WO2013137109A1 - 粘着剤組成物、及び、粘着シート - Google Patents
粘着剤組成物、及び、粘着シート Download PDFInfo
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- WO2013137109A1 WO2013137109A1 PCT/JP2013/056325 JP2013056325W WO2013137109A1 WO 2013137109 A1 WO2013137109 A1 WO 2013137109A1 JP 2013056325 W JP2013056325 W JP 2013056325W WO 2013137109 A1 WO2013137109 A1 WO 2013137109A1
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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
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
- C09J167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
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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
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
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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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/423—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing cycloaliphatic groups
- C08G18/4233—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing cycloaliphatic groups derived from polymerised higher fatty acids or alcohols
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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
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
- C08G63/54—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation the acids or hydroxy compounds containing carbocyclic rings
- C08G63/553—Acids or hydroxy compounds containing cycloaliphatic rings, e.g. Diels-Alder adducts
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
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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
- 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
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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
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
- C09J167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
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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
- C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
- C09J171/02—Polyalkylene oxides
-
- 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
- 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]
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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
- C08G2170/00—Compositions for adhesives
- C08G2170/40—Compositions for pressure-sensitive adhesives
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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
- C09J2467/00—Presence of polyester
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
- Y10T428/2852—Adhesive compositions
Definitions
- the present invention relates to a polyester-based pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet using the composition.
- the adhesive sheet for surface protection (surface protective sheet) is often peeled off after being bonded and repeatedly bonded. Therefore, appropriate wettability is required, and it is required that the appearance can be improved by hand bonding and re-bonding can be performed.
- a silicone-based pressure-sensitive adhesive having high wettability has been used as a pressure-sensitive adhesive for surface protection, but it has a problem of high cost.
- Patent Document 1 polyester-based pressure-sensitive adhesives using plant-derived dimer acid and dimer diol have been studied (Patent Document 1), but this also has a problem of high cost.
- a plasticizer is used, and the plasticizer component bleeds out and adheres to the adherend after being attached to the display surface as the adherend. Problems such as have occurred.
- An object of the present invention is to provide a polyester-based pressure-sensitive adhesive composition that can be used for the production of a pressure-sensitive adhesive sheet having excellent properties (no adhesive residue) and workability, and a pressure-sensitive adhesive sheet including a surface protection application using the same.
- the polyester pressure-sensitive adhesive composition of the present invention is a polyester pressure-sensitive adhesive composition containing at least a polyester obtained by polycondensation of a carboxylic acid component and a diol component, and a crosslinking agent,
- the carboxylic acid component contains 50 to 90% by weight of a dicarboxylic acid having a side chain and 10 to 50% by weight of a tricarboxylic acid having a side chain, and the weight average molecular weight of the polyester is 5000 to 150,000.
- the diol component preferably contains an aliphatic diol having 3 to 10 carbon atoms.
- the polyester pressure-sensitive adhesive composition of the present invention preferably further contains a polyether polyol.
- the pressure-sensitive adhesive sheet of the present invention is a pressure-sensitive adhesive sheet in which a pressure-sensitive adhesive layer obtained by crosslinking the polyester-based pressure-sensitive adhesive composition is formed on at least one side of a support, and the gel fraction of the pressure-sensitive adhesive layer is 70. It is preferable that the amount be ⁇ 98% by weight.
- the pressure-sensitive adhesive sheet of the present invention preferably has a glass adhesive strength of 0.5 N / 25 mm or less.
- the pressure-sensitive adhesive sheet of the present invention is preferably used for surface protection.
- the present invention can be produced from plant-derived raw materials without using an expensive silicone-based pressure-sensitive adhesive, etc., has good wettability to the adherend, lightly peelable (removable), and stain resistant ( It is possible to provide a polyester-based pressure-sensitive adhesive composition that can be used for producing a pressure-sensitive adhesive sheet excellent in workability, and a pressure-sensitive adhesive sheet using the same.
- the polyester used in the polyester-based pressure-sensitive adhesive composition of the present invention is a polyester obtained by polycondensation of at least a carboxylic acid component and a diol component, and the carboxylic acid component contains 50 dicarboxylic acids having side chains.
- it does not specifically limit as a synthesis method of polyester A well-known polymerization method can be used.
- the polyester is preferably manufactured from plant-derived materials.
- plant-derived raw materials are biodegradable and are said to be so-called carbon neutral, and are environmentally friendly and environmentally friendly pressure-sensitive adhesives can be obtained.
- the polyester-based pressure-sensitive adhesive composition of the present invention includes at least a carboxylic acid component, and the carboxylic acid component includes at least a dicarboxylic acid including two and three carboxyl groups, and a tricarboxylic acid.
- the acid component contains 50 to 90% by weight of a dicarboxylic acid having a side chain and 10 to 50% by weight of a tricarboxylic acid having a side chain, preferably 60 to 85% by weight of the dicarboxylic acid, tricarboxylic acid 15 to 40% by weight, more preferably 65 to 80% by weight of the dicarboxylic acid and 20 to 35% by weight of tricarboxylic acid.
- a three-dimensional cross-linked structure can be effectively formed inside the polymer, which is a preferred embodiment.
- the dicarboxylic acid has a side chain and has two carboxyl groups as functional groups, and preferably the side chain is an alkyl group.
- the side chain is an alkyl group.
- dicarboxylic acid examples include plant-derived dicarboxylic acids, such as sebacic acid derived from castor oil, dimer acid derived from oleic acid, erucic acid, and the like. Adipic acid, azelaic acid, 1,4-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid, dodecenyl succinic anhydride, fumaric acid, succinic acid, dodecanedioic acid, hexahydrophthalic anhydride, tetrahydrophthalic anhydride , Maleic acid, maleic anhydride, itaconic acid, citraconic acid, and other aliphatic and alicyclic dicarboxylic acids, terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid 4,4'-diphenyldicarboxy
- the tricarboxylic acid has a side chain and has three carboxyl groups as functional groups, and preferably the side chain is an alkyl group.
- the flexibility is increased, and further, the side chain is an alkyl group, thereby making it difficult to cause hydrolysis of the polyester, and further containing a tricarboxylic acid.
- a polyester polymerized using a dicarboxylic acid is linear, but by using a tricarboxylic acid, it becomes possible to form a network structure (three-dimensional cross-linked structure), and in accordance therewith, an adhesive.
- the layer is hard and the adhesive strength of the pressure-sensitive adhesive layer (adhesive sheet) can be kept low, making it easy to achieve light releasability (removability) without causing deformation or destruction of the substrate during peeling. It is possible to make it more excellent in workability, which is a preferable mode.
- the tricarboxylic acid include plant-derived tricarboxylic acids, for example, aliphatic carboxylic acids such as aconitic acid, citric acid, isocitric acid, oxalosuccinic acid, tricarballylic acid, hemimellitic acid, and trimesin.
- plant-derived tricarboxylic acids for example, aliphatic carboxylic acids such as aconitic acid, citric acid, isocitric acid, oxalosuccinic acid, tricarballylic acid, hemimellitic acid, and trimesin.
