WO2013161759A1 - 透明粘接着シート用組成物、その製造方法及び透明粘接着シート - Google Patents
透明粘接着シート用組成物、その製造方法及び透明粘接着シート Download PDFInfo
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- WO2013161759A1 WO2013161759A1 PCT/JP2013/061782 JP2013061782W WO2013161759A1 WO 2013161759 A1 WO2013161759 A1 WO 2013161759A1 JP 2013061782 W JP2013061782 W JP 2013061782W WO 2013161759 A1 WO2013161759 A1 WO 2013161759A1
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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
-
- 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
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
-
- 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
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/29—Laminated material
-
- 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]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
-
- 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
-
- 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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
Definitions
- the present invention relates to a transparent adhesive sheet composition, a production method thereof, and a transparent adhesive sheet comprising the transparent adhesive sheet composition.
- an adhesive having excellent heat resistance and light resistance is often used for bonding optical members used in electronic parts such as liquid crystal display devices and touch panels.
- the pressure-sensitive adhesive is literally a pressure-sensitive adhesive, it can be used for bonding applications such as adhesives that require high peel strength and shear stress, and sealing applications for electronic components that require strength. It was difficult.
- an adhesive that is excellent in tackiness and flexibility at the beginning, is cured by heat and light, and becomes an adhesive that expresses high strength, so-called adhesive or adhesive sheet attracts attention has been.
- Such adhesive sheets can be used for bonding with convex parts such as lens parts of lens sheets of liquid crystal displays and projection televisions, and thin layers such as plastic films or plastic sheets used as optical components.
- an adhesive composition comprising a (meth) acrylic polymer, a graft polymer obtained by graft polymerization of a chain containing a cyclic ether group-containing monomer, and a photocationic polymerization initiator (Patent Document 1).
- An curable sheet (Patent Document 2) has been proposed.
- the photocation curable adhesive composition has problems such as water absorption or corrosion caused by an acid derived from a photocation polymerization initiator, which is a drawback of photocation polymerization.
- the active energy ray-curable adhesive sheet obtained by semi-curing the active energy ray-curable composition is not preferable from the viewpoint of safety in the working environment because it contains a large amount of uncured low molecular weight components. There was a problem.
- the present situation is that an excellent composition for an adhesive sheet having all characteristics such as tackiness, step following ability, curability and adhesiveness at a high level has not been obtained.
- the problem to be solved by the present invention is that, when initial bonding with an adherend, it exhibits moderate tackiness and step following ability due to sufficient flexibility as an adhesive, and is equivalent to an adhesive by photocuring after bonding.
- An object is to provide an adhesive sheet.
- a composition for a transparent adhesive sheet that can be suitably used for optical component having a step, electronic component, organic EL element sealing, circuit board wiring protection, its production method, and transparent adhesive comprising the composition
- An object of the present invention is to provide a transparent adhesive sheet having an adhesion layer.
- the present inventors have obtained a (meth) acrylic copolymer having a specific structural unit, (B) a crosslinking agent, (C) It discovered that the composition for transparent adhesive sheets which consists of a photoinitiator was favorable in transparency, adhesiveness, level
- the present invention is indicated by [1] to [10] below.
- each R 1 independently represents a hydrogen atom or a methyl group
- each R 2 independently represents an alkylene group having 1 to 6 carbon atoms
- R 3 represents a residual hydroxyl group of the polyolefin polyol or hydrogenated polyolefin polyol.
- Chemical formula (II): (In the chemical formula (II), R 4 represents a hydrogen atom or a methyl group, R 5 represents an alkylene group having 1 to 6 carbon atoms, and R 6 represents a dehydroxylated residue of the polyolefin polyol or hydrogenated polyolefin polyol. .)
- the composition for transparent adhesive sheets containing the (meth) acrylic-type copolymer which has a structural unit shown by (B), (B) crosslinking agent, and (C) photoinitiator.
- the (meth) acrylic copolymer having the structural unit represented by the chemical formula (I) and the chemical formula (II) is one or more (meth) acryloyl group-containing monomers (those having an isocyanate group)
- the composition for transparent adhesive sheets according to [1] which has a structural unit derived from.
- (A) The (meth) acrylic copolymer having the structural unit represented by the chemical formula (I) and the chemical formula (II) is synthesized by the following step (1) and step (2).
- Step (2) A part of the terminal hydroxyl group of the structural unit represented by the chemical formula (II) of the (meth) acrylic copolymer synthesized in the step (1) is urethanated with (meth) acryloyloxyalkyl isocyanate, A step of synthesizing a (meth) acrylic copolymer having a structural unit represented by chemical formula (I).
- composition for transparent adhesive sheet according to any one of [1] to [3], comprising 0.2 to 5% by mass of an initiator.
- crosslinking agent is at least one compound selected from the group consisting of a polyfunctional melamine compound, a polyfunctional epoxy compound, and a polyfunctional isocyanate compound.
- a composition for transparent adhesive sheet wherein the acid value of the composition for transparent adhesive sheet according to any one of [1] to [6] is 0 to 5 mgKOH / g or less.
- a transparent adhesive having a transparent adhesive layer obtained by crosslinking the transparent adhesive sheet composition according to any one of [1] to [7] with (B) a crosslinking agent. Attached sheet.
- a transparent adhesive sheet wherein the transparent adhesive sheet according to [8] is formed on one side of a transparent substrate.
- Step (1) A (meth) acrylic copolymer having a structural unit represented by the chemical formula (I) and the chemical formula (II) is synthesized by the following steps (1) and (2).
- Step (2) The method for producing a transparent adhesive sheet composition as described in any one of [4] to [7].
- Step (1) One or more (meth) acryloyl group-containing monomers (excluding those having an isocyanate group) and (meth) acryloyloxyalkyl in the presence of a polyolefin polyol or hydrogenated polyolefin polyol and a tin-based catalyst.
- the composition for transparent adhesive sheet of the present invention includes a step followability by including a (meth) acrylic copolymer having a specific structural unit, that is, a polyolefin polyol or a hydrogenated polyolefin polyol skeleton, in the composition, and Adhesive strength to the substrate is improved. Furthermore, by causing the unsaturated group introduced into the (meth) acrylic copolymer to react by photocuring, it is possible to exhibit peel resistance equivalent to that of the adhesive and high shear stress. Therefore, it can be suitably used as a transparent adhesive sheet that can be used for electronic parts having steps, sealing of organic EL elements, and wiring protection of circuit boards.
- the (meth) acryloyl group means CH 2 ⁇ CH—CO— or CH 2 ⁇ C (CH 3 ) —CO—
- the isocyanate group means —N ⁇ C ⁇ O.
