Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/06—Non-macromolecular additives organic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/08—Macromolecular additives
• • 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
  • C09J175/06—Polyurethanes from polyesters
• • 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
  • C09J175/08—Polyurethanes from polyethers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J201/00—Adhesives based on unspecified macromolecular compounds
  • C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
  • C09J201/10—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups

Definitions

• the present invention relates to a moisture-curable hot melt adhesive.
• Reactive polyurethane hot melt adhesives containing isocyanate functional groups conventionally prepared from prepolymers that are irreversibly cured by the action of moisture in the atmosphere or moisture contained in materials that are bonded to each other (hereinafter, "PU hot”).
• PU hot PU hot
• melt adhesive is known.
• a prepolymer as described in Patent Document 1 is a reaction product of a polyester polyol and a compound obtained by reacting a desired polyether polyol with a polyisocyanate, and is such a reactive PU hot.
• the melt adhesive can be generally used as an adhesive for adhering various materials such as plastic, glass, metal, leather, and wood.
• the solidification time of the PU hot melt adhesive without interaction of the starting components can be adjusted in the range of seconds to minutes by changing the mixing ratio of the crystalline or amorphous components at room temperature. ..
• the crystalline structure of the PU hot melt adhesive reduces the melt viscosity of the adhesive and improves coatability, as well as good low temperature elasticity due to the short solidification time and low glass transition temperature after coating.
• Curing accompanied by a cross-linking reaction between the components of the reactive PU hot melt adhesive proceeds in a few days due to the reaction between the isocyanate group and water, whereby a thermosetting polyurea is formed.
• the PU hot melt adhesive after this exhibits the property that it no longer melts or, for example, does not dissolve in a solvent. For this reason, the cured adhesive exhibits good heat resistance and also good resistance to chemicals such as plasticizers, solvents, oils, fuels and the like.
• adhesives such as those described above have high concentrations of free monomeric polyisocyanates, such as 4,4'-diisocyanatodiphenylmethane (4,4'-MDI), due to the preparation of these adhesives. ), 2,4-Diisocyanatotoluene, or 2,6-diisocyanatotoluene (TDI) remains.
• TDI 2,6-diisocyanatototoluene
• Such a monomeric polyisocyanate exhibits the vapor pressure at which the monomeric component is released into the ambient environment in a gaseous state at the coating temperature of the adhesive (about 100 ° C to about 180 ° C). Installation of equipment is required.
• polyurea is formed by the reaction with water. Then, when polyurea is formed, carbon dioxide is released from the adhesive. Therefore, foaming occurs in the adhesive region to which the adhesive is adhered. As a result, the surface of the member constituting the joint expands and the adhesive strength decreases.
• the reactive hot melt adhesive needs to have a balance between stability during heating (does not increase viscosity and does not cure) and curability at room temperature.
• the reactive PU hot melt adhesive has a drawback that it is not sufficiently stable when heated. That is, the reactive PU hot melt adhesive needs to be heated and melted before coating, and at that time, the isocyanate group at the end of the molecular chain reacts with the urethane bond or urea bond in the molecular chain to form an allophanate bond or biuret. Bonds were formed, three-dimensional crosslinked structures were formed, and the viscosity of the composition was increased or gelled.
• the adhesive composition described in Patent Document 4 is a pressure-sensitive adhesive (adhesive), and tack remains even after curing, so stickiness may become a problem depending on the application. Further, the composition described in Patent Document 5 may not have sufficient rising strength, and the moisture-curable hot-melt adhesive composition described in Patent Document 6 ensures a sufficient bonding time. It is difficult to achieve both with sufficient rising strength.
• Japanese Unexamined Patent Publication No. 4-227714 Japanese Unexamined Patent Publication No. 2-08686 Japanese Unexamined Patent Publication No. 2014-205764 Japanese Patent No. 6027146 Japanese Patent No. 5738849 Japanese Patent No. 5254804
• an object of the present invention is to provide a moisture-curable hot-melt adhesive capable of achieving both good rising strength and a sufficient length of bondable time.
• the present invention provides a moisture-curable hot melt adhesive containing an alkoxysilyl group-containing urethane prepolymer (A) represented by the following general formula (a).
• A represents a residue after removing two isocyanate groups from the divalent diisocyanate
• Y is an isocyanate group which is a reaction product of the diisocyanate (i) and the polyol (ii).
• Represents a residue from which -OC ( O) -NH-A-NCO has been removed from the terminal urethane prepolymer (a1)
• W represents active hydrogen from the compound (a2) containing an alkoxysilyl group and an active hydrogen group.
• the polyol (ii) is a polyether polyol (ii-1), and the compound (a2) containing an alkoxysilyl group and an active hydrogen group is solid at room temperature and is an alkoxysilyl.
• It is a methyl methacrylate-based polymer (a2-1) having a group and a hydroxyl group, where X represents O, S, or NR 1 , where R 1 is a hydrogen atom or 1 to 20 Cs. It represents a linear or branched monovalent hydrocarbon group having an atom, which may optionally include a cyclic moiety, or represents a group of the general formula (b).
• R 2 and R 3 represent each other independently of a hydrogen atom or a group selected from the group consisting of -R 5 , -COOR 5 and -CN, and R 4 is a hydrogen atom or a hydrogen atom or.
• -CH 2 -COOR 5 , -COOR 5 , -CONHR 5 , -CON (R 5 ) 2 , -CN, -NO 2 , -PO (OR 5 ) 2 , -SO 2 R 5 , and -SO 2 OR 5 represents a group selected from the group consisting of, R 5 is a hydrocarbon group having 1 to 20 C atoms, a may include one or more heteroatoms optionally group Represented, n is a number of 1 or more.
• the moisture-curable hot-melt adhesive of the present invention it is possible to provide a moisture-curable hot-melt adhesive capable of achieving both good rising strength and a sufficient length of bonding time.
• Room temperature or "room temperature” is a temperature of 23 ° C.
• solid at room temperature means that the substance of interest (eg, a given composition) is a crystalline substance, a partially crystalline substance, and / or a glassy amorphous substance, from 23 ° C. Also means having a high softening point (measured by the annular method) or melting point.
• the melting point is, for example, the maximum value of the curve measured during the heating operation by dynamic differential calorimetry (differential scanning calorimetry [DSC]), and the target material changes from the solid state to the liquid state.
• DSC dynamic differential calorimetry
• the “bondable time” is the time that can be bonded from the time when the adhesive is applied to the adherend to the time when it is bonded to another adherend.
• the “bondable time” can be measured according to the Japanese adhesive industry standard JAI7-1991.
• the "set time” is the time until the hot melt adhesive bonded to the adherend is cooled and solidified to show the initial adhesive strength.
• the rising strength after application to the adherend is sufficiently high (in other words, the time until sufficient adhesive strength due to solidification is exhibited is practically short), and the hot melt adhesive is adhered.
• the time until the hot melt adhesive and the other adherend cannot be properly adhered to the adherend to which the agent is applied that is, the time required for bonding. Is required to be long enough.
• the rising strength is the strength exerted by the solidification of the hot melt adhesive, and the solidification means that the hot melt adhesive is melted by heating and then cooled to become a solid state. Then, after the reactive hot melt adhesive is solidified, the crosslinking reaction proceeds due to the silyl group and the like in the component, and the curing proceeds.
• the present inventor has made a specific compounding component by including a region of an amorphous molecule while containing a crystal structure. It has been found that a sufficient rising strength and a sufficient bonding time of a sufficient length can be achieved at the same time by selecting the material. Furthermore, it has been found that by including a reactive group in a prepolymer or the like constituting the adhesive, the cross-linking reaction can proceed mainly after the adhesive has solidified, and the final strength of the adhesive can be sufficiently improved.
• the bonding time can be adjusted by including a crystalline compound in the material constituting the hot melt adhesive, and a region corresponding to an amorphous molecule such as an ether bond of a polyether can be partially used. Flexibility is ensured by including it, and for example, by containing a prepolymer having a reactive group at the terminal, a cross-linking reaction mainly started after the adhesive is applied is allowed to proceed with the passage of time, and the final strength is achieved. It was found that it can be sufficiently improved.
• the moisture-curable hot-melt adhesive according to the present invention contains an alkoxysilyl group-containing urethane prepolymer (A) represented by the following general formula (a) (hereinafter referred to as component (A)). Mold hot melt adhesive.
• A represents a residue after removing two isocyanate groups from the divalent diisocyanate
• Y is an isocyanate group which is a reaction product of the diisocyanate (i) and the polyol (ii).
• Represents a residue from which -OC ( O) -NH-A-NCO has been removed from the terminal urethane prepolymer (a1) (hereinafter referred to as Y residue), and W represents an alkoxysilyl group and an active hydrogen group.
• R 2 and R 3 represent each other independently of a hydrogen atom, or a group selected from the group consisting of -R 5 , -COOR 5 , and -CN, and R 4 is a hydrogen atom, or-.
• R 5 is a hydrocarbon group having 1 to 20 C atoms, it represents one or more may groups contain a hetero atom optionally n is a number of 1 or more.
• the moisture-curable hot-melt adhesive according to the present invention is composed of the alkoxysilyl group-containing urethane prepolymer (A) of the general formula (a) (hereinafter, referred to as the component (A)).
• the component (A) is generally an isocyanate group-terminated urethane prepolymer (a1) represented by the formula (I) (hereinafter referred to as a component (a1)) and an alkoxysilyl represented by the formula (II). It is obtained by reacting a compound (a2) containing a group and an active hydrogen group (hereinafter, referred to as a component (a2)).
• the method for preparing the component (a1) is not particularly limited, but for example, the component (a1) is a diisocyanate (i) (hereinafter referred to as a component (i)) and a polyol (ii) (hereinafter, a component (ii)). ) May be prepared as a reaction product with). Further, the component (ii) may contain a polyether polyol (ii-1) (hereinafter, referred to as a component (ii-1)). Here, the component (ii) is referred to as a polyester polyol (ii-2) (hereinafter referred to as a component (ii-2)) in addition to the component (ii-1) or in place of a part of the component (ii-1).
• a polycarbonate polyol (ii-3) (hereinafter, referred to as a component (ii-3)) can be further contained.
• the component (ii-2) may be a crystalline aliphatic polyester polyol (ii-2-1) (hereinafter, referred to as a component (ii-2-1)).
• the component (a2) is a methyl methacrylate-based polymer (a2-1) (hereinafter referred to as a component (a2-1)) which is solid at room temperature and has an alkoxysilyl group and a hydroxyl group at the terminal.
• the component (a2) is an alkoxysilane (a2-2) having an active hydrogen group in addition to the component (a2-1) or in place of a part of the component (a2-1) (hereinafter, the component (a2-2). ) May be further included.
• the component (A) includes a hydroxyl group-terminated polymer (a1 ′′) represented by the formula (III) (hereinafter referred to as a component (a1 ′′)), an alkoxysilyl group represented by the formula (IV), and an isocyanate. It can also be obtained by reacting with a compound (a2 ") containing a group (hereinafter, referred to as a component (a2")).
• the component (a2 ") is obtained by reacting a compound (a2) containing an alkoxysilyl group and an active hydrogen group with a diisocyanate (formula: OCN-A-NCO).
• A, X, and W are the same as above.
• the moisture-curable hot melt adhesive includes a silane-based adhesive (B) (hereinafter referred to as component (B)) and a modified resin (C) (hereinafter, component).
• a component (D) a fluorinated polymer
• E silylated polymer
