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
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/66—Mercaptans
• • 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
  • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
  • C08G75/02—Polythioethers
  • C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
  • C08G75/045—Polythioethers from mercapto compounds or metallic derivatives thereof from mercapto compounds and unsaturated compounds
• • 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
  • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16

Definitions

• the present invention relates to a curable resin composition, an adhesive containing the composition, a cured product obtained by curing the same, and a semiconductor device containing the cured product.
• UV curable adhesives Adhesives that are cured by ultraviolet (UV) irradiation
• UV curable adhesives there is also a type of adhesive that is temporarily fixed by UV irradiation and fully cured by heating (hereinafter also referred to as “UV-thermosetting adhesive”) (see, for example, Patent Document 1).
• UV curable adhesives contain polyfunctional acrylate compounds and polyfunctional thiol compounds. Such adhesives cure by enethiol reaction (radical addition of thiol groups to double bonds in (meth)acryloyloxy groups) and homopolymerization (radical polymerization of (meth)acryloyloxy groups).
• UV curable adhesives are especially often used in the manufacture of semiconductor devices that require high-precision positioning during assembly, such as image sensor modules.
• image sensor modules the relative positional relationship between each part is extremely important. Therefore, in assembling the image sensor module, it is necessary to position each component with high precision. Therefore, the use of this adhesive, which can be cured in a short period of time by UV irradiation, in the manufacture of image sensor modules is extremely useful because it improves assembly efficiency.
• Assemblies made using UV curable adhesives may be heated and/or cooled with considerable temperature changes. For example, if a UV curable adhesive is cured by UV irradiation followed by heating, the assembly is heated after UV curing and then cooled. In addition, the UV-cured assembly may be placed in an environment that can reach high temperatures, such as inside a car in the summer.
• the present invention aims to provide a UV-curable curable resin composition that gives a cured product that is difficult to peel off from an adherend even when the ambient temperature changes. do.
• the present invention provides a UV-curable curable resin composition that gives a cured product that is difficult to peel off from an adherend even when the ambient temperature changes in the process of heating and/or cooling after UV curing. Also intended to
• the present inventors arrived at the present invention as a result of extensive research in order to solve the above problems.
• the present invention includes, but is not limited to, the following inventions.
• curable resin composition according to the preceding item 1, further comprising (E) a heat curing accelerator.
• the modifier consists essentially of (b1) a monofunctional (meth)acrylate compound and [(B) the total number of (meth)acryloyloxy groups for the modifier + the total number of epoxy groups for (B) the modifier ]/[(C) the total number of thiol groups in the polyfunctional thiol compound] is 0.2 to 0.5, the curable resin composition according to any one of the preceding items 1 to 7.
• the modifier consists essentially of (b2) an epoxy resin, and [total number of (meth)acryloyloxy groups for (B) modifier + total number of epoxy groups for (B) modifier]/[(C )
• a cured product obtainable by curing the curable resin composition according to any one of the preceding items 1 to 9 or the adhesive according to the preceding item 10.
• a semiconductor device comprising the cured product according to 11 above.
• a sensor module comprising the cured product according to 11 above.
• the curable resin composition of the present invention comprises (A) a polyfunctional (meth)acrylate compound, (B) a modifier, (C) a polyfunctional thiol compound and (D) a photoradical initiator. Contains as an ingredient.
• a polyfunctional (meth)acrylate compound (B) a modifier, (C) a polyfunctional thiol compound and (D) a photoradical initiator.
• acrylic acid (or derivatives thereof) and “methacrylic acid” (or derivatives thereof) are collectively referred to as "(meth) acrylic acid”, “(meth) acrylate”, “(meth) acrylic ”, “(meth)acryloyl”, etc. may be used. Each of these terms may be used as an independent term or as part of another term.
• (meth)acrylic acid means “acrylic acid and/or methacrylic acid”
• (meth)acryloyloxy group means “acryloyloxy group and/or methacryloyloxy group”.
• the curable resin composition of the present invention contains (A) a polyfunctional (meth)acrylate compound.
• the polyfunctional (meth)acrylate compound used in the present invention is a compound containing a total of two or more (meth)acryloyloxy groups that react with thiol groups in the polyfunctional thiol compound described below.