- the (meth) acrylic copolymer means a polymer having a plurality of structural units derived from a compound having a (meth) acryloyl group, and is modified to have the functional group by an addition reaction after polymerization. Also included.
- composition for transparent adhesive sheet comprises (A) chemical formula (I): (In the chemical formula (I), each R 1 independently represents a hydrogen atom or a methyl group, each R 2 independently represents an alkylene group having 1 to 6 carbon atoms, and R 3 represents a residual hydroxyl group of the polyolefin polyol or hydrogenated polyolefin polyol.
- R 4 represents a hydrogen atom or a methyl group
- R 5 represents an alkylene group having 1 to 6 carbon atoms
- R 6 represents a dehydroxylated residue of the polyolefin polyol or hydrogenated polyolefin polyol. .
- a (meth) acrylic copolymer having a structural unit (B) a crosslinking agent, and (C) a photopolymerization initiator.
- the “dehydroxylated residue” means a partial structure other than the hydroxyl group of a compound having a hydroxyl group.
- the polyolefin polyol or hydrogenated polyolefin polyol is also referred to as “polyolefin polyol or the like”.
- the (meth) acrylic copolymer having a structural unit represented by (A) chemical formula (I) or chemical formula (II) of the present invention is preferably one or more (meth) acryloyl group-containing monomers (having isocyanate groups). Excluding those having a structural unit derived from).
- R 2 and R 5 in the chemical formulas (I) and (II) are each independently an alkylene group having 1 to 6 carbon atoms, preferably 2 to 5 carbon atoms, more preferably 2 to 4 carbon atoms.
- R 3 and R 6 are each independently a hydroxyl group-removed residue such as a polyolefin polyol, which will be described later.
- the method for synthesizing a (meth) acrylic copolymer having a structural unit represented by chemical formula (I) or chemical formula (II) is not particularly limited, but (A) chemical formula (I) or chemical formula (II) It is preferable that the (meth) acrylic copolymer having the structural unit represented by is synthesized by the following steps (1) and (2).
- Step (1) One or more (meth) acryloyl group-containing monomers (excluding those having an isocyanate group) and (meth) acryloyloxyalkyl isocyanate (in the following) in the presence of a polyolefin polyol or the like and a tin-based catalyst And a (meth) acrylic copolymer having a structural unit represented by the chemical formula (II) by copolymerizing “sometimes referred to as a (meth) acryloyl group-containing monomer having an isocyanate group as a functional group”) Is synthesized.
- Step (2) A part of the terminal hydroxyl group of the structural unit represented by the chemical formula (II) of the (meth) acrylic copolymer synthesized in the step (1) is urethanated with (meth) acryloyloxyalkyl isocyanate, A (meth) acrylic copolymer having a structural unit represented by the chemical formula (I) is synthesized.
- step (1) copolymerization of a (meth) acryloyl group-containing monomer (excluding those having an isocyanate group) and (meth) acryloyloxyalkyl isocyanate, and the (meth) acryloyloxyalkyl isocyanate and polyolefin polyol, etc. It is possible to synthesize a (meth) acrylic copolymer having a polyolefin skeleton in the side chain while preventing phase separation of (meth) acrylic polymer, which is a heterogeneous polymer, and polyolefin polyol, by proceeding with the addition reaction simultaneously. It becomes possible.
- the polyolefin polyol remaining without being incorporated into the (meth) acrylic copolymer in the step (1) is subjected to an addition reaction with the isocyanate group of the (meth) acryloyloxyalkyl isocyanate added in the step (2), so that an unsaturated group is obtained. Can be introduced.
- transduced the unsaturated group can be incorporated in a transparent adhesive sheet
- step (1) it is preferable to add 1.5 to 4 mol of polyolefin polyol or the like, and 1.6 to 3.5 mol of polyolefin polyol or the like with respect to 1 mol of (meth) acryloyloxyalkyl isocyanate. preferable.
- the charged amount of polyolefin polyol or the like is less than 1.5 mol with respect to 1 mol of (meth) acryloyloxyalkyl isocyanate, it is not preferable because the polyolefin polyol or the like crosslinks the (meth) acrylic polymer at the time of synthesis. There is a case.
- the amount of polyolefin polyol or the like charged is more than 4 mol, a large amount of polyolefin polyol or the like contained in the transparent adhesive sheet composition was present, and the transparent adhesive sheet composition was photocured. Since there exists a tendency for the intensity
- a known radical polymerization method can be used as a method of copolymerizing the (meth) acryloyl group-containing monomer (excluding those having an isocyanate group) and (meth) acryloyloxyalkyl isocyanate in the step (1).
- the radical polymerization method include a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, and a polymerization method by ultraviolet irradiation. In view of transparency, water resistance, cost, etc., a solution polymerization method and a UV polymerization method are preferable, and a solution polymerization method can be particularly preferably used.
- the (meth) acryloyl group-containing monomer (excluding those having an isocyanate group) used for the polymerization of the (A) (meth) acrylic copolymer in the present invention is not particularly limited, and may be used alone or in two kinds. The above can be used in combination.
- the amount of the (meth) acryloyl group-containing monomer (excluding those having an isocyanate group) is (meth) acryloyl group-containing monomer (excluding those having an isocyanate group) and copolymerized therewith (meta ) It is preferably 90 to 99.5 mol%, more preferably 93 to 99 mol%, still more preferably 95 to 98 mol%, based on the total of acryloyloxyalkyl isocyanate. If the amount of the (meth) acryloyl group-containing monomer (excluding those having an isocyanate group) is less than 90 mol%, too much polyolefin polyol or the like added to the (meth) acrylic copolymer will increase.
- the cohesive force of the acrylic copolymer may be too small, which may not be preferable, and if it exceeds 99.5 mol%, the polyolefin polyol added to the (meth) acrylic copolymer will be too small, so that transparent adhesive There is a tendency that the step following property of the sheet becomes insufficient.
- Examples of (meth) acryloyloxyalkyl isocyanate ((meth) acryloyloxyalkyl isocyanate used in step (1)) suitably used for the polymerization of (A) (meth) acrylic copolymer in the present invention include: 2- (meth) acryloyloxyethyl isocyanate, 3- (meth) acryloyloxypropyl isocyanate, 4- (meth) acryloyloxybutyl isocyanate, 5- (meth) acryloyloxypentyl isocyanate, 6- (meth) acryloyloxyhexyl isocyanate Etc.
- 2- (meth) acryloyloxyethyl isocyanate is preferred from the viewpoint of reactivity with a hydroxyl group.
- the carbon number of R 5 is larger than 6, reactivity with polyolefin polyol or the like tends to be low.