• component (E) may be further contained.
• hot melt adhesive according to the present invention may be configured as a photocurable adhesive.
• the moisture-curable hot-melt adhesive according to the present invention is composed of the alkoxysilyl group-containing urethane prepolymer (A) represented by the general formula (a), and the method for preparing the component (A) is not particularly limited. ..
• the component (i) and the component (ii) are reacted to prepare the component (a1), and the obtained component (a1) and the component (a2) are reacted.
• a moisture-curable hot melt adhesive according to the present invention is added by adding a component (B), a component (C), a component (D), a component (E), and / or other additives to the component (A).
• the component (A) may be prepared by reacting the component (a2) with the component (i) or the component (ii) and further reacting the component (ii) or the component (i), or the component (i).
• (I), component (ii), and component (a2) may be reacted at the same time to prepare.
• the hot melt adhesive according to the present invention is in a solid state at room temperature and is applied to the adherend in a state of being heated and melted.
• each component will be described in detail.
• the moisture-curable hot-melt adhesive according to the present invention may be referred to as "reactive hot-melt adhesive” or "one-component moisture-curable reactive hot-melt adhesive”.
• the alkoxysilyl group-containing urethane prepolymer (A) is a polymer having an alkoxysilyl group represented by the general formula (a) and containing a urethane bond.
• the alkoxysilyl group-containing urethane prepolymer (A) is a polymer that requires a polyether skeleton (a skeleton obtained by removing hydroxyl groups from a polyether polyol), and contains a polymer containing a polyether skeleton and an alkoxysilyl group.
• the linking of this urethane bond is a linking by a linking group of the following general formula (V) generated by a reaction between a terminal hydroxyl group of an acrylic polymer containing a polyether polyol and an alkoxysilyl group and a linking agent (diisocyanate compound).
• the component (A) is preferably in a solid state at room temperature.
• the (a1) isocyanate group-terminated urethane prepolymer according to the present invention can be prepared by a conventionally known method. For example, it can be prepared by reacting a predetermined diisocyanate component (component (i)) with a predetermined polyol component (component (ii)).
• the diisocyanate and the polyether polyol are mixed with each other in a molar ratio of the isocyanate group of the diisocyanate to the hydroxyl group of the polyether polyol (hereinafter referred to as isocyanate group / hydroxyl group molar ratio). Is obtained in a state where the molar ratio is more than 1, that is, the isocyanate group is reacted in an excessive amount with respect to the hydroxyl group.
• the isocyanate group / hydroxyl group molar ratio is preferably 1.5 or more, more preferably 1.8 or more, further preferably 1.9 or more, preferably 3.0 or less, and more preferably 2.5 or less. .1 or less is more preferable. Good coatability can be obtained as long as the isocyanate group / hydroxyl group molar ratio is within the relevant range.
• the isocyanate group-terminated urethane prepolymer is a diisocyanate having an isocyanate group having an insufficient molar ratio with respect to the hydroxyl group of the polyether polyol (for example, 1,6-diisocyanatohexane (HDI), 2,4).
• the polyether polyol for example, 1,6-diisocyanatohexane (HDI), 2,4
• TDI diisocyanatotoluene
• TDI 2,6-diisocyanatotoluene
• MDI 2,4'-diisocyanatodiphenylmethane
• MDI 4,4'-diisocyanatodiphenylmethane
• polyether polyol and the diisocyanate may be reacted in the presence of an aliphatic diisocyanate trimmer (for example, hexamethylene-diisocyanate, etc.) in an amount of up to 5% by weight, or the prepolymerization reaction may occur.
• trimmer for example, hexamethylene-diisocyanate, etc.
• This type of trimmer may be added after completion.
• the polyisocyanate according to the present invention is not particularly limited, and examples thereof include diisocyanate.
• the (i) diisocyanate is not particularly limited, and examples thereof include compounds represented by the following formula (c).
• A is a residue after removing two isocyanate groups from the divalent diisocyanate, and is an aliphatic hydrocarbon group having 1 to 20 carbon atoms and 3 to 3 carbon atoms including an alicyclic structure. Represents a hydrocarbon group having 6 to 20 carbon atoms and containing 20 hydrocarbon groups or an aromatic ring.
• aromatic diisocyanates such as phenylenediocyanate, tolylene diisocyanate, diphenylmethane diisocyanate and naphthalenedi isocyanate, hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene isocyanate and the like.
• aromatic diisocyanates such as phenylenediocyanate, tolylene diisocyanate, diphenylmethane diisocyanate and naphthalenedi isocyanate, hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, x
• polyol examples include polyester-based polyols, polyether-based polyols, acrylic polyols, polycarbonate polyols, polyolefin polyols, castor oil polyols, and the like, or mixtures or copolymers thereof.
• the (ii) polyol component contains (ii-1) a polyether polyol as an essential component of the present invention.
• the component (ii) can further contain a polyester polyol (ii-2) and / or a polycarbonate polyol (ii-3).
• the component (ii-2) may be a crystalline aliphatic polyester polyol (ii-2-1).
• the (a1) isocyanate group-terminated urethane prepolymer according to the present invention is the component (ii).
• the molar ratio of the isocyanate group of the diisocyanate to the hydroxyl group of the polyol is such that the diisocyanate and [(ii-2) and / or (ii-3)] are linked by the diisocyanate.
• the isocyanate group / hydroxyl group molar ratio is preferably 1.2 or more, more preferably 1.3 or more, still more preferably 1.4 or more, from the viewpoint of obtaining good coatability. Further, from the viewpoint of obtaining good curability, 1.9 or less is preferable, 1.7 or less is more preferable, and 1.6 or less is further preferable.
• polyether polyol examples include polypropylene glycol (PPG), polyethylene glycol (PEG), polytetramethylene glycol (PTMG) and the like. These polyols are not limited, but the number average molecular weight is preferably 500 or more, more preferably 1,000 or more, further preferably 2,000 or more, preferably 30,000 or less, more preferably 20,000 or less, 15. More preferably 000 or less. Further, the polyether polyol is preferably a diol.
• polyether polyol a compound obtained by copolymerizing two or more kinds of polyether polyols may be used, and examples thereof include a polyoxyethylene-oxypropylene block copolymerized diol.
• the diol is preferable because the terminal group is a primary hydroxyl group and the reactivity with the isocyanate group is good.
• the polyoxyethylene-oxypropylene block copolymerized diol preferably has an ethylene oxide content of 5% by weight or more, preferably 90% by weight or less, more preferably 40% by weight or less, still more preferably 20% by weight or less.
• polyester-based polyol used as the polyol component (hereinafter, may be simply referred to as "polyester polyol") is a polyester having more than one OH group (preferably two terminal OH groups). means.
• the moisture-curable hot-melt adhesive according to the present invention has (ii) a functional value of at least 2 in the polyol component and is solid (preferably at least partially crystalline solid) at room temperature. Contains at least one polyester polyol.
• the moisture-curable hot melt adhesive is (ii) one or more polyester polyols having at least 2 functional values and at least partially crystalline in the polyol component, at least 2 functional values.
• the “at least partially crystalline” polyester polyol means that the polyester polyol is not completely crystalline and contains a partially or additionally constant amorphous portion.
• Such a polyester polyol has a crystalline melting point (Tm) and a glass transition temperature (hereinafter, may be referred to as "Tg").
• Tm crystalline melting point
• Tg glass transition temperature
• the melting point indicates the temperature at which the crystalline portion melts.
• the melting point can be determined as the main endothermic peak (crystal melting peak), for example, by differential thermal analysis by DSC measurement. According to DSC measurements (heating and cooling rates in the second heating process are 10 K / min), the melting point of at least partially crystalline polyester polyols is from about 35 ° C to about 120 ° C.
• the glass transition temperature of at least partially crystalline polyester polyols is generally well below, for example, room temperature.
• Suitable partially crystalline polyester polyols (hereinafter referred to as "crystalline aliphatic polyester polyols") are known to those skilled in the art.
• the polyester polyol may be a polyester polyol linked with a diisocyanate.
• a compound obtained by reacting a compound having two or more hydroxyl groups with a polybasic acid can be used.
• Polycaprolactone derivatives based on bifunctional starter molecules, such as 1,6-hexanediol, can also be used.
• examples of the compound having two or more hydroxyl groups include ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,5. -Number of carbon atoms of pentandiol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, etc.
• linear aliphatic diols examples thereof include aliphatic triols such as trimethylol ethane, trimethylol propane, pentaerythritol, and glycerin.
• the number of carbon atoms of the linear aliphatic diol is preferably 4 to 14, and more preferably 6 to 12. These compounds may be used alone or in combination of two or more.
• polybasic acid examples include linear aliphatic dicarboxylic acids having 2 to 16 carbon atoms such as oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, and 1,12-dodecanedicarboxylic acid. Can be used. Among these, from the viewpoint of enhancing crystallinity, the number of carbon atoms of the linear aliphatic dicarboxylic acid is preferably 6 to 14, and more preferably 8 to 12. These polybasic acids can be used alone or in combination of two or more.
• a long-chain aliphatic polyester polyol represented by the following general formula (VI) is preferable.
• R 6 and R 7 each independently represent a linear alkylene group having an even number of carbon atoms, and the total number of carbon atoms of R 6 and R 7 is 12 or more. Is. Further, n indicates 3 to 40.
• R 6 in the general formula (VI) a linear alkylene group having an even number of carbon atoms can be mentioned, and the range in which the total number of carbon atoms of R 6 and R 7 is 12 or more. Can be selected as appropriate.
• the R 7 is preferably a linear alkylene group having an even number of 4 or more carbon atoms.
• the R 7 is preferably a linear alkylene group having an even number of 10 or more carbon atoms.
• the crystallinity of the obtained urethane prepolymer can be enhanced, which is excellent.
• a moisture-curable hot-melt adhesive having both initial adhesive strength and normal adhesive strength can be obtained.
• n in the general formula (VI) is 3 to 40, preferably in the range of 9 to 25, and more preferably in the range of 9 to 15.
• crystalline aliphatic polyester polyol examples include polyhexamethylene adipate, polyhexamethylene sevacate, polyhexamethylene dodecanete, polydodecamethylene decanete and the like, and polyhexamethylene sevacate and polyhexamethylene dodeca. Nate and polydodecamethylene decanate are preferred.
• the crystalline fat is preferably 30 ° C. or lower, which is lower than the melting point of the crystalline aliphatic polyester polyol.
• it has high resistance to the repulsion (force to peel off) of the base material and can be fixed in a short time, so it has a decorative color on the surface of the base material such as plywood, MDF (medium density fiberboard), particle board, etc.
• It can be used as a decorative building member obtained by laminating a decorative sheet or film, decorative paper, veneer, metal foil, etc. with a pattern.
• the crystalline aliphatic polyester polyol preferably has a number average molecular weight of 1,500 or more, more preferably 2,500 or more, further preferably 3,500 or more, preferably 10,000 or less, and 7,000 or less. More preferably, 6,000 or less is further preferable.
• the number average molecular weight is preferably in the range of 20,000 or more and 200,000 or less.
• the melting point of the crystalline aliphatic polyester polyol is preferably 35 ° C. or higher, more preferably 45 ° C. or higher, further preferably 55 ° C. or higher, preferably 120 ° C. or lower, more preferably 100 ° C. or lower, and further preferably 80 ° C. or lower. preferable.
• Aromatic polyester polyol for example, a reaction product of an aromatic polycarboxylic acid and a low molecular weight aliphatic polyol can be used.
• aromatic polycarboxylic acid for example, orthophthalic acid, phthalic anhydride), isophthalic acid, and terephthalic acid can be used. These aromatic polycarboxylic acids can be used alone or in combination of two or more.
