WO2019073980A1 - 光硬化性粘着剤組成物、及び接着方法 - Google Patents
光硬化性粘着剤組成物、及び接着方法 Download PDFInfo
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- WO2019073980A1 WO2019073980A1 PCT/JP2018/037620 JP2018037620W WO2019073980A1 WO 2019073980 A1 WO2019073980 A1 WO 2019073980A1 JP 2018037620 W JP2018037620 W JP 2018037620W WO 2019073980 A1 WO2019073980 A1 WO 2019073980A1
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- adhesive composition
- sensitive adhesive
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
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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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
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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
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
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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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
Definitions
- the present invention relates to a photocurable pressure-sensitive adhesive composition and a bonding method.
- the present invention relates to a photocurable pressure-sensitive adhesive composition having a high peel strength of the pressure-sensitive adhesive at high temperature, and a bonding method.
- an isocyanate group in an isocyanate group-containing compound [a] which is a reaction product of a polyol (a1) and a polyisocyanate (a2) is a hydroxyl group of a hydroxyl group-containing (meth) acrylate (a3) and a saturated alcohol
- an active energy ray-curable pressure-sensitive adhesive composition comprising a polyisocyanate derivative [A] formed by forming a urethane bond with the hydroxyl group of (a4) and an ethylenically unsaturated monomer [B]. It is done.
- the active energy ray-curable pressure-sensitive adhesive composition described in Patent Document 1 is a composition which is cured by ultraviolet irradiation with a high pressure mercury lamp, and the balance between the adhesion to a substrate and the weather resistance is good.
- Patent Document 1 According to the ultraviolet irradiation by the high pressure mercury lamp described in Patent Document 1, since the ultraviolet light of low wavelength is contained, the photopolymerization initiator having a good surface curing property is efficiently decomposed, and there is a surface which is not susceptible to oxygen inhibition. However, when using a high pressure mercury lamp, a large space is required because a duct for removing generated ozone is required. Further, in Patent Document 1, although the retention strength of the adhesive is measured at 40 ° C., the peel strength at high temperature exceeding 40 ° C. is not examined, and the improvement of the peel strength of the adhesive at high temperature is solved It has not been.
- the problem to be solved by the present invention is a photocurable pressure-sensitive adhesive composition containing a urethane oligomer having a crosslinkable silicon group, and the photopolymerization proceeds rapidly even in the presence of oxygen such as in the air, and it is long It is an object of the present invention to provide a photocurable pressure-sensitive adhesive composition and a bonding method, which do not require light irradiation or oxygen shielding equipment and can significantly improve the peel strength of the pressure-sensitive adhesive at high temperatures.
- the present invention provides a photocurable composition
- a photocurable composition comprising (A) a radically polymerizable urethane oligomer having a crosslinkable silicon group, (B) a monofunctional radically polymerizable compound, and (C) a photoinitiator.
- An adhesive composition is provided.
- the (B) monofunctional radically polymerizable compound is composed of a monofunctional (meth) acrylate, a vinyl monofunctional compound having an amide group, and a monofunctional N-vinyl compound. It is preferred that it is at least one compound selected from the group.
- this invention provides the product which has a hardened
- the present invention is a method of bonding a plurality of adherends in order to achieve the above object, wherein (A) radically polymerizable urethane oligomer having a crosslinkable silicon group, and (B) monofunctional radically polymerizable A coating step of applying a photocurable adhesive composition containing a compound and (C) photoinitiator to at least one adherend, and a photocurable adhesive composition applied to one adherend And a light irradiation step of irradiating light emitted from the LED in the presence of oxygen, and the other adherend on the photocurable pressure-sensitive adhesive composition applied to one adherend and irradiated with light (but the other And d) adhering a protective sheet for the adhesive surface as an adherend.
- the present invention provides a method for producing an adhesive body produced using the above-mentioned adhesion method in order to achieve the above object.
- a photocurable pressure-sensitive adhesive composition containing a urethane oligomer having a crosslinkable silicon group which is photopolymerized even in the presence of oxygen such as in the air It is possible to provide a photocurable pressure-sensitive adhesive composition and a bonding method, which rapidly progress, do not require long-time light irradiation and oxygen blocking equipment, and greatly improve the peel strength of the pressure-sensitive adhesive at high temperatures.
- the photocurable pressure-sensitive adhesive composition of the present invention is a composition which exhibits tackiness quickly by irradiation of light such as active energy rays emitted from a light emitting diode (LED), and which is then moisture-cured. It is a composition in which the peel strength at high temperature of the pressure-sensitive adhesive after moisture curing is significantly improved. That is, the photocurable pressure-sensitive adhesive composition contains (A) a radically polymerizable urethane oligomer having a crosslinkable silicon group, (B) a monofunctional radically polymerizable compound, and (C) a photoinitiator.
- the photocurable pressure-sensitive adhesive composition may be referred to as a radically polymerizable oligomer (hereinafter, A 'component, or simply as a "radically polymerizable oligomer”) excluding a radically polymerizable urethane oligomer having a crosslinkable silicon group (A) And / or tackifying resins may also be included.
- a 'component or simply as a "radically polymerizable oligomer”
- high temperature refers to a temperature that exceeds normal temperature and is about 80 ° C.
- the main chain skeleton of the oligomer is an oligomer having a number average molecular weight of 1,000 or more, such as polyether type, polyester type, non-aromatic polycarbonate type, acrylic type, and diene polymer type (hereinafter, “polymerization having a crosslinkable silicon group Oligomeric ").
- the number average molecular weight of the polymerizable oligomer having a crosslinkable silicon group is preferably 2,000 or more, more preferably 3,000 or more, in terms of polystyrene in GPC from the viewpoint that the pressure-sensitive adhesive exhibits good peel strength. The above is more preferable.
- the number average molecular weight is preferably about 100,000 or less, more preferably 50,000 or less, still more preferably 30,000 or less, from the viewpoint that the photocurable pressure-sensitive adhesive composition ensures appropriate viscosity and good workability. preferable.
- the glass transition point (Tg) is preferably 10 ° C. or less, more preferably 0 ° C. or less, and still more preferably ⁇ 10 ° C. or less.
- the radical polymerizable group in the polymerizable oligomer having a crosslinkable silicon group is contained in and / or at the end of the urethane oligomer, and from the viewpoint of obtaining a pressure-sensitive adhesive having sufficient peel strength, the terminal of the urethane oligomer is preferable.
- the crosslinkable silicon group in the polymerizable oligomer having a crosslinkable silicon group may be contained in and / or at an end of the urethane oligomer, and may be linked to the urethane oligomer via a (thio) urethane bond or a urea bond.
- the peel strength of the photocurable pressure-sensitive adhesive composition according to the present invention is significantly improved as compared with the conventional pressure-sensitive adhesive, and It has been found that the pressure-sensitive adhesive peels off from the interface with the pressure-sensitive adhesive and the pressure-sensitive adhesive is not cohesively broken. The reason for this is not clear, but it is presumed that at least the cause of the significant improvement of the peel strength at high temperatures is not due to the improvement of the cohesion due to the increase of the crosslinking point.
- the photocurable pressure-sensitive adhesive composition according to the present invention has a peel strength of the pressure-sensitive adhesive at high temperature by curing the crosslinkable silicon group by moisture reaction by dark reaction after curing by light reaction. Is a composition that improves significantly.
- the crosslinkable silicon group is a group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of being crosslinked by a silanol condensation reaction.
- a crosslinkable silicon group the crosslinkable silicon group represented by Formula (1) is mentioned.
- R 1 represents an alkyl group having 1 to 20 carbon atoms, a substituted alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 7 to 20 carbon atoms
- X is a hydrolyzable group, and when two or more X are present, they may be the same or different.
- a represents 0, 1, 2 or 3;
- a is preferably 2 or 3. When a is 3, the curing rate is higher than when a is 2.
- R 1 examples include alkyl groups such as methyl and ethyl, substituted alkyl groups such as methoxymethyl, and cycloalkyl groups such as cyclohexyl.
- a methyl group is preferable, and from the viewpoint of increasing the curing rate, a substituted alkyl group in which the ⁇ carbon is substituted with a polar group is preferable.
- hydrolysable group shown by said X What is necessary is just a conventionally well-known hydrolysable group.
- An alkoxy group is preferable from the viewpoint of mild hydrolyzability and easy handling. Among the alkoxy groups, those having a smaller number of carbon atoms are more reactive, and the reactivity becomes lower as the number of carbon atoms increases, as in the order of methoxy group> ethoxy group> propoxy group. Although it can be selected according to the purpose and application, usually, a methoxy group or an ethoxy group is used.
- a is preferably 2 or more in consideration of the curability.
- crosslinkable silicon group examples include trialkoxysilyl groups such as trimethoxysilyl group and triethoxysilyl group (-Si (OR 2 ) 3 ); dialkoxyl groups such as methyldimethoxysilyl group and methyldiethoxysilyl group And alkoxysilyl groups (-SiR 1 (OR 2 ) 2 ).
- R 1 is the same as above
- R 2 is an alkyl group such as a methyl group or an ethyl group.
- the crosslinkable silicon group is preferably a trimethoxysilyl group or a triethoxysilyl group from the viewpoint of high reactivity, and a trimethoxysilyl group is more preferable. From the viewpoint of obtaining a cured product having flexibility, methyldimethoxysilyl group and methyldiethoxysilyl group are preferable.
- the end of the urethane oligomer is preferred as the position at which the crosslinkable silicon group is contained.
- the ratio of the crosslinkable silicon group is preferably 10% or more from the viewpoint of improving the peel strength of the pressure-sensitive adhesive after curing at high temperature with respect to the total number of radically polymerizable groups and crosslinkable silicon groups in the urethane oligomer. It is more preferably at least 40%, still more preferably at least 40%.
- it is preferably 90% or less, more preferably 80% or less, and still more preferably 70% or less.
- the polymerizable oligomer having a crosslinkable silicon group is a reaction product of a hydroxyl group-containing oligomer and an organic polyisocyanate, a hydroxyl group-containing radically polymerizable compound, a crosslinkable silicon group such as 3-mercaptopropyltrimethoxysilane, and an isocyanate reactive group Can be synthesized by reacting with a compound having In addition, as a isocyanate reactive group, a mercapto group, an amino group, a substituted amino group etc. are mentioned.
- a reaction product of an oligomer having a hydroxyl group and a crosslinkable silicon group (hereinafter referred to as "a hydroxyl group and a crosslinkable silicon group-containing oligomer") with an organic polyisocyanate is reacted with a hydroxyl group-containing radically polymerizable compound. It can also be synthesized.
- the hydroxyl group and the crosslinkable silicon group-containing oligomer can be synthesized by copolymerizing a monomer having a crosslinkable silicon group at the time of synthesis of the hydroxyl group-containing oligomer.
- a hydroxyl group-containing oligomer may be synthesized using an initiator having a crosslinkable silicon group, a chain transfer agent having a crosslinkable silicon group, etc.
- a crosslinkability such as 3-isocyanatopropyltrimethoxysilane It can also be synthesized by reacting a compound containing a silicon group and an isocyanate group.
- a polymerizable oligomer having a crosslinkable silicon group is synthesized by reacting an isocyanate group-containing (meth) acrylate with a hydroxyl group and a crosslinkable silicon group-containing oligomer, or a hydroxyl group-terminated urethane oligomer having a crosslinkable silicon group.
- the hydroxyl group terminal urethane oligomer which has a crosslinkable silicon group can be synthesize
- hydroxyl group-containing oligomers polyether-based hydroxyl group-containing oligomers, polyester-based hydroxyl group-containing oligomers, non-aromatic polycarbonate-based hydroxyl group-containing oligomers, acrylic-based hydroxyl group-containing oligomers, having a number average molecular weight of about 1,000 to 50,000
- the diene polymer system hydroxyl group containing oligomer etc. are mentioned. From the viewpoint of imparting flexibility to the cured product, diols and monools are preferred, and from the viewpoint of curability, diols are preferred.
- hydroxyl group-containing oligomers which are liquid at 50 ° C. are preferable in terms of ease of handling at the time of blending and handling of the composition. These hydroxyl group-containing oligomers can be used alone or in combination of two or more.