• a polyfunctional (meth)acrylate compound has a structure in which one molecule of a compound having two or more hydroxyl groups is esterified with a total of two or more molecules of (meth)acrylic acid (unesterified hydroxyl groups There may be).
• the polyfunctional (meth)acrylate compound may contain (meth)acryloyl groups that are not in the form of (meth)acryloyloxy groups, as long as the above structural requirements are met.
• N,N'-methylenebisacrylamide is not a polyfunctional (meth)acrylate compound.
• the polyfunctional (meth)acrylate compound preferably has a molecular weight of 100 to 10,000, more preferably 200 to 5,000, and more preferably 200 to 3,000. is more preferred, and it is particularly preferred to include those of 200-800.
• polyfunctional (meth)acrylate compounds include - a di(meth)acrylate of bisphenol A; - a di(meth)acrylate of bisphenol F; - polyfunctional (meth) acrylate having an isocyanuric skeleton; - di(meth)acrylate of dimethyloltricyclodecane; - polyfunctional (meth)acrylates of trimethylolpropane or oligomers thereof; - polyfunctional (meth)acrylates of ditrimethylolpropane; - polyfunctional (meth)acrylates of pentaerythritol or oligomers thereof; - polyfunctional (meth)acrylates of dipentaerythritol; and - di(meth)acrylates of neopentyl glycol-modified trimethylolpropane; - di(meth)acrylates of polyethylene glycol; - di(meth)acrylates of polypropylene glycol; - di(meth)acrylates of linear or
• polyfunctional (meth)acrylate refers to a compound containing two or more (meth)acryloyloxy groups.
• polyfunctional (meth)acrylate of trimethylolpropane or its oligomer refers to an ester of one molecule of trimethylolpropane or its oligomer and two or more molecules of (meth)acrylic acid.
• the polyfunctional (meth)acrylate compound preferably contains a bifunctional (meth)acrylate compound.
• a bifunctional (meth)acrylate compound is a polyfunctional (meth)acrylate compound having a total of two (meth)acryloyloxy groups.
• trifunctional and tetrafunctional (meth)acrylate compounds are polyfunctional (meth)acrylate compounds having 3 and 4 (meth)acryloyloxy groups.
• a silane coupling agent having a plurality of (meth)acrylate groups is not included in the polyfunctional (meth)acrylate compound.
• the polyfunctional (meth)acrylate compound does not contain silicon atoms.
• the curable resin composition of the present invention contains (B) a modifier.
• the (B) regulator used in the present invention is the following (b1) and/or (b2): (b1) Monofunctional (meth)acrylate compounds (b2) Epoxy resins having no reactive unsaturated double bonds.
• the monofunctional (meth)acrylate compound used in the present invention is a compound containing one (meth)acryloyloxy group. This (meth)acryloyloxy group reacts with a thiol group in the polyfunctional thiol compound described later.
• a monofunctional (meth)acrylate compound has a structure in which one molecule of a compound having one or more hydroxyl groups is esterified with one molecule of (meth)acrylic acid (there is an unesterified hydroxyl group). may be).
• a silane coupling agent having one (meth)acrylate group is not included in the monofunctional (meth)acrylate compound.
• the monofunctional (meth)acrylate compound does not contain silicon atoms.
• Examples of monofunctional (meth)acrylate compounds include: - ethyl (meth)acrylate, trifluoroethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, isoamyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, isobornyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate Acrylates, Phenoxyethyl (meth)acrylate, Benzyl (meth)acrylate, Tetrahydrofurfuryl (meth
• the monofunctional (meth)acrylate compound preferably has a molecular weight of 100 to 1000, more preferably 120 to 500, even more preferably 140 to 400. It is particularly preferred to include those of ⁇ 300.
• the monofunctional (meth)acrylate compound does not have an epoxy group in its molecule. If the monofunctional (meth)acrylate compound has an epoxy group in its molecule, the crosslink density may increase when heated after UV curing. This is because such a monofunctional (meth)acrylate compound is incorporated into the polymer chain by homopolymerizing the double bond in the (meth)acryloyloxy group during UV curing, and the monofunctional (meth)acrylate compound This is because the epoxy groups of can react with thiol groups in other polymer chains under heating to form new crosslinks.