- aromatic tricarboxylic acids such as acids
- trimer acids that are trimers of unsaturated aliphatic carboxylic acids such as oleic acid.
- the commercial item containing a dicarboxylic acid component can be used with a tricarboxylic acid component.
- trimer acid which is a trimer of unsaturated aliphatic carboxylic acid such as oleic acid, is preferable from the viewpoint of being derived from plants and being friendly to the global environment.
- trimer acid which is a trimer of unsaturated aliphatic carboxylic acid such as oleic acid, is preferable from the viewpoint of being derived from plants and being friendly to the global environment.
- the polyester pressure-sensitive adhesive composition of the present invention contains at least a diol component, and the diol component can be used without particular limitation as long as it has two hydroxyl groups in the molecule.
- An aliphatic diol having 3 to 10 carbon atoms is used, and more preferably, an aliphatic diol having 4 to 8 carbon atoms is used.
- the diol component By using the diol component, low adhesion and high wettability will be realized, and when using the aliphatic diol, if the carbon number is less than 3, the boiling point will be low, During the production (polymerization) of the polyester, the diol component tends to volatilize, increasing the viscosity, making it impossible to control the polymerization of the polyester.
- diol component examples include fatty acid esters derived from castor oil, dimer diols derived from oleic acid, erucic acid, glycerol monostearate, and the like, as long as they are plant-derived diols.
- an aliphatic diol having 3 to 10 carbon atoms from the viewpoint of cost and ease of handling during polymerization.
- the molar ratio of the carboxylic acid component to the diol component is preferably 1: 1.08 to 2.10, more preferably 1: 1.09 to 2.05, and more preferably 1.10 to 2.00. Is more preferable.
- the molar ratio is less than 1: 1.08, the molecular weight of the resulting polyester is increased, the number of hydroxyl groups that become functional groups is reduced, and even if a crosslinking agent (for example, a polyfunctional isocyanate) is used, a crosslinking reaction occurs. It becomes difficult to promote the pressure-sensitive adhesive layer, and a pressure-sensitive adhesive layer having a desired gel fraction cannot be obtained.
- the polyester used in the polyester-based pressure-sensitive adhesive composition of the present invention has a weight average molecular weight of 5000 to 150,000, preferably 5500 to 100,000, more preferably 6000 to 50,000.
- the weight average molecular weight is less than 5,000, the adhesive strength of the pressure-sensitive adhesive using the polyester may be reduced, and the pressure-sensitive adhesive sheet (pressure-sensitive adhesive layer) itself may not be fixed to the adherend.
- the weight average molecular weight exceeds 150,000, the thickening during the production (polymerization) of the polyester becomes violent and the handling property is inferior.
- the polymerization (condensation polymerization) reaction between the carboxylic acid component and the diol component may be performed using a solvent, or may be performed under reduced pressure without a solvent, and a conventionally known method is used. it can.
- polymerization catalyst used in the polymerization (condensation polymerization) reaction those used for normal polyester polymerization catalysts can be used, and are not particularly limited.
- titanium-based, tin-based, antimony, and the like titanium-based, tin-based, antimony, and the like.
- metal compounds such as those based on zinc, zinc and germanium, and strong acid compounds such as p-toluenesulfonic acid and sulfuric acid can be used.
- the polyester pressure-sensitive adhesive composition of the present invention preferably further contains a polyether polyol, and more preferably contains at least one reactive functional group at the molecular end.
- the polyether polyol can be inserted into the pressure-sensitive adhesive composition by containing (compounding) the polyether polyol and causing a crosslinking reaction using a crosslinking agent. Thereby, it can be made further low adhesiveness, without contaminating a to-be-adhered body, and becomes a preferable aspect.
- the polyether polyol is not particularly limited, and a conventionally known one can be used.
- polyethylene glycol polypropylene glycol, polybutylene glycol, polytetramethylene glycol, polytrimethylene ether glycol, etc.
- Polyoxyalkylene glycol 1 to 20 mol% of a copolymer polyether polyol of 3-methyltetrahydrofuran and tetrahydrofuran (for example, “PTG-L1000”, “PTG-L2000”, “PTG-L3000”, etc., manufactured by Hodogaya Chemical Co., Ltd.)
- a bifunctional polyether polyol such as a polyether glycol of copolymerized neopentyl glycol and tetrahydrofuran, or a trifunctional polyester such as trimethylolpropane tripolyoxyethylene ether.
- Ether polyols such as tetrafunctional polyether polyols such as pentaerythritol polyoxyethylene ether.
- a block copolymer type such as polyoxyethylene polyoxypropylene glycol, or a random copolymer type may be used.
- aliphatic hydrocarbon groups such as methyl group, ethyl group, allyl group, propyl group, butyl group, 2-ethylhexyl group, phenyl group, methylphenyl group, nonylphenyl group, benzyl group, etc.
- the terminal hydroxyl group may be modified with this aromatic hydrocarbon group to eliminate the reactivity.
- the reactivity is completely lost, so that the crosslinking reaction with the polymer cannot be performed, which causes bleeding on the pressure-sensitive adhesive surface.
- Particularly good adhesive properties can be obtained with a structure having a branching difference in a molecular skeleton such as polypropylene glycol or polybutylene glycol. This is presumably because the polymer chain has high mobility and the contribution in the vicinity of the adhesive surface is increased. Further, a type in which one end of these is modified is further useful. This is presumably because the molecular mobility is further increased due to the free polymer chain at one end that has become non-reactive after modification.
- plant-derived polyether polyol is preferable from the viewpoint of being friendly to the global environment. These can be used alone or in combination of two or more.
- the number average molecular weight (Mn) of the polyether polyol is preferably 500 to 3500, and more preferably 1000 to 3000. If the number average molecular weight is less than 500, effects such as low contamination cannot be obtained, and if it is more than 3500, the compatibility with the polyester is poor, and there is a risk of appearance failure, which is not preferable.
- the blending amount of the polyether glycol is preferably 25 to 300 parts by weight, more preferably 50 to 250 parts by weight, and still more preferably 80 to 200 parts by weight with respect to 100 parts by weight of the polyester.
- the blending amount is less than 30 parts by weight, effects such as low contamination cannot be obtained.
- the blending amount is more than 300 parts by weight, the compatibility with the polyester is poor, appearance failure, bleedout, etc. occur, and the adherend There is a possibility of leaving a contamination on the surface, which is not preferable.
- the molecular weight of the polyether polyol is preferably a number average molecular weight of 100 to 5000, more preferably 200 to 4000, and still more preferably 300 to 3000 when the terminal functional group is unmodified.
- the number average molecular weight is preferably 100 to 1500, more preferably 200 to 1200, and still more preferably 300 to 1000.
- the molecular weight is smaller than 100, the effect of improving the adhesive property is small, and when it is larger than 1500, bleeding out occurs.
- One or a combination of two or more can be used.
