法
および
(ロ)モノマー(a'-1)および(a'-2)
(a'-1)全モノマー成分に対し、60~96質量%に該当する量の
(メタ)アクリル酸アルキルエステル
(a'-2)全モノマー成分に対し、0.01~5質量%に該当する量の
ヒドロキシ(メタ)アクリル酸アルキルエステル
を共重合させることにより得られる重量平均分子量(Mw)35万以下の第1ポリマー(成分(A-1))と、
モノマー(a'-3)および(a'-4)
(a'―3)全モノマー成分に対し、3~30質量%に該当する量のカル
ボン酸ビニルエステル
(a'-4)全モノマー成分に対し、0.1~10質量%に該当する量の
ビニル基含有酸無水物
を共重合させることにより得られる重量平均分子量(Mw)5万以下の第2ポリマー(成分(A-2))
を別個に調製し、これをブレンドする方法である。 The method is
(A) The following monomers (a-1) to (a-4)
(A-1) (Meth) acrylic acid alkyl ester 60 to 96% by mass
(A-2) Hydroxy (meth) acrylic acid alkyl ester 0.01 to 5% by mass
(A-3) Carboxylic acid vinyl ester 3 to 30% by mass
(A-4) Vinyl group-containing acid anhydride 0.1 to 10% by mass
And a method for obtaining an acrylic polymer having a weight average molecular weight (Mw) of 350,000 or less and (b) monomers (a′-1) and (a′-2)
(A′-1) (meth) acrylic acid alkyl ester in an amount corresponding to 60 to 96% by mass relative to all monomer components (a′-2) corresponding to 0.01 to 5% by mass relative to all monomer components A first polymer (component (A-1)) having a weight average molecular weight (Mw) of 350,000 or less obtained by copolymerizing an amount of hydroxy (meth) acrylic acid alkyl ester
Monomers (a′-3) and (a′-4)
(A′-3) Carbonic acid vinyl ester in an amount corresponding to 3 to 30% by mass with respect to all monomer components (a′-4) Amount corresponding to 0.1 to 10% by mass with respect to all monomer components A second polymer having a weight average molecular weight (Mw) of 50,000 or less (component (A-2)) obtained by copolymerizing a vinyl group-containing acid anhydride
Are prepared separately and blended.
(イ)下記モノマー(a-1)ないし(a-4)
(a-1)(メタ)アクリル酸アルキルエステル 60~96質量%
(a-2)ヒドロキシ(メタ)アクリル酸アルキルエステル
0.01~5質量%
(a-3)カルボン酸ビニルエステル 3~30質量%
(a-4)ビニル基含有酸無水物 0.1~10質量%
を共重合させ、重量平均分子量(Mw)35万以下のアクリル系ポリマーを得る方法
および
(ロ)モノマー(a'-1)および(a'-2)
(a'-1)全モノマー成分に対し、60~96質量%に該当する量の
(メタ)アクリル酸アルキルエステル
(a'-2)全モノマー成分に対し、0.01~5質量%に該当する量の
ヒドロキシ(メタ)アクリル酸アルキルエステル
を共重合させることにより得られる重量平均分子量(Mw)35万以下の第1ポリマー(成分(A-1))と、
モノマー(a'-3)および(a'-4)
(a'―3)全モノマー成分に対し、3~30質量%に該当する量のカル
ボン酸ビニルエステル
(a'-4)全モノマー成分に対し、0.1~10質量%に該当する量の
ビニル基含有酸無水物
を共重合させることにより得られる重量平均分子量(Mw)5万以下の第2ポリマー(成分(A-2))
を別個に調製し、これをブレンドする方法である。 The method is
(A) The following monomers (a-1) to (a-4)
(A-1) (Meth) acrylic acid alkyl ester 60 to 96% by mass
(A-2) Hydroxy (meth) acrylic acid alkyl ester 0.01 to 5% by mass
(A-3) Carboxylic acid vinyl ester 3 to 30% by mass
(A-4) Vinyl group-containing acid anhydride 0.1 to 10% by mass
And a method for obtaining an acrylic polymer having a weight average molecular weight (Mw) of 350,000 or less and (b) monomers (a′-1) and (a′-2)
(A′-1) (meth) acrylic acid alkyl ester in an amount corresponding to 60 to 96% by mass relative to all monomer components (a′-2) corresponding to 0.01 to 5% by mass relative to all monomer components A first polymer (component (A-1)) having a weight average molecular weight (Mw) of 350,000 or less obtained by copolymerizing an amount of hydroxy (meth) acrylic acid alkyl ester
Monomers (a′-3) and (a′-4)
(A′-3) Carbonic acid vinyl ester in an amount corresponding to 3 to 30% by mass with respect to all monomer components (a′-4) Amount corresponding to 0.1 to 10% by mass with respect to all monomer components A second polymer having a weight average molecular weight (Mw) of 50,000 or less (component (A-2)) obtained by copolymerizing a vinyl group-containing acid anhydride
Are prepared separately and blended.
まず、方法(イ)によるポリマーの調製は、前記(a-1)ないし(a-4)のモノマーおよび必要によりこれらと重合可能なモノマーを同一の反応容器中で重合させることにより行われる。
First, the preparation of the polymer by the method (a) is performed by polymerizing the monomers (a-1) to (a-4) and, if necessary, a monomer polymerizable with them in the same reaction vessel.
使用される成分(a-1)としては、アルキル基の炭素数が1~18の直鎖または分岐を有する(メタ)アクリル酸アルキルエステルが好ましく、具体的には、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸プロピル、(メタ)アクリル酸イソプロピル、(メタ)アクリル酸ブチル、(メタ)アクリル酸イソブチル、(メタ)アクリル酸ペンチル、(メタ)アクリル酸ヘキシル、(メタ)アクリル酸2-エチルヘキシル、(メタ)アクリル酸オクチル、(メタ)アクリル酸ノニル、(メタ)アクリル酸デシル、(メタ)アクリル酸ドデシル、(メタ)アクリル酸ラウリルが挙げられる。これらのうち、得られる粘着のガラス転移温度を好適な範囲にすることができるという理由から、アクリル酸ブチル、アクリル酸2-エチルヘキシルが好ましく用いられる。
The component (a-1) used is preferably a linear or branched (meth) acrylic acid alkyl ester having 1 to 18 carbon atoms in the alkyl group, specifically, methyl (meth) acrylate, (Meth) ethyl acrylate, (meth) propyl acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, ( Examples include 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, and lauryl (meth) acrylate. Of these, butyl acrylate and 2-ethylhexyl acrylate are preferably used because the glass transition temperature of the resulting adhesive can be within a suitable range.
また、成分(a-2)としては、(メタ)アクリル酸2-ヒドロキシエチル、(メタ)アクリル酸2-ヒドロキシプロピル、(メタ)アクリル酸3-ヒドロキシプロピル、(メタ)アクリル酸4-ヒドロキシブチル、(メタ)アクリル酸2-ヒドロキシ-3-クロロプロピル、(メタ)アクリル酸2-ヒドロキシ-3-フェノキシプロピル、(メタ)アクリル酸エチレングリコール、(メタ)アクリル酸ポリエチレングリコール、(メタ)アクリル酸プロピレングリコール、(メタ)アクリル酸ポリプロピレングリコール等のアクリル酸アルキレングリコール等の水酸基を少なくとも1つ有するモノマーが挙げられる。これらの中でも、上記(a-1)の(メタ)アクリル酸アルキルエステルとの共重合性が良好で、後述する成分(B)のイソシアネート系架橋剤との反応性が良好であるという理由から、アクリル酸2-ヒドロキシエチル、アクリル酸4-ヒドロキシブチルが好ましく用いられる。
Component (a-2) includes 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. , (Meth) acrylic acid 2-hydroxy-3-chloropropyl, (meth) acrylic acid 2-hydroxy-3-phenoxypropyl, (meth) acrylic acid ethylene glycol, (meth) acrylic acid polyethylene glycol, (meth) acrylic acid Examples thereof include monomers having at least one hydroxyl group such as propylene glycol and alkylene glycol acrylate such as polypropylene glycol (meth) acrylate. Among these, for the reason that the copolymerization with the (meth) acrylic acid alkyl ester of (a-1) is good and the reactivity with the isocyanate-based crosslinking agent of the component (B) described later is good, 2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate are preferably used.