- the polymerization initiator used in the radical copolymerization of the (meth) acryloyl group-containing monomer (excluding those having an isocyanate group) and (meth) acryloyloxyalkyl isocyanate is not particularly limited, and is appropriately selected from known ones. Can be used.
- a polymerization initiator can be used individually or in combination of 2 or more types.
- the amount of the polymerization initiator used may be a normal amount, for example, a total of 100 parts by weight of (meth) acryloyl group-containing monomer (excluding those having an isocyanate group) and (meth) acryloyloxyalkyl isocyanate.
- it can be selected from the range of about 0.01 to 5 parts by mass, preferably in the range of 0.02 to 4 parts by mass, and more preferably 0.03 to 3 parts by mass.
- solvents include esters such as ethyl acetate, n-propyl acetate and n-butyl acetate, aromatic hydrocarbons such as toluene and benzene, aliphatic hydrocarbons such as n-hexane and n-heptane, Examples thereof include organic solvents such as cycloaliphatic hydrocarbons such as cyclohexane and methylcyclohexane, and ketones such as methyl ethyl ketone and methyl isobutyl ketone.
- a solvent can be used individually or in combination of 2 or more types.
- polyolefin polyol used in the production of the (A) (meth) acrylic copolymer in the present invention for example, commercially available various polyols of saturated and unsaturated alkyl compounds can be used. Specific examples include polyethylene polyol, polypropylene polyol, polybutadiene polyol, polyisoprene polyol, hydrogenated polybutadiene polyol, hydrogenated polyisoprene polyol, and the like. Of these, hydrogenated 1,2-polybutadiene polyol or hydrogenated polyisoprene polyol is preferable in terms of light resistance, transparency (non-crystallinity), and workability (liquid state).
- the hydrogenated 1,2-polybutadiene refers to a hydrogen atom that has been converted into a single bond by reacting hydrogen with the double bond portion of 1,2-polybutadiene. The same applies to hydrogenated polyisoprene.
- the number average molecular weight of the polyolefin polyol and the like used in the present invention is preferably 500 to 5000, more preferably 1000 to 4000, and further preferably 1500 to 3500.
- the number average molecular weight is smaller than 500, the step following property of the transparent adhesive sheet tends to be deteriorated. If the number average molecular weight is greater than 5000, the viscosity of the adhesive tends to be too high.
- Dehydroxylated residues such as the polyolefin polyols described above correspond to R 3 or R 6 in the chemical formulas (I) and (II).
- step (1) in order to obtain a (meth) acrylic copolymer having a structural unit represented by chemical formula (II), an addition reaction such as polyolefin polyol is performed on the isocyanate group, that is, a urethanization reaction.
- a known urethanization catalyst can be used for the urethanization reaction, and a tin-based catalyst is particularly preferable.
- tin-based catalysts include dibutyltin dilaurate, dibutyltin diethylhexoate, dioctyltin dilaurate, and the like, and dioctyltin dilaurate is preferred from the viewpoint of safety.
- the amount of urethanization catalyst used is based on the total mass of raw materials used for the reaction (that is, (meth) acryloyl group-containing monomers (excluding those having an isocyanate group), (meth) acryloyloxyalkyl isocyanate, polyolefin polyol, etc. (Based on the total mass), it is usually 10 to 300 wtppm, preferably 30 to 250 wtppm, more preferably 50 to 200 wtppm.
- This urethanization catalyst can also be used as a curing agent for a crosslinking agent added when producing a transparent adhesive sheet.
- the reaction conditions for the addition reaction are usually preferably 30 to 100 ° C. and continued for about 1 to 10 hours.
- the said wtppm means mass ppm.
- step (2) the isocyanate group of (meth) acryloyloxyalkyl isocyanate is added to a part of the terminal hydroxyl groups of the structural unit represented by chemical formula (II) of the (meth) acrylic copolymer synthesized in step (1).
- An unsaturated group is introduced into the acrylic copolymer by addition reaction.
- the polymerization initiator used in step (1) it is important to sufficiently decompose the polymerization initiator used in step (1).
- the polymerization initiator used in the step (1) can be sufficiently eliminated by setting the temperature in the system to 80 ° C. or more and aging for 3 hours or more.
- Step (2) in the present invention that is, (meth) acryloyloxyalkyl isocyanate is formed on a part of terminal hydroxyl groups of the structural unit represented by chemical formula (II) of the (meth) acrylic copolymer synthesized in step (1).
- the (meth) acryloyloxyalkyl isocyanate used in the step of addition reaction is not particularly limited as long as the alkyl group has 1 to 6 carbon atoms, and the isocyanate group is preferably used for polymerization in the step (1).
- the same thing as the (meth) acryloyl-group containing monomer which has a functional group can be illustrated.
- the (meth) acryloyloxyalkyl isocyanate used in step (1) and the (meth) acryloyloxyalkyl isocyanate used in step (2) are the same as long as the alkyl group has 1 to 6 carbon atoms. You may use and a different thing may be used.
- R 1, R 2 derived from (meth) acryloyloxy alkyl isocyanate step (1) R 1, R 2 derived from (meth) acryloyloxy alkyl isocyanate step (2) is , Each may be the same or different.
- the carbon number of R 2 when the carbon number of R 2 is larger than 6, the reactivity tends to decrease.
- Conditions for addition reaction of (meth) acryloyloxyalkyl isocyanate to a part of terminal hydroxyl groups of the structural unit represented by chemical formula (II) of the (meth) acrylic copolymer synthesized in step (1) of step (2) In general, it is preferably carried out continuously at 30 to 100 ° C. for about 1 to 10 hours.
- a process (1) and a process (2) may be performed continuously, after finishing a process (1), after taking out once and performing a process (2), the point of workability
- the above (meth) acryloyl group-containing monomer excluding those having an isocyanate group
- the above (meta) in addition to acryloyloxyalkyl isocyanate, other monomers can be used as appropriate.
- Examples of the other monomers include vinyl monomers such as vinyl acetate, vinyl propionate, vinyl laurate, vinyl alcohol, sodium vinyl sulfonate, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, 2-hydroxyethyl vinyl ether, ethylene, Olefins such as butadiene and vinyl chloride, allyl monomers such as allyl alcohol, allyl glycidyl ether, allyl sulfonic acid, allyl amide, and allyl carbonate, carboxyl group-containing monomers such as itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid, Acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride, cyclohexylmaleimide, isopropylmaleimide, N-cyclohexylmaleimide, itaco Imide group-containing monomers such as im
- the molecular weight of the (A) (meth) acrylic copolymer in the present invention is preferably 50,000 to 1,000,000, more preferably 80,000 to 800,000, more preferably 100,000 to 500,000. More preferably it is.
- the weight average molecular weight is less than 50,000, the cohesive force of the polymer becomes small, and the adhesion may be low.