• polybasic acids can be used in combination with the aromatic polycarboxylic acid, if necessary.
• the content of the aromatic polycarboxylic acid is preferably 60% by mass or more, more preferably 80% by mass or more, based on all the polybasic acids.
• polybasic acids examples include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, 1,12-dodecanecarboxylic acid and the like. These polybasic acids can be used alone or in combination of two or more. Among these polybasic acids, adipic acid and sebacic acid are preferable.
• Examples of the low molecular weight aliphatic polyol include linear aliphatic diols having 2 to 16 carbon atoms, and among the linear aliphatic diols, ethylene glycol, 1,4-butanediol, and 1, 6-Hexanediol is preferable, ethylene glycol and 1,6-hexanediol are more preferable.
• low molecular weight aliphatic polyols examples include neopentyl glycol, 1,3-butanediol, 2,2-diethyl-1,3-propanediol, 2,2-diethylpropanediol, and 3-methyl-1,5.
• branched chain aliphatic diols such as pentandiol, 2-ethyl-2-butyl-1,3-propanediol, 2-methyl-1,8-octanediol, 2,4-diol-1,5-pentanediol
• neopentyl glycol and 3-methyl-1,5-pentanediol are preferable, and neopentyl glycol is more preferable.
• examples of the low molecular weight aliphatic polyol include low molecular weight aliphatic polyols having an ether bond such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol and tripropylene glycol, and among these, diethylene glycol. Is preferable.
• an aromatic polyol obtained by carrying out a ring-opening addition reaction of ethylene oxide, propylene oxide, ⁇ -butyrolactone, ⁇ -caprolactone or the like with bisphenol A, bisphenol F or the like can also be used. Then, an aromatic polyol obtained by carrying out a ring-opening addition reaction of bisphenol A and ethylene oxide is preferable.
• These low molecular weight aliphatic polyols can be used alone or in combination of two or more.
• neopentyl glycol and diethylene glycol are preferably used from the viewpoint of enhancing the amorphous property.
• the number average molecular weight of the aromatic polyester polyol is preferably 900 or more, more preferably 1,000 or more, preferably 5,000 or less, and more preferably 3,000 or less.
• aromatic polyester polyol for example, an aromatic polyester polyol having a number average molecular weight of 2,000 or more and 5,000 or less and a glass transition temperature of 30 ° C. or more (hereinafter, “normal temperature solid fragrance”). (Refered to be referred to as "group polyester polyol”) and, for example, an aromatic polyester polyol having a number average molecular weight of 400 or more and 3,500 or less and having a glass transition temperature of 20 ° C. or less (hereinafter, "aromatic of room temperature liquid”). It is referred to as "polyester polyol").
• An aromatic polyester polyol that is solid at room temperature can be produced, for example, by a method of condensing an aromatic polycarboxylic acid with a low molecular weight aliphatic polyol.
• the room temperature solid aromatic polyester polyol ethylene glycol or neopentyl glycol as a low molecular weight aliphatic polyol, isophthalic acid or terephthalic acid as an aromatic polycarboxylic acid, and the glass transition temperature should be 30 ° C or higher. It is preferable to use an aromatic polyester polyol obtained by appropriately combining with and subjected to a condensation reaction by a known method.
• An aromatic polyester polyol that is solid at room temperature is a compound having a glass transition temperature of 30 ° C. or higher, and more preferably has a glass transition temperature in the range of 30 ° C. or higher and 70 ° C. or lower.
• Aromatic polyester polyol that is liquid at room temperature for example, an aromatic polyester polyol obtained by reacting a low molecular weight aliphatic polyol having an ether bond, a branched chain aliphatic diol, or the like with an aromatic polycarboxylic acid is used. Can be done.
• Aromatic polyester polyols that are liquid at room temperature have a glass transition temperature of 20 ° C or lower. Further, it is preferable that the aromatic polyester polyol, which is a liquid at room temperature, has a glass transition temperature in the range of ⁇ 30 ° C. or higher and 20 ° C. or lower. Within this range, a moisture-curable hot-melt adhesive capable of exhibiting even more excellent normal adhesive strength can be obtained.
• the alicyclic polyester polyol uses, for example, an alicyclic polyol and an aliphatic polycarboxylic acid (or an acid derivative thereof), or an aliphatic polyol and an alicyclic polycarboxylic acid (or an acid derivative thereof). It can be produced by a known reaction method using the above. The manufacturing method is not particularly limited.
• alicyclic polyol examples include cyclopentanediol, cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol A and the like, and addition of these polyols with alkylene oxides such as ethylene oxide (EO) and propylene oxide (PO). Things can also be used. These can be used alone or in combination of two or more.
• alkylene oxides such as ethylene oxide (EO) and propylene oxide (PO). Things can also be used. These can be used alone or in combination of two or more.
• aliphatic polyol examples include linear aliphatic diols having 2 to 16 carbon atoms, polyalkylene oxide oligomers, branched chain aliphatic diols, aliphatic triols, and the like, among which 1,6- Hexadiol, 1,8-octanediol, 1,10-decanediol and neopentyl glycol are preferable, and neopentyl glycol is more preferable.
• Examples of the alicyclic polycarboxylic acid include cyclohexanedicarboxylic acid and cyclopentanedicarboxylic acid, and among these, cyclohexanediadipate (CHDA) is preferable.
• CHDA cyclohexanediadipate
• aliphatic polycarboxylic acid examples include linear aliphatic dicarboxylic acids having 2 to 16 carbon atoms.
• adipic acid, sebacic acid, decanedioic acid and dodecanedioic acid are preferable, and sebacic acid and dodecanedioic acid are more preferable. These can be used alone or in combination of two or more.
• alicyclic polycarboxylic acid and the aliphatic polycarboxylic acid for example, a lower alkyl ester derivative such as a methyl ester, an acid anhydride, a corresponding acid derivative such as an acid halide, or the like may be used.
• the number average molecular weight (Mn) of the alicyclic polyester polyol is preferably 500 or more, more preferably 700 or more, preferably 5,000 or less, more preferably 3,000 or less, still more preferably 2,000 or less. If the Mn of the alicyclic polyester polyol is within the range, the moisture-curable polyurethane hot-melt adhesive has an appropriate melt viscosity, is excellent in coating workability (viscosity suitability), and has excellent adhesive strength, and the base material and the surface member ( It is possible to prevent the surface member from peeling off at the complicated shape portion of the base material after the sheet, the film, the metal foil, the paper, etc.) are bonded together.
• Examples of the aliphatic polyester polyol that is liquid at room temperature include aliphatic polyester polyols that have a number average molecular weight of 4,000 or more and 7,000 or less and have a branched chain aliphatic group and are liquid at room temperature.
• Aliphatic polyester polyols that are liquid at room temperature are a number in the range of 4,000 or more and 7,000 or less from the viewpoint of maintaining both good wettability and high initial adhesive strength of the obtained adhesive in a low temperature atmosphere. It is essential to have an average molecular weight.
• the number average molecular weight of the aliphatic polyester polyol liquid at room temperature is less than 4,000, the wettability of the obtained adhesive to the substrate in a low temperature atmosphere may be lowered, and the normal adhesive strength may be significantly lowered. ..
• the number average molecular weight exceeds 7,000, the crosslink density of the cured product made of the obtained adhesive becomes large, so that the heat-resistant water adhesive strength may decrease.
• the aliphatic polyester polyol which is liquid at room temperature, has a branched chain aliphatic group from the viewpoint of improving the normal adhesive strength to a poorly adherent substrate.
• the branched chain aliphatic groups include 2,2-dimethyl-1,3-propylene group, 2-methyl-1,3-propylene group, 1,2-diethyl-1,3-propylene group and 3,2-diethyl.
• -1,3-propylene group, 3-methyl-1,5-pentane group, 2-ethyl-2-butyl-propylene group, 2-methyl-1,8-octane group, 2,4-diethyl-1,5 -A branched chain aliphatic diol group such as a pentan group can be mentioned.
• a 2,2-dimethyl-1,3-propylene group and a 3-methyl-1,5-pentane group are preferable, and a 2,2-dimethyl-1,3-propylene group is more preferable.
• Aliphatic polyester polyols that are liquid at room temperature include a method of condensing a branched aliphatic diol and a polycarboxylic acid, and a method of ring-opening polymerization of caprolactone, ⁇ -butyl lactone, etc. using the branched chain aliphatic diol as an initiator.
• a moisture-curable polyurethane hot-melt adhesive having good wettability in a low temperature environment can be obtained by using an aliphatic polyester polyol obtained by reacting with 4 to 10 linear aliphatic dicarboxylic acids. More preferred.
• a low molecular weight aliphatic polyol or an aliphatic polycarboxylic acid other than the compounds described above can be used in combination, if necessary.
• aliphatic polyols As other low molecular weight aliphatic polyols, other aliphatic polyols and the like can be used. Among these, it is preferable to use a linear aliphatic diol having 2 to 12 carbon atoms.
• aliphatic polycarboxylic acid for example, adipic acid, sebacic acid, azelaic acid, decamethylenedicarboxylic acid and the like can be used in combination. Among these, it is preferable to use a linear aliphatic dicarboxylic acid having 4 to 10 carbon atoms.
• the (ii) polyol component may contain a polycarbonate polyol.
• the hydrolysis resistance and the moisture-resistant adhesiveness of the moisture-curable hot-melt adhesive according to the present invention can be improved.
• polycarbonate polyol for example, a compound obtained by reacting a carbonic acid ester and / or phosgene with a diol can be used.
• carbonic acid ester for example, dimethyl carbonate, diphenyl carbonate and the like can be used. These compounds may be used alone or in combination of two or more.
• diol examples include linear aliphatic diols such as 1,5-pentanediol, 1,6-hexanediol, and 1,9-nonanediol; neopentyl glycol, 3-methyl-1,5-pentanediol, and 2, -Branch chain aliphatic diols such as methyl-1,8-octanediol; 1,4-cyclohexanedimethanol, bisphenol A and the like can be used. These compounds may be used alone or in combination of two or more.
• the polycarbonate polyol having only one kind of linear aliphatic diol is solid at room temperature and has crystallinity.
• polycarbonate polyol liquid at room temperature As the polycarbonate polyol obtained by copolymerizing at least two kinds of diols, for example, a copolymerized polycarbonate diol in which the glycol component is 3-methyl-1,5-pentanediol and 1,6-hexanediol. Examples thereof include a copolymerized polycarbonate diol composed of 1,5-pentanediol and 1,6-hexanediol, and a copolymerized polycarbonate diol composed of 2-methyl-1,8-octanediol and 1,9-nonanediol.
• these polycarbonate polyols that are liquid at room temperature the flexibility of the cured film of the moisture-curable hot-melt adhesive according to the present invention can be improved.
• the number average molecular weight of the polycarbonate polyol is preferably 500 or more, more preferably 1,000 or more, and preferably 5,000 or less, from the viewpoint of further improving the adhesiveness of the moisture-curable hot-melt adhesive according to the present invention. , 4,000 or less is more preferable.
• the glass transition temperature (Tg) of the polycarbonate polyol is preferably in the range of -30 to 20 ° C. from the viewpoint of further improving drop impact resistance and adhesiveness.
• the various polyester polyols and polycarbonate polyols are liquid (glass transition temperature Tg ⁇ 20 ° C.) or solid at room temperature.
• the polyester polyol and the polycarbonate polyol which are solid at room temperature are amorphous (Tg> 20 ° C.) or at least partially crystalline.
• the compound (a2) containing an alkoxysilyl group and an active hydrogen group is a compound that reacts with the isocyanate group-terminated urethane prepolymer (a1) and has an alkoxysilyl group and an active hydrogen group, and is a compound having an alkoxysilyl group and an active hydrogen group, and has an active hydrogen group and an active hydrogen group. It is preferable to have an alkoxysilyl group at the end, and it is preferable to have at least one active hydrogen group at the end.
• the compound (a2) containing an alkoxysilyl group and an active hydrogen group may randomly have an active hydrogen group at a portion other than the terminal together with the terminal.
• the compound (a2) containing an alkoxysilyl group and an active hydrogen group preferably has an average of 0.3 or more hydroxyl groups from the viewpoint of improving the final strength and heat resistance due to the crosslinking reaction of the alkoxysilyl group. It is more preferable to have 5 or more, and it is further preferable to have 0.8 or more.