- polyether based hydroxyl group containing oligomer examples include polyethylene glycol, polypropylene glycol, polyoxyethylene polyoxypropylene glycol, polypropylene triol, and polytetramethylene glycol. From the viewpoint of imparting flexibility to the cured product, polypropylene glycol (PPG) and polytetramethylene glycol (PTMG) are preferred. From the viewpoint of imparting flexibility to the cured product, polypropylene monool is more preferable. In order to improve the degree of crosslinking of the cured product, triol and tetraol are preferred.
- Examples of the synthesis method of the polyoxyalkylene polymer include, but not particularly limited to, a polymerization method using an alkali catalyst such as KOH and a polymerization method using a double metal cyanide complex catalyst. According to a polymerization method using a double metal cyanide complex catalyst, it is possible to obtain a polyoxyalkylene polymer having a high molecular weight of Mw (weight average molecular weight) / Mn (number average molecular weight) of 1.6 or less and a narrow molecular weight distribution. From the viewpoint of improving the coating workability of the composition (a viewpoint of reducing the viscosity), the polypropylene polyol preferably has Mw / Mn of 1.6 or less. From the viewpoint of imparting flexibility to the cured product, it is preferable to use a polypropylene polyol having a number average molecular weight of 6,000 or more.
- polyester-based hydroxyl group containing oligomers include reaction products of diol components and polyvalent carboxylic acids, and addition reaction products of diol components and lactones.
- a liquid polyester-based hydroxyl group-containing oligomer is preferable, and as the diol component, a branched aliphatic glycol having 5 or more carbon atoms such as neopentyl glycol (NPG) or 2-methyl-1,5-pentanediol (MPD) is preferable.
- NPG neopentyl glycol
- MPD 2-methyl-1,5-pentanediol
- dicarboxylic acids having 5 or more carbon atoms such as adipic acid and sebacic acid are preferable.
- Non-aromatic polycarbonate-based hydroxyl group-containing oligomer for example, a component selected from diol components such as 1,4-butanediol, 1,6-hexanediol, 1,5-pentanediol and the like, short chain such as dimethyl carbonate and the like Mention may be made of polycarbonate diols which can be obtained by reaction with dialkyl carbonates.
- non-crystalline such as 1,6-hexanediol / 1,5-pentanediol copolymerization, 1,6-hexanediol / 1,4-butanediol copolymerization, etc.
- non-crystalline such as 1,6-hexanediol / 1,5-pentanediol copolymerization, 1,6-hexanediol / 1,4-butanediol copolymerization, etc.
- Nonaromatic polycarbonate-based hydroxyl group-containing oligomers which are liquid at 20 ° C. are preferred.
- the acrylic hydroxyl group-containing oligomer is preferably an acrylic hydroxyl group-containing oligomer in which the position of the hydroxyl group is at the end of the main chain of the oligomer, and is preferably a liquid acrylic hydroxyl group-containing oligomer at 20 ° C.
- Examples of (meth) acrylic acid ester monomers constituting the main chain of acrylic hydroxyl group-containing oligomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate and (meth) acrylic acid Examples thereof include (meth) acrylic acid alkyl esters having 1 to 18 carbon atoms such as 2-ethylhexyl and stearyl (meth) acrylate. These may be used alone or in combination of two or more.
- a crosslinkable silicon group is introduced into the main chain of the acrylic hydroxyl group-containing oligomer by using an alkoxysilyl group-containing (meth) acrylic acid ester such as ⁇ - (meth) cryloyloxypropyltrimethoxysilane in combination.
- an acrylic acid alkyl ester having 4 to 8 carbon atoms and a methacrylic acid alkyl ester having 10 and 12 carbon atoms are preferable, and n-butyl acrylate and 2-ethylhexyl acrylate are more preferable, because acrylic resin having 4 to 8 carbon atoms is preferable because acrylic resin is excellent in flexibility.
- the acid n-butyl is most preferred.
- (meth) acrylic acid represents acrylic acid and / or methacrylic acid.
- a living radical polymerization method is used from the viewpoint of obtaining an acrylic hydroxyl group-containing oligomer having a narrow molecular weight distribution and a low viscosity and having a hydroxyl group at the molecular chain terminal. It is preferred to use.
- an acrylic hydroxyl group-containing oligomer having a hydroxyl group at one end is obtained, a reaction using a thiol compound having a hydroxyl group such as 2-mercaptoethanol described in JP-A-2000-344823 and a metallocene compound can be used.
- a reaction using a compound having a thiol group such as thioglycerol (3-mercapto-1,2-propanediol) described in JP-A-2000-128911 and a secondary hydroxyl group can also be used.
- An acrylic hydroxyl group-containing oligomer having two hydroxyl groups at one end is preferable from the viewpoint of good flexibility of the cured product and maintenance and improvement of adhesion.
- the number average molecular weight of the acrylic hydroxyl group-containing oligomer is preferably 2,000 or more, preferably 5,000 or more, and more preferably 8,000 or more, from the viewpoint of securing good flexibility of the pressure-sensitive adhesive.
- the number average molecular weight is preferably about 100,000 or less, more preferably 50,000 or less, and still more preferably 30,000 or less, from the viewpoint of securing an appropriate viscosity of the composition and ensuring good workability.
- diene polymerization system hydroxyl group containing oligomer examples include 1,2-polybutadienediol, a hydrogenated product of 1,2-polybutadienediol, and 1,4-polybutadienediol.
- organic polyisocyanates examples include aromatic polyisocyanates such as tolylene diisocyanate (TDI), aromatic aliphatic polyisocyanates such as xylylene diisocyanate (XDI), isophorone diisocyanate (IPDI), etc. Alicyclic polyisocyanates and aliphatic polyisocyanates such as hexamethylene diisocyanate (HMDI) can be mentioned.
- aromatic polyisocyanates such as tolylene diisocyanate (TDI)
- aromatic aliphatic polyisocyanates such as xylylene diisocyanate (XDI), isophorone diisocyanate (IPDI)
- HMDI hexamethylene diisocyanate
- hydroxyl group-containing radically polymerizable compound examples include a hydroxyl group-containing (meth) acrylate compound and a hydroxyl group-containing (meth) acrylamide compound, and may be used alone or in combination of two or more.
- hydroxyl group-containing (meth) acrylate compound examples include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and glycerol mono (meth) acrylate.
- R ′ represents a hydrogen atom or a methyl group
- R ′ represents a hydrogen atom or a methyl group
- R ′ represents a hydrogen atom or a methyl group
- R ′ represents a hydrogen atom or a methyl group
- it is disposed in a part connected and sandwiched between two polar groups ((meth) acryloyloxy group and urethane bond)
- the —CH 2 group contained is a secondary hydroxyl group, which can suppress the inhibition of polymerization by oxygen. Therefore, it is particularly preferable from the viewpoint that oxygen inhibition is unlikely to occur and the surface curability is good.
- Mechanism to suppress the inhibition of polymerization by oxygen The following mechanism is presumed as a mechanism which suppresses the polymerization inhibition by oxygen. That is, in radical polymerization, the polymerization inhibition by oxygen occurs, and the reaction rate of the monomer decreases. In particular, a decrease in reaction rate occurs in the surface layer exposed to air. Oxygen inhibition is caused by the low polymerization ability of peroxy radicals generated by trapping in oxygen the initiating radicals generated from the photoinitiator and the polymerization terminal radical generated in the polymerization process of monomers, and are caused by the termination of the polymerization reaction.
- a compound having a plurality of electron withdrawing groups a compound in which an active radical is easily generated in a portion sandwiched by the plurality of electron withdrawing groups, for example, the above-mentioned ((1) Meta)
- an ⁇ -carbon radical of a secondary hydroxyl group newly generated by extracting hydrogen from the polymerizable oligomer by a hydrogen-extractable peroxy radical. Is believed to initiate polymerization.
- the generated ⁇ -carbon radical of secondary hydroxyl group can also capture oxygen, the effect of reducing the oxygen concentration in the system is also considered. It is speculated that oxygen inhibition is suppressed by these mechanisms.
- Examples of the hydroxyl group-containing (meth) acrylamide compound include N-substituted (meth) acrylamides (for example, N-monosubstituted (meth) acrylamide and N, N-disubstituted (meth) acrylamide).
- the (meth) acrylamide compound which has a hydroxyl group of 113518 gazette is mentioned.
- examples of the hydroxyl group-containing (meth) acrylamide compound include 3-hydroxypropyl (meth) acrylamide, 2-hydroxyethyl (meth) acrylamide, 4-hydroxybutyl (meth) acrylamide and the like. These hydroxyl group-containing (meth) acrylamides may be used alone or in combination of two or more.
- 2-hydroxyethyl (meth) acrylamide has an extremely excellent property that there is no skin irritation (1) and no skin irritation (primary irritation index: PII)
- PII skin irritation index
- isocyanate group-containing (meth) acrylates examples include 2-isocyanate ethyl (meth) acrylate and the like.
- Component B Monofunctional Radically Polymerizable Compound
- monofunctional (meth) acrylates vinyl monofunctional compounds having an amide group
- monofunctional N-vinyl compounds having a number average molecular weight of less than 1,000.
- the blending ratio of the component B is 100 parts by mass of the component A or the component A and the component A '(radically polymerizable oligomer).
- 2,000 parts by mass or less is preferable, 1,000 parts by mass or less is more preferable, and 300 parts by mass or less is the most preferable.
- 2 parts by mass or more is preferable, 100 parts by mass is more preferable, 5 parts by mass or more is more preferable, and 10 parts by mass or more is most preferable.
- the monofunctional (meth) acrylate When added to the photocurable pressure-sensitive adhesive composition, the monofunctional (meth) acrylate which is the component B lowers the viscosity without reducing the adhesiveness, and from the viewpoint of improving the coating properties (workability) of the composition. preferable.
- a monofunctional (meth) acrylate having a number average molecular weight of less than 1,000 can be used as the monofunctional (meth) acrylate.
- the monofunctional (meth) acrylate is preferably liquid at 50 ° C. from the viewpoint of ease of compounding and the like.
- R 3 is a hydrogen atom or a methyl group
- m is an integer of 2 to 4
- n is an integer of 1 to 20
- R 4 is a hydrogen atom or an unsubstituted or substituted alkyl group, The unsubstituted or substituted phenyl group is shown.
- compounds of general formula (2) in which R 4 is a hydrogen atom (meth) acrylates having a hydroxyl group such as aliphatic epoxy (meth) acrylates; R in general formula (2) (Meth) acrylates having an alkoxy group such as a compound of 4 unsubstituted or substituted alkyl group; compounds of the general formula (2) where R 4 is an unsubstituted or substituted phenyl group; aromatics such as aryl (meth) acrylate (Meth) acrylates; long-chain hydrocarbon (meth) acrylates having 8 to 20 carbon atoms; alicyclic (meth) acrylates; (meth) acrylates having a heterocyclic group; (meth) acrylates having an alkoxysilyl group Can be mentioned.
- a long-chain hydrocarbon-based (meth) acrylate having 8 to 20 carbon atoms and / or a compound of the general formula (2) is preferable, and a long carbon number of 8 to 20, from the viewpoint that the tackiness of the pressure-sensitive adhesive is excellent.
- a chain hydrocarbon (meth) acrylate, a (meth) acrylate having a hydroxyl group, and a (meth) acrylate having an alkoxy group are more preferable, and a long chain hydrocarbon (meth) acrylate having 8 to 20 carbon atoms is most preferable.
- (meth) acrylate having a hydroxyl group a monomer represented by the following general formula (3) and having one 3- (meth) acryloyloxy-2-hydroxypropyl group linked by a polar linking group A (hereinafter referred to as “ 3 Ac2 HPM "), and is preferred from the viewpoint that oxygen inhibition hardly occurs.
- R 3 represents a hydrogen atom or a methyl group
- A represents a polar linking group
- R 5 represents an organic group.
- R 6 Represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and two R 6 groups may be the same or different and may be linked to have a ring structure).
- the linking group is preferably an ether (-O-) linking group, an ester linking group, or a urethane linking group from the viewpoint of suppressing polymerization inhibition by oxygen, and an ether linking group or a urethane linking group is more preferable. Ether linking groups are most preferred for their availability.