- the weight average molecular weight is greater than 1,000,000, the viscosity of the transparent adhesive sheet composition may become too high, which is not preferable.
- the value of the weight average molecular weight in the present invention is measured at normal temperature using gel permeation chromatography (Shodex GPC-101 manufactured by Showa Denko KK) at the following conditions, and is calculated in terms of polystyrene.
- Analytical column Showa Denko LF-804 Reference column: OHpakSB-800RL manufactured by Showa Denko KK Column temperature: 40 ° C
- Sample 0.2% by weight tetrahydrofuran solution of copolymer
- Standard sample Standard sample for exclusion chromatography (polystyrene)
- Flow rate 1 ml / min
- Eluent Tetrahydrofuran detector: RI detector
- the crosslinking agent (B) used in the transparent adhesive sheet composition of the present invention is not particularly limited as long as it is a polyfunctional compound having at least two groups bonded to hydroxyl groups such as polyolefin polyol. Can do.
- a crosslinking agent can be used individually or in mixture of 2 or more types. In the present invention, by using the crosslinking agent (B), when the acrylic adhesive layer is formed, the acrylic polymer has a crosslinked structure, and the durability of the transparent adhesive sheet is improved.
- Examples of the crosslinking agent (B) that can be used in the present invention include polyfunctional melamine compounds, polyfunctional epoxy compounds, and polyfunctional isocyanate compounds.
- polyfunctional melamine compound examples include methylated trimethylol melamine and butylated hexamethylol melamine.
- polyfunctional epoxy compound diglycidyl aniline, glycerol diglycidyl ether, etc. are mentioned, for example.
- polyfunctional isocyanate compound for example, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), 2-methyl-1,5-pentane diisocyanate, 3-methyl-1,5 -Pentane diisocyanate, isophorone diisocyanate, cyclohexyl diisocyanate, tolylene diisocyanate (TDI), hydrogenated tolylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, reaction product of trimethylolpropane and tolylene diisocyanate, trimethylolpropane and hexamethylene Reaction products with diisocyanate, polyether polyisocyanate, polyester polyisocyanate, hydrogenated xylene diiso Aneto include hydrogenated tetramethyl xylene diisocyanate.
- HDI 1,6-hexamethylene diisocyanate
- a polyfunctional isocyanate compound (isocyanate crosslinking agent) as a crosslinking agent because of its reactivity with hydroxyl groups such as polyolefin polyol, and 1,6-hexamethylene diisocyanate of an aliphatic isocyanate (in terms of yellowing resistance).
- HDI high-density polyethylene diisocyanate
- IPDI isophorone diisocyanate
- diphenylmethane diisocyanate are preferably used.
- the amount of the crosslinking agent (B) used is not particularly limited, but is preferably 0.01 to 10 parts by mass, for example, with respect to 100 parts by mass of the (A) (meth) acrylic copolymer.
- the amount is preferably 0.02 to 9 parts by mass, more preferably 0.05 to 8 parts by mass.
- (C) Photopolymerization initiator There is no restriction
- photoinitiators Only 1 type of these photoinitiators may be used independently, and 2 or more types may be used together.
- these (C) photopolymerization initiators bis (2,4,6-trimethylbenzoyl) -diphenylphosphine oxide and / or 1-hydroxycyclohexyl phenyl ketone is used from the viewpoint of transparency. preferable.
- These (C) photoinitiators are used individually or in combination of 2 or more types.
- the content of the photopolymerization initiator is 0.2 to 5 in the transparent adhesive sheet composition from the viewpoint of the balance between photocurability and the strength and adhesiveness of the obtained transparent adhesive sheet. % By mass, preferably 0.5 to 3% by mass, more preferably 0.8 to 2% by mass. When the content of the (C) photopolymerization initiator in the transparent adhesive sheet composition is less than 0.2% by mass, photocuring tends to be insufficient. When the content of the (C) photopolymerization initiator in the transparent adhesive sheet composition exceeds 5% by mass, the heat resistant yellowing of the transparent adhesive sheet obtained tends to decrease.
- the acid value of the composition for transparent adhesive sheets is 0. It is preferably ⁇ 5 mg KOH / g. More preferably, it is 0 to 0.3 mgKOH / g, and still more preferably 0 to 0.1 mgKOH / g. When the acid value is higher than 5 mgKOH / g, there is a possibility of metal corrosion, which is not preferable.
- the acid value of the composition is a value measured according to JIS K0070. For example, measurement is performed as follows.
- a polymerizable monomer may be added to the composition for transparent adhesive sheet of the present invention as long as the transparency is not lowered.
- a polymerizable monomer the monomer which can be used for superposition
- a tackifier resin may be added to the composition for transparent adhesive sheet of the present invention as long as the transparency is not lowered.
- tackifying resins include rosin resins such as rosin and rosin esterified products; terpene resins such as diterpene polymers and ⁇ -pinene-phenol copolymers; aliphatic (C5) and aromatic ( Petroleum resin such as C9); styrene resin, phenol resin, xylene resin and the like. It is possible to add hydrogenated rosin, disproportionated rosin esterified products, aliphatic and aromatic petroleum resins, high Tg acrylic resins, etc. to the transparent adhesive sheet with few unsaturated double bonds in terms of light resistance. preferable.
- the addition amount of the tackifying resin is preferably 1 to 10 parts by mass with respect to 100 parts by mass of the transparent adhesive sheet composition.
- the transparent adhesive sheet composition of the present invention may contain various known additives as long as the transparency is not impaired.
- Additives include plasticizers, surface lubricants, leveling agents, softeners, antioxidants, antioxidants, light stabilizers, UV absorbers, polymerization inhibitors, benzotriazole-based light stabilizers, phosphate esters System and other flame retardants, and antistatic agents such as surfactants.
- composition for transparent adhesive sheet of the present invention may be diluted with an organic solvent for the purpose of adjusting the viscosity during coating.
- organic solvent used include methyl ethyl ketone, methyl isobutyl ketone, acetone, ethyl acetate, n-propyl acetate, tetrahydrofuran, dioxane, cyclohexanone, n-hexane, toluene, xylene, n-propanol and isopropanol.
- organic solvents may be used alone or in combination of two or more.
- n-propyl acetate is preferable from the viewpoint of solubility of polyolefin polyol and the like.
- the transparent adhesive sheet of the present invention is a transparent adhesive sheet characterized by having a transparent adhesive layer obtained by crosslinking the composition for transparent adhesive sheet with (B) a crosslinking agent. . More specifically, it is used for applications such as sealing optical parts, electronic parts, organic EL elements, and circuit board wiring protection optical members. Moreover, as for the transparent adhesive sheet
- transparent substrates examples include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, cycloolefin, cellophane, diacetyl cellulose, triacetyl cellulose, acetyl cellulose butyrate, polyvinyl chloride, polyvinylidene chloride, and polyvinyl alcohol.