• the alkoxysilyl group-containing urethane prepolymer (A) and reducing the viscosity of the polymer it is preferable to have 1.7 or less hydroxyl groups on average, and more preferably 1.4 or less. It is more preferable to have 1.2 or less. In particular, one having a single hydroxyl group at the end is preferable.
• the boiling point of the compound having an active hydrogen group is preferably 100 ° C. or higher, more preferably 150 ° C. or higher, and even more preferably 200 ° C. or higher.
• the moisture-curable hot-melt adhesive according to the present invention contains (a2-1) a methyl methacrylate-based polymer which is solid at room temperature and has an alkoxysilyl group and a hydroxyl group at the terminal as a component (a2). contains.
• the component (a2-1) preferably has an alkoxysilyl group, and may be, for example, an alkoxysilyl group-containing methyl methacrylate-based polymer having a hydroxyl group.
• An alkoxysilyl group-containing methyl methacrylate polymer having a hydroxyl group can be synthesized, for example, by introducing a hydroxyl group into an alkoxysilyl group-containing (meth) acrylic acid ester polymer described later.
• the alkoxysilyl group-containing methyl methacrylate polymer has only one hydroxyl group, gelation can be suppressed.
• various known methods can be used for introducing the hydroxyl group into the alkoxysilyl group-containing methyl methacrylate-based polymer. The following method can be mentioned as an example of the method for introducing a hydroxyl group.
• the hydroxyl group may be introduced at a place other than the terminal, or a monomer having a hydroxyl group may be added separately.
• a method for introducing a hydroxyl group a method of polymerizing using a thiol compound having a hydroxyl group and a metallocene compound is preferable from the viewpoint that one hydroxyl group can be introduced.
• the thiol compound having a hydroxyl group include 2-mercaptoethanol and the like.
• the number of hydroxyl groups (average value) of the component (a2-1) is preferably 0.5 or less, more preferably 0.3 or less, and 0.1 or less per molecule of the polymer of the component (a2-1). Is more preferable.
• the number average molecular weight of the component (a2-1) is preferably 1,000 or more, more preferably 2,000 or more, further preferably 3,000 or more, preferably 50,000 or less, and more preferably 30,000 or less. It is preferable, and more preferably 15,000 or less.
• a (meth) acrylic acid alkyl ester having a hydroxyl group is preferable.
• Such compounds include, for example, monohydroxy acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl acrylate; glycerin mono (glycerin mono ( Examples thereof include polyhydroxyacrylates such as meth) acrylates. Of these, monohydroxyacrylates are preferred.
• the compounding ratio of the unsaturated compound having a hydroxyl group is such that the number of hydroxyl groups of the unsaturated compound having a hydroxyl group is 0.5 or more and 3 or less on average with respect to the hydroxyl group per molecule of the polymer of the component (a2-1).
• the ratio is preferably 1.1 or more and 2 or less.
• the moisture-curable hot melt adhesive according to the present invention may contain a residue obtained by removing an active hydrogen group from an alkoxysilane having an amino group, a hydroxyl group, or a mercapto group.
• the active hydrogen group includes an amino group, a hydroxyl group, or a mercapto group.
• Examples of the alkoxysilane (a2-2) having an active hydrogen group include compounds represented by the following general formula (VII).
• R 8 is a monovalent hydrocarbon group having 1 to 12 C atoms in a linear or branched manner, and optionally has one or more CC multiple bonds. Represents a group that may have and / or may optionally have an alicyclic and / or aromatic moiety. In particular, R 8 represents a methyl, ethyl, or isopropyl group.
• R 9 is an acyl residue or a linear or branched monovalent hydrocarbon group with 1-12 C atoms and optionally has one or more CC multiple bonds. Represents a group which may and / or may optionally have an alicyclic and / or aromatic moiety.
• R 9 is preferably an acyl or alkyl group having 1 to 5 C atoms, particularly a methyl, ethyl, or isopropyl group.
• R 10 is a linear or branched divalent hydrocarbon group having 1 to 12 C atoms, optionally having a cyclic and / or aromatic moiety, and optionally. Represents a group that may optionally have one or more heteroatoms.
• R 10 is preferably an alkylene residue having 1 to 3 C atoms, particularly 3 C atoms.
• a represents 0, 1, or 2, and particularly represents a value of 0 or 1.
• the group X is the same as above.
• Examples of the compound represented by the general formula (VII) include mercaptosilane such as ⁇ -mercaptopropyltrimethoxysilane and 2-ethoxy-4 (5)-(2-triethoxysilylethyl). Examples thereof include hydroxyl group-containing silanes such as cyclohexane-1-ol and aminosilanes. Examples of the aminosilane include primary aminosilane (eg, 3-aminopropyltrimethoxysilane); secondary aminosilane (eg, N-butyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane).
• Michael-type adduct of primary aminosilane eg, N- (3-trimethoxysilylpropyl) aminosuccinic acid dimethyl and diethyl ester
• primary aminosilane eg, N- (3-trimethoxysilylpropyl) aminosuccinic acid dimethyl and diethyl ester
• aminosilane analogs e.g., aminosilane, secondary aminosilane, in particular R 5 of the general formula (VIII) can be mentioned aminosilane not H.
• Michael-type adducts are preferred, especially N- (3-trimethoxysilylpropyl) aminosuccinic acid diethyl ester.
• R 8 , R 9 , R 10 , R 5 , and a are the same as above.
• the (A) alkoxysilyl group-containing urethane prepolymer according to the present invention is composed of a "hard segment” of a methyl methacrylate-based copolymer that is solid at room temperature and a "soft segment” of a polyether.
• )-(Soft segment)-(Hard segment) "type block polymer structure, which can impart toughness to the moisture-curable hot melt adhesive and improve the rising strength. Further, by introducing the crystalline polyester into the "soft segment” of the polyether, a sufficient bonding time and improvement in rising strength can be imparted.
• the adhesiveness and heat resistance can be further improved by the cross-linking reaction of the alkoxysilyl group of the hard segment.
• the block polymer structure has a polyether skeleton (PE skeleton), a crystalline polyester skeleton (PEs skeleton), and a methyl methacrylate-based copolymer skeleton (PAc skeleton), the polyether, the crystalline polyester, and the methyl methacrylate It serves as a compatibilizer for the system copolymer, and can be compatible with incompatible crystalline polyester and methyl methacrylate-based copolymer by itself.
• PE skeleton polyether skeleton
• PEs skeleton crystalline polyester skeleton
• PAc skeleton methyl methacrylate-based copolymer skeleton
• the weight ratio of the PE skeleton, the PEs skeleton, and the PAc skeleton is such that the PE skeleton is 15 parts by weight or more and 55 parts by weight when the total of the PE skeleton, the PEs skeleton, and the PAc skeleton is 100 parts by weight.
• the PEs skeleton is preferably 15 parts by weight or more and 50 parts by weight or less
• the PAc skeleton is preferably 10 parts by weight or more and 45 parts by weight or less.
• Compound having one active hydrogen group and no alkoxysilyl group By using a compound having one active hydrogen group having reactivity with an isocyanate group and not having an alkoxysilyl group (hereinafter referred to as a compound having only one active hydrogen group), an alkoxysilyl group is used.
• the number of silyl groups of the contained urethane prepolymer (A) can be adjusted (that is, decreased). Thereby, the crosslink density of the alkoxysilyl group-containing urethane prepolymer (A) after curing can be adjusted, and as a result, the flexibility and / or elongation of the cured film can be adjusted.
• examples of the active hydrogen group having a reactivity with the isocyanate group include a hydroxyl group, an amino group, a mercapto group and the like, and a hydroxyl group and an amino group are preferable, and a moisture-curable hot melt adhesive can be stably produced. From the viewpoint, a secondary amino group is more preferable.
• a compound having only one active hydrogen group may be used as the component (a3).
• Examples of the compound having only one active hydrogen group include linear or branched alkyl alcohols such as 2-ethylhexanol, lauryl alcohol, stearyl alcohol and behenyl alcohol, and hydroxyl groups such as propylene glycol monoacetate and diethylene glycol monoacetate.
• Examples thereof include alcohols having a functional group, alcohols having a polyoxyalkylene chain such as polyoxypropylene monool, and the like.
• Examples of the compound having one amino group as an active hydrogen group include primary amines such as octylamine, dodecylamine, cetylamine, stearylamine, and behenylamine; dibutylamine, butyloctylamine, dioctylamine, disstearylamine, and butylstearyl. Secondary amines such as amines can be mentioned.
• the number of crosslinkable silicon groups in one molecule of the alkoxysilyl group-containing urethane prepolymer is preferably 1.0 or more, more preferably 1.2 or more, and 1.4, in terms of curability.
• the above is more preferable, and 1.6 or more are particularly preferable. From the viewpoint of physical properties, an average of 4.0 or less is preferable, 3.0 or less is more preferable, 2.0 or less is further preferable, and 1.8 or less is particularly preferable.
• the moisture-curable hot-melt adhesive according to the present invention can further contain (B) a silane-based adhesive-imparting agent.
• the silane-based adhesive-imparting agent exhibits an adhesive-imparting effect by moisture curing, and can improve final strength other than rising adhesive strength, water-resistant adhesiveness, and heat-resistant adhesiveness.
• the alkoxysilyl group of the (B) silane-based adhesive imparting agent is a methoxy group, an ethoxy group, or the like from the viewpoint of the hydrolysis rate.
• the number of alkoxy groups of the silyl group is preferably 2 or more, more preferably 3 or more.
• the functional group of the (B) silane-based adhesive-imparting agent an amino group, an epoxy group and the like are preferable from the viewpoint of adhesiveness, and an amino group is more preferable.
• silane-based adhesion imparting agent aminosilane, ketimine-based silane, epoxysilane, acrylicsilane-based silane, vinylsilane-based coupling agent, mercaptosilane, ureasilane-based coupling agent, isocyanuratesilane, isocyanatesilane and the like are used. be able to.
• aminosilane examples include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- ( ⁇ -aminoethyl) -3-aminopropyltrimethoxysilane, and N- ( ⁇ -aminoethyl) -3-.
• Mono-silylaminosilanes such as aminopropyltriethoxysilane, N- ( ⁇ -aminoethyl) -3-aminopropylmethyldiethoxysilane, bis- (trimethoxysilylpropyl) amines, bis- (triethoxysilylpropyl) amines, Examples thereof include bis-silylaminosilane such as bis- (triethoxysilylpropyl) ethylenediamine, N- [2- (vinylbenzylamino) ethyl] -3-aminopropyltrimethoxysilane, and aminoethyl-aminopropyltrimethoxysilane.
• Examples of the ketimine-based silane include N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propaneamine.
• Examples of the epoxysilane include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 3-glycidoxypropylmethyldi. Examples thereof include ethoxysilane.
• Examples of the acrylic silane-based silane include 3-methacryloxypropyltrimethoxysilane.
• Examples of the vinylsilane-based coupling agent include vinyltrimethoxysilane, methylvinyldimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, and allyltri ( ⁇ -methoxysilane).
• Examples of the mercaptosilane include 3-mercaptopropyltrimethoxysilane.
• Examples of the ureasilane-based coupling agent include 3-ureidopropyltrimethoxysilane and 3-ureidopropyltriethoxysilane.
• Examples of the isocyanate silane include tris- (trimethoxysilylpropyl) isocyanate.
• Examples of isocyanatesilane include 3-isocyanatepropyltriethoxysilane.
• the (B) silane-based adhesion-imparting agent the above-mentioned reaction product of aminosilane and epoxysilane, the reaction product of aminosilane and isocyanatesilane, the reaction product of aminosilane and silane having (meth) acryloyloxy group, and aminosilane.
• Aminosilane reaction product such as a reaction product of bisphenol A diglycidyl ether, phenylglycidyl ether, etc., a reaction product of aminosilane and polyisocyanate, a reaction product of aminosilane and polyacrylate; Condensed condensates (preferably aminosilane condensates partially condensed from the above aminosilane, isocyanatesilane, aminosilane reactants, and mixtures of reactants); amino-modified silyl polymers, silylated aminos, which are derivatives of these modifications. Examples include polymers, unsaturated aminosilane complexes, phenylamino long chain alkylsilanes, aminosilylated silicones, silylated polyesters, photoaminosilane generators and the like.