更に、成分(a-3)のモノマーとしては、酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、カプロン酸ビニル、カプリン酸ビニル、ラウリン酸ビニル、ミリスチン酸ビニル、パルミチン酸ビニル、ステアリン酸ビニル、シクロヘキサンカルボン酸ビニル、ピバリン酸ビニル、オクチル酸ビニル、モノクロロ酢酸ビニル、メタクリル酸ビニル、クロトン酸ビニル、ソルビン酸ビニル、安息香酸ビニル、桂皮酸ビニル等のカルボン酸ビニルエステルが挙げられ、なかでも、重合溶剤への分散性、重合性、入手の容易性から酢酸ビニルが好ましく用いられる。
Further, the monomer of component (a-3) includes vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, cyclohexanecarboxylic acid. Examples include vinyl esters such as vinyl, vinyl pivalate, vinyl octylate, vinyl monochloroacetate, vinyl methacrylate, vinyl crotonate, vinyl sorbate, vinyl benzoate, and vinyl cinnamate. Vinyl acetate is preferably used from the viewpoint of dispersibility, polymerizability, and availability.
更にまた、成分(a-4)としては、無水マレイン酸、無水イタコン酸、テトラヒドロ無水フタル酸等のビニル基含有酸無水物を挙げることができ、なかでも、(a-1)の(メタ)アクリル酸アルキルエステルとの相溶性差のバランスが良好で、海島構造を形成しやすいことから無水マレイン酸が好ましく用いられる。
Furthermore, examples of the component (a-4) include vinyl group-containing acid anhydrides such as maleic anhydride, itaconic anhydride, and tetrahydrophthalic anhydride. Among them, (meth) of (a-1) Maleic anhydride is preferably used because it has a good balance in the difference in compatibility with the alkyl acrylate ester and easily forms a sea-island structure.
これらのモノマー成分の配合量は、成分(a-1)が全モノマー成分中、60~96質量%(以下、「%」で示す)、成分(a-2)が0.01~5%、成分(a-3)が3~30%、成分(a-4)が0.1~10%である。
The blending amount of these monomer components is such that component (a-1) is 60 to 96% by mass (hereinafter referred to as “%”) in all monomer components, component (a-2) is 0.01 to 5%, Component (a-3) is 3 to 30%, and component (a-4) is 0.1 to 10%.
上記モノマーの重合反応自体は、従来公知の方法で行うことができるが、得られたポリマーのMwが35万を超えると、従来技術と同様、粘着剤製造の際の溶剤の使用量を減らすことが難しくなるので、実験的に適切な重合条件を確立し、Mwが35万以下とすることが必要である。
The monomer polymerization reaction itself can be carried out by a conventionally known method. However, if the Mw of the obtained polymer exceeds 350,000, the amount of solvent used in the production of the pressure-sensitive adhesive can be reduced, as in the prior art. Therefore, it is necessary to establish appropriate polymerization conditions experimentally and to set Mw to 350,000 or less.
ポリマーのMwを35万未満にするためには、例えば、ノルマルドデシルメルカプタンのような連鎖移動剤を用いて重合反応を制御したり、重合溶剤として連鎖移動定数の大きいメチルエチルケトンのような溶剤を用いて重合する等の方法が挙げられる。
In order to make the polymer Mw less than 350,000, for example, a polymerization reaction is controlled using a chain transfer agent such as normal dodecyl mercaptan, or a solvent such as methyl ethyl ketone having a large chain transfer constant is used as a polymerization solvent. The method of superposing | polymerizing etc. is mentioned.
以上の方法(イ)により調製されたポリマーは、モノマー(a-1)である(メタ)アクリル酸アルキルエステル及び(a-2)であるヒドロキシ(メタ)アクリル酸アルキルエステルと、モノマー(a-3)であるカルボン酸ビニルエステル及び(a-4)ビニル基含有酸無水物との相溶性が悪いため、モノマー(a-1)および(a-2)主体で形成されたポリマーを海成分、モノマー(a-3)および(a-4)主体で形成されたポリマーを島成分とする海島構造のものとなる。
The polymer prepared by the above method (a) is composed of a monomer (a-1) (meth) acrylic acid alkyl ester and a (a-2) hydroxy (meth) acrylic acid alkyl ester, and a monomer (a- 3) Since the compatibility with the carboxylic acid vinyl ester and (a-4) vinyl group-containing acid anhydride is poor, the polymer formed mainly of the monomers (a-1) and (a-2) is a sea component, A sea-island structure having a polymer formed mainly of monomers (a-3) and (a-4) as island components is obtained.
なお、上記方法により得られたポリマーが、海島構造を有するかどうかは、例えば、このポリマーからGPC等でMw5万以下の成分を分取し、次いでこの成分をGC-MS等で解析し、上記成分中のカルボン酸ビニルエステルの含有割合が70%以上であることにより確認することができる。
Whether the polymer obtained by the above method has a sea-island structure is determined by, for example, separating a component having an Mw of 50,000 or less from this polymer by GPC or the like, and then analyzing the component by GC-MS or the like. It can confirm that the content rate of the carboxylic acid vinyl ester in a component is 70% or more.
一方、方法(ロ)によるポリマーの調製は、前記モノマー(a'-1)および(a'-2)と、モノマー(a'-3)および(a'-4)とをそれぞれ別個に、必要によりこれらと重合可能なモノマーとともに重合させてそれぞれMw35万以下の第1ポリマーおよびMw5万以下の第2ポリマーを重合し、次いでこれらをブレンドすることにより行われる。
On the other hand, the preparation of the polymer by the method (b) requires the monomers (a′-1) and (a′-2) and the monomers (a′-3) and (a′-4) separately. To polymerize these together with a polymerizable monomer to polymerize a first polymer having an Mw of 350,000 or less and a second polymer having an Mw of 50,000 or less, and then blending them.
方法(ロ)において使用されるモノマー(a'-1)、モノマー(a'-2)、モノマー(a'-3)および(a'-4)は、それぞれ方法(イ)で使用されるモノマー(a-1)、モノマー(a-2)、モノマー(a-3)および(a-4)に対応する同一物である。
Monomer (a′-1), monomer (a′-2), monomer (a′-3) and (a′-4) used in method (b) are the monomers used in method (a), respectively. These are the same corresponding to (a-1), monomer (a-2), monomers (a-3) and (a-4).
また、第1ポリマーおよび第2ポリマーを得るための重合反応自体は、従来公知の方法で行うことができるが、それぞれMwを35万以下、5万以下とする必要があるので、実験的に適切な重合条件を確立することが必要である。
In addition, the polymerization reaction itself for obtaining the first polymer and the second polymer can be carried out by a conventionally known method, but it is necessary to make Mw 350,000 or less and 50,000 or less, respectively. It is necessary to establish proper polymerization conditions.
例えば、第1ポリマーのMwを35万以下にするためには、ノルマルドデシルメルカプタンのような連鎖移動剤を用いて重合反応を制御したり、重合溶剤として連鎖移動定数の大きいメチルエチルケトンのような溶剤を用いて重合する等の方法が挙げられる。
For example, in order to reduce the Mw of the first polymer to 350,000 or less, the polymerization reaction is controlled using a chain transfer agent such as normal dodecyl mercaptan, or a solvent such as methyl ethyl ketone having a large chain transfer constant is used as a polymerization solvent. Examples thereof include a polymerization method.