- ethylene-vinyl acetate copolymer polystyrene, polycarbonate, polymethylpentene, polysulfone, polyetheretherketone, polyethersulfone, polyetherimide, polyimide, fluorine resin, nylon, acrylic resin and the like.
- polyethylene terephthalate, cycloolefin, and polycarbonate which are excellent in transparency and durability, are preferable.
- a transparent adhesive sheet is a transparent base film or a release film.
- the transparent adhesive sheet composition of the present invention is applied with a solution in which the composition for transparent adhesive sheet is dissolved in a solvent, and the applied solution is dried by heating and cross-linked. It can be obtained by forming an adhesive layer.
- the film thickness of the transparent adhesive sheet is preferably 5 to 200 ⁇ m, more preferably 10 to 150 ⁇ m, and even more preferably 20 to 100 ⁇ m. When the film thickness of a transparent adhesive sheet becomes thinner than 5 micrometers, there exists a tendency for bonding of a transparent adhesive sheet to become difficult. If the film thickness of the transparent adhesive sheet is greater than 200 ⁇ m, the solvent remains on the sheet, which is not preferable because of the problem of odor.
- a known coating method for coating (coating) in the method for forming a transparent adhesive sheet of the present invention, a known coating method can be used, and a conventional coater, for example, a gravure roll coater, a reverse roll coater, or a kiss roll.
- a coater, dip roll coater, bar coater, knife coater, spray coater, comma coater, direct coater and the like can be used.
- the glass transition temperature of the transparent adhesive sheet before UV curing of the present invention is preferably ⁇ 70 to 0 ° C. from the viewpoint of the adhesive strength and the step following ability of the transparent adhesive sheet. More preferably, it is ⁇ 50 to 0 ° C. or less. When it is lower than ⁇ 70 ° C., the transparent adhesive sheet obtained is too soft and the cohesive force of the transparent adhesive sheet may be too low, which is not preferable. Moreover, when higher than 0 degreeC, since level
- the glass transition temperature (Tg) refers to that obtained from the following method. That is, a 10 mg sample was taken from the transparent adhesive sheet, and the differential scanning calorimeter (DSC) was used to perform differential scanning by changing the temperature from ⁇ 80 ° C. to 200 ° C. at a heating rate of 10 ° C./min. Calorimetric measurement is performed, and the endothermic start temperature due to glass transition is defined as Tg. When two Tg's are observed, an arithmetic average value of the two Tg's is taken.
- DSC differential scanning calorimeter
- the cohesion force of a transparent adhesive sheet can be heightened by irradiating UV.
- the composition for transparent adhesive sheets of this invention contains (A) (meth) acrylic-type copolymer which has a specific structural unit, it contains the transparent adhesive layer which consists of this composition.
- the step following property of the transparent adhesive sheet and the adhesive force to the substrate are good.
- the transparent adhesive sheet of the present invention can be suitably used for electronic components having steps, sealing of organic EL elements, and wiring protection of circuit boards.
- the hydroxyl value is determined by adding a pyridine solution containing acetic anhydride to the composition, acetylating the hydroxyl group of the (meth) acrylic copolymer, and then removing excess acetylating reagent with water. The resulting acetic acid was added dropwise with potassium hydroxide solution. The end point was an inflection point on the dropping curve, and the hydroxyl value of the composition was calculated from the amount of dripping up to the end point of the potassium hydroxide solution.
- the hydroxyl value of the composition is a value obtained from the result measured in accordance with the above-mentioned JIS K1557-1, and the acid value of the composition is a value obtained from the result measured in accordance with the above-described JIS K0070. is there.
- Step (1) In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer and a stirrer, 500 parts of n-propyl acetate, hydrogenated polyolefin diol (manufactured by Nippon Soda Co., Ltd., GI-3000, hydroxyl value ( (Product value) 29.5 mg KOH / g, number average molecular weight 3800) 293 parts (0.10 mol), dioctyltin dilaurate 0.03 parts (0.04 mmol), 2-ethylhexyl acrylate 97 parts (0.51 mol) 98 parts (0.46 mol) of isobornyl acrylate, 4.0 parts (0.03 mol) of 2-methacryloyloxyethyl isocyanate, 0.1 part of 2,2-azoisobutylnitrile, and 95 Polymerized at 8 ° C.
- Step (2) 7.8 parts (0.05 mol) of 2-methacryloyloxyethyl isocyanate was placed in the reaction vessel containing the (meth) acrylic copolymer obtained in Step (1), in an air stream. An addition treatment was performed at 60 ° C. for 4 hours, and a (meth) acrylic copolymer (A) having a double bond equivalent of 10,000 g / mol, a hydroxyl value of 15 mg KOH / g, a glass transition temperature of ⁇ 20 ° C., and a weight average molecular weight of 300,000. -1) was obtained.
- A acrylic copolymer having a double bond equivalent of 10,000 g / mol, a hydroxyl value of 15 mg KOH / g, a glass transition temperature of ⁇ 20 ° C., and a weight average molecular weight of 300,000. -1) was obtained.
- Examples 1 to 4, Comparative Examples 1 and 2 Each of the compositions shown in Table 2 was blended with a crosslinking agent and a photopolymerization initiator, and the solid content concentration was adjusted with n-propyl acetate, and the adhesive composition solution (solid content concentration: 50% by mass) was added to room temperature.
- the composition solution for transparent adhesive sheets was prepared by mixing using a disper below. This solution was cast and applied on one side of a 50 ⁇ m thick polyethylene terephthalate (PET) film so that the thickness after drying was 50 ⁇ m (coating layer thickness 100 ⁇ m), at 50 ° C. for 5 minutes and at 110 ° C.
- PET polyethylene terephthalate
- the film was dried by heating for 3 minutes, and the side of the release-treated surface of the separator that had been subjected to the release treatment on one side of a 50 ⁇ m thick PET film was covered with the adhesive side. And aging was performed at 40 degreeC for 72 hours, and the transparent adhesive sheet (PET base material type) was produced.
- Glass transition temperature of transparent adhesive sheet A 10 mg sample was taken from the transparent adhesive sheet, and a differential scanning calorimeter (DSC) was used to change the temperature from ⁇ 80 ° C. to 200 ° C. at a heating rate of 10 ° C./min. Measurement was performed, and the endothermic start temperature due to glass transition was defined as Tg. In addition, when two Tg was observed, it was decided to take the arithmetic mean value of two Tg. The results are shown in Table 2.