• the epoxy resin not having a reactive unsaturated double bond [(b2) epoxy resin] used in the present invention is a compound containing one or more epoxy groups and not having a reactive unsaturated double bond.
• the reactive unsaturated double bond means, under UV irradiation or heating, a thiol group in a polyfunctional thiol compound and/or a (meth) acryloyloxy group in a polyfunctional (meth)acrylate compound (exactly, its double bond that can react with the double bond in the Generally, epoxy groups and thiol groups do not react under UV irradiation, but they can react under heating.
• the (b2) epoxy resin usually does not react with the polyfunctional thiol compound under UV irradiation, but when a thermosetting accelerator (in particular, a basic component) is present in the system or on the surface of the adherend, under heating Only its epoxy groups can react with polyfunctional thiol compounds.
• Silane coupling agents containing one or more epoxy groups and having no reactive unsaturated double bonds are not included in epoxy resins having no reactive unsaturated double bonds.
• epoxy resins without reactive unsaturated double bonds do not contain silicon atoms.
• Epoxy resins are roughly divided into monofunctional epoxy resins and polyfunctional epoxy resins.
• the epoxy resin may contain only one of these, or may contain both of them. From the viewpoint of thermosetting properties, (b2) the epoxy resin preferably contains a polyfunctional epoxy resin. (b2) It is particularly preferred that the epoxy resin contains a bifunctional epoxy resin.
• a monofunctional epoxy resin is a compound that contains one epoxy group and does not have a reactive unsaturated double bond.
• monofunctional epoxy resins include n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, p-s-butylphenyl glycidyl ether, styrene oxide, ⁇ -pinene oxide, 4-tert.
• Polyfunctional epoxy resins are compounds containing two or more epoxy groups and no reactive unsaturated double bonds. Polyfunctional epoxy resins are roughly classified into aliphatic polyfunctional epoxy resins and aromatic polyfunctional epoxy resins. Aliphatic polyfunctional epoxy resins are polyfunctional epoxy resins having structures that do not contain aromatic rings.
• aliphatic polyfunctional epoxy resins include: - (poly)ethylene glycol diglycidyl ether, (poly)propylene glycol diglycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, poly Tetramethylene ether glycol diglycidyl ether, glycerin diglycidyl ether, neopentyl glycol diglycidyl ether, 1,2-epoxy-4-(2-methyloxiranyl)-1-methylcyclohexane, cyclohexane type diglycidyl ether, dicyclo diepoxy resins such as pentadiene-type diglycidyl ethers; - triepoxy resins such as trimethylolpropane triglycidyl ether,
• aromatic polyfunctional epoxy resin is a polyfunctional epoxy resin having a structure containing an aromatic ring.
• Many conventional epoxy resins such as bisphenol A type epoxy resin, are of this type.
• aromatic polyfunctional epoxy resins include: - bisphenol A type epoxy resin; - branched polyfunctional bisphenol A type epoxy resins such as p-glycidyloxyphenyldimethyltrisbisphenol A diglycidyl ether; - bisphenol F type epoxy resin; - novolac type epoxy resins; - tetrabromobisphenol A type epoxy resin; - a fluorene-type epoxy resin; - biphenyl aralkyl epoxy resins; - diepoxy resins such as 1,4-phenyldimethanol diglycidyl ether; -biphenyl-type epoxy resins such as 3,3',5,5'-tetramethyl-4,4'-diglycidyloxybiphenyl; -glycidylamine type epoxy resins such as dig
• the epoxy resin includes a liquid epoxy resin.
• liquid epoxy resin means an epoxy resin that is in a liquid physical state at 25°C.
• the modifier is (b1) a monofunctional (meth)acrylate compound.
• the (B) modifier includes either or both of (b1) a monofunctional (meth)acrylate compound and (b2) an epoxy resin.
• the modifier comprises both (b1) a monofunctional (meth)acrylate compound and (b2) an epoxy resin.
• the curable resin composition of the present invention contains a polyfunctional thiol compound.