このようにして得られた第1ポリマーと第2ポリマーは、次いで、常法に従ってブレンドされ、粘着剤用ポリマーとされる。
The first polymer and the second polymer thus obtained are then blended according to a conventional method to form a pressure-sensitive adhesive polymer.
以上の方法(イ)あるいは方法(ロ)で得られたポリマーは、更に成分(B)のイソシアネート系架橋剤にて架橋し、粘着剤組成物とすることができる。
The polymer obtained by the above method (a) or method (b) can be further crosslinked with an isocyanate-based crosslinking agent as component (B) to obtain a pressure-sensitive adhesive composition.
この架橋に用いられる成分(B)のイソシアネート系架橋剤としては、トリレンジイソシアネート、クロルフェニレンジイソシアナート、ヘキサメチレンジイソシアナート、テトラメチレンジイソシアナート、イソホロンジイソシアネート、キシリレンジイソシアネート、ジフェニルメタンジイソシアネート、水添されたジフェニルメタンジイソシアネートなどのイソシアネートモノマー及びこれらイソシアネートモノマーをトリメチロールプロパンなどと付加したイソシアネート化合物やイソシアヌレート化合物、ビュレット型化合物、さらにはポリエーテルポリオールやポリエステルポリオール、アクリルポリオール、ポリブタジエンポリオール、ポリイソプレンポリオールなど付加反応させたウレタンプレポリマー型のイソシアネート等が挙げられる。
Examples of the isocyanate-based crosslinking agent for component (B) used for this crosslinking include tolylene diisocyanate, chlorophenylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, water Isocyanate monomers such as diphenylmethane diisocyanate added and isocyanate compounds, isocyanurate compounds, burette type compounds obtained by adding these isocyanate monomers with trimethylolpropane, etc., as well as polyether polyols, polyester polyols, acrylic polyols, polybutadiene polyols, polyisoprene polyols Urethane prepolymer-type isocyanate produced by addition reaction Etc. The.
また、この成分(B)の使用量は、前記ポリマーの固形分100質量部に対し、0.5質量部ないし5質量部程度であり、好ましくは、1.0質量部ないし3.0質量部である。
The amount of component (B) used is about 0.5 to 5 parts by weight, preferably 1.0 to 3.0 parts by weight, based on 100 parts by weight of the solid content of the polymer. It is.
更に、本発明の粘着剤組成物には、本発明の効果を損なわない範囲で必要に応じ、粘着性付与樹脂、酸化防止剤、紫外線吸収剤、可塑剤、帯電防止剤、難燃剤、充填材等の任意成分を配合しても良い。
Furthermore, the pressure-sensitive adhesive composition of the present invention includes a tackifier resin, an antioxidant, an ultraviolet absorber, a plasticizer, an antistatic agent, a flame retardant, and a filler as necessary within the range that does not impair the effects of the present invention. You may mix | blend arbitrary components, such as.
本発明において、粘着剤として使用するポリマーのMwが従来のポリマーと比べ小さいにもかかわらず十分な粘着性能を有する理由は、これが海島構造を有し、その海成分と島成分に異なる機能を持たせたことによるものである。すなわち、海成分は、アクリル酸アルキルエステルポリマーを主体とするものであるが、これにヒドロキシ(メタ)アクリル酸アルキルエステルを組み込んだことで、架橋点としての水酸基が導入される。一方、島成分はカルボン酸ビニルエステルポリマーを主体とするものであるが、これに無水マレイン酸を組み込んだことで、架橋点としてのカルボキシル基が導入される。
In the present invention, the reason why the polymer used as a pressure-sensitive adhesive has a sufficient adhesion performance even though the Mw of the polymer is smaller than that of a conventional polymer is that it has a sea-island structure, and the sea component and the island component have different functions. This is because of That is, the sea component is mainly composed of an acrylic acid alkyl ester polymer, but by incorporating a hydroxy (meth) acrylic acid alkyl ester into this, a hydroxyl group as a crosslinking point is introduced. On the other hand, the island component is mainly composed of a carboxylic acid vinyl ester polymer. By incorporating maleic anhydride into this, a carboxyl group as a crosslinking point is introduced.
そして、水酸基およびカルボキシル基のイソシアネート化合物との反応性は、水酸基>カルボキシル基であることから、架橋割合は、海成分>島成分の関係になるものと推定される。
And, since the reactivity of the hydroxyl group and carboxyl group with the isocyanate compound is hydroxyl group> carboxyl group, the crosslinking ratio is estimated to be in the relationship of sea component> island component.
従って、海成分は低分子―高架橋となり強靭で凝集力の高い性質を持ち、島成分は超低分子―低架橋となり柔軟で糸引き性を持った性質にする事が出来る。この海部分と島部分が強靭さと柔軟性の相反する特性を有することで、Mwが小さいにも拘わらず、優れた粘着性能を有するものと考えられる。
Therefore, the sea component is a low-molecular-high bridge and has a strong and cohesive property, and the island component is an ultra-low molecule-low-crosslink and has a flexible and stringing property. It is considered that the sea part and the island part have the characteristics that the toughness and the flexibility are contradictory, so that the adhesive part has excellent adhesive performance even though the Mw is small.
次に実施例等を挙げ、本発明を更に詳しく説明するが、本発明はこれら実施例等に何ら制約されるものではない。
Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
実 施 例 1
攪拌機、環流冷却管、温度計及び窒素導入管を備えた反応装置に、アクリル酸ブチル(BA)40重量部、アクリル酸2-エチルヘキシル(2EHA)49重量部、アクリル酸2-ヒドロキシエチル(2HEA)0.5重量部、酢酸ビニル(VAc)10重量部、無水マレイン酸(MM)1重量部、連鎖移動剤であるノルマルドデシルメルカプタン(NDM)0.025重量部及びメチルエチルケトン(MEK)50重量部を仕込み、反応容器内の空気を窒素ガスで置換した。 Example 1
In a reactor equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube, 40 parts by weight of butyl acrylate (BA), 49 parts by weight of 2-ethylhexyl acrylate (2EHA), 2-hydroxyethyl acrylate (2HEA) 0.5 parts by weight, vinyl acetate (VAc) 10 parts by weight, maleic anhydride (MM) 1 part by weight, chain transfer agent normal dodecyl mercaptan (NDM) 0.025 part by weight and methyl ethyl ketone (MEK) 50 parts by weight The air in the reaction vessel was replaced with nitrogen gas.
攪拌機、環流冷却管、温度計及び窒素導入管を備えた反応装置に、アクリル酸ブチル(BA)40重量部、アクリル酸2-エチルヘキシル(2EHA)49重量部、アクリル酸2-ヒドロキシエチル(2HEA)0.5重量部、酢酸ビニル(VAc)10重量部、無水マレイン酸(MM)1重量部、連鎖移動剤であるノルマルドデシルメルカプタン(NDM)0.025重量部及びメチルエチルケトン(MEK)50重量部を仕込み、反応容器内の空気を窒素ガスで置換した。 Example 1
In a reactor equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube, 40 parts by weight of butyl acrylate (BA), 49 parts by weight of 2-ethylhexyl acrylate (2EHA), 2-hydroxyethyl acrylate (2HEA) 0.5 parts by weight, vinyl acetate (VAc) 10 parts by weight, maleic anhydride (MM) 1 part by weight, chain transfer agent normal dodecyl mercaptan (NDM) 0.025 part by weight and methyl ethyl ketone (MEK) 50 parts by weight The air in the reaction vessel was replaced with nitrogen gas.