- the transparent adhesive sheet is cut to a size of 25 mm ⁇ 100 mm, the PET film on which the transparent adhesive sheet is peeled off is peeled off, and the adhesive surface (measurement surface) is a test plate with a 2 kg rubber roller (width) : About 50 mm) was reciprocated once to prepare a measurement sample.
- a glass plate was used as a test plate.
- the obtained sample for measurement is left for 24 hours in an environment of 23 ° C. and 50% humidity.
- the longitudinal direction of the transparent adhesive sheet is pulled in the 180 ° direction at a peeling rate of 300 mm / min.
- the test was conducted, and the adhesive strength (N / 25 mm) of the transparent adhesive sheet to the glass plate was measured.
- the obtained measured value was defined as the adhesive strength before UV curing, and the results are shown in Table 2.
- an ultraviolet irradiation device made by Eye Graphics Co., Ltd., UV irradiation device 3 kw, high pressure mercury lamp
- irradiation distance 26 cm lamp moving speed 2.0 m /
- a measurement sample that was photocured by irradiating ultraviolet rays under conditions of min and an irradiation amount of about 500 mJ / cm 2 was allowed to stand for 24 hours in an environment of 23 ° C. and humidity of 50%, and the peeling speed was 300 mm according to JIS Z0237.
- a tensile test in the direction of 180 ° is performed per minute, the adhesive strength (N / 25 mm) of the transparent adhesive sheet to the glass plate is measured, and the obtained measured value is defined as the adhesive strength after UV curing. Indicated.
- Step following capability A glass with a printed step, on which a black linear print having a length of 50 mm, a width of 1 mm, and a height of 15 ⁇ m is applied to a glass plate having a thickness of 0.5 mm, a length of 50 mm, and a width of 40 mm in a stripe shape with a line interval of 1 mm.
- the transparent adhesive sheet is cut to a size of 50 mm ⁇ 40 mm, and the PET film that has been subjected to the release treatment is peeled off, and the transparent adhesive sheet is bonded, and 5 atm, 70 ° C., After fixing by performing heating and pressing under conditions of 10 minutes, the floating of the adhesive layer at the step portion was visually observed.
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Abstract
Description
化学式(II):
で示される構造単位を有する(メタ)アクリル系共重合体と、(B)架橋剤と、(C)光重合開始剤とを含む透明粘接着シート用組成物。
工程(1):ポリオレフィンポリオール又は水添ポリオレフィンポリオール、及び、スズ系触媒の存在下で、一種以上の(メタ)アクリロイル基含有モノマー(イソシアネート基を有するものを除く。)と(メタ)アクリロイルオキシアルキルイソシアネートを共重合し、化学式(II)に示される構造単位を有する(メタ)アクリル系共重合体を合成する工程。
工程(2):工程(1)で合成された(メタ)アクリル系共重合体の化学式(II)に示される構造単位の末端水酸基の一部を(メタ)アクリロイルオキシアルキルイソシアネートでウレタン化して、化学式(I)に示される構造単位を有する(メタ)アクリル系共重合体を合成する工程。
工程(1):ポリオレフィンポリオール又は水添ポリオレフィンポリオール、及び、スズ系触媒の存在下で、一種以上の(メタ)アクリロイル基含有モノマー(イソシアネート基を有するものを除く。)と(メタ)アクリロイルオキシアルキルイソシアネートを共重合し、化学式(II)に示される構造単位を有する(メタ)アクリル系共重合体を合成する工程。
工程(2):工程(1)で合成された(メタ)アクリル系共重合体の化学式(II)に示される構造単位の末端水酸基の一部を(メタ)アクリロイルオキシアルキルイソシアネートでウレタン化して、化学式(I)に示される構造単位を有する(メタ)アクリル系共重合体を合成する工程。
本発明の透明粘接着シート用組成物は、(A)化学式(I):
化学式(II):
本発明の(A)化学式(I)、化学式(II)で示される構造単位を有する(メタ)アクリル系共重合体は、好ましくは、一種以上の(メタ)アクリロイル基含有モノマー(イソシアネート基を有するものを除く。)由来の構造単位を有する。
工程(1):ポリオレフィンポリオール等、及び、スズ系触媒の存在下で、一種以上の(メタ)アクリロイル基含有モノマー(イソシアネート基を有するものを除く。)と(メタ)アクリロイルオキシアルキルイソシアネート(以下において、単に「イソシアネート基を官能基に持った(メタ)アクリロイル基含有モノマー」ということがある。)を共重合して、化学式(II)に示される構造単位を有する(メタ)アクリル系共重合体を合成する。
工程(2):工程(1)で合成された(メタ)アクリル系共重合体の化学式(II)に示される構造単位の末端水酸基の一部を(メタ)アクリロイルオキシアルキルイソシアネートでウレタン化して、化学式(I)に示される構造単位を有する(メタ)アクリル系共重合体を合成する。