- R 5 As an organic group of R 5 , a substituted or unsubstituted alkylene group, a substituted or unsubstituted phenyl group and a group of the following general formula (4) can be mentioned.
- m is an integer of 2 to 4
- n is an integer of 1 to 20
- R 7 represents a hydrogen atom, an unsubstituted or substituted alkyl group, or an unsubstituted or substituted phenyl group.
- the organic group of R 5 is preferably an alkyl group having 8 to 18 carbon atoms.
- a crosslinkable silicon group-containing group such as a 3-triethoxysilylpropyl group as the organic group of R 5 is preferable from the viewpoint of dual curing (post curing) to improve adhesiveness and adhesiveness at high temperature.
- monofunctional (meth) acrylates are as follows. First, as long-chain hydrocarbon (meth) acrylates having 8 to 20 carbon atoms, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, isostearyl (meth) acrylate, etc. It can be mentioned.
- alicyclic (meth) acrylates examples include isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and dicyclopentenyl oxyethyl (meth) acrylate.
- the (meth) acrylate having a hydroxyl group for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexane dimethanol mono (meth) acrylate, glycerol mono Hydroxyalkyl (meth) acrylates such as (meth) acrylates; polyalkylene glycol mono (meth) acrylates such as polyethylene glycol mono (meth) acrylates, polypropylene glycol mono (meth) acrylates, and polyethylene glycol-polypropylene glycol copolymers It can be mentioned.
- aromatic (meth) acrylate benzyl (meth) acrylate, phenol alkylene oxide modified (meth) acrylate, alkylphenol alkylene oxide modified (meth) acrylate, p-cumylphenol alkylene oxide modified (meth) acrylate, and o-phenyl Phenol alkylene oxide modified (meth) acrylate etc. are mentioned.
- ethylene oxide, a propylene oxide, etc. are mentioned as alkylene oxide.
- alkoxypolyethylene glycol mono (meth) acrylates such as ethoxydiethylene glycol (meth) acrylate
- alkoxypolypropylene glycol mono (meth) acrylates such as methoxytripropylene glycol (meth) acrylate
- alkoxypolyethylene glycol -Polypropylene glycol copolymer etc. can be mentioned.
- (meth) acrylate having a carboxyl group As (meth) acrylate having a carboxyl group, (meth) acrylic acid, polycaprolactone modified product of (meth) acrylic acid, Michael addition type polymer of (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, and anhydride Examples thereof include phthalic acid adducts and adducts of 2-hydroxyethyl (meth) acrylate and succinic anhydride.
- Examples of the (meth) acrylate having a heterocyclic group include tetrahydrofurfuryl (meth) acrylate, N- (meth) acryloyloxyethyl hexahydrophthalimide and the like, and examples of the (meth) acrylate having an amino group include N, N -Dimethylaminoethyl acrylate etc. are mentioned.
- Examples of (meth) acrylates having an alkoxysilyl group include 3- (trimethoxysilyl) propyl (meth) acrylate and the like, and examples of (meth) acrylates having an epoxy group include glycidyl (meth) acrylate and cyclohexene oxide Examples thereof include (meth) acrylates, and examples of (meth) acrylates having a phosphoric acid group include 2- (meth) acryloyloxyethyl acid phosphate and the like.
- (meth) acrylate having a fluoroalkyl group, (meth) acrylate having a tribromophenyl group, and the like can be mentioned.
- a (meth) acrylate having a polar group such as a hydroxyl group, a carboxyl group or a phenoxy group is preferable because it enhances the cohesion of the adhesive and improves the adhesive strength.
- the (meth) acrylate having an alicyclic group is preferable in that it has good curability, is less likely to reduce the adhesive strength, and has a good performance balance.
- the blending ratio of the component B is 2,000 parts by mass or less with respect to 100 parts by mass of the component A (or the total of the component A and the component A ') from the viewpoint of exhibiting the effect of improving the adhesive force by the component A
- 1,000 parts by mass or less is more preferable, and 300 parts by mass or less is the most preferable.
- 2 parts by mass or more is preferable, 100 parts by mass is more preferable, 5 parts by mass or more is more preferable, and 10 parts by mass or more is the most preferable.
- vinyl monofunctional compounds having an amide group and monofunctional N-vinyl compounds are preferable in terms of reactivity and resistance to oxygen inhibition.
- vinyl monofunctional compound having an amide group examples include compounds having one vinyl group having an amide group, and examples thereof include N-vinyl such as N-vinyl-2-pyrrolidone and N-vinyl-2-caprolactam. Cyclic amides; acrylamides such as N, N-diethyl (meth) acrylamide, N- (2-hydroxyethyl) acrylamide, (meth) acryloyl morpholine, etc. may be mentioned. Acryloyl morpholine is preferred in terms of a good balance of curability, physical properties and safety.
- Examples of the monofunctional N-vinyl compound include compounds having one monofunctional N-vinyl group, and examples thereof include N-vinyl pyrrolidone, N-vinyl caprolactam, and N-vinyl acetamide.
- N-vinyl pyrrolidone is preferable from the viewpoint of a good balance of curability and physical properties.
- C component photo initiator
- a photoinitiator a photo radical generator, a photo base generator, a photo acid generator etc.
- the photo radical generator is a compound that generates radicals by irradiation of active energy rays such as ultraviolet rays and electron beams.
- active energy rays such as ultraviolet rays and electron beams.
- the photopolymerization initiator (C) when used as the polymerization initiator, it can be suitably used for heat-resistant members, and thus can be used for various applications.
- Photoradical generators examples include benzyl ketals such as 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one and the like.
- ⁇ -Aminoacetophenone series such as ⁇ -hydroxyacetophenone series, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone series, bis Acyl phosphine oxides such as (2,4,6-trimethylbenzoyl) -phenyl phosphine oxide, benzophenones such as methyl benzoylbenzoate, thioxanthones such as isopropyl thioxanthone, 1.2-octanedione, 1- [4- ( Oxime esters such as phenylthio)-, 2- (O-benzoyloxime)], bis
- photoinitiators of benzyl ketal type, ⁇ -hydroxyacetophenone type, ⁇ -amino acetophenone type, acyl phosphine oxide type, oxime ester type and titanocene type are preferable because they have high sensitivity and a small addition amount.
- a light source containing ultraviolet light of a short wavelength such as a metal halide lamp, an electrodeless lamp (fusion lamp) or a high pressure mercury lamp as a light source
- the surface curability is good and oxygen inhibition occurs.
- UV-LED ultraviolet light emitting diode
- Ie Sensitive to long-wavelength ultraviolet light (i-line (wavelength 365 nm), h-line (wavelength 405 nm), g-line (wavelength 436 nm), etc.), and ⁇ - It is preferable to use an aminoacetophenone type, an acyl phosphine oxide type, an oxime ester type, and a titanocene type photo radical initiator, and an ⁇ -aminoacetophenone type, an acy
- UV-LED As a light source, low power consumption and long life, no duct is necessary because ozone is not generated, heat generation at the time of irradiation is small, thermal damage to the adherend is small, and lighting only at the time of irradiation Since it is preferable to use a UV-LED having merits, it is possible to start photopolymerization initiation of ⁇ -aminoacetophenone type, acyl phosphine oxide type, oxime ester type and titanocene type, which have high sensitivity to long wavelength active energy rays. It is preferred to use an agent.
- the photocurable pressure-sensitive adhesive composition according to the present invention has good surface curability even when it is cured by active energy rays of long wavelength, and can reduce the influence of oxygen inhibition.
- the photobase generator also acts as a curing catalyst for the crosslinkable silicon group when irradiated with light, it is particularly preferable to use the photobase generator since the A component of the present invention contains the crosslinkable silicon group Also, when the photocurable pressure-sensitive adhesive composition contains (B) a monofunctional radically polymerizable compound, and (B) the monofunctional radically polymerizable compound contains a crosslinkable silicon group, a high effect is exhibited.
- produces an amine compound by the effect
- a photolatent primary amine that generates an amine compound having a primary amino group by the action of active energy rays, and an amine compound having a secondary amino group by the action of active energy rays Any of a photolatable secondary amine to be generated and a photolatent tertiary amine to generate an amine compound having a tertiary amino group by the action of active energy rays can be used.
- the photolatable tertiary amine is more preferable in that the generated base shows high catalytic activity.
- the photolatent primary amine and the photolatent secondary amine for example, an ortho-nitrobenzyl urethane compound described in WO 2015/088021; a dimethoxybenzyl urethane compound; a benzoin carbamate; o-acyl oximes O-carbamoyl oximes; N-hydroxyimido carbamates; formanilide derivatives; aromatic sulfonamides; cobalt amine complexes and the like.
- photolatable tertiary amine for example, ⁇ -amino ketone derivative, ⁇ -ammonium ketone derivative, benzylamine derivative, benzyl ammonium salt derivative, ⁇ -amino alkene derivative, ⁇ -ammonium alkene derivative described in WO2015-088021 And amine imides, benzyloxycarbonylamine derivatives which generate an amidine by light, and salts of carboxylic acid and tertiary amine.
- photobase generators preferred is a photolatable tertiary amine from the viewpoint that the generated base exhibits high catalytic activity, and from the viewpoint of high base generation efficiency and good storage stability as a composition, benzyl ammonium Salt derivatives, benzyl-substituted amine derivatives, ⁇ -amino ketone derivatives and ⁇ -ammonium ketone derivatives are preferred.
- the addition amount of the photoinitiator is not particularly limited, but when the addition amount is small, the curing does not proceed to the deep part and curing failure may occur, so "A component” or "A component and A 'component” 0.05 weight part or more is preferable with respect to 100 weight part, 0.1 weight part or more is more preferable, and 1 weight part or more is still more preferable. If the amount of the initiator is large, the initiator may remain, which may adversely affect the curing properties. Therefore, the amount added is 30 parts by weight with respect to 100 parts by weight of the "component A” or the "component A and component A". The following is preferable, 20 parts by weight or less is more preferable, and 10 parts by weight or less is more preferable.
- a photocurable adhesive composition contains a photobase generator as a photoinitiator.
- a silicon compound having a Si—F bond can also be added.
- a silicon compound having a Si—F bond various compounds containing a silicon group having a Si—F bond (hereinafter sometimes referred to as a fluorosilyl group) can be used. Both inorganic compounds and organic compounds can be used as the silicon compound having a Si—F bond.
- a silicon compound having a Si—F bond an organic compound having a fluorosilyl group is preferable, and an organic polymer having a fluorosilyl group is more preferable because of its high safety.
- low molecular weight organosilicon compounds having a fluorosilyl group are preferable in that the composition has a low viscosity.
- silicon compounds having a Si-F bond examples include fluorosilanes described in WO2015-088021, compounds having a fluorosilyl group described in WO2015-088021, and fluorosilyls described in WO2015-088021. And organic polymers having a group.
- the photocurable pressure-sensitive adhesive composition according to the present invention may further contain (A) a radically polymerizable oligomer (A ′ component) excluding a radically polymerizable urethane oligomer having a crosslinkable silicon group.
- a ′ component a radically polymerizable oligomer excluding the polymerizable oligomer having a crosslinkable silicon group of the component A, and has a number average molecular weight in which the radically polymerizable group is bonded to the oligomer terminal or side chain There are more than 1,000 oligomers.
- the position of the radically polymerizable group in the radically polymerizable oligomer is preferably the terminal of the radically polymerizable oligomer from the viewpoint of obtaining a pressure-sensitive adhesive having a sufficient peel strength.
- a radically polymerizable group a (meth) acryloyloxy group and a (meth) acryloyl (substituted) amino group are mentioned, From the point of storage stability, the compound which has a (meth) acryloyloxy group is preferable. Further, from the viewpoint of reactivity, compounds having a (meth) acryloyl (substituted) amino group are preferable.
- radically polymerizable oligomers As radically polymerizable oligomers, radically polymerizable urethane oligomers, acrylic (meth) acrylates (eg, “RC-100C”, “RC-200C”, “RC-300C” manufactured by Kaneka Corp .: described in Japanese Patent No. 4786921) Vinyl polymers having (meth) acryloyl group), diene-based (meth) acrylates (eg, “UC-1” manufactured by Kuraray Co., Ltd .: Esterified product of maleic anhydride adduct of polyisoprene polymer and 2-hydroxyethyl methacrylate Etc.).
