WO2023058602A1 - Composition de résine durcissable et corps durci - Google Patents

Composition de résine durcissable et corps durci Download PDF

Info

Publication number
WO2023058602A1
WO2023058602A1 PCT/JP2022/036988 JP2022036988W WO2023058602A1 WO 2023058602 A1 WO2023058602 A1 WO 2023058602A1 JP 2022036988 W JP2022036988 W JP 2022036988W WO 2023058602 A1 WO2023058602 A1 WO 2023058602A1
Authority
WO
WIPO (PCT)
Prior art keywords
curable resin
resin composition
group
prepolymer
mass
Prior art date
Application number
PCT/JP2022/036988
Other languages
English (en)
Japanese (ja)
Inventor
千鶴 金
穣 末▲崎▼
Original Assignee
積水化学工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 積水化学工業株式会社 filed Critical 積水化学工業株式会社
Publication of WO2023058602A1 publication Critical patent/WO2023058602A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/83—Chemically modified polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08L101/10—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups
    • 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
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers

Definitions

  • the present invention relates to a curable resin composition and its cured product, for example, a curable resin composition used for adhesives, sealants and the like and its cured product.
  • the main chain is a (meth)acrylic polymer, characterized by containing a prepolymer having an alkoxysilyl group, and a photoacid generator and/or a photobasic generator. Active energy radiation curable compositions are disclosed.
  • Patent Document 2 discloses a prepolymer in which an alkoxysilyl group is bonded to a urethane bond via a methylene spacer in a main chain having polyether or polyester units and a urethane bond.
  • Patent Document 2 exemplifies metal-containing curing catalysts such as organic titanium or tin compounds, metal-free alkaline catalysts, and the like as catalysts, and it is assumed that curing is performed by moisture curing.
  • the prepolymer used is ⁇ -silane in which the alkoxysilyl group is bonded to the ⁇ -position carbon.
  • the alkoxysilyl group of the prepolymer is ⁇ -silane, it is difficult to cure the prepolymer immediately after irradiation with active energy rays.
  • Patent Document 2 since the alkoxysilyl group contained in the prepolymer is ⁇ -silane, it cures quickly by contact with moisture or the like, but has a problem of low storage stability.
  • an object of the present invention is to provide a curable resin composition that is rapidly cured by active energy ray irradiation and has good storage stability.
  • the present inventors found that the above problems can be solved by including a prepolymer having a reactive silyl group bonded to the ⁇ -position carbon and a photoacid generator in the curable resin composition. and completed the following invention. That is, the present invention provides the following [1] to [9].
  • the prepolymer (A) has at least one skeleton selected from the group consisting of a polyether skeleton, a polyester skeleton, and a polycarbonate skeleton.
  • R 1 is each independently a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 20 carbon atoms
  • R 2 is each independently optionally substituted carbon number. 1 to 20 hydrocarbon groups or hydrogen atoms.
  • a is an integer from 1 to 3;
  • R 3 each independently may be bonded to a carbon atom via a hydrogen atom, a nitrogen atom, a phosphorus atom, an oxygen atom, a sulfur atom or a carbonyl group, or may be substituted; ⁇ 20 monovalent hydrocarbon groups.
  • Y is an x-valent polymer chain having at least one skeleton selected from the group consisting of a polyether skeleton, a polyester skeleton, and a polycarbonate skeleton, where x is an integer of 1-10.
  • the curable resin composition according to any one of [1] to [11] above, wherein the prepolymer (A) has a weight average molecular weight of 3000 or more and 100000 or less.
  • the curable resin composition of the present invention contains a prepolymer (A) having a reactive silyl group bonded to the ⁇ -position carbon and a photoacid generator (B).
  • the curable resin composition of the present invention contains a prepolymer (A) having a reactive silyl group bonded to the ⁇ -position carbon.
  • the prepolymer (A) has a reactive silyl group bonded to the ⁇ -position carbon, and by using a photoacid generator (B) described later, an active energy ray Cures quickly after irradiation.
  • a photoacid generator (B) described later an active energy ray Cures quickly after irradiation.
  • storage stability can be improved.
  • the prepolymer (A) preferably has two or more reactive silyl groups bonded to the ⁇ -position carbon in the molecule. Since the prepolymer (A) has a plurality of reactive silyl groups in the molecule, it is appropriately cured by irradiation with energy rays, and the curable resin composition is suitably used as an adhesive, sealant, encapsulant, or the like. become able to. Also, from the viewpoint of curability, the prepolymer (A) preferably has reactive silyl groups bonded to the ⁇ -position carbon at both ends.
  • Prepolymer (A) preferably has at least one skeleton selected from the group consisting of a polyether skeleton, a polyester skeleton, and a polycarbonate skeleton.
  • a polyether skeleton a polyether skeleton and a polyester skeleton
  • a polycarbonate skeleton a polycarbonate skeleton.
  • One of the skeletons described above may be used alone, or two or more of them may be used in combination.
  • two or more skeletons for example, a polyether skeleton and a polyester skeleton