分析カラム:昭和電工株式会社製 LF-804
リファレンスカラム:昭和電工株式会社製 OHpakSB-800RL
カラム温度:40℃
試料:共重合体の0.2質量%テトラヒドロフラン溶液
標準試料:排除クロマトグラフィ用の標準試料(ポリスチレン)
流量:1ml/分
溶離液:テトラヒドロフラン
検出器:RI検出器
本発明の透明粘接着シート用組成物に用いられる(B)架橋剤としては、ポリオレフィンポリオール等の水酸基と結合する基を少なくとも2つ以上有する多官能性の化合物であれば特に制限なく用いることができる。(B)架橋剤は単独で又は2種以上混合して使用することができる。本発明では、(B)架橋剤を用いることにより、アクリル系粘接着剤層を形成する際にアクリル系ポリマーが架橋構造化して、透明粘接着シートの耐久性が向上する。本発明で使用できる(B)架橋剤としては、例えば、多官能性メラミン化合物、多官能性エポキシ化合物、多官能性イソシアネート化合物等を例示することができる。
本発明における(C)光重合開始剤としては、特に制限は無く、公知のものを使用することができる。例えば、ジエトキシアセトフェノン、2-ヒドロキシ-2-メチル-1-フェニルプロパン-1-オン、ベンジルジメチルケタール、4-(2-ヒドロキシエトキシ)フェニル-(2-ヒドロキシ-2-プロピル)ケトン、1-ヒドロキシシクロヘキシルフェニルケトン、2-メチル-2-モルホリノ(4-チオメチルフェニル)プロパン-1-オン、2-ベンジル-2-ジメチルアミノ-1-(4-モルホリノフェニル)ブタノン、2-ヒドロキシ-2-メチル-1-[4-(1-メチルビニル)フェニル]プロパノンオリゴマーなどのアセトフェノン類;ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテルなどのベンゾイン類;ベンゾフェノン、o-ベンゾイル安息香酸メチル、4-フェニルベンゾフェノン、4-ベンゾイル-4’-メチル-ジフェニルサルファイド、3,3’,4,4’-テトラ(t-ブチルパーオキシカルボニル)ベンゾフェノン、2,4,6-トリメチルベンゾフェノン、4-ベンゾイル-N,N-ジメチル-N-[2-(1-オキソ-2-プロペニルオキシ)エチル]ベンゼンメタナミニウムブロミド、(4-ベンゾイルベンジル)トリメチルアンモニウムクロリドなどのベンゾフェノン類;2-イソプロピルチオキサントン、4-イソプロピルチオキサントン、2,4-ジエチルチオキサントン、2,4-ジクロロチオキサントン、1-クロロ-4-プロポキシチオキサントン、2-(3-ジメチルアミノ-2-ヒドロキシ)-3,4-ジメチル-9H-チオキサントン-9-オンメソクロリドなどのチオキサントン類;2,4,6-トリメチルベンゾイル-ジフェニルフォスフィンオキサイド、ビス(2,6-ジメトキシベンゾイル)-2,4,4-トリメチル-ペンチルフォスフィンオキサイド、ビス(2,4,6-トリメチルベンゾイル)-ジフェニルフォスフィンオキサイドなどのアシルフォスフィンオキサイド類などが挙げられる。これらの光重合開始剤は1種のみが単独で用いられてもよいし、2種以上が併用されてもよい。これらの(C)光重合開始剤の中では、透明性の点から、ビス(2,4,6-トリメチルベンゾイル)-ジフェニルフォスフィンオキサイド、及び/又は、1-ヒドロキシシクロヘキシルフェニルケトンを用いるのが好ましい。これらの(C)光重合開始剤は、単独で又は2種類以上を組み合わせて使用される。
f:0.1N水酸化カリウム-エタノール溶液のファクター
S:試料の採取量(g)
本発明の透明粘接着シートは、上記の透明粘接着シート用組成物を(B)架橋剤で架橋させてなる透明粘接着層を有することを特徴とする透明粘接着シートである。より具体的には、光学部品、電子部品、有機EL素子の封止、回路基板の配線保護光学部材を貼り合わせる用途などに用いられる。また、本発明の透明粘接着シートは、透明粘接着シートが透明基材の片面に形成されていても良い。透明基材としては、例えば、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート、ポリエチレン、ポリプロピレン、シクロオレフィン、セロファン、ジアセチルセルロース、トリアセチルセルロース、アセチルセルロースブチレート、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリビニルアルコール、エチレン-酢酸ビニル共重合体、ポリスチレン、ポリカーボネート、ポリメチルペンテン、ポリスルホン、ポリエーテルエーテルケトン、ポリエーテルスルホン、ポリエーテルイミド、ポリイミド、フッソ樹脂、ナイロン、アクリル樹脂等を挙げることができる。なかでも、透明性、耐久性に優れたポリエチレンテレフタレート、シクロオレフィン、ポリカーボネートが好ましい。
工程(1):冷却管、窒素導入管、温度計および撹拌装置を備えた反応容器に、酢酸n-プロピルを500部、水添ポリオレフィンジオール(日本曹達株式会社製、GI-3000、水酸基価(商品記載値)29.5mgKOH/g、数平均分子量3800)を293部(0.10mol)、ジオクチル錫ジラウレートを0.03部(0.04mmol)、2-エチルヘキシルアクリレートを97部(0.51mol)、イソボルニルアクリレートを98部(0.46mol)、2-メタクリロイルオキシエチルイソシアネートを4.0部(0.03mol)、2,2-アゾイソブチルニトリルを0.1部入れ、窒素気流中で95℃にて8時間重合処理をし、水酸基価21mgKOH/g、ガラス転移温度-20℃、重量平均分子量30万の(メタ)アクリル系共重合体を得た。
上記(メタ)アクリル系共重合体(A-1)の合成と同様にして、表1に記載の(メタ)アクリロイル基含有モノマー、(メタ)アクリロイルオキシアルキルイソシアネート、ポリオレフィンポリオール等、及びスズ系触媒の組成で(メタ)アクリル系共重合体(A-2)~(A-4)及び(X-1)~(X-2)を得た。
表2に示す組成でそれぞれ架橋剤、光重合開始剤を配合し、さらに酢酸n-プロピルで固形分濃度を調節して、粘接着剤組成物溶液(固形分濃度:50質量%)を室温下でディスパーを用いて混合することで透明粘接着シート用組成物溶液を調製した。この溶液を、厚さ50μmのポリエチレンテレフタレート(PET)フィルムの片面に、乾燥後の厚さが50μm(塗布層厚さ100μm)となるように流延塗布し、50℃で5分間および110℃で3分間加熱乾燥させ、さらに厚さ50μmのPETフィルムの片面に剥離処理が施されているセパレータの剥離処理面側を粘接着剤側にカバーした。そして、40℃で72時間エージングを行ない、透明粘接着シート(PET基材タイプ)を作製した。
上記JIS K0070に準拠して測定した結果から求めた。表2に各透明粘接着シート用組成物の酸価を示す。
上記透明粘接着シートから10mgの試料を採取して、示差走査熱量計(DSC)を用いて、10℃/分の昇温速度で-80℃から200℃まで温度を変化させて示差走査熱量測定を行ない、ガラス転移による吸熱開始温度をTgとした。なお、Tgが2つ観察された場合には、2つのTgの相加平均値をとることとした。結果を表2に示す。
前記透明粘接着シートを25mm×100mmの大きさに切り取り、透明粘接着シートの剥離処理が施されているPETフィルムを剥がし、粘着面(測定面)を試験板に2kgのゴムローラー(幅:約50mm)を1往復させることにより貼付し、測定用サンプルを作製した。試験板としてガラス板を用いた。得られた測定用サンプルについて、23℃、湿度50%の環境下で24時間放置し、JIS Z0237に準じて、透明粘接着シートの長手方向について、剥離速度300mm/分で180°方向の引張試験を行ない、透明粘接着シートのガラス板に対する粘着力(N/25mm)を測定し、得られた測定値をUV硬化前粘着力とし、結果を表2に示した。