- acrylic (meth) acrylates eg, “RC-100C”, “RC-200C”, “RC-300C” manufactured by Kaneka Corp .: described in Japanese Patent No. 4786921
- diene-based (meth) acrylates e
- a skeleton of an oligomer of a polyether type, a polyester type, a non-aromatic polycarbonate type, an acrylic type, and a diene polymer type can be mentioned.
- the number average molecular weight of the radically polymerizable oligomer is preferably 2,000 or more, more preferably 3,000 or more, and even more preferably 5,000 or more in terms of polystyrene in GPC from the viewpoint that the pressure-sensitive adhesive exhibits good peel strength.
- the number average molecular weight is preferably about 100,000 or less, more preferably 50,000 or less, still more preferably 30,000 or less, from the viewpoint of securing an appropriate viscosity of the photocurable pressure-sensitive adhesive and ensuring good workability.
- a liquid at 50 ° C. it is preferable to show a liquid at 50 ° C., more preferable to show a liquid at 20 ° C., and it is further preferable to show a liquid at 0 ° C., from the viewpoint of securing ease of handling when blending with other components.
- a radically polymerizable oligomer having a glass transition point (Tg) of 10 ° C. or less is preferable, and a radically polymerizable oligomer having a glass transition point (Tg) of 10 ° C. or less is more preferable, from the viewpoint of making the adhesive flexible at low temperatures and maintaining and improving adhesion.
- the compounding ratio of the component A ′ is preferably 200 parts by mass or less, and more preferably 150 parts by mass or less with respect to 100 parts by mass of the component A, from the viewpoint of exhibiting the effect of improving the peel strength of the pressure sensitive adhesive at high temperature. Preferably, 80 parts by mass or less is the most preferable. From the viewpoint of improving the cohesion of the pressure-sensitive adhesive immediately after photocuring, 2 parts by mass or more is preferable, 100 parts by mass is more preferable, 5 parts by mass or more is more preferable, and 10 parts by mass or more is most preferable.
- the radically polymerizable urethane oligomer can be synthesized by reacting the hydroxyl group-containing radical polymerizable compound with the reaction product of the hydroxyl group-containing oligomer and the organic polyisocyanate. Moreover, it can also synthesize
- the photocurable pressure-sensitive adhesive composition according to the present invention may further contain a tackifier resin.
- the tackifying resin is not particularly limited, and, for example, a resin having a polar group such as rosin ester resin, phenol resin, xylene resin, xylene phenol resin, terpene phenol resin, or the like, aromatic, aliphatic having relatively small polarity
- Conventional tackifier resins such as aromatic copolymer systems or various petroleum resins such as alicyclic resins or coumarone resins, low molecular weight polyethylene resins, terpene resins, and resins obtained by hydrogenating these resins can be used. These may be used alone or in combination of two or more.
- these resins include, as aromatic petroleum resins, ⁇ -methylstyrene homopolymer resin [FTR Zero series, Mitsui Chemicals Co., Ltd. product], styrene monomer homopolymer resin [FTR 8000 series, Mitsui Chemical Co., Ltd. product, styrenic monomer / aromatic monomer copolymer resin [FMR series, Mitsui Chemicals Co., Ltd. product], ⁇ -methylstyrene / styrene copolymer resin [FTR 2000 series, Mitsui Chemical (c) And aromatic series styrene resins.
- styrene based monomer / aliphatic based monomer copolymer based resin As aliphatic-aromatic copolymer based petroleum resin, styrene based monomer / aliphatic based monomer copolymer based resin [FTR 6000 series, Mitsui Chemicals Co., Ltd. product], styrene based monomer / ⁇ -methylstyrene / aliphatic based monomer Examples thereof include aliphatic-aromatic copolymer-based styrene resins such as copolymer resins [FTR 7000 series, manufactured by Mitsui Chemicals, Inc.].
- the solubility parameter (hereinafter abbreviated as "SP value" in principle) calculated by the Small method using Hoy's constant is preferably 7.9 to 11.0, 8.2 to 9.8 is more preferred, and 8.5 to 9.5 is most preferred.
- the adhesive strength of the pressure-sensitive adhesive it is preferable to select a resin having a polarity matched to the polarity of the adherend.
- a tackifying resin for a low polarity adherend it is preferable to use a low polarity tackifying resin, and when using a high polarity adherent, it is preferable to use a high polarity tackifying resin.
- a tackifier resin When a tackifier resin is used for a wide adherend from adherends having high polarity to adherends having low polarity, it is preferable to use a mixture of a tackifier resin having a low polarity and a tackifier resin having a high polarity.
- the polarity (SP value) of terpene phenol resin the U series of YS Polystar (manufactured by Yashara Chemical Co., Ltd.) has an SP value of 8.69, the T series has an SP value of 8.81, the S series has an SP value of 8.98, the G series Is SP value 9.07 and K series is SP value 9.32.
- the aromatic petroleum resin is preferably an aromatic styrene resin or an aliphatic-aromatic copolymer-based styrene resin, and more preferably a terpene phenol resin or an aliphatic-aromatic copolymer-based styrene resin. From the viewpoint of excellent adhesion, terpene phenol resin is most preferable. In addition, from the viewpoint of VOC, it is preferable to use an aliphatic-aromatic copolymer-based styrene resin
- the blending ratio of the tackifier resin is preferably 5 to 200 parts by mass, and more preferably 10 to 150 parts by mass with respect to 100 parts by mass of the component A or the components A and B. From the viewpoint of exerting the adhesive strength, 5 parts by mass or more is preferable, and from the viewpoint of maintaining the hardness of the cured product in an appropriate range, exerting sufficient adhesive strength, and securing good workability, 200 parts by mass or less is preferable.
- composition of the present invention if necessary, polyfunctional (meth) acrylate, silane coupling agent, amino group-containing silanes, photoaminosilane generating compound, extender, plasticizer, water absorbent, condensation reaction promoting catalyst Photosensitizers, photopolymerization accelerators, curing catalysts, physical property modifiers for improving tensile properties, etc., reinforcing agents, coloring agents, flame retardants, anti-sagging agents, antioxidants, anti-aging agents, ultraviolet absorbers, solvents Various additives such as perfumes, pigments, dyes, fillers, diluents, polymerization inhibitors, solid polymers and the like may be added.
- Multifunctional (meth) acrylate As polyfunctional (meth) acrylates having two or more (meth) acryloyl groups, 1,6-hexadiol di (meth) acrylate, neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate , Polypropylene glycol di (meth) acrylate, 2,2-bis (4- (meth) acryloxydiethoxyphenyl) propane, or 2,2-bis (4- (meth) acryloxytetraethoxyphenyl) propane, etc.
- Trifunctional (meth) acrylates such as functional (meth) acrylate, trimethylolpropane tri (meth) acrylate, tris [(meth) acryloyloxyethyl] isocyanurate, dimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate ) Acrylate, or Pentaerythritol ethoxy tetra (meth) acrylate such as 4 or more functional groups is (meth) acrylate and the like.
- the molecular weight of the polyfunctional (meth) acrylate is less than 1,000.
- the compounding ratio of the polyfunctional (meth) acrylate is 10 parts by mass or less with respect to 100 parts by mass of the component A (or the total of the component A and the component A ') from the viewpoint of exerting the effect of suppressing oxygen inhibition by the component A Is preferable, 5 parts by mass or less is more preferable, and 2 parts by mass or less is the most preferable. From the viewpoint of securing sufficient cohesion under high temperature conditions, 0.01 parts by mass or more is preferable, 100 parts by mass or more is preferable, 0.05 parts by mass or more is more preferable, and 0.1 parts by mass or more is the most preferable.
- silane coupling agent acts as an adhesion promoter.
- silane coupling agents include epoxy group-containing silanes such as ⁇ -glycidoxypropyltrimethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane; ⁇ -aminopropyltrimethoxysilane, N Amino group-containing silanes such as-( ⁇ -aminoethyl) - ⁇ -aminopropyltrimethoxysilane; ketimines such as N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine -Type silanes; mercapto group-containing silanes such as ⁇ -mercaptopropyltrimethoxysilane; vinyl type unsaturated group-containing silanes such as vinyltrimethoxysilane and ⁇ -methacryloyloxyprop
- amino group-containing silanes are reacted with an epoxy group-containing compound containing the above silanes, an isocyanate group-containing compound, and a (meth) acryloyl group-containing compound to use an amino group-modified amino group-containing silane. May be
- amino group-containing silanes act as silanol condensation catalysts.
- ketimine type silanes form amino group-containing silanes in the presence of water and act as a silanol condensation catalyst. Therefore, it is preferable to use a silane coupling agent other than amino group-containing silanes and ketimine-type silanes.
- amino group-containing silanes or ketimine-type silanes are used, the type and / or amount of use thereof is adjusted within the range in which the purpose and effect of the present invention are achieved.
- photo aminosilane generating compound The use of amino group-containing silanes and ketimine-type silanes may be limited in the present invention. However, when it is desirable to use amino group-containing silanes or ketimine-type silanes as an adhesion imparting agent, no compound having an amino group is generated before light irradiation, and amino group-containing silanes are A compound to be generated (hereinafter also referred to as a photoaminosilane generating compound) can be used.
- the photofunctional group described in WO2015 / 088021 is exemplified by an o-nitrobenzyl group, a p-nitrobenzyl group, an oxime residue, a benzyl group, a benzoyl group, and these substituted groups and the like. Certain compounds are mentioned.
- photoaminosilane generating compounds in which the photofunctional group is o-nitrobenzyl group include 2-nitrobenzyl-N- [3- (trimethoxysilyl) propyl] carbamate and 2-nitrobenzyl-N- [3- (triethoxy) And silyl) propyl] carbamate, 3,4-dimethoxy-2-nitrobenzyl-N- [3- (trimethoxysilyl) propyl] carbamate and the like.
- photoaminosilane generating compounds in which the photofunctional group is p-nitrobenzyl group include 4-nitrobenzyl-N- [3- (trimethoxysilyl) propyl] carbamate and the like.
- Examples of the photoaminosilane generating compound in which the photofunctional group is a benzyl group include 1- (3,5-dimethoxyphenyl) -1-methylethyl-N- [3- (trimethoxysilyl) propyl] carbamate and the like.
- Examples of photoaminosilane generating compounds in which the photofunctional group is an oxime residue group include benzophenone O- ⁇ [3- (trimethoxysilyl) propyl] ⁇ oxime and the like.
- the compounding ratio of the silane coupling agent is not particularly limited, but it is preferably 0.01 to 20% by mass, more preferably 0.025 to 10% by mass in the composition. These silane coupling agents can be used alone or in combination of two or more.
- silane coupling agent or silicate As the water absorbent, it is preferable to use the above-mentioned silane coupling agent or silicate.
- the silicate is not particularly limited, and examples thereof include tetramethoxysilane, tetraalkoxysilane and the like, and partial hydrolytic condensates thereof.
- condensation reaction promoting catalyst for crosslinkable silicon groups other than the component C and the compound having a Si—F bond
- known curing catalysts can be widely used, and there is no particular limitation.
- organic metal compounds, amines And fatty acid, organic acidic phosphoric acid ester compounds, etc. and it is particularly preferable to use a silanol condensation catalyst.
- silanol condensation catalyst for example, organotin compounds; dialkyltin oxides; reaction products of dibutyltin oxide and phthalic acid esters, etc .; titanates; organoaluminum compounds; chelate compounds such as titanium tetraacetylacetonate; Organic acid bismuth etc. are mentioned.
- the resulting composition may become more toxic.
- the component C or the compound having a Si-F bond of the present invention acts as a condensation reaction promoting catalyst, when a curing catalyst other than these is used, the condensation reaction of the crosslinkable silicon group may progress regardless of light irradiation. Therefore, it is preferable to use in the range which can achieve the objective and effect of this invention.
- the photosensitizer is preferably a carbonyl compound having a triplet energy of 225 to 310 kJ / mol.