• the polyfunctional thiol compound used in the present invention includes (meth)acryloyloxy groups (more precisely, double bonds therein) in the polyfunctional (meth)acrylate compound and the monofunctional (meth)acrylate compound, and the reaction It is a compound containing two or more thiol groups that react with epoxy groups in an epoxy resin that does not have a polyunsaturated double bond.
• the polyfunctional thiol compound preferably has 3 or more thiol groups.
• the polyfunctional thiol compound more preferably contains a trifunctional thiol compound and/or a tetrafunctional thiol compound.
• Trifunctional and tetrafunctional thiol compounds are thiol compounds having 3 and 4 thiol groups, respectively.
• the thiol equivalent weight of the polyfunctional thiol compound is preferably 90-150 g/eq, more preferably 90-140 g/eq, even more preferably 90-130 g/eq.
• the polyfunctional thiol compound includes a thiol compound having a hydrolyzable partial structure such as an ester bond in the molecule (i.e. hydrolyzable) and a thiol compound having no such partial structure (i.e. non-hydrolyzable).
• hydrolyzable polyfunctional thiol compounds include trimethylolpropane tris (3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.: TMMP), tris-[(3-mercaptopropionyloxy)-ethyl]- Isocyanurate (manufactured by SC Organic Chemical Co., Ltd.: TEMPIC), pentaerythritol tetrakis (3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.: PEMP), tetraethylene glycol bis (3-mercaptopropionate) (SC Organic Chemical Co., Ltd.: EGMP-4), dipentaerythritol hexakis (3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.: DPMP), pentaerythritol tetrakis (3-mercaptobutyrate) (manufactured by
• non-hydrolyzable polyfunctional thiol compounds include 1,3,4,6-tetrakis (2-mercaptoethyl) glycoluril (manufactured by Shikoku Kasei Co., Ltd.: TS-G), (1,3 , 4,6-tetrakis(3-mercaptopropyl)glycoluril (manufactured by Shikoku Kasei Co., Ltd.: C3 TS-G), 1,3,4,6-tetrakis(mercaptomethyl)glycoluril, 1,3,4, 6-tetrakis(mercaptomethyl)-3a-methylglycoluril, 1,3,4,6-tetrakis(2-mercaptoethyl)-3a-methylglycoluril, 1,3,4,6-tetrakis(3-mercaptopropyl )-3a-methylglycoluril, 1,3,4,6-tetrakis(mercaptomethyl)-3a,6a-d
• the curable resin composition of the present invention - The total number (total amount) of (meth)acryloyloxy contained in the (A) polyfunctional (meth)acrylate compound, - The total number (total amount) of (meth)acryloyloxy contained in the (B) regulator, - The total number (total amount) of epoxy groups contained in the (B) modifier, and - The total number (total amount) of thiol groups contained in the (C) polyfunctional thiol compound
• [(A) the total number of (meth)acryloyloxy groups for the polyfunctional (meth)acrylate compound]/[(C) the total number of thiol groups for the polyfunctional thiol compound] is 0.4 to 0.8
• [(B) the total number of (meth)acryloyloxy groups for the modifier + (B) the total number of epoxy groups for the modifier]/[(C) the total number of thiol groups for the polyfunctional thiol compound] is 0.05 to 0.65.
• the total number of (meth)acryloyloxy groups for the polyfunctional (meth)acrylate compound is the mass (g) of the polyfunctional (meth)acrylate compound contained in the (A) polyfunctional (meth)acrylate compound.
• the (meth)acryloyl equivalent can be calculated as a quotient obtained by dividing the molecular weight of the polyfunctional (meth)acrylate compound by the number of (meth)acryloyloxy groups in one molecule of the polyfunctional (meth)acrylate compound.
• the total number of (meth)acryloyloxy groups for (B) modifier can also be determined in the same manner as for (A) polyfunctional (meth)acrylate compound.
• the curable resin composition of the present invention preferably contains a polyfunctional (meth)acrylate compound having a (meth)acryloyl equivalent of 60 to 300 g/eq, more preferably a (meth)acryloyl equivalent of 70 to 250 g/eq. More preferably, it contains a polyfunctional (meth)acrylate compound having a (meth)acryloyl equivalent of 80 to 220 g/eq.