- the blending amount of the polyether polyol is preferably 1 to 50 parts by weight, more preferably 3 to 45 parts by weight, and still more preferably 5 to 5 parts by weight with respect to 100 parts by weight of the polyester when the terminal functional group is unmodified. 40 parts by weight. If the amount is less than 1 part by weight, the effect of improving the adhesive property cannot be obtained, and if it exceeds 50 parts by weight, bleeding out occurs. Further, with respect to those in which some terminal functional groups are modified, the amount is preferably 1 to 35 parts by weight, more preferably 3 to 32 parts by weight, and still more preferably 5 to 28 parts by weight with respect to 100 parts by weight of the polyester. is there. If the amount is less than 1 part by weight, the effect of improving the adhesive properties cannot be obtained, and if it exceeds 35 parts by weight, bleeding out occurs, which is not preferable.
- the polyester pressure-sensitive adhesive composition of the present invention contains a crosslinking agent.
- a pressure-sensitive adhesive layer can be formed by crosslinking reaction of the pressure-sensitive adhesive composition using a crosslinking agent.
- the crosslinking agent is not particularly limited, and conventionally known crosslinking agents can be used.
- polyvalent isocyanurate examples include hexamethylene diisocyanate polyisocyanurate. By using these, it is possible to achieve the purpose of obtaining transparency and a high gel fraction of the obtained pressure-sensitive adhesive layer, which is effective.
- Commercially available products of the polyvalent isocyanurates can also be used. Specifically, trade names “Duranate TPA-100” (manufactured by Asahi Kasei Chemicals), trade names “Coronate HK”, “Coronate HX”, “Coronate 2096”. (Nippon Polyurethane Industry Co., Ltd.).
- the polyfunctional isocyanate compound is, for example, preferably a compound having at least 2 or more isocyanate groups in the molecule, more preferably 3 or more, and is not particularly limited. Aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates and the like can be mentioned.
- aliphatic polyisocyanates examples include 1,2-ethylene diisocyanate, 1,2-tetramethylene diisocyanate, 1,3-tetramethylene diisocyanate, tetramethylene diisocyanate such as 1,4-tetramethylene diisocyanate, Hexamethylene diisocyanates such as 2-hexamethylene diisocyanate, 1,3-hexamethylene diisocyanate, 1,4-hexamethylene diisocyanate, 1,5-hexamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,5-hexamethylene diisocyanate 2-methyl-1,5-pentane diisocyanate, 3-methyl-1,5-pentane diisocyanate, lysine diisocyanate and the like.
- alicyclic polyisocyanates examples include isophorone diisocyanate, cyclohexyl diisocyanate such as 1,2-cyclohexyl diisocyanate, 1,3-cyclohexyl diisocyanate, 1,4-cyclohexyl diisocyanate, 1,2-cyclopentyl diisocyanate, 1, Examples thereof include cyclopentyl diisocyanate such as 3-cyclopentyl diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated tetramethylxylene diisocyanate, and 4,4′-dicyclohexylmethane diisocyanate.
- aromatic polyisocyanates examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, and 2, 2′-diphenylmethane diisocyanate.
- aliphatic polyisocyanates aliphatic polyisocyanates
- alicyclic polyisocyanates aromatic polyisocyanates
- dimers and trimers of araliphatic polyisocyanates may be used as the polyfunctional isocyanate compound.
- diphenylmethane diisocyanate dimer or trimer reaction product of trimethylolpropane and tolylene diisocyanate, reaction product of trimethylolpropane and hexamethylene diisocyanate, polymethylene polyphenyl isocyanate
- Polymers such as polyether polyisocyanate and polyester polyisocyanate are listed.
- polyfunctional isocyanate compound Commercially available products can also be used as the polyfunctional isocyanate compound.
- trimer adduct of trimethylolpropane and tolylene diisocyanate the trade name “Coronate L” (manufactured by Nippon Polyurethane Industry Co., Ltd.)
- trimer adduct of trimethylolpropane and hexamethylene diisocyanate trade name “Coronate HL” (manufactured by Nippon Polyurethane Industry Co., Ltd.) and the like can be mentioned.
- polyfunctional melamine compound examples include methylated methylol melamine and butylated hexamethylol melamine
- polyfunctional epoxy compound examples include diglycidyl aniline and glycerin diglycidyl ether.
- the type and blending amount of the crosslinking agent are not particularly limited, but the pressure-sensitive adhesive sheet is preferably blended so that the gel fraction of the formed pressure-sensitive adhesive layer is 70 to 98% by weight, more preferably 72. It is blended so that it is ⁇ 97 wt%, particularly preferably 74 to 96 wt%. If the gel fraction is less than 70% by weight, the adhesive strength (peeling force) may increase with time or the adherend may be contaminated when peeling the adhesive layer (adhesive sheet). This is not preferable in terms of handling properties (workability). On the other hand, if the gel fraction exceeds 98% by weight, the adhesive strength becomes too low, and the adhesive sheet itself may not be fixed to the adherend, and this is particularly undesirable because it cannot be used for surface protection. .
- the blending amount of the crosslinking agent is preferably 0.001 to 30 parts by weight, more preferably 0.001 to 25 parts by weight with respect to 100 parts by weight of the polyester.
- the blending amount is less than 0.001 part by weight, when the pressure-sensitive adhesive layer is used, the cohesive force cannot be improved and there is a risk of causing a decrease in heat resistance. This is not preferable because, after bonding, the adhesive strength increases with time or the adherend is contaminated.
- a crosslinking catalyst can be appropriately used.
- the catalyst include tetra-n-butyl titanate, tetraisopropyl titanate, butyltin oxide, dioctyltin diurarate, and the like. These can be used alone or in combination of two or more.
- the amount of the catalyst is not particularly limited, but is preferably 0.01 to 1 part by weight, more preferably 0.05 to 0.5 part by weight with respect to 100 parts by weight of the polyester. If the blending amount is less than 0.01 parts by weight, the effect of catalyst addition may not be obtained, and if it exceeds 1 part by weight, the shelf life may be significantly shortened, and the coating stability may be reduced. It is not preferable.
- acetylacetone, methanol, methyl orthoacetate and the like can be appropriately added as a retarder.
- a pressure-sensitive adhesive layer having desired characteristics can be obtained by combining the polyester with a tackifier resin together with the crosslinking agent.
- the tackifying resin is not particularly limited, and conventionally known ones can be used.
- terpene-based tackifying resin phenol-based tackifying resin, rosin-based tackifying resin, aliphatic petroleum Resin, aromatic petroleum resin, copolymer petroleum resin, alicyclic petroleum resin, xylene resin, epoxy tackifier resin, polyamide tackifier resin, ketone tackifier resin, elastomer tackifier resin, etc.
- a biomass degree means what computed the ratio of the plant-derived use raw material from the weight of the plant-derived use raw material with respect to the weight of the whole use raw material which comprises the said polyester-type adhesive composition.