- thioxanthone such as isopropylthioxanthone and a derivative thereof, dialkoxyanthracene derivative such as 9, 10-dibutoxyanthracene, 2- Benzophenone such as methyl benzoylbenzoate and its derivatives, coumarin derivatives such as 3-acyl coumarin, 3,3'-carbonylbiscoumarin and the like, and the like
- thioxanthone and its derivatives and coumarin derivatives are preferable, and thioxanthone and its derivatives, benzophenone and the like
- the derivatives and coumarin derivatives are more preferred.
- the proportion of the photosensitizer is not particularly limited, but is preferably 0.01 to 5% by mass, and more preferably 0.025 to 2% by mass in the composition. These photosensitizers may be used alone or in combination of two or more.
- Photopolymerization accelerator A photopolymerization accelerator can be used in combination with the initiator for the purpose of accelerating the curing reaction by the photopolymerization initiator.
- Photopolymerization accelerators include tertiary amines such as triethylamine, triethanolamine and 2-dimethylaminoethanol; aryl phosphines such as triphenyl phosphine; aryl phosphine oxides such as triphenyl phosphine oxide; triphenyl phosphite And phosphines including aryl phosphates such as triphenyl phosphate (aryl group may have a substitution); thiols represented by ⁇ -thioglycol and the like.
- Preferred phosphines are trifunctional phosphine derivatives, more preferably triaryl phosphines, most preferably triphenyl phosphines.
- a resin filler resin fine powder
- an inorganic filler an inorganic filler
- a functional filler can be used.
- the filler may be surface-treated with a silane coupling agent, a titanium chelating agent, an aluminum coupling agent, a fatty acid, a fatty acid ester, a rosin or the like.
- a particulate filler made of an organic resin or the like can be used.
- the resin filler organic fine particles of ethyl polyacrylate resin, polyurethane resin, polyethylene resin, polypropylene resin, urea resin, melamine resin, benzoguanamine resin, phenol resin, acrylic resin, styrene resin and the like can be used.
- the resin filler may contain the black resin filler. Even in the case of using a long wavelength LED lamp or the like, it is possible to obtain good deep area curability and to achieve excellent light shielding properties and deep area curability.
- inorganic filler examples include talc, clay, calcium carbonate, magnesium carbonate, anhydrous silicon, hydrous silicon, calcium silicate, titanium dioxide, titanium black, carbon black and the like.
- the conductive filler described in JP-A-2013-14734, JP-A-2017-2267, JP-A-2011-508012 and the like As the functional filler, for example, the conductive filler described in JP-A-2013-14734, JP-A-2017-2267, JP-A-2011-508012 and the like; the heat insulation and the lightness etc. described in JP-A-2016-199668 etc. Hollow particles; Core-shell particles having excellent sound insulation and damping properties described in JP-A-2016-199669 etc .; Layered silicates excellent in gas-barrier etc. described in JP-A-2016-199670 etc; It is possible to use the light-reflecting filler described herein; the electromagnetic wave shielding material described in JP-A-2016-199750 and the like.
- a solvent having a flash point (open type) of 50 ° C. or more is used as a diluent.
- Physical properties such as viscosity can be adjusted by containing a diluent.
- various diluents can be used as the diluent.
- saturated hydrocarbon solvents such as normal paraffin and isoparaffin, ⁇ -olefin derivatives such as Linearn dimer (trade name of Idemitsu Kosan Co., Ltd.), aromatic hydrocarbon solvents, alcohol solvents, ester solvents
- aromatic hydrocarbon solvents such as solvents, citric acid ester solvents such as acetyl triethyl citrate, and ketone solvents.
- the flash point of the diluent is preferably 60 ° C. or more, more preferably 70 ° C. or more.
- a diluent having a high flash point generally tends to have a low dilution effect on the composition, it is preferable to use a diluent having a flash point of 250 ° C. or less.
- the flash point of a liquid mixture is said flash point.
- a saturated hydrocarbon solvent is preferable, and normal paraffin and isoparaffin are more preferable.
- the carbon number of normal paraffins and isoparaffins is preferably 10 to 16.
- the compounding ratio of the diluent is preferably in the range of 0 to 50 parts by mass with respect to 100 parts by mass of the component A or 100 parts by mass of the component A and the component A ', in the range of 0.1 to 30 parts by mass It is more preferable to blend in the range of 0.1 to 15 parts by mass.
- the diluent may be used alone or in combination of two or more.
- the content of the liquid medium is preferably 5% by weight or less, more preferably 3% by weight or less, still more preferably 1% by weight or less, based on the whole composition. Most preferred is a composition that is substantially free of (i.e., a substantially solvent-free composition).
- substantially does not contain a liquid medium means that the composition does not contain any liquid medium, or the content thereof is 0.1% by mass or less of the composition.
- a solvent having a flash point of 50 ° C. or less is used as a volatile solvent.
- the polymerization inhibitor is not particularly limited, and examples thereof include radical scavengers such as hindered phenols and hindered amines, phosphorus secondary antioxidants, diethylhydroxylamine, sulfur, t-butyl catechol, potassium triiodide, N-nitrosophenylhydroxyamine aluminum salt etc. may be mentioned.
- the polymerization inhibitors may be used alone or in combination of two or more.
- Solid polymer As a solid polymer, a polymer solid at 20 ° C. can be used. As a solid polymer, the homopolymer which superposed
- a block polymer comprising a hard polymer block A having a glass transition temperature of 0 ° C. or more, preferably 30 ° C. or more, and a soft polymer block B having a glass transition temperature less than 0 ° C., preferably ⁇ 10 ° C. or less Is preferred.
- a block polymer of the hard polymer block A and the soft polymer block B there may be mentioned a non-acrylic block copolymer consisting of a styrenic polymer block A and a polymer block B comprising a conjugated diene polymer or a hydrogenated product thereof.
- a block copolymer of styrene and a conjugated diene such as butadiene or isoprene, or a hydrogenated product thereof can be mentioned.
- JP-A-2003-277521 is composed of a hard polymer block A such as styrene or its derivative, methyl methacrylate and an acrylic polymer block B such as butyl acrylate and 2-ethylhexyl acrylate. Particularly preferred are acrylic block copolymers.
- acrylic block copolymer a triblock copolymer of polymethyl methacrylate-poly n-butyl acrylate-polymethyl methacrylate is preferable from the viewpoint of solubility, adhesiveness and transparency.
- the bonding method of the present invention is not a method of producing a pressure-sensitive adhesive product such as a pressure-sensitive adhesive sheet or a pressure-sensitive adhesive tape, but directly applies a raw material serving as a pressure-sensitive adhesive upon light irradiation to an adherend to form a pressure-sensitive adhesive on the adherend
- a raw material serving as a pressure-sensitive adhesive upon light irradiation to an adherend to form a pressure-sensitive adhesive on the adherend This is a method of bonding the other adherend to this. That is, in the bonding method of the present invention, the photocurable pressure-sensitive adhesive composition is not used after being formed into a form such as a tape, and is applied directly to one adherend and directly applied to the other adherend. It is used for adhesion (that is, the other adherend is not a film or the like such as a release liner, but is actually an adherend adhered to one adherend).
- the adhesion method of the present invention can be used for adhesion of electronic and electrical parts etc., and is particularly suitable for adhesion of electronic parts.
- “for on-site application” indicates that the photocurable pressure-sensitive adhesive composition is used as it is for bonding at a site where an electronic component or the like is produced. That is, in the present invention, a pressure-sensitive adhesive is processed into a shape such as a tape to prepare a molded body, and the photocurable pressure-sensitive adhesive composition of the present invention is used instead of using the molded body at a place different from the processing place. It is applied to one adherend as it is, and in this state (or at the site), it refers to an application of sticking one adherend to the other adherend.
- the method for producing the photocurable pressure-sensitive adhesive composition is not particularly limited, and for example, component A, component B, and component C are blended in predetermined amounts, and, if necessary, component A ', tackifying resin, and / or Alternatively, it can be manufactured by blending other compounded substances and stirring with degassing. There is no restriction
- the photocurable pressure-sensitive adhesive composition according to the present invention may be of a one-component type or a two-component type, if necessary, but it can be suitably used particularly as a one-component type.
- the photocurable pressure-sensitive adhesive composition according to the present invention is a composition that exhibits adhesiveness by light irradiation and cures, and can be cured in normal temperature (for example, 23 ° C.) in air, and normal temperature photocurable curing Although it is suitably used as a pressure sensitive adhesive, if necessary, curing may be promoted by heating as appropriate.
- the photocurable pressure-sensitive adhesive composition according to the present invention exhibits adhesiveness and cures when irradiated with light.
- An adhesive can be obtained by this curing.
- the photocurable adhesive composition concerning this invention is moisture-hardened by the dark reaction after photocuring.
- various adhesive-containing products such as electronic circuits, electronic components, construction materials, automobiles and the like can be manufactured using the photocurable adhesive composition according to the present invention.
- the photocurable pressure-sensitive adhesive composition according to the present invention is irradiated with light, but when active energy rays are applied during curing, curing by ultraviolet light or visible light is possible as active energy rays. Available.
- the ultraviolet light also includes g-ray (wavelength 436 nm), h-ray (wavelength 405 nm), i-ray (wavelength 365 nm), and the like.
- the active energy ray source is not particularly limited, but can be appropriately selected according to the reaction wavelength of the photoinitiator to be used.
- light sources include metal halide lamps, high power metal halide lamps (containing indium etc.), electrodeless lamps (fusion lamps), low pressure mercury lamps, high pressure mercury lamps, super high pressure mercury lamps, mercury-xenon lamps, argon lasers, A xenon lamp, a xenon flash lamp, an LED etc. are mentioned.
- Each of these light sources has different emission wavelengths and energy distributions. Therefore, these light sources are preferably selected according to the reaction wavelength of the photo initiator and the like. Further, a xenon flash lamp or an LED capable of intermittently emitting active energy rays is preferable because the influence of heat on the adherend can be minimized. In particular, a UV-LED having merits such as low power consumption and long life is more preferable because it has lower radiation heat, smaller size and high freedom of design of a light irradiation device as compared with other ultraviolet lamps.
- the emission wavelength of the UV-LED can be selected according to the combination with the photopolymerization initiator, but is preferably 280 nm or more and 450 nm or less, more preferably 300 nm or more and 450 nm or less, and still more preferably 350 nm or more and 450 nm or less.
- a UV-LED is most preferable as a light source.
- the irradiation energy for example, in the case of UV, preferably 10 ⁇ 20,000mJ / cm 2, more preferably 20 ⁇ 10,000mJ / cm 2, more preferably 50 ⁇ 5,000mJ / cm 2. If it is less than 10 mJ / cm 2 , the curability may be insufficient. If it is more than 20,000 mJ / cm 2 , time and cost are wasted even if light is irradiated more than necessary, and the substrate may be damaged. There is.
- the method for applying the photocurable pressure-sensitive adhesive composition according to the present invention to an adherend is not particularly limited, but application methods such as screen printing, stencil printing, roll printing, dispenser application, spin coating and the like are suitably used.
- a photocurable adhesive composition can be apply
- the photocurable pressure-sensitive adhesive composition according to the present invention is applied to at least one adherend (application step).
- the photocurable pressure-sensitive adhesive composition may be applied to one adherend, or the photocurable pressure-sensitive adhesive composition may be applied to each of both adherends.
- a photocurable adhesive composition can be apply
- light is irradiated to this photocurable adhesive composition (light irradiation process).
- the photocurable pressure-sensitive adhesive composition exhibits tackiness by light irradiation.
- attachment method of this invention is moisture-hardened by the water
- a product that is, an adhesive body
- adherends are adhered to each other
- protective members such as a protective sheet for the adhesive surface are excluded.
- the photocurable pressure-sensitive adhesive composition used in the adhesion method of the present invention is suitable for on-site application, and one adherend and the other adherend are directly adhered by the photocurable pressure-sensitive adhesive composition. It is because
- the photocurable pressure-sensitive adhesive composition according to the present invention is a quick-curing type composition excellent in workability, and the cured product can be suitably used as a pressure-sensitive adhesive.