  • two or more prepolymers (A) having skeletons different from each other may be used. They may be used together.
  • the prepolymer (A) becomes suitable and easy to use as an adhesive, sealant, encapsulant, or the like.
  • the prepolymer (A) for example, has a polyether skeleton, so that the cured product has good flexibility and moisture resistance, and has a polyester skeleton, so that the cured product has a well-balanced mechanical strength, flexibility, etc. Good and easy to be good.
  • the mechanical strength, moisture resistance, etc. of the cured product tend to be good.
  • the prepolymer (A) more preferably has at least one of a polyether skeleton, a polyester skeleton, and a polycarbonate skeleton in the main chain, and has a reactive silyl group at both ends. Further, it is more preferable that both terminal reactive silyl groups are bonded to the ⁇ -position carbon adjacent to the urethane bond.
  • a reactive silyl group bonded to the ⁇ -position carbon is represented by the following formula (1), for example.
  • R 1 is each independently a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 20 carbon atoms
  • R 2 is each independently optionally substituted carbon number. 1 to 20 hydrocarbon groups or hydrogen atoms.
  • a is an integer from 1 to 3;
  • hydrocarbon groups for R 1 and R 2 include alkyl groups, alkenyl groups, aryl groups and aralkyl groups.
  • Alkyl groups include methyl, ethyl, n-propyl, isopropyl, 1-n-butyl, 2-n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, and neopentyl.
  • various hexyl groups such as tert-pentyl group and n-hexyl group
  • various heptyl groups such as n-heptyl group
  • various octyl groups such as n-octyl group, isooctyl group and 2,2,4-trimethylpentyl group
  • Nonyl groups such as n-nonyl groups
  • various decyl groups such as n-decyl groups
  • various dodecyl groups such as n-dodecyl groups
  • chain alkyl groups represented by various octadecyl groups such as n-octadecyl groups, cyclopentyl groups
  • Cyclic alkyl groups such as cyclohexyl group, cycloheptyl group and methylcyclohexyl group are included.
  • Alkenyl groups include vinyl, 1-propenyl and 2-propenyl groups
  • aryl groups include phenyl, naphthyl, anthryl and phenanthryl groups.
  • the aryl group may be an alkylaryl group, and specific examples thereof include tolyl, xylyl, and ethylphenyl groups.
  • Aralkyl groups include benzyl groups and ⁇ - and ⁇ -phenylethyl groups.
  • a halogen atom is mentioned as a substituent in R ⁇ 1> , R ⁇ 2> .
  • Halogen atoms include fluorine, chlorine, bromine, and iodine atoms.
  • Substituted R 1 and R 2 include 3,3,3-trifluoro-n-propyl group, 2,2,2,2′,2′,2′-hexafluoroisopropyl group, heptafluoroisopropyl group, etc. and haloaryl groups such as o-, m- and p-chlorophenyl groups.
  • a is preferably 2 or 3 from the viewpoint of curability.
  • R 1 and R 2 may be the same or different.
  • the plurality of R 1 's may be the same or different from each other, and similarly the plurality of R 2 's may be the same or different from each other.
  • the reactive silyl group bonded to the ⁇ -position preferably has at least one of an alkoxy group and a hydroxyl group bonded to a silicon atom, and among these, an alkoxy group is more preferable. Therefore, each R 1 is preferably independently selected from an alkyl group and a hydrogen atom, more preferably from an alkyl group.
  • the reactive silyl group having at least one of an alkoxy group and a hydroxyl group bonded to a silicon atom facilitates increasing the curing speed by irradiation with active energy rays.
  • the alkoxy group in the reactive silyl group (that is, R 1 which is an alkyl group in formula (1)) preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms, and 1 or 2 carbon atoms. More preferably, one having 1 carbon atom is most preferable.
  • R 2 is preferably an alkyl group that may be substituted with a halogen atom, and more preferably an alkyl group.
  • the alkyl group of R 2 which may be substituted with a halogen atom preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms, further preferably 1 or 2 carbon atoms, and most preferably 1 carbon atom. .
  • the reactive silyl group preferably methyldimethoxysilyl group, trimethoxysilyl group, ethyldiethoxysilyl group, methyldiethoxysilyl group, ethyldimethoxysilyl group, triethoxysilyl group, phenyldimethoxysilyl group, phenyldiethoxy
  • Examples include silyl groups, among which at least one of a methyldimethoxysilyl group and a trimethoxysilyl group is more preferable.
  • the prepolymer (A) may also have a reactive silyl group bonded to the ⁇ -position carbon adjacent to a functional group such as a vinyl group, other than the bond (Z) described above.
  • R' has the definition given as R 1 or is a -CH(COOR'')-CH 2 -COOR'' group.
  • R′′ may be the same or different and have the definition given for R 1 .
  • the ⁇ -position carbon may be bonded to either the carbon atom or the nitrogen atom that constitutes the urethane bond, but is preferably bonded to the nitrogen atom that constitutes the urethane bond.
  • the prepolymer (A) preferably has a structure represented by formula (2) below.
  • R 1 , R 2 and a are the same as above.
  • R 3 each independently may be bonded to a carbon atom via a hydrogen atom, a nitrogen atom, a phosphorus atom, an oxygen atom, a sulfur atom or a carbonyl group, or may be substituted; ⁇ 20 monovalent hydrocarbon groups.