• total number of (meth) acryloyl groups for (A) polyfunctional (meth) acrylate compound having (meth) acryloyl equivalent of 300 g/eq or less]/[(A) total polyfunctional (meth) acrylate compound (Meth) total number of acryloyl groups] is preferably 0.7 to 1, more preferably 0.8 to 1, still more preferably 0.9 to 1, particularly preferably 0.95 to 1 is.
• the curable resin composition of the present invention It is preferable because the curability of the product tends to be good, and a tough crosslinked structure can be easily obtained in the cured product given by this composition.
• the (A) polyfunctional (meth)acrylate compound having a (meth)acryloyl equivalent of 300 g/eq or less as described above does not have a poly(alkylene glycol) skeleton.
• the curable resin composition of the present invention has a (meth)acryloyl equivalent of 60 to 300 g/eq and does not have a poly(alkylene glycol) skeleton, (A) polyfunctional (meth) Contains acrylate compounds.
• the adhesiveness to the adherend is easily imparted to the cured product provided by this composition (that is, the cured product becomes difficult to peel off from the adherend).
• a poly(alkylene glycol) skeleton means a poly(oxyalkylene) chain composed of two or more oxyalkylene groups, such as a poly(oxyethylene) chain that can be introduced by ethylene oxide (EO) modification, propylene oxide ( PO) refers to poly(oxypropylene) chains and the like that can be introduced by modification.
• EO ethylene oxide
• PO propylene oxide
• the (A) polyfunctional (meth)acrylate compound having a (meth)acryloyl equivalent of 300 g/eq or less as described above preferably has a poly(alkylene glycol) skeleton. This is because when the curable resin composition of the present invention contains such a polyfunctional (meth)acrylate compound (A), the cured product provided by the composition becomes brittle and easily peeled off from the adherend. be. The reason for this is that poly(alkylene glycol) skeletons are present relatively densely in such a polyfunctional (meth)acrylate compound (A). It is speculated that the structures may be formed.
• the curable resin composition of the present invention may contain (A) a polyfunctional (meth)acrylate compound having a (meth)acryloyl equivalent of 60 to 300 g/eq and having a poly(alkylene glycol) skeleton.
• [(meth)acryloyl groups for (A) polyfunctional (meth)acrylate compounds having a (meth)acryloyl equivalent of 60 to 300 g/eq and a poly(alkylene glycol) skeleton The total number]/[(A) the total number of (meth)acryloyl groups for the entire polyfunctional (meth)acrylate compound] is preferably 0.5 or less, more preferably 0.4 or less, and still more preferably It is 0.3 or less, particularly preferably 0.2 or less, and most preferably 0.1 or less. In one aspect of the invention, this ratio is between 0 and 0.5, preferably between 0 and 0.4, more preferably between 0 and 0.3, particularly preferably between 0 and
• the total number of epoxy groups for a modifier is the quotient of the mass (g) of the epoxy resin containing no reactive unsaturated double bonds contained in the modifier divided by the epoxy equivalent weight of that epoxy resin. (the sum of such quotients for each epoxy resin, if epoxy resins without more than one type of reactive unsaturated double bond are involved).
• the epoxy equivalent can be determined by the method described in JIS K7236. If the epoxy equivalent cannot be obtained by this method, it may be calculated as a quotient obtained by dividing the molecular weight of the epoxy resin by the number of epoxy groups in one molecule of the epoxy resin.
• the total number of thiol groups for the polyfunctional thiol compound is the quotient obtained by dividing the mass (g) of the polyfunctional thiol compound contained in the (C) polyfunctional thiol compound by the thiol equivalent of the polyfunctional thiol compound (multiple When multiple functional thiol compounds are included, the sum of such quotients for each polyfunctional thiol compound).
• a thiol equivalent can be determined by an iodometric titration method. This method is widely known and disclosed, for example, in paragraph 0079 of JP-A-2012-153794. If the thiol equivalent cannot be determined by this method, the molecular weight of the polyfunctional thiol compound may be calculated as a quotient divided by the number of thiol groups in one molecule of the polyfunctional thiol compound.
• the curable resin composition has (A) a portion of the polyfunctional (meth)acrylate compound substituted with (B) the modifier, and (C) the amount of the polyfunctional thiol compound
• the total amount of (A) polyfunctional (meth)acrylate compound and (B) modifier is approximately equivalent.