- the photocurable pressure-sensitive adhesive composition according to the present invention can be applied directly to an adherend because it is liquid before light irradiation, and can be easily applied to an adherend having a complicated shape. And a photocurable adhesive composition exhibits adhesiveness rapidly by light irradiation, even if it does not interrupt
- the photocurable pressure-sensitive adhesive composition according to the present invention the photocurable pressure-sensitive adhesive composition exhibiting adhesiveness after application and photoirradiation of the photocurable pressure-sensitive adhesive composition on one adherend Since the other adherend can be attached to each other, even when the adherend does not transmit light such as ultraviolet light, a plurality of adherends can be easily attached to each other.
- the photocurable pressure-sensitive adhesive composition according to the present invention does not cure when the active energy ray is not irradiated, and does not block from the air even in the presence of oxygen (that is, even without covering with a film or the like) It is a composition which is cured by active energy ray irradiation, and is a composition having a rapid curing property excellent in rising adhesion after active energy ray irradiation. Therefore, a predetermined bonding possible time can be secured after light irradiation. Furthermore, in the present invention, a UV-LED can be used as a light source, in which case damage to the adherend can be reduced.
- the peel strength at high temperature (a temperature of about 80 ° C.) can be significantly improved.
- the epoxy group of the C12, 13 mixed alcohol glycidyl ether opens and bonds with the acrylic acid to form an ester bond.
- this ring opening occurs at either the ⁇ position or the ⁇ position
- the ⁇ adduct opened at the ⁇ position is the main component
- the ⁇ adduct opened at the ⁇ position is the accessory component.
- the production ratio of ⁇ -adduct to ⁇ -adduct is 100 / 0.01 to 100/70, preferably 100 / 0.1 to 100/50 in molar ratio.
- Synthesis Example 1 a product having a compound, which is usually an ⁇ adduct, as a main component and a ⁇ adduct as an accessory component is obtained.
- the product can be isolated by separation according to known separation methods.
- Synthesis Example 1 a mixture containing an ⁇ -adduct and a ⁇ -adduct is obtained as a monoacrylate of component A. That is, the product obtained in Synthesis Example 1 is a product obtained by leaving all or part of the ⁇ adduct in the product obtained by the above synthesis method, and is a composition containing the ⁇ adduct as the main component.
- main component refers to a component containing 60 mol% or more in the product
- subcomponent refers to a component containing 40 mol% or less.
- Example 1 Each compounding substance is respectively added to a flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging pipe, and water-cooled condenser at the mixing ratio shown in Table 1, and the mixture is stirred and mixed according to Example 1.
- An adhesive composition was prepared.
- each component A the compounds synthesized in the above synthesis examples 2 to 3 were used.
- the B component C12MAc the compound synthesized in the above Synthesis Example 1 was used.
- the compounds synthesized in the above-mentioned Synthesis Example 4 and Synthesis Example 5 were used as DL-10000-1 and DL-10000-2 of the A ′ component, respectively.
- Component B Monofunctional Radically Polymerizable Compound
- 2-HBA light acrylate HOB-A; manufactured by Kyoeisha Chemical Co., Ltd., 2-hydroxybutyl acrylate
- ACMO ACMO; manufactured by kj Chemicals Inc., acryloyl morpholine
- C component: photo initiator Irgacure 379 (Irgacure 379; manufactured by BASF, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone)
- Tackifying resin YS-K125 (YS Polystar K125; manufactured by Yasuhara Chemical Co., Ltd .; terpene phenol resin) (Other condensation reaction promoting catalysts) Neostan U-830 (Neostan U-830; manufactured by Nitto Kasei Co., Ltd., dioctyl tin versatate)
- UV irradiation conditions UV-LED lamp (wavelength 365 nm, illuminance: 1000 mW / cm 2 ), accumulated light amount: 3000 mJ) / Cm 2 ].
- the second adherend (austenite stainless steel) is bonded to the first adherent so as to sandwich the UV-irradiated photocurable adhesive composition in an area of 25 mm ⁇ 80 mm, Pressure was applied using a 2 kg roller.
- the test piece was produced by this (The test piece for a normal temperature peeling adhesive strength test and the test piece for high temperature peeling adhesive strength were produced.). Then, it was aged for 7 days under an atmosphere of 23 ° C. and 50% humidity.
- Examples 1 to 9 exhibited good properties of at least 1.0 (N / 25 mm) or more in the high-temperature peel adhesion strength test.
- the peel strength was 0.1 (N / 25 mm), and the strength was extremely weak.
- the adhesive peeled off at the adhesive interface between the adherend and the adhesive in the high-temperature peeling adhesive strength test, which indicates that the improvement of the adhesive strength is not due to the improvement of the cohesion. It was done.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
A成分の架橋性ケイ素基を有するラジカル重合性ウレタンオリゴマーは架橋性ケイ素基を有し、ラジカル重合性基がウレタン結合(-OC(=O)N-)を介してオリゴマーの主鎖骨格に連結されたオリゴマーである。オリゴマーの主鎖骨格はポリエーテル系、ポリエステル系、非芳香族ポリカーボネート系、アクリル系、ジエン重合体系等の数平均分子量が1,000以上のオリゴマーである(以下、「架橋性ケイ素基を有する重合性オリゴマー」という場合がある。)。
架橋性ケイ素基はケイ素原子に結合した水酸基や加水分解性基を有しシラノール縮合反応により架橋することができる基である。架橋性ケイ素基としては、式(1)で表される架橋性ケイ素基が挙げられる。
架橋性ケイ素基を有する重合性オリゴマーは、水酸基含有オリゴマーと有機ポリイソシアネートとの反応物に、水酸基含有ラジカル重合性化合物と、3-メルカプトプロピルトリメトキシシラン等の架橋性ケイ素基及びイソシアネート反応性基を有する化合物とを反応させることによって合成できる。なお、イソシアネート反応性基としては、メルカプト基、アミノ基、置換アミノ基等が挙げられる。
水酸基含有オリゴマーとしては、数平均分子量が約1,000~50,000である、ポリエーテル系水酸基含有オリゴマー、ポリエステル系水酸基含有オリゴマー、非芳香族ポリカーボネート系水酸基含有オリゴマー、アクリル系水酸基含有オリゴマー、及びジエン重合体系水酸基含有オリゴマー等が挙げられる。硬化物に柔軟性を付与する観点からはジオール及びモノオールが好ましく、硬化性の観点からはジオールが好ましい。また、配合時の取扱い易さ、及び組成物の取扱い易さからは、50℃で液状の水酸基含有オリゴマーが好ましい。これらの水酸基含有オリゴマーは単独で用いることも、2種類以上を併用することもできる。
ポリエーテル系水酸基含有オリゴマーとしては、ポリエチレングリコール、ポリプロピレングリコール、ポリオキシエチレンポリオキシプロピレングリコール、ポリプロピレントリオール、及びポリテトラメチレングリコール等が挙げられる。硬化物に柔軟性を付与する観点からはポリプロピレングリコール(PPG)、ポリテトラメチレングリコール(PTMG)が好ましい。硬化物に柔軟性を付与する観点からは、ポリプロピレンモノオールがより好ましい。硬化物の架橋度を向上させる場合は、トリオール、テトラオールが好ましい。
ポリエステル系水酸基含有オリゴマーとしては、例えば、ジオール成分と多価カルボン酸との反応生成物、ジオール成分とラクトンとの付加反応生成物を挙げることができる。液状のポリエステル系水酸基含有オリゴマーが好ましく、ジオール成分としては、ネオペンチルグリコール(NPG)、2-メチル-1,5-ペンタンジオール(MPD)等の炭素数5以上の分岐脂肪族グリコールが好ましい。また、多価カルボン酸としては、アジピン酸、セバシン酸等の炭素数5以上のジカルボン酸が好ましい。