  • Y is an x-valent polymer chain having at least one skeleton selected from the group consisting of a polyether skeleton, a polyester skeleton, and a polycarbonate skeleton, where x is an integer of 1-10.
  • the hydrocarbon group having 1 to 20 carbon atoms which may be substituted for R 3 includes an alkyl group, an alkenyl group, an aryl group, an aralkyl group and the like, and the substituent for R 3 includes a halogen atom. be done. The details of these are the same as described for R 1 and R 2 above, and will be omitted.
  • the carbon atom in CR 3 2 of formula (2) is the ⁇ -position carbon atom.
  • R 3 is preferably a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrogen atom. Therefore, the group represented by CR 3 2 is more preferably a methylene group.
  • x is preferably 2 or 3, more preferably 2, and prepolymer (A) preferably has reactive silyl groups at both ends as described above.
  • Y is an x-valent polymer chain having at least one skeleton selected from the group consisting of a polyether skeleton, a polyester skeleton, and a polycarbonate skeleton.
  • Y may be bound to CR 3 2 (i.e., the carbon atom at the ⁇ -position) via a bond containing a nitrogen atom, an oxygen atom, a sulfur atom or a carbon atom, preferably via the bond (Z) described above. 2 , more preferably CR 3 2 via a urethane bond.
  • Y is polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxymethyltetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene-polyoxybutylene copolymer, bisphenol-type polyoxyalkylene
  • It is a polymer chain having a polyoxyalkylene such as a modified product, a polyester, or a polycarbonate.
  • the polymer chain preferably has a structure selected from a polyoxyalkylene structure, a polyester structure, and a polycarbonate structure, more preferably a polyoxyalkylene structure, and particularly preferably a polyoxypropylene structure.
  • the polymer chain preferably has at least two urethane bonds.
  • the urethane bond is preferably arranged at least at the terminal of Y, and more preferably at least at both terminals of Y. Moreover, in addition to the end of Y, it may be arranged in the middle of the polymer chain that constitutes Y. Therefore, the polymer chain may have a structure in which a plurality of structures selected from polyoxyalkylene structures, polyester structures, and polycarbonate structures are linked via urethane bonds. Of course, the polymer chain does not have to have urethane bonds other than at the ends. Therefore, Y may be a structure having urethane bonds at both ends of polyoxyalkylene, polyester, or polycarbonate. In this specification, the prepolymer (A) having at least two urethane bonds is polyurethane.
  • the prepolymer (A) is preferably a reaction product of a compound (A1) represented by the following formula (2-1) and a compound (A2) having a polymer chain.
  • R 1 , R 2 , R 3 and a in formula (2-1) are the same as above.
  • Za is preferably a reactive group that reacts with the compound (A2) having a polymer chain to form the bond (Z) described above, preferably Za is -NCO (isocyanate group) in the following formula (2- Compound (a1) represented by 2) is preferred.
  • R 1 , R 2 , R 3 and a in formula (2-1) are the same as above.
  • Compound (A1) can easily react with compound (A2) having a polymer chain by using compound (a1) represented by formula (2-2).
  • compound (a1) represented by formula (2-2) By including a hydroxyl group in the compound (A2) having a polymer chain, a urethane bond can be introduced at a position adjacent to the ⁇ -position carbon atom.
  • the structure of the prepolymer (A) when the prepolymer (A) is a polyurethane having at least two urethane bonds will be described in more detail below.
  • the prepolymer (A) is polyurethane
  • it is preferably a reaction product of the compound (a1) represented by the above formula (2-2) and the polyol compound (a2).
  • the polyol compound (a2) used here preferably has at least one skeleton of a polyether skeleton, a polyester skeleton, and a polycarbonate skeleton, and more specifically, polyester polyol, polyether polyol, and polycarbonate polyol. etc.
  • These polyol compounds (a2) may be used singly or in combination of two or more.
  • polyether polyol should have two or more hydroxyl groups, it preferably has two hydroxyl groups.
  • Polyether polyols are, for example, polyethylene glycol, polypropylene glycol, polybutylene glycol, ring-opening polymer of tetrahydrofuran, ring-opening polymer of 3-methyltetrahydrofuran, and random copolymers or block copolymers of these or derivatives thereof. , bisphenol-type polyoxyalkylene modified products, and the like.
  • the bisphenol-type polyoxyalkylene modified product is a polyether polyol obtained by addition reaction of an alkylene oxide (e.g., ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, etc.) to the active hydrogen portion of the bisphenol-type molecular skeleton.
  • the polyether polyol may be a random copolymer or a block copolymer.
  • one or more alkylene oxides are preferably added to both ends of the bisphenol-type molecular skeleton.
  • the bisphenol type is not particularly limited, and includes A type, F type, S type and the like, preferably bisphenol A type.
  • polyether polyol it is also preferable to use a polyol having a structure represented by the following formula (3).
  • a polyol having a structure represented by the following formula (3) it becomes easier to improve the flexibility of the cured product.
  • polypropylene glycol polypropylene glycol
  • a methyl group such as 3-methyltetrahydrofuran.