• [(A) the total number of (meth)acryloyloxy groups for the polyfunctional (meth)acrylate compound + the total number of (meth)acryloyloxy groups for (B) the modifier + (B) the total number of (meth)acryloyloxy groups for the modifier total number of epoxy groups]/[total number of thiol groups for (C) polyfunctional thiol compound] is 0.8 to 1.2, preferably 0.9 to 1.1, more preferably 0.95 to 1 .1.
• the curable resin composition of the present invention includes (A) the total number of (meth)acryloyloxy groups for the polyfunctional (meth)acrylate compound, (B) the total number of (meth)acryloyloxy groups for the modifier, ( B) the total number of epoxy groups for the modifier and (C) the total number of thiol groups for the polyfunctional thiol compound satisfies the above conditions, (A) the polyfunctional (meth)acrylate compound, (B) the regulator agent and (C) a polyfunctional thiol compound.
• [(A) the total number of (meth) acryloyloxy groups for the polyfunctional (meth) acrylate compound] / [(C) the total number of thiol groups for the polyfunctional thiol compound] is greater than 0.8, the surrounding Due to expansion and/or shrinkage of the adherend due to changes in temperature, the cured product after UV curing tends to separate from the adherend (that is, poor adhesion reliability).
• [(A) the total number of (meth)acryloyloxy groups for the polyfunctional (meth)acrylate compound]/[(C) the total number of thiol groups for the polyfunctional thiol compound] is preferably 0.45 to 0.7, more preferably 0.5 to 0.7, still more preferably 0.5 to 0.65.
• total number of (meth)acryloyloxy groups for (B) modifier + total number of epoxy groups for (B) modifier]/[total number of thiol groups for (C) polyfunctional thiol compound] is 0. If it is less than 05, the cured product after UV curing tends to peel off from the adherend due to expansion and/or shrinkage of the adherend due to changes in ambient temperature (that is, poor adhesion reliability). On the other hand, [total number of (meth)acryloyloxy groups for (B) modifier + total number of epoxy groups for (B) modifier]/[total number of thiol groups for (C) polyfunctional thiol compound] is 0.
• the content in the cured product of the structure generated by the reaction of (A) the polyfunctional (meth)acrylate compound and (C) the polyfunctional thiol compound is excessively low, so the adhesion after UV curing treatment becomes insufficient.
• [(B) the total number of (meth)acryloyloxy groups for the modifier + (B) the total number of epoxy groups for the modifier]/[(C) the total number of thiol groups for the polyfunctional thiol compound] is , preferably 0.2 to 0.5, more preferably 0.30 to 0.45.
• (B) the modifier consists essentially of (b1) a monofunctional (meth)acrylate compound (substantially free of (b2) epoxy resin).
• [total number of (meth)acryloyloxy groups for (B) modifier + total number of epoxy groups for (B) modifier]/[total number of thiol groups for (C) polyfunctional thiol compound] is It is preferably 0.2 to 0.5, more preferably 0.25 to 0.45. If this ratio is less than 0.2, the effect of the modifier (B) for lowering the crosslink density of the cured product becomes small, and the cured product tends to peel off. On the other hand, if this ratio exceeds 0.5, UV curability may deteriorate.
• the modifier consists essentially of (b2) an epoxy resin (substantially free of (b1) monofunctional (meth)acrylate compounds).
• [total number of (meth)acryloyloxy groups for (B) modifier + total number of epoxy groups for (B) modifier]/[total number of thiol groups for (C) polyfunctional thiol compound] is It is preferably 0.2 to 0.5, more preferably 0.25 to 0.45. If this ratio is less than 0.2, the effect of the modifier (B) for imparting flexibility to the cured product is reduced, and the cured product tends to peel off. On the other hand, if this ratio exceeds 0.5, UV curability may deteriorate.
• the (B) modifier comprises both (b1) a monofunctional (meth)acrylate compound and (b2) an epoxy resin.