- terpene-based tackifier resins examples include terpene resins, terpene phenol resins, and aromatic-modified terpene resins. Specific examples include ⁇ -pinene polymers, ⁇ -pinene polymers, dipentene polymers, and the like. A terpene resin modified with phenol, aromatic, hydrogenation, or hydrocarbon can be used.
- phenolic tackifier resin specifically, condensates of various phenols such as phenol, m-cresol, 3,5-xylenol, p-alkylphenol, resorcin, and formaldehyde can be used. Furthermore, resole obtained by addition reaction of the phenols and formaldehyde under an alkali catalyst, novolak, unmodified or modified rosin obtained by condensation reaction of the phenols and formaldehyde under an acid catalyst, and these A rosin-modified phenol resin obtained by adding phenol to an rosin such as a derivative in the presence of an acid catalyst and subjecting it to thermal polymerization can be used.
- rosin-based tackifying resin examples include rosin resin, polymerized rosin resin, hydrogenated rosin resin, rosin ester resin, hydrogenated rosin ester resin, rosin phenol resin, and the like.
- rosin resin polymerized rosin resin
- hydrogenated rosin resin rosin ester resin
- hydrogenated rosin ester resin rosin phenol resin
- rosin phenol resin examples include rosin resin, polymerized rosin resin, hydrogenated rosin resin, rosin ester resin, hydrogenated rosin ester resin, rosin phenol resin, and the like.
- gum rosin wood rosin
- tall oil An unmodified rosin such as rosin (raw rosin), a hydrogenated, disproportionated, polymerized, or other chemically modified modified rosin, or a derivative thereof can be used.
- the compounding amount of the tackifying resin is preferably 0 to 50 parts by weight, more preferably 2 to 30 parts by weight, and particularly preferably 5 to 20 parts by weight with respect to 100 parts by weight of the polyester. If the blending amount exceeds 50 parts by weight, the adhesive strength is increased, and re-peeling after exposure to a high temperature environment may be difficult, which is not preferable.
- the properties of the pressure-sensitive adhesive layer (pressure-sensitive adhesive) used in the pressure-sensitive adhesive sheet of the present invention are not impaired, ultraviolet absorbers, light stabilizers, release modifiers, plasticizers, softeners, fillers, pigments and dyes, etc.
- Common additives such as coloring agents, anti-aging agents, and surfactants can be used.
- the thickness of the pressure-sensitive adhesive layer (after drying) can be appropriately selected. For example, it is preferably about 1 to 100 ⁇ m, more preferably about 3 to 80 ⁇ m, and particularly preferably about 5 to 60 ⁇ m. .
- the thickness of the pressure-sensitive adhesive layer is less than 1 ⁇ m, it is difficult to obtain a sufficient adhesive force, the pressure-sensitive adhesive sheet (pressure-sensitive adhesive layer) itself cannot be fixed to the adherend, and it may be easy to peel off. If the thickness exceeds 100 ⁇ m, the adhesive strength may increase with time and may be difficult to peel off, which is not preferable.
- any form of a single layer and a laminated body may be sufficient.
- the pressure-sensitive adhesive sheet of the present invention can be obtained by forming the pressure-sensitive adhesive layer on at least one side of a support. In addition, if it has the range which does not impair the characteristic as an adhesive sheet of this invention, even if it has an intermediate
- the support is not particularly limited, and conventionally known ones can be used, and various supports (substrates) such as plastic films, porous materials such as paper and nonwoven fabric can be used. .
- various supports such as plastic films, porous materials such as paper and nonwoven fabric can be used.
- a plastic film when using as a surface protection use, it is a preferable aspect to use a plastic film from viewpoints, such as durability.
- the plastic film include polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, ethylene / propylene copolymer, ethylene / 1-butene copolymer, and ethylene / vinyl acetate copolymer.
- Polyolefin film such as coalescence, ethylene / ethyl acrylate copolymer, ethylene / vinyl alcohol copolymer, polyester film such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyacrylate film, polystyrene film, nylon 6, Examples thereof include polyamide films such as nylon 6,6 and partially aromatic polyamide, polyvinyl chloride film, polyvinylidene chloride film, and polycarbonate film.
- the support body which consists of polylactic acid, a cellulose, etc. which are obtained from a plant-derived raw material can be used suitably.
- various additives used for ordinary adhesive tape substrates such as ultraviolet absorbers, light stabilizers, antioxidants, fillers, pigments and dyes are used. can do.
- the surface of the support (base material) can be subjected to a conventional surface treatment in order to improve the adhesion with the pressure-sensitive adhesive layer.
- a conventional surface treatment for example, chromic acid treatment, ozone exposure, flame exposure, high pressure Oxidation treatment by chemical or physical methods such as electric shock exposure and ionizing radiation treatment may be applied, and coating treatment with a primer may be applied.
- a coating treatment with a release agent such as a silicone-based resin or a fluorine-based resin may be performed. .
- the thickness of the support (base material) can be appropriately selected according to the material and form thereof, but is preferably 1000 ⁇ m or less, more preferably about 1 to 1000 ⁇ m, and more preferably 2 to The thickness is particularly preferably about 500 ⁇ m, more preferably about 3 to 300 ⁇ m, and particularly preferably about 5 to 250 ⁇ m.
- a conventionally known method can be adopted.
- a pressure-sensitive adhesive composition (a pressure-sensitive adhesive composition solution obtained by dissolving a pressure-sensitive adhesive composition in a solvent or a hot melt) is used.
- To form a pressure-sensitive adhesive layer to transfer (transfer) the pressure-sensitive adhesive layer coated / formed on the release liner onto the support, and to extrude the pressure-sensitive adhesive layer forming material onto the support (base)
- the adhesive sheet in this invention contains an adhesive film, an adhesive tape, etc.
- a conventionally known method can be adopted.
- roll coating, gravure coating, reverse roll coating, roll brush coating, air knife coating, spray coating examples include extrusion coating with a die coater.
- the release liner is not particularly limited, and a conventionally known release liner can be appropriately used.
- a conventionally known release liner can be appropriately used.
- surface of a base material base material for peeling liners
- the release liner substrate may be in any form of a single layer or a plurality of layers.
- various thin leaf bodies such as a plastic film, paper, foam, and metal foil can be used, and a plastic film is particularly preferable.
- the raw material for the plastic film include polyesters such as polyethylene terephthalate, polyolefins such as polypropylene and ethylene-propylene copolymers, and thermoplastic resins such as polyvinyl chloride.
- the thickness of the release liner substrate can be appropriately selected according to the purpose.
- the formation of the pressure-sensitive adhesive layer is not particularly limited.
- the temperature for drying after applying the pressure-sensitive adhesive composition (solution) is usually 60 to 150 ° C., preferably 70 to 140 ° C.
- parts in the examples means “parts by weight”.
- the physical properties of the polyester are shown in Table 1, and the content of the adhesive layer (adhesive sheet) and the evaluation results are shown in Table 2.
- the physical properties of the polyether polyol used in the examples are shown in Table 3.
- ⁇ Preparation of polyester A> A four-necked separable flask is equipped with a stirrer, thermometer, nitrogen inlet tube, and trapped condenser tube.