  • a polyether polyol composed of a ring-opening polymerization compound of tetrahydrofuran having a substituent is preferable, more preferably polypropylene glycol and a ring-opening polymerization compound of tetrahydrofuran (THF), and more preferably polypropylene glycol.
  • the ring-opening polymerization compound of tetrahydrofuran (THF) compound is generally polytetramethylene ether glycol.
  • polyether polyol may be used individually by 1 type, and may be used in combination of 2 or more type.
  • R represents a hydrogen atom, a methyl group, or an ethyl group
  • l is an integer of 0 to 5
  • m is an integer of 2 to 500
  • n is an integer of 1 to 10.
  • l is preferably 0 to 4
  • m is preferably 20 to 500, more preferably 50 to 400
  • n is preferably 1 to 5.
  • the case where l is 0 means the case where the carbon bonded to R is directly bonded to oxygen.
  • the sum of n and l is more preferably 1 or more, more preferably 1 to 3.
  • R is more preferably a hydrogen atom or a methyl group, particularly preferably a methyl group.
  • polycarbonate polyol The polycarbonate polyol may have two or more hydroxyl groups, but a polycarbonate diol having two hydroxyl groups is preferred.
  • Preferred specific examples of polycarbonate diols include compounds represented by the following formula (4).
  • R is a divalent hydrocarbon group having 4 to 16 carbon atoms, and n is an integer of 2 to 500.
  • R may be an aromatic saturated hydrocarbon group having an aromatic ring or an aliphatic saturated hydrocarbon group, preferably an aliphatic saturated hydrocarbon group.
  • R is an aliphatic saturated hydrocarbon group
  • the heat resistance tends to be good.
  • yellowing or the like due to heat deterioration or the like is less likely to occur, and weather resistance is improved.
  • R composed of an aliphatic saturated hydrocarbon group may have a chain structure or a cyclic structure, but preferably has a chain structure from the viewpoint of easily improving stress relaxation properties and flexibility.
  • R in the chain structure may be linear or branched.
  • n is preferably 5-200, more preferably 10-150, even more preferably 20-50.
  • R is preferably 5-12.
  • R may be linear groups such as a tetramethylene group, pentylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, and, for example, a 3-methylpentylene group. It may be branched such as a methylpentylene group such as a methylpentylene group or a methyloctamethylene group. Plural R's in one molecule may be the same or different. Therefore, one molecule may contain two or more types of R, and in that case, one molecule preferably contains two or three types of R.
  • the polycarbonate polyol may be a copolymer containing R having 6 or less carbon atoms and R having 7 or more carbon atoms in one molecule. It is preferable that it is a hydrogen group.
  • R may contain a linear saturated aliphatic hydrocarbon group, or may contain a branched saturated aliphatic hydrocarbon group.
  • branched and linear R may be used in combination, or linear R may be used alone.
  • Polycarbonate polyols may be used singly or in combination of two or more.
  • polyester polyol examples include polyester polyols obtained by reacting polyvalent carboxylic acids with polyols, poly- ⁇ -caprolactone polyols obtained by ring-opening polymerization of ⁇ -caprolactone, and the like.
  • the polyester polyol preferably has two or more hydroxyl groups, preferably two hydroxyl groups.
  • Examples of the above-mentioned polyvalent carboxylic acids that are raw materials for polyester polyols include phthalic acid, terephthalic acid, isophthalic acid, 1,5-naphthalic acid, 2,6-naphthalic acid, succinic acid, glutaric acid, adipic acid, and pimelic acid.
  • polyester polyols examples include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, and 1,6-hexanediol.
  • diethylene glycol diethylene glycol, cyclohexanediol, 3-methyl-1,5-pentanediol, and the like.
  • at least one selected from 1,6-hexanediol, 3-methyl-1,5-pentanediol, and 1,4-butanediol is preferable from the viewpoint of easily increasing adhesive strength at high temperatures.
  • Polyol compound (a2) having a urethane bond As the polyol compound (a2) for obtaining polyurethane, it is also preferable to use a polyol compound (a2) having a urethane bond.
  • the use of the polyol compound (a2) having a urethane bond facilitates adjustment of the molecular weight of the prepolymer (A) within a desired range.
  • a polyol compound (a2) having no urethane bond may be used as the polyol compound (a2).
  • the polyol compound (a2) having a urethane bond includes, for example, at least one raw material polyol of polyester polyol, polyether polyol, and polycarbonate polyol, and a polyisocyanate compound having two or more isocyanate groups in one molecule. It can be obtained by reacting.
  • the polyester polyol, polyether polyol, and polycarbonate polyol used here are as described above, and the description thereof is omitted. That is, polyester polyols having urethane bonds, polyether polyols having urethane bonds, and polycarbonate polyols having urethane bonds can also be used as the polyol compound (a2) for obtaining polyurethane.
  • the reaction between the raw material polyol and the polyisocyanate compound is usually carried out so that the molar amount of hydroxyl groups (OH) in the raw material polyol is greater than the molar amount of isocyanate groups (NCO) in the polyisocyanate compound. good.
  • the polyol compound (a2) having a urethane bond can be easily made to contain a hydroxyl group.