• the molecular weight of the (B) silane-based adhesive imparting agent is preferably 320 or more because it is difficult for the compound having a molecular weight of 320 or more to volatilize when the hot melt is melted, more preferably 400 or more, and further preferably 450 or more.
• a silane-based adhesive that has two or more silyl groups such as bis-silylaminosilane, isocyanuratesilane, aminosilane reactant, and aminosilane condensate is more preferable because it has adhesiveness and is difficult to volatilize when the hot melt adhesive is melted.
• Aminosilane reactants and aminosilane condensates are more preferred, with aminosilane reactants being most preferred.
• the aminosilane reaction product may be reacted by adding a reaction material separately during the mixing step.
• the silane-based adhesive imparting agent may be used alone or in combination of two or more.
• the amount of the silane-based adhesive imparting agent used is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more, and particularly preferably 1 part by mass or more with respect to 100 parts by mass of the component (A). , 20 parts by mass or less is preferable, 10 parts by mass or less is more preferable, and 5 parts by mass or less is particularly preferable. If it is less than 0.01 parts by mass, the effect of imparting adhesiveness and the effect as a curing catalyst are insufficient, while if it exceeds 20 parts by mass, the action as a catalyst according to the amount added is not remarkable and it is economical. Not preferable.
• Optical aminosilane generator When the hot melt adhesive according to the present invention is configured as a photocurable adhesive, a compound that does not generate a compound having an amino group before light irradiation but generates amino group-containing silanes by light irradiation. (Hereinafter, also referred to as a photoaminosilane generator) can be used.
• the photoaminosilane generator the photofunctional group described in WO2015-088021 is an o-nitrobenzyl group, a p-nitrobenzyl group, an oxime residue, a benzyl group, a benzoyl group, a substituted group thereof, or the like. Some compounds are mentioned.
• photoaminosilane generators in which the photofunctional group is an o-nitrobenzyl group include 2-nitrobenzyl-N- [3- (trimethoxysilyl) propyl] carbamate and 2-nitrobenzyl-N- [3-(. Examples thereof include triethoxysilyl) propyl] carbamate and 3,4-dimethoxy-2-nitrobenzyl-N- [3- (trimethoxysilyl) propyl] carbamate.
• Examples of the photoaminosilane generator in which the photofunctional group is a p-nitrobenzyl group include 4-nitrobenzyl-N- [3- (trimethoxysilyl) propyl] carbamate and the like.
• Examples of the photoaminosilane generator in which the photofunctional group is a benzyl group include 1- (3,5-dimethoxyphenyl) -1-methylethyl-N- [3- (trimethoxysilyl) propyl] carbamate. ..
• Examples of photoaminosilane generators in which the photofunctional group is an oxime residue include benzophenone O- ⁇ [3- (trimethoxysilyl) propyl] ⁇ oxime.
• the modified resin is mixed in order to control the bonding time of the compounding system and reduce the melt viscosity, and has a function of modifying and adjusting the physical properties.
• the modified resin can improve the bonding time and the rising adhesive strength.
• the component (C) according to the present invention exerts a different function depending on the type of the segment constituting the target resin to which the component (C) is added. That is, when the component (C) is added mainly to a resin composed of hard segments, it exerts a function of adjusting physical properties as a modified resin, and when added to a resin mainly composed of soft segments, it acts as a tackifier resin. Demonstrate the function of. Since the skeleton of the component (A) according to the present invention is mainly composed of hard segments, the resin exemplified below acts as a modified resin.
• modified resin examples include terpene-based resins, aromatic-modified terpene resins and hydrocarbon-modified terpene resins hydrogenated thereto, terpene-phenol resins obtained by copolymerizing terpenes and phenols, and phenol resins.
• styrene-based block copolymers and hydrogen additives thereof include styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), and styrene-ethylenebutylene-styrene block.
• SBS styrene-butadiene-styrene block copolymer
• SIS styrene-isoprene-styrene block copolymer
• SIBS styrene-ethylenebutylene-styrene block copolymer
• a terpene phenol resin or an aromatic petroleum resin is preferable from the viewpoint of good compatibility with an organic polymer having a crosslinkable silicon group and good heating stability of the adhesive.
• aromatic petroleum resin aromatic styrene resin and aliphatic-aromatic copolymer styrene resin are preferable, and terpene phenol resin and aliphatic-aromatic copolymer styrene resin are more preferable.
• an aliphatic-aromatic copolymer system styrene resin it is preferable to use an aliphatic-aromatic copolymer system styrene resin.
• the amount of the modified resin (C) added to 100 parts by mass of the component (A) is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, particularly preferably 30 parts by mass or more, and 200 parts by mass or less. It is preferably 150 parts by mass or less, more preferably 120 parts by mass or less.
• cross-linking catalyst examples include a cross-linking catalyst (silanol catalyst) of an alkoxysilyl group-containing urethane prepolymer, and for example, a divalent organic tin compound such as a titanic acid ester, a tetravalent organic tin compound, and octylate tin.
• fluorinated polymer examples include an organic polymer having a Si—F bond, and an organic polymer having a fluorosilyl group described in WO2015-088021 (hereinafter, also referred to as “fluorinated polymer”) and the like. Can be mentioned.
• fluorinated polymer a polymer having a fluorosilyl group such as a difluoromethylsilyl group, a difluoromethoxysilyl group, a difluoroethoxysilyl group and a trifluorosilyl group at the end of the main chain or the side chain is preferable.
• the polymer described in the liquid polymer compound described later can be used, and among these polymers, a polyoxyalkylene polymer and / or (meth) acrylic acid. It is preferable because the ester-based polymer is easy to handle and has a great effect of prolonging the bonding time.
• the number average molecular weight of the fluorinated polymer is preferably 3,000 or more, preferably 100,000 or less, more preferably 50,000 or less, and particularly preferably 30,000 or less in terms of polystyrene in GPC.
• a fluorinated polymer When a fluorinated polymer is used, it is preferably 0.01 part by mass or more, more preferably 0.05 part by mass or more, and 0.1 part by mass or more with respect to 100 parts by mass of (A) alkoxysilyl group-containing urethane prepolymer. Is more preferable, 80 parts by mass or less is preferable, 30 parts by mass or less is more preferable, and 20 parts by mass or less is further preferable.
• the (D) cross-linking catalyst a titanic acid ester, a tetravalent organic tin compound, a divalent organic tin compound, a tertiary amine compound, and amidin can be obtained from the viewpoint of high catalytic effect and sufficient heat resistance. Compounds or their carboxylates and fluorinated polymers are preferred.
• the (D) cross-linking catalyst is composed of a tertiary amine compound, a divalent tin compound, a fluorinated polymer, and a titanium acid ester from the viewpoint that the silyl cross-linking is difficult to be cleaved by moist heat and the physical properties are not easily deteriorated.
• At least one catalyst selected from the group is preferable, at least one catalyst selected from the group consisting of a tertiary amine compound, a divalent tin compound, and a fluorinated polymer is more preferable, and a fluorinated polymer is particularly preferable.
• the transesterification reaction of the low molecular weight alcohol for example, methanol or ethanol
• the low molecular weight alcohol for example, methanol or ethanol
• the melt adhesive is melted in a heating oven prior to application and remains in a liquid state for a relatively long period of time (typically at least one working day), so it is hot for industrial applications.
• a divalent organic tin compound, a tertiary amine compound, and a fluorinated polymer are preferable.
• the cross-linking reaction is further promoted when used in combination with a ketimine structure-containing alkoxysilane.
• the amount of the other cross-linking catalyst added is preferably 0.01 part by mass or more with respect to 100 parts by mass of the (A) alkoxysilyl group-containing urethane prepolymer, and is 0. 0.05 parts by mass or more is more preferable, 0.2 parts by mass or more is further preferable, 10 parts by mass or less is more preferable, 5 parts by mass or less is more preferable, and 3 parts by mass or less is further preferable.
• a photolatent amine compound that does not have catalytic activity before light irradiation and generates an amine compound by light irradiation is used. be able to.
• the photolatent amine compound include 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. Both the generated photolatent secondary amine and the photolatent tertiary amine that generates an amine compound having a tertiary amino group by the action of active energy rays can be used.
• a photolatent tertiary amine is more preferable from the viewpoint that the generated base exhibits high catalytic activity, the base generation efficiency is good, and the storage stability as a composition is good. Therefore, a benzylammonium salt derivative, a benzyl-substituted amine derivative, an ⁇ -aminoketone derivative, and an ⁇ -ammonium ketone derivative are preferable, and in particular, a base is not generated when not exposed to light, and a base is efficiently generated when exposed to light. Therefore, a benzylammonium salt derivative and a benzyl-substituted amine derivative are more preferable.
• various photobase generators described in International Publication No. WO2015 / 0087709 can be used. These photobase generators may be used alone or in combination of two or more.
• the silylated polymer is mixed with the reactive hot melt adhesive for the purpose of controlling the bonding time of the reactive hot melt adhesive and reducing the melt viscosity, and improves the physical properties of the reactive hot melt adhesive. Has the function of denaturing and / or adjusting.
• the silylated polymer can improve the coating workability and the rising adhesive strength.
• silylated polymer examples include silylated polyurethane and silyl terminal polymer, and examples of the silylated polyurethane include silylated polyurethane 1 and silylated polyurethane 2, which will be described in detail below.
• silylated polyurethane is preferable, and silylated polyurethane 2 is more preferable.
• the silyl-terminated polymer and the silylated polyurethane 1 are preferable, and the silylated polyurethane 1 is more preferable.
• a silylated polyurethane which is solid at room temperature and has a crystalline aliphatic polyester skeleton and / or a crystalline polycarbonate skeleton is used.
• a silylated polyurethane having a crystalline aliphatic polyester skeleton is more preferable, and a silylated polyurethane having a long-chain aliphatic polyester skeleton is further preferable.
• a silylated polymer having a polyoxyalkylene skeleton and liquid at room temperature is preferable, and a silylated polymer having a polyoxypropylene skeleton is preferable. More preferably, a silyl-terminated polyether having a polyoxypropylene skeleton is further preferable.
• a long-chain alkyl polyester having a number average molecular weight of 1,000 or more and 2,000 or less is particularly preferable.
• silylated polyurethane having an aromatic polyester skeleton is preferable.
• Cyrilized polyurethane having an aromatic polyester skeleton that is solid at room temperature is more preferable.
• aromatic polyesters having a number average molecular weight of 1,000 or more and 2,000 or less are preferable from the viewpoint of lowering the melt viscosity.
• the silylated polymer is an organic polymer having a crosslinkable silicon group.
• the crosslinkable silicon group include a group represented by the general formula (IX) described in the section “Alkoxysilyl group-containing methyl methacrylate-based polymer” described later.
• the number of crosslinkable silicon groups may be one or two or more.
• the crosslinkable silicon group may be attached to the main chain, the side chain, or both of the polymer. From the viewpoint of excellent physical properties of the cured product such as tensile properties of the cured product, it is preferable that the crosslinkable silicon group is present at the end of the molecular chain.
• the average number of crosslinkable silicon groups in one molecule of the silylated polymer is 1.0 or more and 5 or less, and more preferably 1.1 or more and 3 or less. If the number of crosslinkable silicon groups contained in the molecule is less than one, the curability becomes insufficient, while if it is too large, the network structure becomes too dense and good mechanical properties are not exhibited.
• the compounding ratio of the component containing the terminal group of the molecular chain and the component containing the crosslinkable silicon group is 0 for 1 mol of the terminal group of the molecular chain. It is preferably 3 mol or more, more preferably 0.5 mol or more, still more preferably 0.7 mol or more.