その後、窒素雰囲気下で攪拌しながら、反応容器を70℃まで昇温し、開始剤アゾビスイソブチロニトリル(AIBN)0.1重量部を添加して、1時間反応させた。その後、AIBN 0.1重量部を添加し、反応温度を80℃まで上昇させながら2時間反応させた。さらに、AIBN 0.2重量部を追加して、反応温度を80℃に保ちながら3時間反応させ、重量平均分子量25万、固形分濃度70%、粘度80ポイズのアクリル系ポリマー(1)溶液を得た。
Thereafter, while stirring in a nitrogen atmosphere, the temperature of the reaction vessel was raised to 70 ° C., 0.1 part by weight of initiator azobisisobutyronitrile (AIBN) was added, and the mixture was reacted for 1 hour. Thereafter, 0.1 part by weight of AIBN was added and reacted for 2 hours while raising the reaction temperature to 80 ° C. Further, 0.2 part by weight of AIBN was added and reacted for 3 hours while maintaining the reaction temperature at 80 ° C. to obtain an acrylic polymer (1) solution having a weight average molecular weight of 250,000, a solid content concentration of 70%, and a viscosity of 80 poise. Obtained.
得られたアクリル系ポリマー(1)溶液の固形分100重量部に対して、粘着付与樹脂である重合ロジンエステル樹脂DP2669(理化ファインテク(株)製)を20重量部、イソシアネート系架橋剤であるコロネートL(日本ポリウレタン工業(株)製)を有効成分が1.4重量部になるように添加して粘着剤組成物を得た。
20 parts by weight of a polymerized rosin ester resin DP2669 (manufactured by Rika Finetech Co., Ltd.), which is a tackifier resin, is an isocyanate-based crosslinking agent with respect to 100 parts by weight of the solid content of the obtained acrylic polymer (1) solution. Coronate L (manufactured by Nippon Polyurethane Industry Co., Ltd.) was added so that the active ingredient was 1.4 parts by weight to obtain a pressure-sensitive adhesive composition.
得られた粘着剤組成物を、紙セパレータ上に乾燥後の厚みが65μmになるように塗工し、80℃で2分間乾燥させた後、不織布の両面に転写して、23℃、65%の環境下で7日間エージングしてテープ厚145μmの不織布両面粘着シートを得た。
The obtained pressure-sensitive adhesive composition was coated on a paper separator so that the thickness after drying was 65 μm, dried at 80 ° C. for 2 minutes, transferred to both surfaces of the nonwoven fabric, and 23 ° C., 65%. Was aged for 7 days to obtain a nonwoven fabric double-sided PSA sheet having a tape thickness of 145 μm.
実 施 例 2~8 および 比 較 例 1~9
表1に示す組成により、実施例1に準じて実施例2ないし8および比較例1ないし9の粘着剤組成物を得た。これを実施例1に記載した方法で不織布両面粘着シートとした。 Examples 2 to 8 and Comparative Examples 1 to 9
According to the composition shown in Table 1, the pressure-sensitive adhesive compositions of Examples 2 to 8 and Comparative Examples 1 to 9 were obtained according to Example 1. This was made into the nonwoven fabric double-sided adhesive sheet by the method described in Example 1.
表1に示す組成により、実施例1に準じて実施例2ないし8および比較例1ないし9の粘着剤組成物を得た。これを実施例1に記載した方法で不織布両面粘着シートとした。 Examples 2 to 8 and Comparative Examples 1 to 9
According to the composition shown in Table 1, the pressure-sensitive adhesive compositions of Examples 2 to 8 and Comparative Examples 1 to 9 were obtained according to Example 1. This was made into the nonwoven fabric double-sided adhesive sheet by the method described in Example 1.
[ 組 成 ]
AA:アクリル酸
DP2669:重合ロジンエステル樹脂(理化ファインテク(株)製)
TR-105:テルペン樹脂(YSレジンTR-105;ヤスハラケミ
カル(株)製)
SEA-100:ロジンエステル樹脂(スーパーエステルA-100;
荒川化学工業(株)製)
C-L:イソシアネート系架橋剤(コロネートL;日本ポリウレタン
(株)製)
T-X:エポキシ架橋剤(テトラッドX;三菱瓦斯化学(株)製)
M-A:金属キレート架橋剤(ナーセムアルミ;日本化学産業(株)
製) [Composition]
AA: Acrylic acid DP2669: Polymerized rosin ester resin (manufactured by Rika Finetech Co., Ltd.)
TR-105: Terpene resin (YS resin TR-105; manufactured by Yasuhara Chemical Co., Ltd.)
SEA-100: Rosin ester resin (Superester A-100;
Arakawa Chemical Industries, Ltd.)
CL: Isocyanate-based crosslinking agent (Coronate L; manufactured by Nippon Polyurethane Co., Ltd.)
TX: Epoxy crosslinking agent (Tetrad X; manufactured by Mitsubishi Gas Chemical Co., Inc.)
MA: Metal chelate crosslinking agent (Narsem Aluminum; Nippon Chemical Industry Co., Ltd.)
Made)
DP2669:重合ロジンエステル樹脂(理化ファインテク(株)製)
TR-105:テルペン樹脂(YSレジンTR-105;ヤスハラケミ
カル(株)製)
SEA-100:ロジンエステル樹脂(スーパーエステルA-100;
荒川化学工業(株)製)
C-L:イソシアネート系架橋剤(コロネートL;日本ポリウレタン
(株)製)
T-X:エポキシ架橋剤(テトラッドX;三菱瓦斯化学(株)製)
M-A:金属キレート架橋剤(ナーセムアルミ;日本化学産業(株)
製) [Composition]
TR-105: Terpene resin (YS resin TR-105; manufactured by Yasuhara Chemical Co., Ltd.)
SEA-100: Rosin ester resin (Superester A-100;
Arakawa Chemical Industries, Ltd.)
CL: Isocyanate-based crosslinking agent (Coronate L; manufactured by Nippon Polyurethane Co., Ltd.)
TX: Epoxy crosslinking agent (Tetrad X; manufactured by Mitsubishi Gas Chemical Co., Inc.)
MA: Metal chelate crosslinking agent (Narsem Aluminum; Nippon Chemical Industry Co., Ltd.)
Made)
試 験 例 1
実施例1~8および比較例1~9で調製した不織布両面粘着シートについて、下記方法で粘着力、保持力および定荷重の試験を行った。この結果を表2に示す。 Test example 1
The nonwoven fabric double-sided PSA sheets prepared in Examples 1 to 8 and Comparative Examples 1 to 9 were tested for adhesive strength, holding power and constant load by the following methods. The results are shown in Table 2.
実施例1~8および比較例1~9で調製した不織布両面粘着シートについて、下記方法で粘着力、保持力および定荷重の試験を行った。この結果を表2に示す。 Test example 1
The nonwoven fabric double-sided PSA sheets prepared in Examples 1 to 8 and Comparative Examples 1 to 9 were tested for adhesive strength, holding power and constant load by the following methods. The results are shown in Table 2.
[ 粘着力 ]
得られた両面粘着シートの片面の紙セパレータを剥離し、剥離した側の粘着剤層に25μmの剥離処理したポリエチレンテレフタレートフィルムを貼り合わせて粘着シートを得た。 [ Adhesive force ]
The paper separator on one side of the obtained double-sided pressure-sensitive adhesive sheet was peeled off, and a 25 μm-released polyethylene terephthalate film was bonded to the peeled pressure-sensitive adhesive layer to obtain a pressure-sensitive adhesive sheet.
得られた両面粘着シートの片面の紙セパレータを剥離し、剥離した側の粘着剤層に25μmの剥離処理したポリエチレンテレフタレートフィルムを貼り合わせて粘着シートを得た。 [ Adhesive force ]
The paper separator on one side of the obtained double-sided pressure-sensitive adhesive sheet was peeled off, and a 25 μm-released polyethylene terephthalate film was bonded to the peeled pressure-sensitive adhesive layer to obtain a pressure-sensitive adhesive sheet.