  • an aromatic polyisocyanate compound and an aliphatic polyisocyanate compound are preferably used.
  • the polyisocyanate compound is preferably a polyisocyanate compound having two or more isocyanate groups in one molecule, more preferably a polyisocyanate compound having two isocyanate groups in one molecule.
  • aromatic polyisocyanate compounds include diphenylmethane diisocyanate, liquid modified diphenylmethane diisocyanate, polymeric MDI, tolylene diisocyanate, naphthalene-1,5-diisocyanate, and the like.
  • aliphatic polyisocyanate compounds include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate, transcyclohexane-1,4-diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and cyclohexane diisocyanate. , bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane diisocyanate, and the like.
  • the mass ratio of urethane bonds is not particularly limited, it is, for example, 0.01% by mass or more, preferably 0.1% by mass or more.
  • the weight average molecular weight of the prepolymer (A) is preferably 3000 or more and 100000 or less. By setting the weight average molecular weight within the above range, it becomes easier to improve storage stability, curability, and the like. Moreover, it becomes easy to provide the curable resin composition with the performance required as an adhesive, a sealant, a sealing agent, or the like. From these viewpoints, the weight average molecular weight of the prepolymer (A) is more preferably 4000 or more and 80000 or less, still more preferably 5000 or more and 50000 or less, and even more preferably 20000 or more and 50000 or less.
  • a weight average molecular weight is a value which measures by a gel permeation chromatography (GPC), and is calculated
  • GPC gel permeation chromatography
  • Shodex LF-804 manufactured by Showa Denko KK
  • tetrahydrofuran is mentioned as a solvent used in GPC.
  • the content of the prepolymer (A) in the curable resin composition is not particularly limited, but is, for example, 10% by mass or more, preferably 30% by mass or more, more preferably 50% by mass or more, based on the total amount of the curable resin composition. , more preferably 70% by mass or more, and for example, 99.99% by mass or less, preferably 99.9% by mass or less, and more preferably 99.7% by mass or less.
  • the curing speed of the curable resin composition can be appropriately increased by the prepolymer (A).
  • the content of the prepolymer (A) to the above upper limit or less, it is possible to allow the curable resin composition to contain an appropriate amount of components other than the prepolymer (A) such as the photoacid generator (B). can.
  • the photoacid generator (B) is a compound that generates an acid when exposed to active energy rays.
  • the prepolymer (A) is cured by the generated acid.
  • the curable resin composition of the present invention contains a photoacid generator (B) in addition to the prepolymer (A), so that it can be rapidly cured by irradiation with active energy rays without impairing storage stability. become able to.
  • the photoacid generator (B) includes onium salts, specifically aromatic sulfonium salts, aromatic iodonium salts, aromatic diazonium salts, aromatic phosphonium salts and the like. Among these, aromatic sulfonium salts and aromatic iodonium salts are preferred, with aromatic sulfonium salts being more preferred. These onium salts may be used singly or in combination of two or more.
  • Each onium salt described above preferably has a counter anion.
  • counter anions include antimony anions such as hexafluoroantimonate anion (SbF 6 ⁇ ), hexachloroantimonate anion (SbCl 6 ⁇ ), and tetrakis(pentafluorophenyl)borate anion (B(C 6 F 5 ) 4 ⁇ ).
  • tetrafluoroborate anion (BF 4 ⁇ ), hexafluorophosphate anion (PF 6 ⁇ ), perfluoroalkylfluorophosphate anion (Rf n PF 6-n : Rf is a perfluoroalkyl group, n is 1 an integer of up to 5), arsenic anions such as hexafluoroarsenate anion (AsF 6 ⁇ ), and sulfonic acid anions such as trifluoromethanesulfonate ion (CF 3 SO 3 ⁇ ).
  • Aromatic sulfonium salts include triarylsulfonium salts, more specifically triphenylsulfonium salts in which each phenyl group may have a substituent.
  • substituents include an alkyl group optionally having an ether bond, a hydroxyl group, a thioalkyl group optionally having a substituent, a thiophenoxy group optionally having a substituent, and the like.
  • the number of carbon atoms in the substituent is not particularly limited, but is about 1 to 10, for example.
  • the counter anion possessed by the aromatic sulfonium salt is not particularly limited and may be appropriately selected from those described above, but antimony anions and boron anions are preferred, and among them, hexafluoroantimonate anion (SbF 6 ⁇ ), Tetrakis(pentafluorophenyl)borate anion (B(C 6 F 5 ) 4 ⁇ ) is more preferred.
  • aromatic sulfonium salt commercially available products may be used.
  • the aromatic iodonium salts include diaryliodonium salts, more specifically diphenyliodonium salts in which each phenyl group may have a substituent. The details of the substituent are as described for the aromatic sulfonium salt, with alkyl groups being more preferred.
  • aromatic iodonium salt commercially available products may be used, such as "Irgacure 250" manufactured by BASF, "IK-1" and “IK-1FG" manufactured by San-Apro Co., Ltd., and the like.
  • examples of aromatic diazonium salts include aryldiazonium salts
  • examples of aromatic phosphonium salts include triarylphosphonium salts.