- a carboxylic acid component (trade name “Prepol 1025”, manufactured by Croda, dimer acid (molecular weight) : 565): 80% by weight, trimer acid as tricarboxylic acid (molecular weight: 846): containing 20% by weight), 1,4-butanediol (molecular weight: 90, manufactured by Wako Pure Chemical Industries, Ltd.) as a diol component
- the carboxylic acid component (100 parts) and the diol component (30.3 parts) were blended so that the molar ratio (carboxylic acid component: diol component molar ratio) was 1: 1.9, and dibutyltin oxide as a catalyst.
- ⁇ Preparation of polyester B> A four-necked separable flask is equipped with a stirrer, thermometer, nitrogen inlet tube, and trapped condenser tube.
- a carboxylic acid component (trade name “Prepol 1025”, manufactured by Croda, dimer acid (molecular weight) : 565): 80% by weight, trimer acid as tricarboxylic acid (molecular weight: 846): containing 20% by weight), 1,4-butanediol (molecular weight: 90, manufactured by Wako Pure Chemical Industries, Ltd.) as a diol component 100 parts of the carboxylic acid component and 25.5 parts of the diol component are blended so that the molar ratio of carboxylic acid component: molar ratio of the diol component is 1: 1.6, and dibutyltin oxide is used as a catalyst.
- ⁇ Preparation of polyester C> A four-necked separable flask is equipped with a stirrer, thermometer, nitrogen inlet tube, and trapped condenser tube.
- a carboxylic acid component (trade name “Prepol 1006”, manufactured by Croda, dimer acid (molecular weight) : 565): 96% by weight, tricarboxylic acid as a tricarboxylic acid (molecular weight: 846): containing 4% by weight), 1,4-butanediol (molecular weight: 90, manufactured by Wako Pure Chemical Industries, Ltd.) as a diol component 100 parts of the carboxylic acid component and 23.9 parts of the diol component are blended so that the molar ratio of carboxylic acid component: mole ratio of the diol component is 1: 1.5, and dibutyltin oxide is used as a catalyst.
- a four-necked separable flask is equipped with a stirrer, thermometer, nitrogen inlet tube, and condenser tube with a trap.
- a carboxylic acid component (trade name “Pripol 1009”, manufactured by Croda, dimer acid (molecular weight) : 565): 99% by weight, trimer acid as tricarboxylic acid (molecular weight: 846): containing 1% by weight), 1,4-butanediol (molecular weight: 90, manufactured by Wako Pure Chemical Industries) as a diol component, 100 parts of the carboxylic acid component and 23.9 parts of the diol component are blended so that the molar ratio of carboxylic acid component: mole ratio of the diol component is 1: 1.5, and dibutyltin oxide is used as a catalyst.
- ⁇ Preparation of polyester E> A four-necked separable flask is equipped with a stirrer, thermometer, nitrogen inlet tube, and trapped condenser tube.
- a carboxylic acid component (trade name “Prepol 1025”, manufactured by Croda, dimer acid (molecular weight) : 565): 80% by weight, trimer acid as tricarboxylic acid (molecular weight: 846): containing 20% by weight), 1,4-butanediol (molecular weight: 90, manufactured by Wako Pure Chemical Industries, Ltd.) as a diol component 100 parts of the carboxylic acid component and 35 parts of the diol component are blended so that the molar ratio of carboxylic acid component: molar ratio of the diol component is 1: 2.2, and dibutyltin oxide (sum) is further added as a catalyst.
- ⁇ Preparation of polyester F> A four-necked separable flask is equipped with a stirrer, thermometer, nitrogen inlet tube, and trapped condenser tube.
- a carboxylic acid component (trade name “Prepol 1025”, manufactured by Croda, dimer acid (molecular weight) : 565): 80% by weight, containing trimer acid (molecular weight: 846): 20% by weight) which is a tricarboxylic acid) and 1,4-butanediol (manufactured by Wako Pure Chemical Industries, molecular weight: 90) as a diol component)
- molar ratio carboxylic acid component: diol ratio
- Example 1 To 100 parts of polyester A, 12 parts of polyhexamethylene diisocyanate (trade name “TPA-100”, manufactured by Asahi Kasei Chemicals) is blended as a cross-linking agent, and 50 to 150 parts of toluene is added as a solvent, followed by coating. Adjust the viscosity to be easy (for example, about 10 Pa ⁇ s) to obtain a polyester-based pressure-sensitive adhesive composition, and use this composition as a base material so that the thickness of the pressure-sensitive adhesive layer (after drying) can be 10 ⁇ m.
- TPA-100 polyhexamethylene diisocyanate
- the film was coated on a polyethylene terephthalate (PET) film (trade name “Lumirror 38S10”, manufactured by Panac Co., Ltd.) having a thickness of 38 ⁇ m and dried at 100 ° C. for 3 minutes to obtain a composition layer. Thereafter, the composition layer was bonded to the release-treated surface of a release-treated polyethylene terephthalate (PET) film (thickness: 38 ⁇ m, trade name “Diafoil MRE # 38”, manufactured by Mitsubishi Plastics). The pressure-sensitive adhesive sheet (for surface protection) having the pressure-sensitive adhesive layer formed on the support was obtained.
- PET polyethylene terephthalate
- PET polyethylene terephthalate
- Example 2 A pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that 10 parts of the crosslinking agent was blended with 100 parts of polyester B.
- Example 3 To 100 parts of polyester A, 25 parts of OH group-type polybutylene glycol (trade name “Uniol PB-500”, manufactured by NOF Corporation, number average molecular weight (Mn): 500) is added, and the crosslinking agent is further added. A pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that 20 parts were blended.
- OH group-type polybutylene glycol trade name “Uniol PB-500”, manufactured by NOF Corporation, number average molecular weight (Mn): 500
- Example 4 Except for blending 50 parts of the crosslinking agent with respect to 100 parts of polyester A and 150 parts of polytetramethylene ether glycol having a number average molecular weight (Mn) of 1000 (trade name “PTG-1000SN”, manufactured by Hodogaya Chemical Co., Ltd.) A pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1.
- Example 5 Except for 100 parts of polyester A, 30 parts of the crosslinking agent and 150 parts of polytetramethylene ether glycol (trade name “PTG-3000SN”, manufactured by Hodogaya Chemical Co., Ltd.) having a number average molecular weight (Mn) of 3000 are blended. In the same manner as in Example 1, an adhesive sheet was obtained.
- PTG-3000SN polytetramethylene ether glycol
- Example 6 Example 1 except that 50 parts of the cross-linking agent and 150 parts of polytetrimethylene ether glycol (trade name “Cerenol H1000”, manufactured by DuPont) having a number average molecular weight (Mn) of 1000 are blended with 100 parts of polyester A In the same manner, an adhesive sheet was obtained.