• the crosslinkable silicon group-containing component may be excessively added to the molecular chain terminal group. In this case, the excess crosslinkable silicon group-containing component functions as an adhesion-imparting agent. If unreacted hydroxyl groups remain, it is preferable to react the unreacted hydroxyl groups with monoisocyanate to inactivate them.
• Examples of the monoisocyanate include monoisocyanates having an alkyl group of C6 to C18 and an isocyanate group bonded to an aryl group of C6 to C18, and for example, stearyl isocyanate, phenyl isocyanate, and naphthyl isocyanate are preferable.
• the silylated polyurethane 1 can be prepared by reacting isocyanate silane with a polymer having a hydroxyl group.
• the silylated polyurethane 1 is prepared by reacting isocyanate silane with a polyester polyol, a polycarbonate polyol or a polyoxyalkylene polyol as a polymer having a hydroxyl group, and has a silylated polyester urethane 1 having a polyester skeleton and a silyl having a polycarbonate skeleton. Examples thereof include the modified polycarbonate urethane 1 and the silylated polyether urethane 1 having a polyoxyalkylene skeleton.
• the polymer having a hydroxyl group may be a polymer having a hydroxyl group linked by diisocyanate.
• the silylated polyurethane 2 can be prepared by reacting an alkoxysilane having an active hydrogen group with a polyurethane polymer containing an isocyanate group.
• silylation is obtained using a reactive group in which the ratio of the active hydrogen group to the isocyanate group is 1: 1 or the ratio of the isocyanate group is slightly excessive. It is preferable to react the polyurethane 2 so that the isocyanate group is not contained at all.
• Polyurethane polymers containing isocyanato groups are prepared, for example, by reacting a plurality of polyols with diisocyanates.
• examples of the polyol include silylated polyether urethane 2 having a polyoxyalkylene skeleton using a polyoxyalkylene polyol.
• Suitable polyols are, in particular, polyether polyols, polyester polyols, and polycarbonate polyols, as well as mixtures of these polyols, with polyoxyalkylene polyols being preferred.
• the silyl-terminated polymer can be prepared by a hydrosilylation reaction of a polymer having a double bond at the terminal.
• the polymer having a double bond at the terminal is a poly (meth) acrylate polymer or a polyether polymer, and examples thereof include a silyl-terminal polyether having a polyoxyalkylene skeleton and a silyl-terminal polyacrylate having a polyacrylate skeleton.
• the silyl-terminated polyether is obtained, for example, by reacting an unsaturated group-containing polyoxyalkylene polymer with a hydrosilane having a crosslinkable silicon group or a mercapto compound having a crosslinkable silicon group to hydrosilylate or mercaptoize.
• This synthesis method is a method for obtaining a polyoxyalkylene polymer (silyl-terminated polyether) having a crosslinkable silicon group.
• a hydrosilylation reaction of an allylic-terminated polyoxyalkylene polymer described in JP-A-2006-077036. Can be mentioned as a synthetic example.
• the unsaturated group-containing polyoxyalkylene polymer can be prepared by reacting an organic polymer having a functional group such as a hydroxyl group with an active group having a reactivity with this functional group and an organic compound having an unsaturated group. ..
• the silyl-terminated polyacrylate is composed of at least one acrylate component and at least one silyl component.
• the silyl-terminated polyacrylate can be obtained, for example, by reacting the alkenyl-terminated acrylate by hydrosilylation. Further, the alkenyl-terminated acrylate can be obtained by a production method using atom transfer radical polymerization (ATRP) or a production method using a reaction between an alkyl-terminal acrylate and a monomer containing a silyl group.
• the alkenyl-terminated acrylate is obtained by a production method by atom transfer radical polymerization (ATRP).
• As the silyl-terminated polyacrylate a silyl-terminated polyacrylate containing butyl acrylate, which is liquid at room temperature and has flexibility, as a main component is preferable.
• Polyoxyalkylene polymer As the main skeleton of the polyoxyalkylene polyol and the unsaturated group-containing polyoxyalkylene polymer, a polyoxyalkylene polymer having a repeating unit represented by the following general formula ( ⁇ ) is preferable.
• R ⁇ represents a linear or branched alkylene group having 1 to 14 carbon atoms, and preferably has 2 to 4 carbon atoms.
• the main chain of the polyoxyalkylene polymer may be composed of only one type of repeating unit or may be composed of two or more types of repeating units.
• a polyoxypropylene-based polymer that is amorphous and has a relatively low viscosity is preferable.
• Examples of the method for synthesizing the polyoxyalkylene polymer include a polymerization method using an alkali catalyst such as KOH, and a polymerization method using a composite metal cyanide complex catalyst (for example, a zinc hexacyanocovalent glyme complex catalyst).
• a polymerization method in which an alkylene oxide is reacted with an initiator in the presence of a composite metal cyanide complex catalyst is preferable because a polymer having a narrow molecular weight distribution can be synthesized.
• complex metal cyanide complex catalyst examples include Zn 3 [Co (CN) 6 ] 2 (zinc hexacyanocovalent complex). Further, a catalyst in which alcohol and / or ether is coordinated as an organic ligand may be used.
• the initiator a compound having at least two active hydrogen groups is preferable.
• the active hydrogen-containing compound include polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol and glycerin, and linear and / or branched polyether compounds having a number average molecular weight of 500 or more and 20,000 or less.
• alkylene oxide examples include ethylene oxide, propylene oxide, and isobutylene oxide.
• polyoxyalkylene polyol are polyoxyethylene polyol and polyoxypropylene polyol, and among them, polyoxyethylene diol, polyoxypropylene diol, polyoxyethylene triol, and polyoxypropylene triol can be mentioned.
• Polyoxyethylene diols, polyoxyethylene triols, polyoxypropylene diols, and polyoxypropylene triols having a molecular weight in the range of 8,000 g / mol or less are preferable.
• ethylene oxide-terminated polyoxypropylene polyols ie, "EO-terminated” compounds; “ethylene oxide end-capped” compounds
• the EO-terminated cap polyoxypropylene polyol is a special polyoxypropylene polyoxyethylene polyol, for example, pure polyoxypropylene polyol after completion of the polyoxypropylation reaction, particularly polyoxypropylene diol and triol with ethylene oxide. It is prepared by additional alkoxylization using, resulting in having a primary hydroxyl group.
• PPG polypropylene glycol
• PPG polypropylene glycol
• Such polyols have an average molecular weight of 250 g / mol or more and 30,000 g / mol or less, particularly 1,000 g / mol or more and 30,000 g / mol or less, and an average OH functional value in the range of 1.6 or more and 3 or less. Is preferable.
• polyether polyol is preferable, particularly polyoxyethylene polyol, polyoxypropylene polyol, and polyoxypropylene polyoxyethylene polyol are more preferable, and polyoxyethylene diol, polyoxypropylene diol, polyoxyethylene triol, and polyoxy are preferable. More preferred are propylene triol, polyoxypropylene polyoxyethylene diol, and polyoxypropylene polyoxyethylene triol.
• the component (A) may contain an alkoxysilyl group-containing methyl methacrylate-based polymer.
• the alkoxysilyl group-containing methyl methacrylate polymer is a (meth) acrylic ester polymer containing methyl methacrylate as an essential monomer.
• the alkoxysilyl group-containing methyl methacrylate-based polymer can impart toughness to the moisture-curable hot-melt adhesive and improve the rising strength and the final strength.
• the heat resistance of the moisture-curable hot melt adhesive can be improved by the cross-linking reaction of the alkoxysilyl group.
• the alkoxysilyl group of the (meth) acrylic ester-based polymer having an alkoxysilyl group which is an alkoxysilyl group-containing methyl methacrylate polymer, and having a glass transition temperature of -20 ° C to 120 ° C, is an alkoxy bonded to a silicon atom. It is a group that has a group and can be crosslinked by a silanol condensation reaction. Examples of the alkoxysilyl group include a group represented by the following general formula (IX).
• R 11 has 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 carbon. an aralkyl group having 7 to 20, when the R 11 there are two or more, they may be the same or may be different.
• X represents an alkoxy group, and when two or more Xs are present, they may be the same or different.
• a indicates 0, 1, 2, or 3. It is preferable that a is 2 or 3 in the alkoxysilyl group of the general formula (IX). When a is 3, the curing rate is higher than when a is 2.
• R 11 examples include an alkyl group such as a methyl group and an ethyl group, a substituted alkyl group such as a methoxymethyl group, and a cycloalkyl group such as a cyclohexyl group.
• a methyl group is preferable, and a substituted alkyl group in which ⁇ carbon is substituted with a polar group is preferable from the viewpoint of increasing the curing rate.
• the alkoxy group represented by X is not particularly limited, and may be any conventionally known alkoxy group.
• the group having a smaller number of carbon atoms has a higher reactivity, and the reactivity decreases as the number of carbon atoms increases in the order of methoxy group> ethoxy group> propoxy group.
• a methoxy group or an ethoxy group is usually used.
• a is preferably 2 or more in consideration of curability.
• alkoxysilyl group a trimethoxysilyl group and a triethoxysilyl group are preferable, and a trimethoxysilyl group is more preferable, from the viewpoint of high reactivity.
• a methyldimethoxysilyl group and a methyldiethoxysilyl group are preferable from the viewpoint of obtaining a cured product having flexibility.
• alkoxysilyl group can be used alone or in combination of two or more.
• the alkoxysilyl group may be present in the main chain, the side chain, or any of them.
• the number (average value) of alkoxysilyl groups in the alkoxysilyl group-containing methyl methacrylate polymer is preferably 0.3 or more, more preferably 0.5 or more, and even more preferably 1 or more per molecule of the polymer. 5 or less is preferable, 3 or less is more preferable, and 2.5 or less is further preferable. If the number of alkoxysilyl groups contained in the molecule is less than 0.3, the curability becomes insufficient, and if it is too large, the network structure becomes too dense and good mechanical properties are not exhibited.
• alkoxysilyl group-containing methyl methacrylate polymer various known methods can be used for introducing the alkoxysilyl group into the (meth) acrylic acid ester polymer.
• the following method can be mentioned as an example of the method for introducing an alkoxysilyl group.
• a method of copolymerizing an unsaturated compound having an alkoxysilyl group is preferable from the viewpoint that an alkoxysilyl group can be easily introduced. Further, a method in which the method (1) and the method (2) are used in combination is also preferable.
• (Unsaturated compound having an alkoxysilyl group) As the unsaturated compound having an alkoxysilyl group used for copolymerization, a (meth) acrylic acid alkyl ester having an alkoxysilyl group or vinylsilane is preferable.
• the compound thereof include 3- (meth) acrylic such as 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, and 3- (meth) acryloxypropyltriethoxysilane.
• vinyl alkoxysilanes such as loxypropylalkoxysilanes and vinyltriethoxysilanes.
• a (meth) acrylic acid alkyl ester having a substituted alkyl group having 3 or less carbon atoms of the alkyl group having an alkoxysilyl group is preferable.
• the compounding ratio of the unsaturated compound having an alkoxysilyl group is such that the alkoxysilyl group having an unsaturated bond having an alkoxysilyl group is on average with respect to the alkoxysilyl group per molecule of the alkoxysilyl group-containing methyl methacrylate-based polymer. It is preferable that the number is 1.1 or more and 5 or less, preferably 1.1 or more and 3 or less.
• methyl methacrylate is an essential monomer component, and the repetition represented by the general formula (X) is repeated. Examples thereof include a methyl methacrylate-based random copolymer having a unit.
• R 12 represents a hydrogen atom or a methyl group
• R 13 represents a hydrocarbon group which may have a substituent.
• the (meth) acrylic acid ester means an acrylic acid ester and / or a methacrylic acid alkyl ester.
• (meth) acrylic acid alkyl ester As the monomer as another repeating unit of methyl methacrylate (MMA), (meth) acrylic acid alkyl ester is preferable.
• the (meth) acrylic acid alkyl ester compound include known compounds. For example, methyl acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate and the like can be mentioned. ..