  • the content of the photoacid generator (B) in the curable resin composition is, with respect to 100 parts by mass of the prepolymer (A), for example, 0.01 parts by mass or more and 20 parts by mass or less, preferably 0.1 parts by mass or more. It is 10 parts by mass or less, more preferably 0.3 parts by mass or more and 6 parts by mass or less.
  • the content of the photoacid generator (B) is 0.01 parts by mass or more, sufficient acid is generated by irradiation with active energy rays, and the curing speed can be appropriately increased.
  • the content is 20 parts by mass or less, the cured product formed from the curable resin composition is prevented from being colored, and the mechanical strength and the like of the cured product are prevented from being lowered.
  • the curable resin composition of the present invention may contain filler (C).
  • the filler (C) By containing the filler (C), the curable resin composition tends to have an appropriate thixotropic property. For example, it is possible to increase the fluidity during application and reduce the fluidity after application. Therefore, it becomes easy to improve the coatability and handleability.
  • the viscosity can be increased, which makes it easier to adjust the applicability and the like, and furthermore, it becomes easier to increase the mechanical strength of the cured product.
  • the filler (C) is preferably an inorganic filler such as silica, talc, titanium oxide, zinc oxide and calcium carbonate. Among these, silica or talc is more preferred.
  • the filler (C) may be subjected to a hydrophobic surface treatment such as silylation treatment, alkylation treatment or epoxidation treatment.
  • a filler (C) may be used individually by 1 type, and 2 or more types may be used in combination.
  • silica as the filler (C).
  • silica for example, fumed silica known by the trade name “Aerosil” can be used.
  • Fumed silica generally has a particle size of less than 1 ⁇ m, for example, a particle size of about 10 to 500 nm.
  • the curable resin composition may contain a filler having a larger particle size than fumed silica.
  • Such a filler has a particle size of, for example, 1 ⁇ m or more, preferably about 1 to 400 ⁇ m. By using a filler with a large particle size, it becomes easier to increase the mechanical strength and the like.
  • the particle diameter the long diameter of each particle is measured by, for example, microscopic observation, and the long diameter is used as the particle diameter.
  • the content of the filler (C) in the curable resin composition is, for example, 1 part by mass or more and 200 parts by mass or less, preferably 2 parts by mass or more and 100 parts by mass or less, more preferably with respect to 100 parts by mass of the prepolymer (A). is 3 parts by mass or more and 50 parts by mass or less.
  • the curable resin composition contains curable resins such as thermosetting resins, photo-curable resins, and moisture-curable resins that are cured by heat, active energy rays, moisture, and the like.
  • curable resins such as thermosetting resins, photo-curable resins, and moisture-curable resins that are cured by heat, active energy rays, moisture, and the like.
  • it may contain a radically polymerizable compound having a photopolymerizable double bond such as a vinyl group or (meth)acrylic group that undergoes polymerization upon irradiation with an active energy ray.
  • the curable resin composition may contain other additives such as colorants, coupling agents, antioxidants, flame retardants, expanded particles, and expanded particles. It may contain additives.
  • the curable resin composition generally does not contain a solvent, but may contain a solvent as necessary within a range that does not impair the effects of the present invention.
  • the above-described curable resin composition total amount basis means a solid content basis, and when the curable resin composition contains a solvent, it is the amount excluding the solvent.
  • a mixer is used to prepare a prepolymer (A) and a photoacid generator (B), and if necessary, a filler (C) and A method of mixing other components and the like can be mentioned.
  • mixers include homodispers, homomixers, universal mixers, planetary mixers, planetary mixers, kneaders, and three rolls.
  • the curable resin composition of the present invention becomes a cured product when cured.
  • the curable resin composition of the present invention is preferably cured by irradiation with active energy rays.
  • Active energy rays are not particularly limited, and include visible light, ultraviolet rays, infrared rays, X-rays, ⁇ rays, ⁇ rays, and ⁇ rays. UV light is preferred.
  • the curable resin composition of the present invention can be suitably used as, but not limited to, adhesives, sealants, encapsulants, and the like.
  • the curable resin composition When the curable resin composition is used as an adhesive, it may be used for bonding between adherends (also referred to as objects).
  • adherends also referred to as objects.
  • the curable resin composition is, for example, placed between adherends and cured by irradiation with active energy rays, and the adherends are adhered by the cured curable resin composition (cured body). All you have to do is Here, the curable resin composition is applied to the adherend, and the curable resin composition is placed between the adherends by overlapping the adherend from above, and then the active energy ray is applied. Irradiate.