- polytetrimethylene ether glycol trade name “Cerenol H1000”, manufactured by DuPont
- Example 7 Except for blending 50 parts of the crosslinking agent and 150 parts of a copolymer polyether polyol (trade name “PTG-L1000”, manufactured by Hodogaya Chemical Co., Ltd.) having a number average molecular weight (Mn) of 1000 with 100 parts of polyester A. In the same manner as in Example 1, an adhesive sheet was obtained.
- a copolymer polyether polyol trade name “PTG-L1000”, manufactured by Hodogaya Chemical Co., Ltd.
- Example 8 Except for 100 parts of polyester A, 40 parts of the cross-linking agent and 150 parts of a copolymer polyether polyol (trade name “PTG-L2000”, manufactured by Hodogaya Chemical Co., Ltd.) having a number average molecular weight (Mn) of 2000 are blended. In the same manner as in Example 1, an adhesive sheet was obtained.
- PTG-L2000 copolymer polyether polyol
- Example 9 Except for 100 parts of polyester A, 30 parts of the cross-linking agent and 150 parts of copolymer polyether polyol (trade name “PTG-L3000”, manufactured by Hodogaya Chemical Co., Ltd.) having a number average molecular weight (Mn) of 3000 are blended. In the same manner as in Example 1, an adhesive sheet was obtained.
- Example 1 A pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that 10 parts of the crosslinking agent was blended with 100 parts of polyester C.
- ⁇ Comparative example 2> A pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that 10 parts of the crosslinking agent was blended with 100 parts of polyester D.
- Weight average molecular weight As for the weight average molecular weight (Mw), about 0.2 g of polyester was collected in a petri dish and dried at 120 ° C. for 2 hours to remove the solvent. Next, 0.01 g of the polyester layer on the petri dish was weighed, added to 10 g of tetrahydrofuran (THF), and left to dissolve for 24 hours. Each molecular weight of this solution was measured from a calibration curve prepared with standard polystyrene using a gel permeation chromatography (GPC) method.
- GPC gel permeation chromatography
- the pressure-sensitive adhesive sheet of the pressure-sensitive adhesive layer 10 um obtained in Examples and Comparative Examples was cut to a width of 25 mm, and the pressure-sensitive adhesive surface of the pressure-sensitive adhesive sheet was bonded to a non-tin-treated surface of alkali glass (manufactured by Matsunami Glass Co., Ltd.).
- the pressure-sensitive adhesive layer 30 um adhesive sheet was bonded to a SUS304 plate (manufactured by Toyo Seiki Co., Ltd.) to give a test piece, and the adhesive strength against blue plate glass (vs. glass adhesive strength) (N / 25 mm) was measured.
- pressure bonding at the time of bonding is performed by reciprocating a 2 kg roller once, and a 180 ° peel adhesive strength (adhesive strength) is obtained with a tensile and compression tester (device name “TG-1kN”, manufactured by Minebea Co., Ltd.). The measurement was performed under the following conditions. Tensile (peeling) speed: 300 mm / min, Measurement conditions: Temperature: 23 ⁇ 2 ° C., Humidity: 65 ⁇ 5% RH
- the adhesive strength to glass is preferably 0.5 N / 25 mm or less, more preferably 0.4 N / 25 mm or less, and still more preferably 0.3 N / 25 mm or less.
- the adhesive strength exceeds 0.5 N / 25 mm, the adhesive strength becomes too high, and light peelability (removability) cannot be realized.
- the adhesive strength becomes too high, and light peelability (removability) cannot be realized.
- it peels thereafter. At this time, adhesive residue may be generated on the adherend or the support (base material) may be damaged, which is not preferable.
- the wetting rate of the pressure-sensitive adhesive sheet of the present invention is preferably 0.6 cm 2 / s or more, more preferably 1.0 cm 2 / s or more, and particularly preferably 3.0 cm 2 / s or more. is there.
- the wetting rate is less than 0.6 cm 2 / s, handling properties and air bubble biting tend to occur, and the appearance of the adherend to which the surface protective sheet is bonded is inferior.