• 2-Ethylhexyl (meth) acrylate, (meth) acrylic from the viewpoint of good compatibility with the polyether skeleton of the isocyanate group-terminated urethane prepolymer having a polyether skeleton (that is, a part of the skeleton of the component (A)).
• a (meth) acrylic acid alkyl ester having an ester bond having 8 or more carbon atoms such as lauryl acid acid and stearyl (meth) acrylic acid is preferable.
• n-butyl acrylate (Tg; -55 ° C), 2-ethylhexyl acrylate (Tg; -70 ° C), lauryl acrylate (Tg; -3 ° C). It is preferable to use a (meth) acrylic acid alkyl ester having a glass transition temperature (Tg) of 0 ° C. or lower.
• Tg glass transition temperature
• the hydrocarbon group such as the alkyl group of the (meth) acrylic acid ester may have a substituent such as a hydroxyl group, an alkoxy group, a halogen atom or an epoxy group.
• examples of such compounds include (meth) acrylic acid ester having a hydroxyl group such as hydroxyethyl (meth) acrylate, (meth) acrylic acid ester having an alkoxy group such as methoxyethyl (meth) acrylate, and glycidyl (meth).
• examples thereof include a (meth) acrylic acid ester having an epoxy group such as acrylate, and a (meth) acrylic acid ester having an amino group such as diethylaminoethyl (meth) acrylate.
• An unsaturated compound (macromonomer or macromer) having a polymer chain such as an acrylic acid ester having a polystyrene chain can also be used.
• alkoxysilyl group-containing (meth) acrylic acid ester-based polymer of the alkoxysilyl group-containing methyl methacrylate-based polymer in addition to the repeating unit derived from the (meth) acrylic acid ester compound, copolymerizability with these is added. It may contain a repeating unit derived from a compound having an ester.
• examples of compounds having copolymerizability with (meth) acrylic acid ester compounds include acrylic acids such as (meth) acrylic acid; amide compounds such as (meth) acrylamide, vinyl ether compounds such as alkyl vinyl ether; and other acrylonitrile, styrene, and the like. Examples thereof include ⁇ -methylstyrene, vinyl chloride and vinyl acetate.
• the amount of the monomer used in the polymer of the alkoxysilyl group-containing methyl methacrylate polymer is preferably 50% by mass or more, more preferably 70% by mass or more in the polymer of the alkoxysilyl group-containing methyl methacrylate polymer. It is preferable, more preferably 80% by mass or more, particularly preferably 90% by mass or more, and most preferably 95% by mass or more. In particular, it is preferable to use the above amount of acrylic acid alkyl ester having no substituent having 2 to 30 carbon atoms of the alkyl group such as methyl methacrylate and butyl acrylate.
• a macromonomer may be used as the monomer used in the polymer of the alkoxysilyl group-containing methyl methacrylate polymer.
• the amount of the macromonomer is preferably 10% by mass or less, more preferably 5% by mass or less in the polymer of the alkoxysilyl group-containing methyl methacrylate-based polymer. It is particularly preferable that it is by mass or less.
• the alkoxysilyl group-containing (meth) acrylic acid ester-based polymer of the alkoxysilyl group-containing methyl methacrylate-based polymer has a glass transition temperature (Tg) of ⁇ 20 ° C. to 120 ° C.
• Tg glass transition temperature
• the glass transition temperature is preferably ⁇ 20 ° C. or higher, more preferably 0 ° C. or higher, further preferably 20 ° C. or higher, preferably 120 ° C. or lower, more preferably 100 ° C. or lower, still more preferably 80 ° C. or lower. If the glass transition temperature is less than ⁇ 20 ° C., the adhesive strength immediately after adhesion tends to be inferior.
• the glass transition temperature exceeds 120 ° C., the melt viscosity becomes high, and it tends to be difficult to apply the hot melt adhesive to the adherend.
• the glass transition temperature can be easily estimated from the type and amount of the monomer component by using the following Fox formula.
• Tg is the glass transition temperature (K) of the acrylic resin
• W 1 , W 2 , ..., W n is the weight fraction of each monomer
• Tg 1 , Tg 2 , ..., Tg n is the glass transition temperature of the homopolymer of each monomer.
• the glass transition temperature of the homopolymer used in the Fox formula the values described in the literature can be used.
• the molecular weight of the alkoxysilyl group-containing (meth) acrylic acid ester-based polymer of the alkoxysilyl group-containing methyl methacrylate polymer is a number average molecular weight (polystyrene-equivalent molecular weight measured by the GPC method), preferably 3,000 or more. 4,000 or more is more preferable, 5,000 or more is further preferable, 200,000 or less is preferable, 100,000 or less is more preferable, and 50,000 or less is further preferable. If the number average molecular weight is less than 3,000, the initial adhesive strength after coating is low, and if it exceeds 200,000, the viscosity during coating work becomes too high and workability deteriorates. Further, the polymer of the alkoxysilyl group-containing methyl methacrylate polymer is preferably solid at room temperature.
• a radical polymerization method can be used as the polymerization method for the alkoxysilyl group-containing methyl methacrylate polymer.
• a usual solution polymerization method or bulk polymerization method using a thermal polymerization initiator such as benzoyl peroxide or azobisisobutyronitrile can be used.
• a method of irradiating light or radiation with a photopolymerization initiator to polymerize can also be used.
• a chain transfer agent such as lauryl mercaptan or 3-mercaptopropyltrimethoxysilane may be used to control the molecular weight.
• a radical polymerization method using a thermal polymerization initiator can be used, and the polymer of the alkoxysilyl group-containing methyl methacrylate-based polymer according to the present invention can be easily obtained by such a method.
• other polymerization methods such as the living radical polymerization method described in JP-A-2000-086998 may be used.
• additives can be used in combination with the reactive hot melt adhesive according to the present invention, if necessary.
• additives include liquid polymer compounds, fillers, diluents, stabilizers, flame retardants, curability modifiers, radical bans, metal deactivators, ozone deterioration inhibitors, and phosphorus-based peroxides.
• oxide decomposing agents include oxide decomposing agents, lubricants, pigments, foaming agents, and mold retardants.
• the liquid polymer compound has the effect of lowering the viscosity of the hot melt adhesive at the time of melting. Further, the liquid polymer compound has an effect of prolonging the bonding time (time that can be bonded after hot melt application).
• the viscosity of the liquid polymer compound at room temperature is preferably 100 Pa ⁇ s or less, more preferably 75 Pa ⁇ s or less, and particularly preferably 50 Pa ⁇ s or less.
• the main chain skeleton of the liquid polymer compound is a polyoxyalkylene polymer such as polyoxypropylene, polyoxytetramethylene, or polyoxyethylene-polyoxypropylene copolymer; an ethylene-propylene polymer, polyisobutylene, or poly.
• Hydrocarbon polymers such as isoprene, polybutadiene, hydrogenated polyolefin-based polymers obtained by hydrogenating these polyolefin-based polymers; condensation of dibasic acids such as adipic acid and glycol, or opening of lactones.
• Polyester-based polymer obtained by ring polymerization (meth) acrylic acid ester-based polymer obtained by radical polymerization of monomers such as ethyl (meth) acrylate and butyl (meth) acrylate; (meth) acrylic acid ester-based monomer, Vinyl-based polymer obtained by radically polymerizing monomers such as vinyl acetate, acrylonitrile, and styrene; graft polymer obtained by polymerizing vinyl monomer in an organic polymer; polysulfide-based polymer; polyamide-based polymer; polycarbonate System polymer; Examples thereof include diallyl phthalate system polymer. Two or more of these skeletons may be included in blocks or randomly.
• the polyoxyalkylene polymer and / or the (meth) acrylic acid ester polymer are preferable because they are easy to handle and have a great effect of prolonging the bonding time.
• the content of the liquid polymer compound is preferably 0 parts by mass or more, preferably 100 parts by mass or less, more preferably 60 parts by mass or less, and further preferably 30 parts by mass or less with respect to 100 parts by mass of the component (A).
• Fillers include, for example, calcium carbonate, magnesium carbonate, titanium oxide, carbon black, molten silica, sedimentary silica, silica clay, white clay, kaolin, clay, talc, wood flour, walnut shell powder, rice husk powder, and anhydrous.
• Inorganic fillers such as silicic acid, quartz powder, aluminum powder, zinc powder, asbestos, glass fiber, carbon fiber, glass beads, alumina, glass balloon, silas balloon, silica balloon calcium oxide, magnesium oxide, silicon oxide, pulp, etc. Examples thereof include wood fillers such as cotton chips, powdered rubbers, recycled rubbers, fine powders of thermoplastic or thermosetting resins, and organic fillers such as hollow bodies such as polyethylene. Only one type of filler may be added, or a plurality of types may be added in combination.
• diluent Physical properties such as viscosity can be adjusted by adding a diluent to the reactive hot melt adhesive according to the present invention. Since the operating temperature (coating, melting) of the adhesive is high, it is preferable to use a solvent (diluent) having a boiling point of 150 ° C. or higher in consideration of safety (fire, health). .. The boiling point of the diluent is preferably 150 ° C. or higher, more preferably 200 ° C. or higher, and even more preferably 300 ° C. or higher.
• diluent examples include phthalates such as dioctylphthalate and diisodecylphthalate; aliphatic dibasic acid esters such as dimethyl adipate and dioctyl adipate; polyethers such as polypropylene glycol and its derivatives; vinyl-based monomers. Oils such as vinyl-based polymers, paraffin-based process oils, and naphthen-based oils obtained by polymerizing the above in various methods; synthetic waxes such as Fisher Tropsch wax, polyethylene wax, polypropylene wax, and atactic polypropylene; paraffin wax, micro Examples thereof include petroleum wax such as crystallin wax. These diluents can be used alone or in combination of two or more.
• the stabilizer examples include an antioxidant, a light stabilizer, an ultraviolet absorber and the like.
• an antioxidant When an antioxidant is used, the weather resistance and heat resistance of the cured product can be improved.
• examples of the antioxidant include hindered phenol-based, monophenol-based, bisphenol-based, and polyphenol-based compounds, and hindered phenol-based compounds are particularly preferable.
• a light stabilizer When a light stabilizer is used, it is possible to prevent photooxidation deterioration of the cured product.
• the light stabilizer examples include compounds such as benzotriazole-based compounds, hindered amine-based compounds, and benzoate-based compounds, and hindered amine-based compounds are particularly preferable.
• the use of an ultraviolet absorber can enhance the surface weather resistance of the cured product.
• the ultraviolet absorber examples include benzophenone-based, benzotriazole-based, salicylate-based, substituted trill-based and metal chelate-based compounds, and benzotriazole-based compounds are particularly preferable. Further, it is preferable to use a phenol-based or hindered phenol-based antioxidant, a hindered amine-based photostabilizer, and a benzotriazole-based ultraviolet absorber in combination.
• flame retardants examples include linear phosphazene and cyclic phosphazene described in JP-A-2002-59146, and phenoxyphosphazene is preferable.
• the flame retardant examples include organic halogen compounds such as decabromobisphenyl ether and tetrabromobisphenol; inorganic halogen compounds such as ammonium bromide; triarylphosphin, trialkylphosphin, bis (diarylphosphino) benzene, and tris.
• organic halogen compounds such as decabromobisphenyl ether and tetrabromobisphenol
• inorganic halogen compounds such as ammonium bromide
• triarylphosphin, trialkylphosphin, bis (diarylphosphino) benzene and tris.
• (Diarylphosphino) Tertiary phosphines such as benzene; Organic phosphate metal salts such as tris (diethylphosphinic acid) aluminum; Inorganic phosphorus-nitrogen compounds such as ammonium polyphosphate and melamine polyphosphate; Nitrogen compounds; Inorganic hydroxides such as magnesium hydroxide and aluminum hydroxide; Antimon oxide, barium metaborate, hydroxoantimonate, zirconium oxide, zirconium hydroxide, molybdenum oxide, ammonium molybdate, zinc borate, ammonium borate, meta Examples thereof include inorganic compounds such as barium borate, talc, silicate, silicon oxide, tin oxide and siloxane compounds.
• the component (A) is preferably contained in the hot melt adhesive in an amount of 50% by mass or more, more preferably 60% by mass or more, and 70% by mass or more. It is particularly preferable that the above is contained from the viewpoint of the characteristics of the hot melt adhesive.