  • the curable resin composition is placed on the adherend by, for example, coating it on the adherend, irradiating the curable resin composition on the adherend with an active energy ray, and then Further, by stacking the adherends, the curable resin composition previously irradiated with the active energy ray may be arranged between the adherends.
  • the curable resin composition is irradiated with the active energy ray before the adherend is superimposed in this manner, the curable resin composition is appropriately adjusted so that it is not completely cured immediately after the irradiation with the active energy ray. do it.
  • the prepolymer (A) may be designed to cure at a slow rate, or the curable resin composition may contain a curable resin other than the prepolymer (A).
  • the curable resin composition may be further heated after the adherend is superimposed.
  • the curable resin composition may be left in a humid environment.
  • the curable resin composition when used as a sealant or a sealant, it may be used for sealing between objects, or may be used for sealing the object itself.
  • the curable resin composition may be placed between objects by the same method as in the case of using it as an adhesive, and the objects may be sealed by the cured curable resin composition.
  • the curable resin composition may be applied to the object, placed on the object, and then cured to seal the object with the cured curable resin composition.
  • the curable resin composition may be used as a sealant or as a sealant and an adhesive.
  • the material of the adherend or object may be any of inorganic materials such as metals, glass and ceramics, organic materials such as plastics, and organic-inorganic composite materials.
  • the shape of the adherend is not particularly limited, and examples thereof include film-like, sheet-like, plate-like, panel-like, tray-like, rod-like, box-like, and housing-like shapes. .
  • the curable resin composition obtained in each example and comparative example was filled in a 12 ml light-shielding ointment pot in a glove box under a nitrogen atmosphere and sealed, and kept in a glove box at room temperature (23 ° C.) for 1 day. Alternatively, it was stored for one week, and the ratio of the viscosity after storage to the viscosity before storage was evaluated as the viscosity increase rate according to the following evaluation criteria. The viscosity was measured with an E-type viscometer under conditions of 25° C. and 10 rpm. AA: less than 1.2 times thickening rate, A: 1.2 times or more and less than 1.5 times thickening rate B: 1.5 times or more thickening rate
  • Example 1 In a glove box under a nitrogen atmosphere, a photoacid generator ( B) 1 mass of ("Irgacure 290", aromatic sulfonium salt manufactured by BASF) was added to obtain a curable resin composition. Curability and storage stability of the resulting curable resin composition were evaluated.
  • Example 2 The procedure was carried out in the same manner as in Example 1, except that "SP-171" (aromatic sulfonium salt) manufactured by ADEKA was used as the photoacid generator (B).
  • SP-171 aromatic sulfonium salt manufactured by ADEKA
  • Example 6 and 7 The procedure was carried out in the same manner as in Example 1, except that the amount of the photoacid generator (B) was changed as shown in Table 1.
  • Example 8 and 9 Except that silica (trade name “SFP-30M” manufactured by Denka) or talc (trade name "P-4" manufactured by Nippon Talc Co., Ltd.) was added as a filler to the prepolymer (A) in the amount shown in Table 1. It was carried out in the same manner as in Example 1.
  • the obtained polyol compound (a2) having a urethane bond and 4.0 parts by mass of the compound (a1) having the structural formula: OCN—CH 2 —Si(OCH 3 ) 3 were mixed and heated at 100° C. for 1 hour. The mixture was stirred and reacted to obtain a prepolymer (A).
  • the proportion of urethane bonds in prepolymer (A) was 2.6% by mass, and the weight average molecular weight was 15,000.
  • the obtained polyol compound (a2) having a urethane bond and 4.0 parts by mass of a compound having the structural formula: OCN—CH 2 —Si(OCH 3 ) 3 were mixed and stirred at 100° C. for 1 hour. It was made to react and the prepolymer (A) was obtained.
  • the obtained polyol compound (a2) having a urethane bond and 4.0 parts by mass of a compound having the structural formula: OCN—CH 2 —Si(OCH 3 ) 3 were mixed and stirred at 100° C. for 1 hour. It was made to react and the prepolymer (A) was obtained.
  • the curable resin compositions of Examples 1 to 9 contain a prepolymer (A) having a reactive silyl group bonded to the ⁇ -position carbon and a photoacid generator (B), so that the curing speed is Fast and good storage stability could be achieved.
  • a prepolymer (A) having a reactive silyl group bonded to the ⁇ -position carbon and a photoacid generator (B) so that the curing speed is Fast and good storage stability could be achieved.
  • the prepolymer contains a reactive silyl group bonded to the ⁇ -position carbon
  • the photoacid generator (B) is not contained, so the curing speed could not be made faster.
  • the curable resin compositions of Comparative Examples 2 and 3 contained a catalyst other than the photoacid generator (B) instead of the photoacid generator (B), the storage stability was not good.
  • the curable resin composition of Comparative Example 4 has insufficient curability because the reactive silyl group in the prepolymer is bonded to the ⁇ -position carbon, and even if it contains the photoacid generator (B), it can be cured. could not be made fast enough.