得られた粘着シートを25mm×150mmの大きさに裁断して試験片を得た。この試験片から紙セパレータを剥離して、SUS板、PP板にそれぞれ貼り合わせ2kgのローラーで3往復加圧貼付し、23℃、65%の環境下で20分間放置した後、剥離速度300mm/minで180度剥離強度(g/25mm)を測定した。
The obtained adhesive sheet was cut into a size of 25 mm × 150 mm to obtain a test piece. The paper separator was peeled off from this test piece, bonded to a SUS plate and a PP plate, respectively, and reciprocally pressed with a 2 kg roller, and allowed to stand in an environment of 23 ° C. and 65% for 20 minutes. 180 degree peel strength (g / 25 mm) was measured in min.
[ 保持力 ]
上記と同様に粘着シートを作成し、20mm幅に裁断して試験片を作成した。この試験片から紙セパレータを剥離して、20mm×20mmの面積が接するようにSUS板に貼り付け、温度80℃、荷重1kgの条件で60分間放置したときのズレの大きさ(mm)又は落下までの時間を測定した(表中↓は、落下を意味する)。 [Holding power]
A pressure-sensitive adhesive sheet was prepared in the same manner as described above, and cut into a width of 20 mm to prepare a test piece. The paper separator is peeled off from this test piece and attached to a SUS plate so that an area of 20 mm × 20 mm is in contact, and the size (mm) or drop when left for 60 minutes at a temperature of 80 ° C. and a load of 1 kg. The time until was measured (↓ in the table means falling).
上記と同様に粘着シートを作成し、20mm幅に裁断して試験片を作成した。この試験片から紙セパレータを剥離して、20mm×20mmの面積が接するようにSUS板に貼り付け、温度80℃、荷重1kgの条件で60分間放置したときのズレの大きさ(mm)又は落下までの時間を測定した(表中↓は、落下を意味する)。 [Holding power]
A pressure-sensitive adhesive sheet was prepared in the same manner as described above, and cut into a width of 20 mm to prepare a test piece. The paper separator is peeled off from this test piece and attached to a SUS plate so that an area of 20 mm × 20 mm is in contact, and the size (mm) or drop when left for 60 minutes at a temperature of 80 ° C. and a load of 1 kg. The time until was measured (↓ in the table means falling).
[ 定荷重 ]
上記と同様に粘着シートを作成し、20×50mmの大きさに裁断して試験片を作成した。この試験片から紙セパレータを剥離して、SUS板、PP板にそれぞれ貼り合わせ、温度80℃で90°の方向に荷重200gをかけ、60分間放置したときのハガレ距離(mm)又は落下までの時間を測定した(表中↓は、落下を意味する)。 [Constant load]
A pressure-sensitive adhesive sheet was prepared in the same manner as described above, and cut into a size of 20 × 50 mm to prepare a test piece. The paper separator is peeled off from this test piece and bonded to an SUS plate and a PP plate, respectively, and a load of 200 g is applied in the direction of 90 ° at a temperature of 80 ° C., and the peeling distance (mm) when left for 60 minutes or until dropping. Time was measured (↓ in the table means falling).
上記と同様に粘着シートを作成し、20×50mmの大きさに裁断して試験片を作成した。この試験片から紙セパレータを剥離して、SUS板、PP板にそれぞれ貼り合わせ、温度80℃で90°の方向に荷重200gをかけ、60分間放置したときのハガレ距離(mm)又は落下までの時間を測定した(表中↓は、落下を意味する)。 [Constant load]
A pressure-sensitive adhesive sheet was prepared in the same manner as described above, and cut into a size of 20 × 50 mm to prepare a test piece. The paper separator is peeled off from this test piece and bonded to an SUS plate and a PP plate, respectively, and a load of 200 g is applied in the direction of 90 ° at a temperature of 80 ° C., and the peeling distance (mm) when left for 60 minutes or until dropping. Time was measured (↓ in the table means falling).
[ 塗工性 ]
B型粘度計により、粘着剤組成物の粘度を測定し、粘度200ポイズ(25℃)未満のものを、塗工性良好(○)、200ポイズ(25℃)以上のものを、塗工性不良(×)として評価した。 [Coating property]
The viscosity of the pressure-sensitive adhesive composition is measured with a B-type viscometer. When the viscosity is less than 200 poise (25 ° C.), the coating property is good (◯), and the viscosity is 200 poise (25 ° C.) or more. Evaluated as defective (x).
B型粘度計により、粘着剤組成物の粘度を測定し、粘度200ポイズ(25℃)未満のものを、塗工性良好(○)、200ポイズ(25℃)以上のものを、塗工性不良(×)として評価した。 [Coating property]
The viscosity of the pressure-sensitive adhesive composition is measured with a B-type viscometer. When the viscosity is less than 200 poise (25 ° C.), the coating property is good (◯), and the viscosity is 200 poise (25 ° C.) or more. Evaluated as defective (x).
[ 輸 送 ]
粘着剤(固形分)使用量を360t/年とし、10tトラック(軽油)で東京-大阪間を輸送したと仮定した場合のCO2排出量と燃料使用量を下記式より算出した。 [Transport]
The amount of CO 2 emission and the amount of fuel used were calculated from the following formula, assuming that the amount of adhesive (solid content) used was 360 t / year and transported between Tokyo and Osaka on a 10 t truck (light oil).
粘着剤(固形分)使用量を360t/年とし、10tトラック(軽油)で東京-大阪間を輸送したと仮定した場合のCO2排出量と燃料使用量を下記式より算出した。 [Transport]
The amount of CO 2 emission and the amount of fuel used were calculated from the following formula, assuming that the amount of adhesive (solid content) used was 360 t / year and transported between Tokyo and Osaka on a 10 t truck (light oil).
CO2排出量(kg) = 燃料使用量(L) × CO2排出係数
CO2排出係数:2.62
燃費:3.5km/L CO 2 emissions (kg) = fuel consumption (L) x CO 2 emission factor CO 2 emission factor: 2.62
Fuel consumption: 3.5km / L
CO2排出係数:2.62
燃費:3.5km/L CO 2 emissions (kg) = fuel consumption (L) x CO 2 emission factor CO 2 emission factor: 2.62
Fuel consumption: 3.5km / L
この結果から、実施例1ないし8の本件発明の成分(a-1)である(メタ)アクリル酸アルキルエステル、成分(a-2)であるヒドロキシ(メタ)アクリル酸アルキルエステル、成分(a-3)であるカルボン酸ビニルエステルおよび成分(a-4)であるビニル基含有酸無水物を所定量共重合して得られる低分子量アクリル系ポリマーをイソシアネート系架橋剤によって架橋してなる粘着剤組成物は、低分子量でありながら良好な粘着性能を有し、さらに、溶剤使用量が少ないため環境への負荷を低減した粘着剤組成物であることが示された。
From these results, the (meth) acrylic acid alkyl ester as the component (a-1) of the present invention of Examples 1 to 8, the hydroxy (meth) acrylic acid alkyl ester as the component (a-2), the component (a- 3) A pressure-sensitive adhesive composition obtained by crosslinking a low molecular weight acrylic polymer obtained by copolymerizing a predetermined amount of a carboxylic acid vinyl ester (3) and a vinyl group-containing acid anhydride (a-4) with an isocyanate crosslinking agent. The product was found to be a pressure-sensitive adhesive composition having a low molecular weight and good adhesive performance, and further reducing the load on the environment due to the small amount of solvent used.