• the reactive hot melt adhesive according to the present invention includes all compounding components (for example, component (A), component (B), component (C), component (D), component (E), and / or other additions. It can be prepared as a one-component type that is preliminarily blended and sealed and stored, and then cured by the humidity in the air after construction. Further, for example, a mixture of the component (A), the component (C), the component (E), and / or other additives and a mixture of the component (B) and the component (D) are mixed before use. It can also be prepared as a component type.
• the method for preparing the reactive hot melt adhesive according to the present invention is not particularly limited.
• the above-mentioned components are blended in a predetermined blending ratio and kneaded at room temperature or under heating using a mixer, roll, kneader or the like.
• a usual method such as dissolving and mixing each component with a small amount of a predetermined solvent can be used.
• the viscosity of the reactive hot melt adhesive according to the present invention at 120 ° C. is preferably 400 Pa ⁇ s or less, more preferably 200 Pa ⁇ s or less, further preferably 100 Pa ⁇ s or less, and particularly preferably 50 Pa ⁇ s or less. If the viscosity at 120 ° C. exceeds 400 Pa ⁇ s, the payability and workability deteriorate, or it becomes necessary to apply at a higher temperature in order to secure the payability and workability. In that case, the range of use is limited, for example, it becomes difficult to use it on a base material having low heat resistance.
• the moisture-curable hot-melt adhesive according to the present invention is excellent in drop impact resistance, waterproofness, flexibility, shape retention after application, etc., and therefore includes metals, resins, papers, wood, stones, and concrete. It can be suitably used for adhesion to various substrates. Specifically, it can be suitably used in production lines for construction, building materials, automobiles, electrical / electronic member applications (for example, bonding of optical members), textile / leather / clothing applications, bookbinding, and the like. Further, it can be suitably used for applications other than production lines such as on-site construction at construction sites and DIY.
• Examples of modes used for bonding optical members include mobile information terminals such as mobile phones and smartphones, information processing terminals such as personal computers and tablet terminals, game machines, televisions, car navigation systems, cameras, speakers, and head mount displays. Applications to sealants can be mentioned.
• the moisture-curable hot melt adhesive according to the present invention may be used as a sealing agent, a coating agent, or a potting agent.
• the construction method includes a step of heating the moisture-curable silylated polyurethane adhesive according to the present invention to a predetermined temperature (heating step) and applying the heated adhesive to the adhesive region of the first adherend.
• heating step a step of heating the moisture-curable silylated polyurethane adhesive according to the present invention to a predetermined temperature
• the adhesive according to the present invention may be applied not only to the adhesive region of the first adherend but also to the adhesive region of the second adherend.
• metal units such as iron, nickel, chromium, aluminum, magnesium, copper, and lead; alloys obtained from the metal units such as stainless steel and brass; zinc, nickel, and the like.
• Metals plated with iron or the like plated with a metal such as chromium; the metal alone, alloys, or plated metal or the like is subjected to chemical conversion treatment such as chromate treatment or phosphate treatment. Metals can be mentioned.
• the resin base material examples include glass, polyamide resin, polyimide resin, polyamideimide resin, acrylic resin, urethane resin, silicon resin, epoxy resin, fluororesin, polystyrene resin, polyester resin, polysulfone resin, and polyether sulfone.
• Resin polyarylate resin, polyvinyl chloride resin, polyvinylidene chloride, norbornen resin, polyolefin resin, alicyclic polyimide resin, cellulose resin, POM (polyacetal), PEEK (polyether ether ketone), PC (polycarbonate), PBT ( Polybutylene terephthalate), PPS (polyphenylene sulfide), POB (polyoxybenzoyl), modified PPE (polyphenylene ether), PEN (polyethylene naphthalate), PEI (polyetherimide), PET (polyethylene terephthalate), LCP (liquid crystal polyester) , Lactic acid polymer, ABS resin, AS resin and the like, and examples thereof.
• the base material may be subjected to pretreatment such as corona treatment, plasma treatment, primer treatment and the like, if necessary.
• (Applying method) As a method of applying the moisture-curable hot melt adhesive to the substrate, for example, a method using a roll coater, a spray coater, a T-tie coater, a knife coater, a comma coater, etc .; a dispenser, inkjet printing, screen printing, offset printing, etc. Examples thereof include a method of applying by a method such as.
• the moisture-curable hot melt adhesive can be precisely applied to a desired portion on the substrate, so that no loss such as punching occurs. preferable.
• a coating method such as a dispenser that handles a composition having high curability at room temperature, it can be suitably used because it has excellent heating stability in a closed heating tank (liquid feeding tank).
• the moisture-curable hot-melt adhesive can be applied to a dotted, linear, dashed line, alternate-dashed line, polygonal shape such as triangular or square, round, elliptical, curved, etc. It can be formed on the substrate continuously or intermittently in various shapes.
• the thickness of the adhesive layer using the moisture-curable hot melt adhesive can be appropriately set according to the intended use.
• the thickness of the adhesive layer is in the range of about 10 ⁇ m to 5 mm.
• the aging conditions for moisture curing after bonding are, for example, a temperature of 20 ° C to 80 ° C, a humidity of 50% to 90%, and a range of about 0.5 to 5 days.
• a laminate having a plurality of base materials and an adhesive layer made of an adhesive obtained by moisture-curing a moisture-curable hot-melt adhesive can be obtained.
• a method of peeling off the adhesive layer from the laminated body and recovering the base material it is possible to use a method of heating the laminated body in the range of 40 ° C. to 150 ° C. because it can be easily peeled off by hand. preferable.
• the moisture-curable hot-melt adhesive according to the present invention is composed of the alkoxysilyl group-containing urethane prepolymer (A) having a specific structure, it has a good rising strength and a sufficient bonding time. It can be compatible. Further, since the reactive hot melt adhesive according to the present invention has a good rising strength, it can be suitably used for an adherend having a curved surface or the like.
• the moisture-curable hot melt adhesive according to the present invention exhibits an appropriate viscosity at the coating temperature, so that the coating workability is also good. Since the moisture-curable silylated polyurethane adhesive according to the present invention is prepared so as to substantially contain no isocyanate group, free monomeric polyisocyanate is not released during heating or the like, and the adhesive does not release free monomeric polyisocyanate. Since polyurea is not substantially formed by the reaction, swelling of the adhesive surface due to the release of carbon dioxide can be prevented, and deterioration of the adhesive strength can be prevented.
• the number average molecular weight was measured by gel permeation chromatography (GPC) under the following conditions. Specifically, the object to be measured was measured by GPC under the following measurement conditions, and the maximum frequency of molecular weight converted with standard polyethylene glycol was taken as the number average molecular weight.
• FT-IR measuring device FT-IR460Plus manufactured by JASCO Corporation The same applies to the IR spectrum measurement conditions in the synthesis example described later.
• An amine-based catalyst (trade name: U-660M, manufactured by San-Apro) was added and reacted at 100 ° C. for 3 hours under a nitrogen atmosphere with stirring to obtain a urethane prepolymer (a1-4). Then, 25.5 g (a2-2; anilinosilane) (trade name: KBM573, manufactured by Shin-Etsu Chemical Co., Ltd.) of N-phenyl-3-aminopropyltrimethoxysilane was added, and the mixture was further stirred at 100 ° C. for 2 hours. As a result, polymer F was obtained. At the end of the reaction, it was confirmed by IR spectrum measurement that the absorption of -NCO derived from the isocyanate group had disappeared.
• the silane compound 2 was synthesized as a silane-based adhesive-imparting agent by reacting two kinds of silane compounds with each other. Specifically, 1 mol of 3-glycidoxypropyltrimethoxysilane (KBM403, manufactured by Shin-Etsu Chemical Co., Ltd.) and N-2- (aminoethyl) -3-aminopropyltrimethoxysilane (KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) ) Weighed 1 mol.
• KBM403 3-glycidoxypropyltrimethoxysilane
• N-2- (aminoethyl) -3-aminopropyltrimethoxysilane KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.
• silane compound 2 as a silane-based adhesion imparting agent was obtained.
• the molecular weight of the silane compound 2 is 458.7 g / mol.
• Methyldimethoxysilane which is a silicon hydride compound, and a platinum vinyl siloxane complex isopropanol solution were added to and reacted with this polymer to obtain a polyoxyalkylene polymer (J) having a methyldimethoxysilyl group at the terminal. ..
• a polyoxyalkylene polymer (J) having a methyldimethoxysilyl group at the terminal J
• the peak top molecular weight was 15,000 and the molecular weight distribution was 1.3.
• Table 1 shows the main compounding substances in Synthesis Examples 2 to 7.
• Examples, comparative examples For each of Examples 1 to 7 and Comparative Examples 1 to 4, the component (A) or the alkoxysilyl group-containing methyl methacrylate polymer (Synthesis Example 10), the component (B), the component (C), and the component (D). ), The component (E), and / or the water absorber were mixed at the blending ratios shown in Table 2, and the mixture was stirred and mixed in an environment of 120 ° C. Finally, defoaming was performed under reduced pressure, and a one-component moisture-curable reactive hot melt adhesive was filled in a metal container for each of the adhesives of Examples 1 to 7 and Comparative Examples 1 to 4.
• -FTR6100 styrene-based monomer / aliphatic monomer copolymer-based, trade name: FTR6100, manufactured by Mitsui Chemicals, Inc.
• -U-830 tin catalyst; dioctyl tin diversate, trade name: Neostan U-830, manufactured by Nitto Kasei Co., Ltd.
• SPUR1050MM number average molecular weight [Mn] 16,400, polydispersity [Mw / Mn], a silylated polyurethane having two end groups of trimethoxysilane and a polyoxypropylene skeleton corresponding to the silylated polyether urethane 1.
• silyl functional group 0.122 mm equivalent / polymer 1 gram, viscosity; 35,000 mPa.s / 23 ° C [ASTM standard D1236], trade name: SPUR + 1050MM, manufactured by Momentive) KBM3103C (decyltrimethoxysilane, trade name: KBM3103C, manufactured by Shin-Etsu Chemical Co., Ltd.)
• the one-component moisture-curable reactive hot-melt adhesive according to Example 1 was heated and melted at 120 ° C. to a thickness of 100 ⁇ m on a first aluminum plate (25 mm ⁇ 75 mm ⁇ 2 mm, degreasing the adhesive surface with acetone). It was applied so as to be. Immediately after application, the area of the area where the second aluminum plate (25 mm ⁇ 75 mm ⁇ 2 mm, degreasing the adhesive surface with acetone) is overlapped with the first aluminum plate so as to sandwich the adhesive is 25 mm ⁇ 25 mm from one end.
• the test pieces were prepared by laminating. After curing the test piece in a 23 ° C.
• the one-component moisture-curable reactive hot-melt adhesive according to Example 1 was heated and melted at 120 ° C., applied to K liner cardboard (250 mm ⁇ 250 mm ⁇ 7 mm) to a thickness of 50 ⁇ m, and applied every predetermined time (1).
• the test pieces (K liner cardboard (25 mm ⁇ 50 mm ⁇ 7 mm)) were bonded to each other every 3 seconds until the minute and every 15 seconds after the 1 minute was exceeded. Then, after laminating each test piece in a 23 ° C.
• the test piece is peeled off by hand, and the time until the bonded portion is not damaged is the time (seconds) that can be bonded. ). Further, the one-component moisture-curable reactive hot melt adhesive according to the other examples and comparative examples was also evaluated in the same manner.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Polyurethanes Or Polyureas (AREA)

Priority Applications (2)

Applications Claiming Priority (2)

Publications (1)

Family

ID=78525729

Family Applications (1)

Country Status (4)

Cited By (1)

Citations (6)

• 2021
  • 2021-04-29 WO PCT/JP2021/017126 patent/WO2021230094A1/ja active Application Filing
  • 2021-04-29 JP JP2022521832A patent/JPWO2021230094A1/ja active Pending
  • 2021-04-29 CN CN202180049661.1A patent/CN115916919A/zh active Pending
  • 2021-05-10 TW TW110116696A patent/TW202200745A/zh unknown

Patent Citations (6)

Also Published As

Similar Documents

Legal Events