Abstract

L'invention concerne une composition de résine durcissable comprenant : un prépolymère (A) ayant un groupe silyle réactif lié au carbone en position α ; et un générateur photoacide (B).
PCT/JP2022/036988 2021-10-04 2022-10-03 Composition de résine durcissable et corps durci WO2023058602A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2021163753 2021-10-04
JP2021-163753 2021-10-04

Publications (1)

Publication Number Publication Date
WO2023058602A1 true WO2023058602A1 (fr) 2023-04-13

Family

ID=85804271

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2022/036988 WO2023058602A1 (fr) 2021-10-04 2022-10-03 Composition de résine durcissable et corps durci

Country Status (2)

Country Link
TW (1) TW202328246A (fr)
WO (1) WO2023058602A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012133443A1 (fr) * 2011-03-29 2012-10-04 株式会社カネカ Composition de résine de revêtement polymérisable sous l'effet d'un rayonnement actinique
JP2015518500A (ja) * 2012-03-30 2015-07-02 ワッカー ケミー アクチエンゲゼルシャフトＷａｃｋｅｒ Ｃｈｅｍｉｅ ＡＧ オルガニルオキシシラン末端ポリマーをベースとする架橋性組成物
US20190194509A1 (en) * 2016-06-24 2019-06-27 Delo Industrie Klebstoffe Gmbh & Co. Kgaa One-component composition based on alkoxysilanes and method of joining or encapsulating components using the composition
US20200048394A1 (en) * 2016-10-14 2020-02-13 Basf Se Hardenable polymer composition
WO2020094453A1 (fr) * 2018-11-08 2020-05-14 Delo Industrie Klebstoffe Gmbh & Co. Kgaa Matière à un composant durcissable à l'humidité et procédé d'assemblage, de scellement et de revêtement au moyen de cette matière

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012133443A1 (fr) * 2011-03-29 2012-10-04 株式会社カネカ Composition de résine de revêtement polymérisable sous l'effet d'un rayonnement actinique
JP2015518500A (ja) * 2012-03-30 2015-07-02 ワッカー ケミー アクチエンゲゼルシャフトＷａｃｋｅｒ Ｃｈｅｍｉｅ ＡＧ オルガニルオキシシラン末端ポリマーをベースとする架橋性組成物
US20190194509A1 (en) * 2016-06-24 2019-06-27 Delo Industrie Klebstoffe Gmbh & Co. Kgaa One-component composition based on alkoxysilanes and method of joining or encapsulating components using the composition
US20200048394A1 (en) * 2016-10-14 2020-02-13 Basf Se Hardenable polymer composition
WO2020094453A1 (fr) * 2018-11-08 2020-05-14 Delo Industrie Klebstoffe Gmbh & Co. Kgaa Matière à un composant durcissable à l'humidité et procédé d'assemblage, de scellement et de revêtement au moyen de cette matière

Also Published As

Publication number Publication date
TW202328246A (zh) 2023-07-16

Similar Documents

Publication Publication Date Title
KR101519459B1 (ko) 오르가닐 옥시실란 말단을 가진 폴리머를 기반으로 하는 가교성 물질
JP6208662B2 (ja) シラン官能性ポリマーに基づく２コンポーネント配合物
JP5511381B2 (ja) 硬化性のシリル化されたポリウレタン組成物から誘導された接着剤樹脂成分を有する固体高分子基質
JP5491391B2 (ja) 塗料接着付与剤を含有する硬化性シリル含有ポリマー組成物
AU2004289779B2 (en) Polymers with improved strength comprising mixed oxyalkyl units
EP2785755B2 (fr) Matières réticulables à base de polyuréthanes à terminaison organyloxysilane
US11021565B2 (en) Silane modified polymers and use of the same in adhesive compositions
JPH06500584A (ja) 特別な可塑剤を含む封止用および接着用コンパウンド
JP2009173919A (ja) 硬化性樹脂組成物及び室温硬化性接着剤組成物
WO2021230373A1 (fr) Composition de résine de type durcissant à l'humidité, adhésif pour composant électronique, corps durci et composant électronique
CN112778493A (zh) 一种聚碳酸亚丙酯多元醇型水性聚氨酯防水乳液及其制备方法与应用
ES2661851T3 (es) Material con memoria de forma a base de un pegamento estructural
JP2008285539A (ja) 硬化性樹脂組成物
WO2023058602A1 (fr) Composition de résine durcissable et corps durci
JP2008285538A (ja) 硬化性樹脂組成物及びそれを用いた接着剤組成物
WO2023085280A1 (fr) Composition de résine durcissable et corps durci
JP2010155896A (ja) 透明接着剤
JP4823491B2 (ja) 湿気硬化型ウレタン接着剤組成物
JP4523763B2 (ja) 接着剤組成物
JP6575811B2 (ja) 湿気硬化型ウレタン組成物、及び被覆材
WO2022260053A1 (fr) Composition de résine photodurcissable/durcissable à l'humidité, adhésif pour composants électroniques, corps durci et composant électronique
WO2013079344A1 (fr) Substances réticulables sur la base de polyuréthanes à terminaison organyloxysilane
JPS6253527B2 (fr)
JPH023489A (ja) 無溶剤ポリウレタン反応型接着剤
JP2017036399A (ja) 表面塗布剤およびそれを用いた方法

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 2022564117

Country of ref document: JP

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22878471

Country of ref document: EP

Kind code of ref document: A1