それに対して、成分(a-3)のカルボン酸ビニルエステルを共重合させていない比較例1は、海島構造の形成が不十分となるため十分な粘着性能を発現させることができず、保持力、定荷重剥離性に劣っている粘着剤組成物であった。また、成分(a-4)のビニル基含有酸無水物を共重合していない比較例2では、海島構造は形成されるものの、島構造となるポリマー中に架橋点となる官能基がほぼ存在しないため、えられた粘着剤組成物は、定荷重剥離性に劣るものとなってしまった。さらに、成分(a-3)のカルボン酸ビニルエステルおよび成分(a-4)のビニル基含有酸無水物の両方を添加していない比較例4では海島構造が形成されないため、島構造由来の柔軟性を付与することができず、保持力、定荷重剥離性、ともに劣る粘着剤組成物となってしまった。
In contrast, Comparative Example 1 in which the carboxylic acid vinyl ester of component (a-3) was not copolymerized was insufficient in formation of the sea-island structure, so that sufficient adhesion performance could not be exhibited, and the holding power The pressure-sensitive adhesive composition was inferior in constant load peelability. In Comparative Example 2 where the vinyl group-containing acid anhydride of component (a-4) was not copolymerized, the sea-island structure was formed, but the functional group serving as a cross-linking point was substantially present in the island-structured polymer. For this reason, the obtained pressure-sensitive adhesive composition was inferior in constant load peelability. Furthermore, in Comparative Example 4 in which neither the carboxylic acid vinyl ester of component (a-3) or the vinyl group-containing acid anhydride of component (a-4) was added, the sea-island structure was not formed. The adhesive composition was inferior in both holding power and constant load peelability.
また、成分(a-2)のヒドロキシ(メタ)アクリル酸アルキルエステルを共重合していない比較例3では、海島構造の海部を形成するポリマーに架橋点となる官能基がほとんど存在しないため、成分(B)であるイソシアネート系架橋剤を加えても十分な凝集力を付与できず、保持力および定荷重剥離性がともに劣る粘着剤組成物となってしまった。さらに、成分(B)のイソシアネート系架橋剤に代えて、エポキシ系架橋剤、金属キレート系架橋剤を使用している比較例5、6では、海島構造の海部と島部とで架橋密度に差を持たせることができないため、海部由来の強靱性、島部由来の柔軟性を両立させることができず定荷重剥離性に劣る粘着剤組成物となっている。
Further, in Comparative Example 3 in which the hydroxy (meth) acrylic acid alkyl ester of component (a-2) was not copolymerized, the polymer that forms the sea part of the sea-island structure has almost no functional group serving as a crosslinking point. Even when the isocyanate-based crosslinking agent (B) was added, sufficient cohesive force could not be imparted, and the pressure-sensitive adhesive composition was inferior in both holding power and constant load peelability. Further, in Comparative Examples 5 and 6 using an epoxy crosslinking agent and a metal chelate crosslinking agent in place of the isocyanate crosslinking agent of component (B), there is a difference in crosslinking density between the sea part and the island part of the sea-island structure. Therefore, the toughness derived from the sea part and the flexibility derived from the island part cannot be achieved, and the pressure-sensitive adhesive composition is inferior in the constant load peelability.
一方、Mw50万のポリマーを用いた比較例7、8のうち、塗工可能な程度に溶剤希釈し固形分濃度を45%にした比較例7では、溶剤使用量が増大するため、輸送に係るCO2排出量や、燃料使用量が増加して環境負荷の高いものとなり、また、溶剤使用量を削減するため固形分濃度を70%とした比較例8では、粘度が高すぎるため作業性が悪く、膜厚が不均一になりやすいなどの塗工性に問題がある粘着剤組成物となってしまった。
On the other hand, among Comparative Examples 7 and 8 using a polymer having an Mw of 500,000, the amount of solvent used is increased in Comparative Example 7 in which the solvent is diluted to the extent that coating is possible and the solid content concentration is 45%. The amount of CO 2 emission and the amount of fuel used increase, resulting in a high environmental load. In addition, in Comparative Example 8 in which the solid content concentration is 70% in order to reduce the amount of solvent used, the workability is high because the viscosity is too high. It was bad and it became an adhesive composition which had a problem in coating property, such as film thickness becoming non-uniform | heterogenous easily.
更にまた、成分(a-4)のビニル基含有酸無水物に代えて、カルボキシル基含有モノマーであるアクリル酸を用いた比較例9では、アクリル酸が島構造に取り込まれにくく、島構造中にカルボキシル基がほとんど存在しないため、定荷重剥離性に劣る粘着剤組成物となってしまった。
Furthermore, instead of the vinyl group-containing acid anhydride of component (a-4), in Comparative Example 9 using acrylic acid, which is a carboxyl group-containing monomer, acrylic acid is less likely to be incorporated into the island structure, Since there was almost no carboxyl group, it became the adhesive composition inferior to constant load peelability.
実 施 例 9
(1)攪拌機、環流冷却管、温度計及び窒素導入管を備えた反応装置に、アクリル酸ブチル(BA)45重量部、アクリル酸2-エチルヘキシル(2EHA)55重量部、アクリル酸2-ヒドロキシエチル(2HEA)0.5重量部、連鎖移動剤であるノルマルドデシルメルカプタン(NDM)0.040重量部及びメチルエチルケトン(MEK)50重量部を仕込み、反応容器内の空気を窒素ガスで置換した。 Example 9
(1) A reactor equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube was charged with 45 parts by weight of butyl acrylate (BA), 55 parts by weight of 2-ethylhexyl acrylate (2EHA), and 2-hydroxyethyl acrylate. (2HEA) 0.5 parts by weight, normal transfer decyl mercaptan (NDM) 0.040 parts by weight and methyl ethyl ketone (MEK) 50 parts by weight were charged, and the air in the reaction vessel was replaced with nitrogen gas.
(1)攪拌機、環流冷却管、温度計及び窒素導入管を備えた反応装置に、アクリル酸ブチル(BA)45重量部、アクリル酸2-エチルヘキシル(2EHA)55重量部、アクリル酸2-ヒドロキシエチル(2HEA)0.5重量部、連鎖移動剤であるノルマルドデシルメルカプタン(NDM)0.040重量部及びメチルエチルケトン(MEK)50重量部を仕込み、反応容器内の空気を窒素ガスで置換した。 Example 9
(1) A reactor equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube was charged with 45 parts by weight of butyl acrylate (BA), 55 parts by weight of 2-ethylhexyl acrylate (2EHA), and 2-hydroxyethyl acrylate. (2HEA) 0.5 parts by weight, normal transfer decyl mercaptan (NDM) 0.040 parts by weight and methyl ethyl ketone (MEK) 50 parts by weight were charged, and the air in the reaction vessel was replaced with nitrogen gas.
その後、窒素雰囲気下で攪拌しながら、反応容器を70℃まで昇温し、開始剤アゾビスイソブチロニトリル(AIBN)0.1重量部を添加して、1時間反応させた。その後、AIBN 0.1重量部を添加し、反応温度を80℃まで上昇させながら2時間反応させた。さらに、AIBN 0.2重量部を追加して、反応温度を80℃に保ちながら3時間反応させた。反応終了後、粘着付与樹脂である重合ロジンエステル樹脂DP2669(理化ファインテク(株)製)を20重量部を添加して、重量平均分子量25万のアクリル系ポリマー溶液(2)を得た。
Thereafter, while stirring in a nitrogen atmosphere, the temperature of the reaction vessel was raised to 70 ° C., 0.1 part by weight of initiator azobisisobutyronitrile (AIBN) was added, and the mixture was reacted for 1 hour. Thereafter, 0.1 part by weight of AIBN was added and reacted for 2 hours while raising the reaction temperature to 80 ° C. Furthermore, 0.2 part by weight of AIBN was added, and the reaction was carried out for 3 hours while maintaining the reaction temperature at 80 ° C. After completion of the reaction, 20 parts by weight of a polymerized rosin ester resin DP2669 (Rika Finetech Co., Ltd.), which is a tackifier resin, was added to obtain an acrylic polymer solution (2) having a weight average molecular weight of 250,000.