- Comparative Examples 1 and 2 since the carboxylic acid component containing dicarboxylic acid and tricarboxylic acid at a desired ratio was not used, it was confirmed that there was a problem with high adhesive strength and light peelability (removability). It was done.
- Comparative Example 3 since a polyester having a smaller weight average molecular weight was used, a pressure-sensitive adhesive sheet having a gelled pressure-sensitive adhesive layer could not be obtained, and contamination such as adhesive residue was observed on the adherend. It was.
- Comparative Example 4 since a polyester having a weight average molecular weight larger than the desired weight was used, the gelation of the polyester was remarkably high, so that it could not be mixed with other raw materials and an adhesive sheet itself could not be obtained. It was.
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Abstract
Description
本発明のポリエステル系粘着剤組成物に用いられるポリエステルは、少なくとも、カルボン酸成分と、ジオール成分とを重縮合して得られるポリエステルであり、前記カルボン酸成分が、側鎖を有するジカルボン酸を50~90重量%、及び、側鎖を有するトリカルボン酸を10~50重量%含有し、前記ポリエステルの重量平均分子量が、5000~150000であることを特徴とするポリエステルである。なお、ポリエステルの合成方法としては、特に限定されるものではなく、公知の重合方法を用いることができる。
本発明のポリエステル系粘着剤組成物は、更に、ポリエーテルポリオールを含有することが好ましく、より好ましくは、分子末端に少なくとも1つ以上の反応性官能基を含有することである。前記ポリエーテルポリオールを含有(配合)し、架橋剤を用いて架橋反応させることにより、粘着剤組成物中にポリエーテルポリオールを挿入することができる。これにより、被着体へ汚染することなく、さらに低接着性にすることができ、好ましい態様となる。
四つ口セパラブルフラスコに攪拌機、温度計、窒素導入管、及びトラップ付き冷却管を付し、これにカルボン酸成分(商品名「プリポール1025」、クローダ社製、ジカルボン酸であるダイマー酸(分子量:565):80重量%、トリカルボン酸であるトリマー酸(分子量:846):20重量%を含有)と、ジオール成分である1,4-ブタンジオール(和光純薬社製、分子量:90)とのモル比(カルボン酸成分:ジオール成分のモル比)が、1:1.9になるように、前記カルボン酸成分100部、前記ジオール成分30.3部を配合し、更に、触媒としてジブチルスズオキシド(和光純薬社製)0.1部を仕込み、窒素雰囲気で撹拌しながら、180℃まで昇温し、この温度を8時間保持した。
その後、窒素導入管、及びトラップ付き冷却管を取り除き、真空ポンプに付け替え、減圧雰囲気(0.002MPa)で撹拌しながら、200℃まで昇温し、この温度を保持した。約2時間反応を続け、ポリエステルAを得た。重量平均分子量(Mw)は、10000であった。
四つ口セパラブルフラスコに攪拌機、温度計、窒素導入管、及びトラップ付き冷却管を付し、これにカルボン酸成分(商品名「プリポール1025」、クローダ社製、ジカルボン酸であるダイマー酸(分子量:565):80重量%、トリカルボン酸であるトリマー酸(分子量:846):20重量%を含有)と、ジオール成分である1,4-ブタンジオール(和光純薬社製、分子量:90)とのモル比(カルボン酸成分:ジオール成分のモル比)が、1:1.6になるように、前記カルボン酸成分100部、前記ジオール成分25.5部を配合し、更に、触媒としてジブチルスズオキシド(和光純薬社製)0.1部を仕込み、窒素雰囲気で撹拌しながら、180℃まで昇温し、この温度を8時間保持した。
その後、窒素導入管、及びトラップ付き冷却管を取り除き、真空ポンプに付け替え、減圧雰囲気(0.002MPa)で撹拌しながら、200℃まで昇温し、この温度を保持した。約4時間反応を続け、ポリエステルBを得た。重量平均分子量(Mw)は、120000であった。
四つ口セパラブルフラスコに攪拌機、温度計、窒素導入管、及びトラップ付き冷却管を付し、これにカルボン酸成分(商品名「プリポール1006」、クローダ社製、ジカルボン酸であるダイマー酸(分子量:565):96重量%、トリカルボン酸であるトリマー酸(分子量:846):4重量%を含有)と、ジオール成分である1,4-ブタンジオール(和光純薬社製、分子量:90)とのモル比(カルボン酸成分:ジオール成分のモル比)が、1:1.5になるように、前記カルボン酸成分100部、前記ジオール成分23.9部を配合し、更に、触媒としてジブチルスズオキシド(和光純薬社製)0.1部を仕込み、窒素雰囲気で撹拌しながら、180℃まで昇温し、この温度を8時間保持した。
その後、窒素導入管、及びトラップ付き冷却管を取り除き、真空ポンプに付け替え、減圧雰囲気(0.002MPa)で撹拌しながら、200℃まで昇温し、この温度を保持した。約10時間反応を続け、ポリエステルCを得た。重量平均分子量(Mw)は、30000であった。
四つ口セパラブルフラスコに攪拌機、温度計、窒素導入管、及びトラップ付き冷却管を付し、これにカルボン酸成分(商品名「プリポール1009」、クローダ社製、ジカルボン酸であるダイマー酸(分子量:565):99重量%、トリカルボン酸であるトリマー酸(分子量:846):1重量%を含有)と、ジオール成分である1,4-ブタンジオール(和光純薬社製、分子量:90)とのモル比(カルボン酸成分:ジオール成分のモル比)が、1:1.5になるように、前記カルボン酸成分100部、前記ジオール成分23.9部を配合し、更に、触媒としてジブチルスズオキシド(和光純薬社製)0.1部を仕込み、窒素雰囲気で撹拌しながら、180℃まで昇温し、この温度を8時間保持した。
その後、窒素導入管、及びトラップ付き冷却管を取り除き、真空ポンプに付け替え、減圧雰囲気(0.002MPa)で撹拌しながら、200℃まで昇温し、この温度を保持した。約10時間反応を続け、ポリエステルDを得た。重量平均分子量(Mw)は、20000であった。
四つ口セパラブルフラスコに攪拌機、温度計、窒素導入管、及びトラップ付き冷却管を付し、これにカルボン酸成分(商品名「プリポール1025」、クローダ社製、ジカルボン酸であるダイマー酸(分子量:565):80重量%、トリカルボン酸であるトリマー酸(分子量:846):20重量%を含有)と、ジオール成分である1,4-ブタンジオール(和光純薬社製、分子量:90)とのモル比(カルボン酸成分:ジオール成分のモル比)が、1:2.2になるように、前記カルボン酸成分100部、前記ジオール成分35部を配合し、更に、触媒としてジブチルスズオキシド(和光純薬社製)0.1部を仕込み、窒素雰囲気で撹拌しながら、180℃まで昇温し、この温度を8時間保持した。
その後、窒素導入管、及びトラップ付き冷却管を取り除き、真空ポンプに付け替え、減圧雰囲気(0.002MPa)で撹拌しながら、200℃まで昇温し、この温度を保持した。約1.5時間反応を続け、ポリエステルEを得た。重量平均分子量(Mw)は、4000であった。
四つ口セパラブルフラスコに攪拌機、温度計、窒素導入管、及びトラップ付き冷却管を付し、これにカルボン酸成分(商品名「プリポール1025」、クローダ社製、ジカルボン酸であるダイマー酸(分子量:565):80重量%、トリカルボン酸であるトリマー酸(分子量:846):20重量%)を含有)と、ジオール成分である1,4-ブタンジオール(和光純薬社製、分子量:90)とのモル比(カルボン酸成分:ジオール成分のモル比)が、1:1.3になるように、前記カルボン酸成分100部、前記ジオール成分20.7部を配合し、更に、触媒としてジブチルスズオキシド(和光純薬社製)0.2部を仕込み、窒素雰囲気で撹拌しながら、180℃まで昇温し、この温度を8時間保持した。
その後、窒素導入管、及びトラップ付き冷却管を取り除き、真空ポンプに付け替え、減圧雰囲気(0.002MPa)で撹拌しながら、200℃まで昇温し、この温度を保持した。約4時間反応を続け、ポリエステルFを得た。重量平均分子量(Mw)は、160000であったが、ゲル化が著しく、非常に高粘度であり、取り扱うのが困難であった。