非芳香族ポリカーボネート系水酸基含有オリゴマーとしては、例えば、1,4-ブタンジオール、1,6-ヘキサンジオール、1,5-ペンタンジオール等のジオール成分から選択される成分と、炭酸ジメチル等の短鎖炭酸ジアルキルとの反応によって得ることができるポリカーボネートジオールとを挙げることができる。特に、異なるユニット鎖長のモノマーを共重合した(1,6-ヘキサンジオール/1,5-ペンタンジオール共重合、1,6-ヘキサンジオール/1,4-ブタンジオール共重合等)非晶性の20℃で液状の非芳香族ポリカーボネート系水酸基含有オリゴマーが好ましい。
アクリル系水酸基含有オリゴマーとしては、水酸基の位置がオリゴマー主鎖骨格の末端にあるアクリル系水酸基含有オリゴマーであることが好ましく、20℃で液状のアクリル系水酸基含有オリゴマーであることが好ましい。アクリル系水酸基含有オリゴマーの主鎖を構成する(メタ)アクリル酸エステル系モノマーとしては、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸n-ブチル、(メタ)アクリル酸2-エチルヘキシル、(メタ)アクリル酸ステアリル等の炭素数1~18の(メタ)アクリル酸アルキルエステル等が挙げられる。これらは、単独で用いても、複数を共重合させてもよい。
ジエン重合体系水酸基含有オリゴマーとしては、例えば1,2-ポリブタジエンジオール、1,2-ポリブタジエンジオールの水素添加物、1,4-ポリブタジエンジオール等が挙げられる。
本発明で用いることができる有機ポリイソシアネートとしては、例えば、トリレンジイソシアネート(TDI)等の芳香族ポリイソシアネート、キシリレンジイソシアネート(XDI)等の芳香族脂肪族ポリイソシアネート、イソホロンジイソシアネート(IPDI)等の脂環式ポリイソシアネート、及びヘキサメチレンジイソシアネート(HMDI)等の脂肪族ポリイソシアネート等を挙げることができる。
水酸基含有ラジカル重合性化合物としては、水酸基含有(メタ)アクリレート化合物と水酸基含有(メタ)アクリルアミド化合物とが挙げられ、単独で用いることも、2種類以上を併用することもできる。
酸素による重合阻害を抑制するメカニズムとしては、以下のメカニズムが推測される。すなわち、ラジカル重合においては酸素による重合阻害が起こり、モノマーの反応率が低下する。特に、空気に触れる表面層において反応率の低下が発生する。酸素阻害は、光開始剤から生成する開始ラジカルやモノマーの重合過程で生成する重合末端ラジカルが酸素にトラップされて生成するパーオキシラジカルの重合能力が低く、重合反応が停止することによって起こる。ここで、複数の電子吸引性基を有する化合物であり、複数の電子吸引性基に挟まれた部分に活性ラジカルが生じやすい化合物、例えば、系内に連鎖移動剤としての機能を有する上記の(メタ)アクリル酸2-ヒドロキシプロピル基を有する重合性オリゴマーが存在する場合、水素引き抜き能を有するパーオキシラジカルが当該重合性オリゴマーから水素を引き抜くことで、新たに生成する2級水酸基のα炭素ラジカルが重合を開始すると考えられる。また、生成した2級水酸基のα炭素ラジカルは酸素を補足することもできるため、系内の酸素濃度を低減させる効果も考えられる。これらのメカニズムにより、酸素阻害が抑制されると推測される。
イソシアネート基を含有する(メタ)アクリレートとしては、例えば、2-イソシアネートエチル(メタ)アクリレート等が挙げられる。
B成分の単官能ラジカル重合性化合物としては、数平均分子量が1,000未満である、単官能(メタ)アクリレート、アミド基を有するビニル系の単官能化合物、単官能N-ビニル化合物等が挙げられる。
B成分である単官能(メタ)アクリレートは、光硬化性粘着剤組成物に添加すると、粘着性を低下させずに粘度を低下させるので、組成物の塗布性(作業性)を向上させる観点から好ましい。単官能(メタ)アクリレートとしては、数平均分子量が1,000未満の単官能(メタ)アクリレートを用いることができる。単官能(メタ)アクリレートは、配合の容易性等の観点からは50℃で液状であることが好ましい。
アミド基を有するビニル系の単官能化合物としては、アミド基を有するビニル基を一つ有する化合物が挙げられ、例えば、N-ビニル-2-ピロリドン、N-ビニル-2-カプロラクタム等のN-ビニル環状アミド;N,N-ジエチル(メタ)アクリルアミド、N-(2-ヒドロキシエチル)アクリルアミド、(メタ)アクリルロイルモルフォリン等のアクリルアミド類が挙げられる。硬化性、物性、及び安全性のバランスが良い点から、アクリロイルモルホリンが好ましい。
単官能N-ビニル化合物としては、単官能N-ビニル基を一つ有する化合物が挙げられ、例えば、N-ビニルピロリドン、N-ビニルカプロラクタム、及びN-ビニルアセトアミド等が挙げられる。硬化性及び物性のバランスが良い点からN-ビニルピロリドンが好ましい。
(C)光開始剤としては、光ラジカル発生剤や、光塩基発生剤、光酸発生剤等を用いることができる。光ラジカル発生剤は、紫外線や電子線等の活性エネルギー線の照射によりラジカルを発生させる化合物である。本発明の組成物において、重合開始剤として(C)光開始剤を用いる場合、熱に弱い部材に対しても好適に用いることができるため、様々な用途に用いることができる。
光ラジカル発生剤としては、例えば、2,2-ジメトキシ-1,2-ジフェニルエタン-1-オン等のベンジルケタール系、2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-オン等のα-ヒドロキシアセトフェノン系、2-(ジメチルアミノ)-2-[(4-メチルフェニル)メチル]-1-[4-(4-モルホリニル)フェニル]-1-ブタノン等のα-アミノアセトフェノン系、ビス(2,4,6-トリメチルベンゾイル)-フェニルホスフィンオキサイド等のアシルホスフィンオキサイド系、ベンゾイル安息香酸メチル等のベンゾフェノン系、イソプロピルチオキサントン等のチオキサントン系、1.2-オクタンジオン、1-[4-(フェニルチオ)-,2-(O-ベンゾイルオキシム)]等のオキシムエステル系、ビス(シクロペンタジエニル)-ビス(2,6-ジフルオロ-3-(ピロール-1-イル)フェニル)チタニウム等のチタノセン系、ベンゾインエーテル系、トリアジン系、ボレート系、カルバゾール系、イミダゾール系等、及びそれらを高分子量化した誘導体が挙げられる。
光塩基発生剤は、光を照射すると架橋性ケイ素基の硬化触媒としても作用するため、特に、本発明のA成分は架橋性ケイ素基を含有しているので光塩基発生剤を用いることが好ましく、また、光硬化性粘着剤組成物が(B)単官能ラジカル重合性化合物を含み、(B)単官能ラジカル重合性化合物が架橋性ケイ素基を含有する場合に高い効果を奏する。
また、光硬化性粘着剤組成物は、光開始剤として光塩基発生剤を含有することが好ましい。硬化促進剤として、Si-F結合を有するケイ素化合物を更に添加することもできる。光硬化性粘着剤組成物が含有するA成分及び/又はB成分が架橋性ケイ素基を有することにより、光硬化性粘着剤組成物が光硬化した後、空気中の水分により光硬化性粘着剤組成物を後硬化させることができる。
本発明に係る光硬化性粘着剤組成物は、(A)架橋性ケイ素基を有するラジカル重合性ウレタンオリゴマーを除くラジカル重合性オリゴマー(A’成分)を更に含有してもよい。A’成分であるラジカル重合性オリゴマーは、A成分の架橋性ケイ素基を有する重合性オリゴマーを除くラジカル重合性オリゴマーであり、ラジカル重合性基がオリゴマー末端又は側鎖に結合された、数平均分子量が1,000以上のオリゴマーある。
ラジカル重合性ウレタンオリゴマーは、前記水酸基含有オリゴマーと前記有機ポリイソシアネートとの反応物に、前記水酸基含有ラジカル重合性化合物を反応させることによって合成できる。また、水酸基含有オリゴマー又は水酸基末端ウレタンオリゴマーに前記イソシアネート基を含有する(メタ)アクリレートを反応させることによって合成することもできる。
本発明に係る光硬化性粘着剤組成物は、粘着付与樹脂を更に含有してもよい。粘着付与樹脂としては、特に制限はなく、例えば、ロジンエステル樹脂、フェノール樹脂、キシレン樹脂、キシレンフェノール樹脂、テルペンフェノール樹脂等の極性基を有する樹脂や、比較的極性の小さい芳香族系、脂肪族-芳香族共重合体系、又は脂環式系等の各種石油樹脂、若しくはクマロン樹脂、低分子量ポリエチレン樹脂、テルペン樹脂、及びこれらを水素添加した樹脂等の通常の粘着付与樹脂を用いることができる。これらは単独で用いても、2種以上を併用してもよい。
本発明の組成物には、必要に応じて、多官能(メタ)アクリレート、シランカップリング剤、アミノ基含有シラン類、光アミノシラン発生化合物、増量剤、可塑剤、水分吸収剤、縮合反応促進触媒、光増感剤、光重合促進剤、硬化触媒、引張特性等を改善する物性調整剤、補強剤、着色剤、難燃剤、タレ防止剤、酸化防止剤、老化防止剤、紫外線吸収剤、溶剤、香料、顔料、染料、フィラー、希釈剤、重合禁止剤、固体ポリマー等の各種添加剤を加えてもよい。
2個以上の(メタ)アクリロイル基を有する多官能(メタ)アクリレートとしては、1,6-ヘキサジオールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、ジシクロペンタニルジ(メタ)アクリレート、ポリプロピレングリコールジ(メタ)アクリレート、2,2-ビス(4-(メタ)アクリロキシジエトキシフェニル)プロパン、又は2,2-ビス(4-(メタ)アクリロキシテトラエトキシフェニル)プロパン等の2官能(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、トリス[(メタ)アクリロイキシエチル]イソシアヌレート等の3官能(メタ)アクリレート、ジメチロールプロパンテトラ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、又はペンタエリスリトールエトキシテトラ(メタ)アクリレート等の4官能以上の(メタ)アクリレートが挙げられる。
シランカップリング剤は接着性付与剤として作用する。シランカップリング剤としては、例えば、γ-グリシドキシプロピルトリメトキシシラン、β-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン等のエポキシ基含有シラン類;γ-アミノプロピルトリメトキシシラン、N-(β-アミノエチル)-γ-アミノプロピルトリメトキシシラン等のアミノ基含有シラン類;N-(1,3-ジメチルブチリデン)-3-(トリエトキシシリル)-1-プロパンアミン等のケチミン型シラン類;γ-メルカプトプロピルトリメトキシシラン等のメルカプト基含有シラン類;ビニルトリメトキシシラン、γ-メタクリロイルオキシプロピルトリメトキシシラン等のビニル型不飽和基含有シラン類;γ-クロロプロピルトリメトキシシラン等の塩素原子含有シラン類;γ-イソシアネートプロピルトリエトキシシラン等のイソシアネート含有シラン類;デシルトリメトキシシラン等のアルキルシラン類;フェニルトリメトキシシラン等のフェニル基含有シラン類等が挙げられるが、これらに限定されるものではない。また、アミノ基含有シラン類と上記のシラン類を含むエポキシ基含有化合物、イソシアネート基含有化合物、(メタ)アクリロイル基含有化合物とを反応させて、アミノ基を変性した変性アミノ基含有シラン類を用いてもよい。
アミノ基含有シラン類はシラノール縮合触媒として作用する。また、ケチミン型シラン類は水分の存在下でアミノ基含有シラン類を生成し、シラノール縮合触媒として作用する。したがって、アミノ基含有シラン類やケチミン型シラン類以外のシランカップリング剤を用いることが好ましい。また、アミノ基含有シラン類やケチミン型シラン類を用いる場合、それらの種類及び/又は使用量は、本発明の目的や効果が達成される範囲内で調整される。
アミノ基含有シラン類やケチミン型シラン類は本発明において使用が制限される場合がある。しかし、接着性付与剤としてアミノ基含有シラン類やケチミン型シラン類を用いることが望ましい場合には、光照射前にはアミノ基を有する化合物を発生せず、光照射によりアミノ基含有シラン類を発生する化合物(以下、光アミノシラン発生化合物とも称する)を用いることができる。光アミノシラン発生化合物としては、WO2015/088021号公報記載の光官能基が、o-ニトロベンジル基、p-ニトロベンジル基、オキシム残基、ベンジル基、及びベンゾイル基や置換されたこれらの基等である化合物が挙げられる。光官能基がo-ニトロベンジル基である光アミノシラン発生化合物としては、2-ニトロベンジル-N-[3-(トリメトキシシリル)プロピル]カルバメイト、2-ニトロベンジル-N-[3-(トリエトキシシリル)プロピル]カルバメイト、3,4-ジメトキシ-2-ニトロベンジル-N-[3-(トリメトキシシリル)プロピル]カルバメイト等が挙げられる。光官能基がp-ニトロベンジル基である光アミノシラン発生化合物としては、4-ニトロベンジル-N-[3-(トリメトキシシリル)プロピル]カルバメイト等が挙げられる。光官能基がベンジル基である光アミノシラン発生化合物としては、1-(3,5-ジメトキシフェニル)-1-メチルエチル-N-[3-(トリメトキシシリル)プロピル]カルバメイト等が挙げられる。光官能基がオキシム残基基である光アミノシラン発生化合物としては、ベンゾフェノンO-{[3-(トリメトキシシリル)プロピル]}オキシム等が挙げられる。
水分吸収剤としては、前述したシランカップリング剤やシリケートを用いることが好ましい。シリケートとしては、特に限定されず、例えば、テトラメトキシシラン、テトラアルコキシシラン等、及びその部分加水分解縮合物が挙げられる。
C成分やSi-F結合を有する化合物を除く他の架橋性ケイ素基の縮合反応促進触媒としては、公知の硬化触媒を広く用いることができ、特に制限はないが、例えば、有機金属化合物、アミン類、脂肪酸、有機酸性リン酸エステル化合物等が挙げられ、特にシラノール縮合触媒を用いることが好ましい。シラノール縮合触媒としては、例えば、有機錫化合物;ジアルキルスズオキサイド;ジブチル錫オキサイドとフタル酸エステルとの反応物等;チタン酸エステル類;有機アルミニウム化合物類;チタンテトラアセチルアセトナート等のキレート化合物類;有機酸ビスマス等が挙げられる。しかしながら、有機錫化合物は添加量に応じて、得られる組成物の毒性が強くなる場合がある。本発明のC成分やSi-F結合を有する化合物が縮合反応促進触媒として作用するため、これら以外の硬化触媒を用いる場合、光照射によらず架橋性ケイ素基の縮合反応が進行する場合があるため、本発明の目的や効果を達成できる範囲内で用いることが好ましい。