(2)別の攪拌機、環流冷却管、温度計及び窒素導入管を備えた反応装置に、アクリル酸ブチル(BA)12重量部、酢酸ビニル(VAc)80重量部、無水マレイン酸(MM)8重量部、連鎖移動剤であるノルマルドデシルメルカプタン(NDM)3重量部及びメチルエチルケトン(MEK)50重量部を仕込み、反応容器内の空気を窒素ガスで置換した。
(2) In a reactor equipped with another stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube, butyl acrylate (BA) 12 parts by weight, vinyl acetate (VAc) 80 parts by weight, maleic anhydride (MM) 8 Part by weight, 3 parts by weight of chain transfer agent normal dodecyl mercaptan (NDM) and 50 parts by weight of methyl ethyl ketone (MEK) were charged, and the air in the reaction vessel was replaced with nitrogen gas.
その後、窒素雰囲気下で攪拌しながら、反応容器を70℃まで昇温し、開始剤アゾビスイソブチロニトリル(AIBN)0.2重量部を添加して、1時間反応させた。その後、AIBN 0.2重量部を添加し、反応温度を80℃まで上昇させながら2時間反応させた。さらに、AIBN 0.4重量部を追加して、反応温度を80℃に保ちながら3時間反応させ、重量平均分子量3.5万のアクリル系ポリマー溶液(3)を得た。
Thereafter, while stirring in a nitrogen atmosphere, the temperature of the reaction vessel was raised to 70 ° C., 0.2 part by weight of an initiator azobisisobutyronitrile (AIBN) was added, and the mixture was reacted for 1 hour. Thereafter, 0.2 part by weight of AIBN was added, and the reaction was carried out for 2 hours while raising the reaction temperature to 80 ° C. Further, 0.4 part by weight of AIBN was added and reacted for 3 hours while maintaining the reaction temperature at 80 ° C. to obtain an acrylic polymer solution (3) having a weight average molecular weight of 35,000.
(3)得られたアクリル系ポリマー溶液(2)の固形分100重量部に対して、アクリル系ポリマー溶液(3)12.5重量部を添加し、得られた固形分濃度70%、粘度80ポイズのアクリル系ブレンドポリマーに、イソシアネート系架橋剤であるコロネートL(日本ポリウレタン工業(株)製)を有効成分が1.4重量部になるように添加して粘着剤組成物を得た。
(3) 12.5 parts by weight of the acrylic polymer solution (3) is added to 100 parts by weight of the solid content of the obtained acrylic polymer solution (2), and the resulting solid content concentration is 70% and the viscosity is 80. An adhesive composition was obtained by adding Coronate L (manufactured by Nippon Polyurethane Industry Co., Ltd.), an isocyanate-based crosslinking agent, to the acrylic polymer blend of Poise so that the active ingredient was 1.4 parts by weight.
得られた粘着剤組成物を実施例1に記載した方法で不織布両面粘着シートとし、試験例に記載された方法で評価した。この結果を表3に示す。
The obtained pressure-sensitive adhesive composition was made into a nonwoven fabric double-sided pressure-sensitive adhesive sheet by the method described in Example 1, and evaluated by the method described in Test Examples. The results are shown in Table 3.
この結果から、ポリマー1(成分(A-1))とポリマー2(成分(A-2))からブレンド法で得られたポリマーでも、共重合により得られた海島構造を有するポリマーと同様な特性を有する粘着剤組成物が得られることが明らかになった。
From this result, the polymer obtained by the blending method from polymer 1 (component (A-1)) and polymer 2 (component (A-2)) has the same characteristics as the polymer having a sea-island structure obtained by copolymerization. It became clear that the adhesive composition which has this was obtained.
本発明によれば、粘着剤を構成するポリマーのMwが従来のものより小さくても粘着性に全く問題のない粘着剤組成物が得られる。そして、ポリマー成分のMwが小さいことにより、粘着剤組成物を調製する際の溶剤量を減らすことができ、環境面やコスト面で優れた効果を得ることができる。
According to the present invention, it is possible to obtain a pressure-sensitive adhesive composition having no problem with the adhesiveness even if the polymer Mw constituting the pressure-sensitive adhesive is smaller than the conventional one. And since Mw of a polymer component is small, the solvent amount at the time of preparing an adhesive composition can be reduced, and the effect excellent in the environmental aspect and the cost side can be acquired.
従って本発明の粘着剤組成物は、環境性および経済性に優れたものとして、従来の粘着剤組成物に代え、広く使用しうるものである。
Therefore, the pressure-sensitive adhesive composition of the present invention can be widely used in place of the conventional pressure-sensitive adhesive composition as having excellent environmental properties and economy.
Claims (10)
- 下記成分(A)および(B)
(A)次のモノマー(a-1)ないし(a-4)を共重合させるこ
とにより得られる重量平均分子量(Mw)35万以下のアクリル
系ポリマー
(a-1)(メタ)アクリル酸アルキルエステル
60~96質量%
(a-2)ヒドロキシ(メタ)アクリル酸アルキルエステル
0.01~5質量%
(a-3)カルボン酸ビニルエステル
3~30質量%
(a-4)ビニル基含有酸無水物
0.1~10質量%
(B)イソシアネート系架橋剤
を含有する粘着剤組成物。 The following components (A) and (B)
(A) Acrylic polymer having a weight average molecular weight (Mw) of 350,000 or less obtained by copolymerizing the following monomers (a-1) to (a-4): (a-1) alkyl (meth) acrylate Esters 60-96 mass%
(A-2) Hydroxy (meth) acrylic acid alkyl ester 0.01 to 5% by mass
(A-3) Carboxylic acid vinyl ester 3 to 30% by mass
(A-4) Vinyl group-containing acid anhydride 0.1 to 10% by mass
(B) A pressure-sensitive adhesive composition containing an isocyanate-based crosslinking agent. - 成分(B)を、成分(A)の固形分100質量部に対し、0.5質量部ないし5質量部程配合する請求項1記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to claim 1, wherein the component (B) is mixed in an amount of about 0.5 to 5 parts by mass with respect to 100 parts by mass of the solid content of the component (A).
- 成分(a-3)が、酢酸ビニルである請求項1または2記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to claim 1 or 2, wherein the component (a-3) is vinyl acetate.
- 成分(a-4)が、無水マレイン酸である請求項1ないし3の何れかの項記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to any one of claims 1 to 3, wherein the component (a-4) is maleic anhydride.
- 成分(B)が、トリレンジイソシアネート、ヘキサメチレンジイソシアナート、テトラメチレンジイソシアナート、キシリレンジイソシアネートからなる群から選ばれるイソシアネート化合物またはこれらのポリオール付加体である請求項1ないし4の何れかの項記載の粘着剤組成物。 The component (B) is an isocyanate compound selected from the group consisting of tolylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, xylylene diisocyanate, or a polyol adduct thereof. The pressure-sensitive adhesive composition according to item.