厚さ0.5mm、長さ50mm、幅40mm、のガラス板上に、長さ50mm、幅1mm、高さ15μm、の黒色線状印刷を線間隔1mmの縞状に施した、印刷段差付きガラス板に、前記透明粘接着シートを50mm×40mmの大きさに切ったものの剥離処理が施されているPETフィルムを剥がして、透明粘接着シートの貼り合わせを行ない、5気圧、70℃、10分の条件で加熱加圧処理を行ない固定した後、段差部分の粘接着層の浮きを目視で観察した。
○;段差のある部分にて粘接着層の浮きが確認されない状態
△;段差のある部分にて僅かに粘接着層の浮きが確認される状態
×;段差のある部分にて粘接着層の明かな浮きが確認される状態
Claims (10)
- (A)前記化学式(I)及び前記化学式(II)で示される構造単位を有する(メタ)アクリル系共重合体が、一種以上の(メタ)アクリロイル基含有モノマー(イソシアネート基を有するものを除く。)由来の構造単位を有する請求項1に記載の透明粘接着シート用組成物。
- (A)前記化学式(I)及び前記化学式(II)で示される構造単位を有する(メタ)アクリル系共重合体が、次の工程(1)及び工程(2)により合成されることを特徴とする請求項2に記載の透明粘接着シート用組成物。
工程(1):ポリオレフィンポリオール又は水添ポリオレフィンポリオール、及び、スズ系触媒の存在下で、一種以上の(メタ)アクリロイル基含有モノマー(イソシアネート基を有するものを除く。)と(メタ)アクリロイルオキシアルキルイソシアネートを共重合して、前記化学式(II)に示される構造単位を有する(メタ)アクリル系共重合体を合成する工程。
工程(2):前記工程(1)で合成された(メタ)アクリル系共重合体の前記化学式(II)に示される構造単位の末端水酸基の一部を(メタ)アクリロイルオキシアルキルイソシアネートでウレタン化して、前記化学式(I)に示される構造単位を有する(メタ)アクリル系共重合体を合成する工程。 - (A)(メタ)アクリル系共重合体100質量部に対して(B)架橋剤を0.01~10質量部含み、透明粘接着シート用組成物中に(C)光重合開始剤を0.2~5質量%含む請求項1~3のいずれかに記載の透明粘接着シート用組成物。
- (B)架橋剤が、多官能性メラミン化合物、多官能性エポキシ化合物及び多官能性イソシアネート化合物からなる群より選択される少なくとも1種の化合物である請求項1~4のいずれかに記載の透明粘接着シート用組成物。
- (C)光重合開始剤が、アシルフォスフィンオキサイド類及び/又はアセトフェノン類である請求項1~5のいずれかに記載の透明粘接着シート用組成物。
- 前記透明粘接着シート用組成物の酸価が、0~5mgKOH/g以下であることを特徴とする請求項1~6のいずれかに記載の透明粘接着シート用組成物。
- 請求項1~7のいずれかに記載の透明粘接着シート用組成物を(B)架橋剤で架橋させてなる透明粘接着層を有することを特徴とする透明粘接着シート。
- 前記透明粘接着シートが透明基材の片面に形成されていることを特徴とする請求項8に記載の透明粘接着シート。
- (A)前記化学式(I)及び前記化学式(II)で示される構造単位を有する(メタ)アクリル系共重合体が、次の工程(1)及び工程(2)により合成されることを特徴とする請求項2、4~7のいずれかに記載の透明粘接着シート用組成物の製造方法。
工程(1):ポリオレフィンポリオール又は水添ポリオレフィンポリオール、及び、スズ系触媒の存在下で、一種以上の(メタ)アクリロイル基含有モノマー(イソシアネート基を有するものを除く。)と(メタ)アクリロイルオキシアルキルイソシアネートを共重合して、前記化学式(II)に示される構造単位を有する(メタ)アクリル系共重合体を合成する工程。
工程(2):前記工程(1)で合成された(メタ)アクリル系共重合体の前記化学式(II)に示される構造単位の末端水酸基の一部を(メタ)アクリロイルオキシアルキルイソシアネートでウレタン化して、前記化学式(I)に示される構造単位を有する(メタ)アクリル系共重合体を合成する工程。
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003171622A (ja) * | 2001-12-06 | 2003-06-20 | Showa Highpolymer Co Ltd | 活性光線硬化型再剥離性粘着剤組成物 |
JP2008001838A (ja) * | 2006-06-23 | 2008-01-10 | Mitsui Chemicals Inc | 半導体ウェハの裏面研削用粘着フィルム及びそれを用いた半導体ウェハの裏面研削方法 |
JP2009185114A (ja) * | 2008-02-04 | 2009-08-20 | Bridgestone Corp | 紫外線反応架橋型接着剤組成物、ゴム複合体、及び基材とゴムとの接着方法 |
JP2012162705A (ja) * | 2010-11-25 | 2012-08-30 | Nippon Shokubai Co Ltd | 光学用紫外線硬化型樹脂組成物、硬化物及び表示装置 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4463467B2 (ja) * | 2002-05-24 | 2010-05-19 | 日油株式会社 | カラーフィルターの保護膜、rgb用画素、ブラックマトリックス又はスペーサーを形成するための光硬化性樹脂組成物及びカラーフィルター |
KR101085839B1 (ko) * | 2004-10-27 | 2011-11-22 | 니치유 가부시키가이샤 | 우레탄 결합 함유 디올(메타)아크릴레이트 화합물, 그제조방법 및 그 중합체 |
JP4826803B2 (ja) * | 2007-03-20 | 2011-11-30 | Jsr株式会社 | 感放射線性樹脂組成物および液晶表示素子用スペーサーとその製造法 |
JP5087414B2 (ja) * | 2008-01-22 | 2012-12-05 | 日東電工株式会社 | 光硬化型アクリル系粘弾性体組成物、アクリル系粘弾性体、アクリル系粘弾性体層テープ又はシート、及びそれらの製造方法 |
KR101274885B1 (ko) * | 2008-07-01 | 2013-06-17 | 쇼와 덴코 가부시키가이샤 | 도료 조성물 및 이것을 사용한 도막 형성 방법 |
CN102181244B (zh) * | 2009-12-29 | 2014-02-12 | 第一毛织株式会社 | 粘结剂及其制法、其组合物、粘结剂层制法和光学元件 |
-
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003171622A (ja) * | 2001-12-06 | 2003-06-20 | Showa Highpolymer Co Ltd | 活性光線硬化型再剥離性粘着剤組成物 |
JP2008001838A (ja) * | 2006-06-23 | 2008-01-10 | Mitsui Chemicals Inc | 半導体ウェハの裏面研削用粘着フィルム及びそれを用いた半導体ウェハの裏面研削方法 |
JP2009185114A (ja) * | 2008-02-04 | 2009-08-20 | Bridgestone Corp | 紫外線反応架橋型接着剤組成物、ゴム複合体、及び基材とゴムとの接着方法 |
JP2012162705A (ja) * | 2010-11-25 | 2012-08-30 | Nippon Shokubai Co Ltd | 光学用紫外線硬化型樹脂組成物、硬化物及び表示装置 |
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