光増感剤としては、225-310kJ/molの三重項エネルギーを有するカルボニル化合物が好ましく、例えば、イソプロピルチオキサントン等のチオキサントンとその誘導体、9,10-ジブトキシアントラセン等のジアルコキシアントラセン誘導体、2-ベンゾイル安息香酸メチル等のベンゾフェノンとその誘導体、3-アシルクマリン、3,3’-カルボニルビスクマリン等のクマリン誘導体等が挙げられ、チオキサントンとその誘導体及びクマリン誘導体が好ましく、チオキサントンとその誘導体、ベンゾフェノンとその誘導体、及びクマリン誘導体がより好ましい。
光重合開始剤による硬化反応を促進させる目的で光重合促進剤を開始剤と併用することができる。光重合促進剤としては、トリエチルアミン、トリエタノールアミン、2-ジメチルアミノエタノール等の第3級アミン類;トリフェニルホスフィン等のアリールホスフィン類、トリフェニルホスフィンオキシド等のアリールホスフィンオキシド類、トリフェニルホスファイト等のアリールホスファイト類、トリフェニルホスフェート等のアリールホスフェート類等を含むホスフィン類(アリール基は置換を有することもできる。);β-チオグリコールで代表されるチオール類等を挙げることができる。好ましいホスフィン類は三官能性ホスフィン誘導体であり、トリアリールホスフィンがより好ましく、トリフェニルホスフィンが最も好ましい。
フィラーとしては樹脂フィラー(樹脂微粉末)や無機フィラー、及び機能性フィラーを用いることができる。フィラーに、シランカップリング剤、チタンキレート剤、アルミカップリング剤、脂肪酸、脂肪酸エステル、ロジン等で表面処理を施してもよい。樹脂フィラーとしては、有機樹脂等からなる粒子状のフィラーを用いることができる。例えば、樹脂フィラーとして、ポリアクリル酸エチル樹脂、ポリウレタン樹脂、ポリエチレン樹脂、ポリプロピレン樹脂、尿素樹脂、メラミン樹脂系、ベンゾグアナミン樹脂、フェノール樹脂、アクリル樹脂、スチレン樹脂等の有機質微粒子を用いることができる。なお、液晶表示装置の周辺部等の遮光性が要求される用途に用いる場合は、樹脂フィラーが黒色の樹脂フィラーを含んでいてもよい。長波長のLEDランプ等を用いた場合においても良好な深部硬化性を得ることができ、優れた遮光性と深部硬化性とを達成できる。
本発明では、引火点(開放式)が50℃以上の溶剤を希釈剤とする。希釈剤を含有することにより、粘度等の物性を調整できる。希釈剤としては、様々な希釈剤を用いることができる。希釈剤としては、例えば、ノルマルパラフィン、イソパラフィン等の飽和炭化水素系溶剤、リニアレンダイマー(出光興産株式会社商品名)等のα-オレフィン誘導体、芳香族炭化水素系溶剤、アルコール系溶剤、エステル系溶剤、クエン酸アセチルトリエチル等のクエン酸エステル系溶剤、ケトン系溶剤等の各種溶剤が挙げられる。
重合禁止剤としては、特に限定されないが、例えば、ヒンダードフェノール及びヒンダードアミン等のラジカル捕捉剤、リン系第二次酸化劣化防止剤、ジエチルヒドロキシルアミン、硫黄、t-ブチルカテコール、三ヨウ化カリウム、N-ニトロソフェニルヒドロキシアミンアルミニウム塩等が挙げられる。重合禁止剤は、単独で用いても、2種以上を併用してもよい。
固体ポリマーとしては20℃において固体のポリマーを用いることができる。固体ポリマーとしては、各種モノマーの中から、その1種を単独で重合したホモポリマー、又は2種以上を共重合したコポリマー(ランダムポリマー又はブロックポリマー)が挙げられる。
本発明の接着方法は、粘着シートや粘着テープ等の粘着製品の製造方法ではなく、光照射により粘着剤となる原料を被着体に直接塗布し、被着体上に粘着剤を生成させ、これに他方の被着体を接着する方法である。すなわち、本発明の接着方法においては、光硬化性粘着剤組成物をテープ等の形体に成形してから用いることはなく、一方の被着体に直接塗布してそのまま他方の被着体への接着に用いる(つまり、他方の被着体は剥離ライナー等のようなフィルム等ではなく、実際に一方の被着体に接着される被着体である。)。
光硬化性粘着剤組成物を製造する方法は特に制限はなく、例えば、A成分、B成分、及びC成分を所定量配合し、また、必要に応じてA’成分や粘着付与樹脂、及び/又は他の配合物質を配合し、脱気攪拌することにより製造できる。各成分及び他の配合物質の配合順は特に制限はなく、適宜決定できる。
本発明に係る光硬化性粘着剤組成物は、光照射前は液状のため被着体に直接塗布でき、形状が複雑な被着体に対しても容易に塗布できる。そして、光硬化性粘着剤組成物は、外気から遮断しなくても(酸素存在下であっても)、光照射によりすばやく粘着性を発揮する。したがって、本発明に係る光硬化性粘着剤組成物によれば、一方の被着体に光硬化性粘着剤組成物を塗布、光照射した後、粘着性を発揮した光硬化性粘着剤組成物に他方の被着体を貼り合わせることができるので、被着体が紫外光等の光を透過しない場合であっても、複数の被着体同士を容易に貼り合わせることができる。
C12、13混合アルコールグリシジルエーテルとアクリル酸とを1mol:2molの比率で、特開2013-82895号公報の実施例1に準じて合成した。過剰のアクリル酸を除去して、2-ヒドロキシ-3-アクリロイルオキシプロピル基を有するC12-13混合アルコールのエーテル(CnH2nOCH2CH(OH)CH2OC(=O)CH=CH2;n=12、13)を主成分とした常温で液状のC12MAcを得た。この化合物のIRスペクトル測定の結果、カルボン酸由来の-OH伸縮の吸収が消失していることが確認された。また、グリシジル基開環に起因する-OH伸縮ピークが生じていることが確認された。
PPG(ポリプロピレングリコール、Mw/Mn=1.1、数平均分子量:10,000)200gにキシリレンジイソシアネート(XDI)2.00mmolとN-フェニル-3-アミノプロピルトリメトキシシラン1.90mmolの反応物21.3gを反応させ、次にグリセリンモノメタクリレート1.27gと重合禁止剤(ヒドロキノン)0.05gとを加え反応させ、数平均分子量が31,000であり、常温で液状の架橋性ケイ素基を有するラジカル重合性PPG骨格を有するウレタンオリゴマー(DC10000-TSi65N)を得た。IRスペクトル測定の結果、イソシアネート基由来の-NCOの吸収が消失し、水酸基由来の-OH伸縮の吸収が残っていることが確認された。
PPG(ポリプロピレングリコール、Mw/Mn=1.1、数平均分子量:10,000)にキシリレンジイソシアネート(XDI)を反応させて得た、イソシアネート基両末端のPPG骨格のウレタンプレポリマー(数平均分子量:9、700)125gに3-メルカプトプロピルトリメトキシシラン3.55gと触媒としてUCAT660M(ジモルフォリノジエチルエーテル)0.05gとを加え反応させ、次に2-ヒドロキシエチルアクリルアミド1.03gと重合禁止剤(ヒドロキノン)0.05gとを加え反応させ、数平均分子量が32,000であり、常温で液状の架橋性ケイ素基を有するラジカル重合性PPG骨格を有するウレタンオリゴマー(DC10000-TSi65S)を得た。IRスペクトル測定の結果、イソシアネート基由来の-NCOの吸収が消失が確認された。
PPG(ポリプロピレングリコール、Mw/Mn=1.1、数平均分子量:10,000)100gにキシリレンジイソシアネート(XDI)4.0gを反応させて得た、イソシアネート基両末端のPPG骨格のウレタンプレポリマー(PU-PPG10000)104.0gにグリセリンモノメタクリレート3.9gと重合禁止剤(ヒドロキノン)0.05gとを加え反応させ、数平均分子量が32,000であり、常温で液状のメタクリル酸2-ヒドロキシプロピル基両末端のPPG骨格のウレタンアクリレート(DL-10000-1)を得た。IRスペクトル測定の結果、イソシアネート基由来の-NCOの吸収が消失し、水酸基由来の-OH伸縮の吸収が残っていることが確認された。
PPG(ポリプロピレングリコール、Mw/Mn=1.1、数平均分子量:10,000)100gにキシリレンジイソシアネート(XDI)4.0gを反応させて得た、イソシアネート基両末端のPPG骨格のウレタンプレポリマー(PU-PPG10000)104.0gに2-ヒドロキシエチルアクリルアミド2.6gと重合禁止剤(ヒドロキノン)0.05gとを加え、70℃で24時間反応させ、数平均分子量が44,000であり、常温で液状のアクリロイルアミノエチル基両末端のPPG骨格のウレタンアクリレート(DL-10000-2)を得た。IRスペクトル測定の結果、イソシアネート基由来の-NCOの吸収が消失していることが確認された。
表1に示す配合割合で、攪拌機、温度計、窒素導入口、モノマー装入管、及び水冷コンデンサーを装着したフラスコに、各配合物質をそれぞれ添加し、混合撹拌して実施例1に係る光硬化性粘着剤組成物を調製した。
(B成分:単官能ラジカル重合性化合物)
2-HBA(ライトアクリレートHOB-A;共栄社化学株式会社製、2-ヒドロキシブチルアクリレート)
ACMO(ACMO;kjケミカルズ株式会社製、アクリロイルモルフォリン)
(C成分:光開始剤)
Irgacure379(Irgacure379;BASF社製、2-(ジメチルアミノ)-2-[(4-メチルフェニル)メチル]-1-[4-(4-モルホリニル)フェニル]-1-ブタノン)
(粘着付与樹脂)
YS-K125(YSポリスターK125;ヤスハラケミカル社製;テルペンフェノール樹脂)
(他の縮合反応促進触媒)
ネオスタンU-830(ネオスタンU-830;日東化成株式会社製、ジオクチル錫バーサテート)
実施例1に係る光硬化性粘着剤組成物を第1の被着材(PETフィルム)にガラス棒を用いて厚さが200μmとなるように塗布した。次に、第1の被着材上の光硬化性粘着剤組成物に紫外線(UV)を照射した[照射条件:UV-LEDランプ(波長365nm、照度:1000mW/cm2)、積算光量:3000mJ/cm2]。UV照射後、直ちに、25mm×80mmの面積で第2の被着材(オーステナイト系ステンレス)を、UV照射された光硬化性粘着剤組成物を挟むように第1の被着材に貼り合わせ、2kgのローラーを用いて圧力を加えた。これにより試験片を作製した(常温剥離接着強さ試験用の試験片と、高温剥離接着強さ用の試験片とを作製した。)。そして、23℃、湿度50%の雰囲気下で7日間養生した。
(AF):被着体と粘着剤の接着界面で剥離された。
Claims (5)
- (A)架橋性ケイ素基を有するラジカル重合性ウレタンオリゴマーと、
(B)単官能ラジカル重合性化合物と、
(C)光開始剤と
を含有する光硬化性粘着剤組成物。 - 前記(B)単官能ラジカル重合性化合物が、単官能(メタ)アクリレート、アミド基を有するビニル系の単官能化合物、及び単官能N-ビニル化合物からなる群から選択される少なくとも1つの化合物である請求項1に記載の光硬化性粘着剤組成物。
- 請求項1又は2に記載の光硬化性粘着剤組成物の硬化物を有する製品。
- 複数の被着体を接着する方法であって、
(A)架橋性ケイ素基を有するラジカル重合性ウレタンオリゴマーと、
(B)単官能ラジカル重合性化合物と、
(C)光開始剤とを含有する光硬化性粘着剤組成物を少なくとも一方の被着体に塗布する塗布工程と、
前記一方の被着体に塗布された光硬化性粘着剤組成物に酸素存在下でLEDから発せられる光を照射する光照射工程と、
前記一方の被着体に塗布され、前記光が照射された前記光硬化性粘着剤組成物に他方の被着体(ただし、他方の被着体として粘着面の保護用シートを除く)を接着する工程と
を備える接着方法。 - 請求項4に記載の接着方法を用いて製造される接着体の製造方法。
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KR1020207011492A KR20200066320A (ko) | 2017-10-11 | 2018-10-09 | 광경화성 점착제 조성물 및 접착 방법 |
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US20220185935A1 (en) * | 2020-12-11 | 2022-06-16 | Threebond Co., Ltd. | Sheet-shaped photocurable composition, photocurable composition solution, method for producing sheet-shaped photocurable composition, and laminated body |
CN114999333A (zh) * | 2022-06-02 | 2022-09-02 | 武汉华星光电半导体显示技术有限公司 | 拼接显示面板 |
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JP2016199656A (ja) * | 2015-04-09 | 2016-12-01 | 協立化学産業株式会社 | 光硬化型接着組成物 |
WO2017098972A1 (ja) * | 2015-12-08 | 2017-06-15 | セメダイン株式会社 | 光硬化性粘着剤を用いる接着方法 |
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EP3081612B1 (en) * | 2013-12-13 | 2018-11-14 | Cemedine Co., Ltd. | Photocurable composition having adhesive properties |
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JP2017105998A (ja) * | 2015-11-30 | 2017-06-15 | Jsr株式会社 | 紫外線硬化性を有する接着剤組成物 |
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US20220185935A1 (en) * | 2020-12-11 | 2022-06-16 | Threebond Co., Ltd. | Sheet-shaped photocurable composition, photocurable composition solution, method for producing sheet-shaped photocurable composition, and laminated body |
CN114999333A (zh) * | 2022-06-02 | 2022-09-02 | 武汉华星光电半导体显示技术有限公司 | 拼接显示面板 |
CN114999333B (zh) * | 2022-06-02 | 2023-10-31 | 武汉华星光电半导体显示技术有限公司 | 拼接显示面板 |
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