- 下記成分(A-1)、(A-2)及び(B)
(A-1)モノマー(a'-1)ないし(a'-2)を共重合させる
ことにより得られる重量平均分子量(Mw)35万以下の第1ポ
リマー
(a'-1)全モノマー成分に対し、60~96質量%に該当す
る量の(メタ)アクリル酸アルキルエステル
(a'-2)全モノマー成分に対し、0.01~5質量%に該当す
る量のヒドロキシ(メタ)アクリル酸アルキルエステル
(A-2)モノマー(a'-3)ないし(a'-4)を共重合させる
ことにより得られる重量平均分子量(Mw)5万以下の第2ポリ
マー
(a'―3)全モノマー成分に対し、3~30質量%に該当する
量のカルボン酸ビニルエステル
(a'-4)全モノマー成分に対し、0.1~10質量%に該当す
る量のビニル基含有酸無水物
(B)イソシアネート系架橋剤
を含有する粘着剤組成物。 The following components (A-1), (A-2) and (B)
(A-1) First polymer having a weight average molecular weight (Mw) of 350,000 or less obtained by copolymerizing monomers (a′-1) to (a′-2) (a′-1) All monomer components (Meth) acrylic acid alkyl ester in an amount corresponding to 60 to 96 mass% (a′-2) in an amount corresponding to 0.01 to 5 mass% of hydroxy (meth) Acrylic acid alkyl ester (A-2) Second polymer (a′-3) having a weight average molecular weight (Mw) of 50,000 or less obtained by copolymerizing monomers (a′-3) to (a′-4) ) Carboxylic acid vinyl ester in an amount corresponding to 3 to 30% by mass with respect to all monomer components (a'-4) Vinyl group-containing acid in an amount corresponding to 0.1 to 10% by mass with respect to all monomer components Anhydride (B) Isocyanate-based crosslinking agent Containing pressure-sensitive adhesive composition. - 成分(B)を、成分(A-1)および(A-2)の合計固形分100質量部に対し、0.5質量部ないし5質量部配合する請求項6記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to claim 6, wherein the component (B) is mixed in an amount of 0.5 to 5 parts by mass with respect to 100 parts by mass of the total solid content of the components (A-1) and (A-2).
- 成分(a'-3)が、酢酸ビニルである請求項6または7記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to claim 6 or 7, wherein the component (a'-3) is vinyl acetate.
- 成分(a'-4)が、無水マレイン酸、無水イタコン酸およびテトラヒドロ無水フタル酸よりなる群から選ばれたものである請求項6ないし8の何れかの項記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to any one of claims 6 to 8, wherein the component (a'-4) is selected from the group consisting of maleic anhydride, itaconic anhydride and tetrahydrophthalic anhydride.
- 成分(B)が、トリレンジイソシアネート、ヘキサメチレンジイソシアナート、テトラメチレンジイソシアナート、キシリレンジイソシアネートからなる群から選ばれるイソシアネート化合物またはこれらのポリオール付加体である請求項6ないし9の何れかの項記載の粘着剤組成物。 The component (B) is an isocyanate compound selected from the group consisting of tolylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, xylylene diisocyanate, or a polyol adduct thereof. The pressure-sensitive adhesive composition according to item.
Priority Applications (1)
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CN201080039262.9A CN102482551B (en) | 2009-09-15 | 2010-07-08 | Adhesive agent composition |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2009212933A JP5540219B2 (en) | 2009-09-15 | 2009-09-15 | Adhesive composition |
JP2009-212933 | 2009-09-15 |
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WO2011033844A1 true WO2011033844A1 (en) | 2011-03-24 |
Family
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PCT/JP2010/061579 WO2011033844A1 (en) | 2009-09-15 | 2010-07-08 | Adhesive agent composition |
Country Status (4)
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JP (1) | JP5540219B2 (en) |
CN (1) | CN102482551B (en) |
TW (1) | TWI486414B (en) |
WO (1) | WO2011033844A1 (en) |
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JP5721537B2 (en) * | 2010-06-15 | 2015-05-20 | 日本合成化学工業株式会社 | Acrylic adhesive for optical members and optical part with adhesive layer |
CN102533178A (en) * | 2011-12-30 | 2012-07-04 | 宁波太古新材料科技有限公司 | Low-VOC (volatile organic compound) double-sided adhesive tape composition and preparation method thereof |
JP2015110685A (en) * | 2012-03-30 | 2015-06-18 | 昭和電工株式会社 | Adhesive composition and removable adhesive double-faced sheet using the same |
CN103045129B (en) * | 2012-12-28 | 2015-07-22 | 宁波大榭开发区综研化学有限公司 | Acrylate adhesive, protective film tape employing same and preparation method of acrylate adhesive |
KR20140140225A (en) * | 2013-05-29 | 2014-12-09 | 동우 화인켐 주식회사 | Composition for adhesive |
KR20150122506A (en) * | 2014-04-23 | 2015-11-02 | 동우 화인켐 주식회사 | Adhesive composition |
JP6371615B2 (en) | 2014-07-11 | 2018-08-08 | 綜研化学株式会社 | Adhesive composition, adhesive sheet, laminate, image display device and input / output device |
JP6390376B2 (en) * | 2014-11-25 | 2018-09-19 | 東洋インキScホールディングス株式会社 | Adhesive and adhesive sheet |
JP6108023B1 (en) * | 2016-02-02 | 2017-04-05 | 東洋インキScホールディングス株式会社 | Adhesive and adhesive sheet |
CN107177316A (en) * | 2017-06-27 | 2017-09-19 | 阜南县力韦包装材料有限公司 | A kind of flexible packing material binding agent of high-temp resisting high-humidity resisting |
TWI701309B (en) * | 2018-12-07 | 2020-08-11 | 長興材料工業股份有限公司 | Cross-linkable copolymer and uses of the same |
JP7286377B2 (en) * | 2019-03-29 | 2023-06-05 | アイカ工業株式会社 | adhesive composition |
CN110577808B (en) * | 2019-09-24 | 2020-06-19 | 苏州世华新材料科技股份有限公司 | High-adhesion-strength chemical-resistant polyacrylate adhesive tape with patterned adhesive regions and preparation method thereof |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS627777A (en) * | 1985-07-05 | 1987-01-14 | Showa Highpolymer Co Ltd | Pressure-sensitive adhesive composition |
JPH0578626A (en) * | 1991-09-20 | 1993-03-30 | Dainippon Ink & Chem Inc | Marking film |
JP2002309211A (en) * | 2001-04-11 | 2002-10-23 | Nippon Shokubai Co Ltd | Weather-resistant film laminate |
JP2002308940A (en) * | 2001-04-11 | 2002-10-23 | Nippon Shokubai Co Ltd | Method for polymerizing polymer for self-adhesive and self-adhesive composition, and self-adhesive product |
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KR100932887B1 (en) * | 2005-12-14 | 2009-12-21 | 주식회사 엘지화학 | Acrylic pressure-sensitive adhesive composition |
CN101358116A (en) * | 2007-07-31 | 2009-02-04 | 上海山富数码喷绘复合材料有限公司 | Acrylic esters oiliness pressure-sensitive glue with 60 solid content and preparation method thereof |
-
2009
- 2009-09-15 JP JP2009212933A patent/JP5540219B2/en active Active
-
2010
- 2010-07-08 CN CN201080039262.9A patent/CN102482551B/en not_active Expired - Fee Related
- 2010-07-08 WO PCT/JP2010/061579 patent/WO2011033844A1/en active Application Filing
- 2010-08-16 TW TW099127299A patent/TWI486414B/en active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS627777A (en) * | 1985-07-05 | 1987-01-14 | Showa Highpolymer Co Ltd | Pressure-sensitive adhesive composition |
JPH0578626A (en) * | 1991-09-20 | 1993-03-30 | Dainippon Ink & Chem Inc | Marking film |
JP2002309211A (en) * | 2001-04-11 | 2002-10-23 | Nippon Shokubai Co Ltd | Weather-resistant film laminate |
JP2002308940A (en) * | 2001-04-11 | 2002-10-23 | Nippon Shokubai Co Ltd | Method for polymerizing polymer for self-adhesive and self-adhesive composition, and self-adhesive product |
Also Published As
Publication number | Publication date |
---|---|
CN102482551B (en) | 2014-04-02 |
JP5540219B2 (en) | 2014-07-02 |
JP2011063639A (en) | 2011-03-31 |
TWI486414B (en) | 2015-06-01 |
CN102482551A (en) | 2012-05-30 |
TW201118141A (en) | 2011-06-01 |
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