ポリエステルA100部に対して、架橋剤として、ポリヘキサメチレンジイソシアネート(商品名「TPA-100」、旭化成ケミカルズ社製)12部を配合し、溶剤としてトルエンを50~150部加えて、塗工加工しやすい粘度(たとえば、10Pa・s程度)に調整し、ポリエステル系粘着剤組成物とし、この組成物を、乾燥させ得られる粘着剤層(乾燥後)の厚みが10μmになるように、基材として、厚さが38μmのポリエチレンテレフタレート(PET)フィルム(商品名「ルミラー38S10」、パナック社製)上に塗布し、100℃で3分間乾燥させ、組成物層を得た。その後、剥離処理したポリエチレンテレフタレート(PET)フィルム(厚さ:38μm、商品名「ダイアホイルMRE♯38」、三菱樹脂社製)の剥離処理面に前記組成物層を貼り合わせ、更に50℃で3日間放置し、粘着剤層を支持体上に形成した粘着シート(表面保護用)を得た。
ポリエステルB100部に対して、前記架橋剤を10部配合した以外は、実施例1と同様の方法で、粘着シートを得た。
ポリエステルA100部に対して、両末端OH基型ポリブチレングリコール(商品名「ユニオールPB-500」、日油社製、数平均分子量(Mn):500)を25部添加し、さらに前記架橋剤を20部配合した以外は、実施例1と同様の方法で、粘着シートを得た。
ポリエステルA100部に対して前記架橋剤を50部、数平均分子量(Mn)が1000のポリテトラメチレンエーテルグリコール(商品名「PTG-1000SN」、保土谷化学社製)を150部配合した以外は、実施例1と同様の方法で、粘着シートを得た。
ポリエステルA100部に対して、前記架橋剤を30部、数平均分子量(Mn)が3000のポリテトラメチレンエーテルグリコール(商品名「PTG-3000SN」、保土谷化学社製)を150部配合した以外は、実施例1と同様の方法で、粘着シートを得た。
ポリエステルA100部に対して前記架橋剤を50部、数平均分子量(Mn)が1000のポリテトリメチレンエーテルグリコール(商品名「CerenolH1000」、DuPont社製)を150部配合した以外は、実施例1と同様の方法で、粘着シートを得た。
ポリエステルA100部に対して、前記架橋剤を50部、数平均分子量(Mn)が1000の共重合ポリエーテルポリオール(商品名「PTG-L1000」、保土谷化学社製)を150部配合した以外は、実施例1と同様の方法で、粘着シートを得た。
ポリエステルA100部に対して、前記架橋剤を40部、数平均分子量(Mn)が2000の共重合ポリエーテルポリオール(商品名「PTG-L2000」、保土谷化学社製)を150部配合した以外は、実施例1と同様の方法で、粘着シートを得た。
ポリエステルA100部に対して、前記架橋剤を30部、数平均分子量(Mn)が3000の共重合ポリエーテルポリオール(商品名「PTG-L3000」、保土谷化学社製)を150部配合した以外は、実施例1と同様の方法で、粘着シートを得た。
ポリエステルC100部に対して、前記架橋剤を10部配合した以外は、実施例1と同様の方法で、粘着シートを得た。
ポリエステルD100部に対して、前記架橋剤を10部配合した以外は、実施例1と同様の方法で、粘着シートを得た。
ポリエステルE100部に対して、前記架橋剤を20部配合した以外は、実施例1と同様の方法で、粘着シートを得た。
ポリエステルFを使用して、粘着シートの作製を試みたが、ポリエステルFのゲル化が著しく、非常に高粘度のため、架橋剤などの原料と混合することができず、粘着シートが得られなかった。
重量平均分子量(Mw)は、ポリエステル約0.2gをシャーレに採取し、120℃×2時間、乾燥させ溶剤を除去した。ついで、前記シャーレ上のポリエステル層0.01gを秤量して、テトラヒドロフラン(THF)10gに添加し、24時間放置して溶解した。この溶液をゲル・パーミエイション・クロマトグラフィ(GPC)法を用い、標準ポリスチレンにより作成した検量線から、それぞれの分子量を測定した。(測定条件)
装置名:東ソー社製、HLC-8220GPC
試験片濃度:0.1重量%(THF溶液)
試験片注入量:20μl
溶離液:THF
流速:0.300ml/min
測定(カラム)温度:40℃
カラム: 試験片カラム;TSKguardcolumn SuperHZ-L(1本)+TSKgel SuperHZM-M(2本)、リファレンスカラム;TSKgel
SuperH-RC(1本)、東ソー製
検出器:示差屈折計(RI)
実施例及び比較例で得られた厚さ30μmの粘着シートを5cm×5cm角に切り出した。切り出した粘着シートから支持体を取り除き、これを試験片とし、この試験片を、重さがわかっているテフロン(登録商標)シートで包み、重量を秤量し、トルエン中に23℃で7日間放置して、試験片中のゾル分を抽出した。その後、120℃で2時間乾燥し、乾燥後の重量を秤量した。ゲル分率を下記の式にて算出した。
ゲル分率(重量%)=(乾燥後の重量-テフロン(登録商標)シート重量)/(乾燥前の重量-テフロン(登録商標)シート重量)×100
実施例、及び比較例により得られた粘着剤層10umの粘着シートを幅25mmにカットし、前記粘着シートの粘着面を、アルカリガラス(松浪硝子社製)の非すず処理面貼り合わせ、また粘着剤層30umの粘着シートをSUS304板(東洋精箔社製)に貼り合わせて、試験片とし、青板ガラスに対する粘着力(対ガラス粘着力)(N/25mm)を測定した。なお、貼り合せの際の圧着は、2kgのローラーを1往復して行い、引張圧縮試験機(装置名「TG-1kN」、ミネベア社製)にて、180°ピール接着力(粘着力)の測定を以下の条件下で行った。
引張(剥離)速度:300mm/分、
測定条件:温度:23±2℃、湿度:65±5%RH
粘着力測定後の被着体の粘着剤層と接した面を目視にて確認し、ブリードアウトの跡の有無や、糊残りの有無などにより、被着体への汚染の有無を評価した。
実施例、及び比較例により得られた粘着シートを幅25mm、長さ70mmにカットし、粘着面をガラス板上に静かに落とし、1秒間当たりの粘着面の広がり面積を、ビデオカメラで動画撮影した後、0.5秒ごとに区切り、濡れによる色の濃淡を二値化し濡れ面積を求め、濡れ速度(cm2/s)を算出し、評価した。
Claims (6)
- 少なくとも、カルボン酸成分と、ジオール成分とを重縮合して得られるポリエステルと、架橋剤とを含有するポリエステル系粘着剤組成物であって、
前記カルボン酸成分が、側鎖を有するジカルボン酸を50~90重量%、及び、側鎖を有するトリカルボン酸を10~50重量%含有し、
前記ポリエステルの重量平均分子量が、5000~150000であることを特徴とするポリエステル系粘着剤組成物。 - 前記ジオール成分が、炭素数3~10の脂肪族ジオールを含有することを特徴とする請求項1に記載のポリエステル系粘着剤組成物。
- 更に、ポリエーテルポリオールを含有することを特徴する請求項1又は2に記載のポリエステル系粘着剤組成物。
- 請求項1~3のいずれかに記載のポリエステル系粘着剤組成物を架橋して得られる粘着剤層を、支持体の少なくとも片面に形成する粘着シートであって、
前記粘着剤層のゲル分率が、70~98重量%であることを特徴とする粘着シート。 - ガラスに対する粘着力が、0.5N/25mm以下であることを特徴とする請求項4に記載の粘着シート。
- 表面保護用途に使用されることを特徴とする請求項4又は5に記載の粘着シート。
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CN106170526B (zh) * | 2014-04-03 | 2020-08-11 | 日东电工株式会社 | 聚酯系粘合剂组合物及粘合片 |
US20160152870A1 (en) * | 2014-12-02 | 2016-06-02 | Nitto Denko Corporation | Surface protective pressure-sensitive adhesive sheet |
WO2018074416A1 (ja) * | 2016-10-21 | 2018-04-26 | 東亞合成株式会社 | ポリエステル系樹脂組成物 |
Also Published As
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EP2826832A4 (en) | 2015-11-04 |
EP2826832B1 (en) | 2017-05-03 |
KR20140136430A (ko) | 2014-11-28 |
US9902886B2 (en) | 2018-02-27 |
KR102061370B1 (ko) | 2019-12-31 |
US20150050493A1 (en) | 2015-02-19 |
JP2013216874A (ja) | 2013-10-24 |
JP6088291B2 (ja) | 2017-03-01 |
CN104114660A (zh) | 2014-10-22 |
EP2826832A1 (en) | 2015-01-21 |
CN104114660B (zh) | 2016-10-19 |
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