• [total number of (meth)acryloyloxy groups for (B) modifier]:[total number of epoxy groups for (B) modifier] is preferably from 1:0.01 to 1:20, More preferably 1:0.05 to 1:15, still more preferably 1:0.1 to 1:10, particularly preferably 1:0.1 to 1:5, most preferably 1: 0.1 to 1:1. Too little [total number of epoxy groups for (B) modifier] relative to [total number of (meth)acryloyloxy groups for (B) modifier] results in poor adhesion after UV curing followed by heat curing. tends to be insufficient.
• the curable resin composition of the present invention contains (D) a photoradical initiator.
• the curable resin composition can be cured by UV irradiation for a short period of time.
• the (D) photoradical initiator that can be used in the present invention is not particularly limited, and known ones can be used.
• photoradical initiators include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, diethoxyacetophenone, 1-(4-isopropylphenyl)-2 -hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2 -propyl)ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin phenyl ether, benzyl dimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone,
• the amount of the photoradical initiator is preferably 0.01 to 10% by mass of the curable resin composition, more preferably 0.05 to 5% by mass, and 0.1 to 3% by mass. % is more preferred.
• each of those parts deforms according to the thermal expansion coefficient of that material. Since the degree of this deformation is not constant for each part due to differences in thermal expansion coefficients, it introduces stresses associated with the deformation of each part into the assembly. The stress that accompanies this deformation acts particularly on the joints of the parts, that is, the cured adhesive. If the cured product is moderately flexible, the cured product will follow the deformation of the components of the assembly, thereby preventing separation of the cured product from the adherend. However, since the cured product provided by the conventional UV-curable adhesive lacks flexibility, it is difficult to follow the deformation of the parts of the assembly, and the cured product sometimes peels off from the adherend.
• Such peeling of the cured product from the adherend is particularly performed when a plurality of adherends are adhered by curing the UV curable adhesive by a heat curing treatment subsequent to the UV curing treatment, and When the material constituting one of the adherends has a glass transition temperature (T g ) lower than the temperature of the heat curing treatment (for example, one of the adherends is polyethylene terephthalate (PET) or polybutylene terephthalate (PBT) manufactured).
• T g glass transition temperature
• a cured product provided by the curable resin composition of the present invention has a lower crosslink density than a cured product provided by a conventional UV-curable adhesive. Such a cured product follows the deformation of the parts of the assembly even if the temperature of the assembly containing it changes, so it is difficult to separate from the adherend.
• a cured product can be obtained by - UV curing treatment by ultraviolet (UV) irradiation, and optionally - thermal curing treatment by heating.
• UV ultraviolet
• the polyfunctional (meth)acrylate compound and the polyfunctional thiol compound are subjected to the UV curing treatment in the presence of (D) a photoradical initiator, - Reaction (1) between a polyfunctional (meth)acrylate compound and a polyfunctional thiol compound, and - Reaction (2) between a polyfunctional (meth)acrylate compound happens. Furthermore, when the product obtained by this UV curing treatment is subjected to a heat curing treatment, - Reaction (3) between a polyfunctional (meth)acrylate compound and a polyfunctional thiol compound happens.
• reaction (1) between a monofunctional (meth)acrylate compound and a polyfunctional thiol compound
• reaction (2) between the polyfunctional (meth)acrylate compound and (b1) the monofunctional (meth)acrylate compound suppress the increase in crosslink density of the cured product.
• reaction (2) extends the polymer chain and widens the spacing of the crosslinks.
• the cured product provided by the curable resin composition of the present invention is a crosslinked polymer.
• (B) modifiers prevents the increase in crosslink density during UV curing and heat curing, so this polymer is less susceptible to conventional curing without (B) modifiers.
• the crosslink density is lower than that of the cured product obtained from the resin composition.
• the epoxy resin remains unreacted in the resulting cured product.
• flexibility is improved by the unreacted (b2) epoxy resin. Therefore, when such a curable resin composition is used, the cured product follows the deformation of the assembly parts caused by changes in ambient temperature, thereby preventing the cured product from peeling from the adherend.
• thermosetting accelerator in particular, a basic component
• subjecting the curable resin composition of the present invention to the above UV curing treatment and heat curing treatment results in (b2) Reaction (4) between the epoxy resin and the polyfunctional thiol compound causes ring-opening of the epoxy groups contained in the (b2) epoxy resin to generate hydroxyl groups.
• This hydroxyl group can contribute to improving the adhesive strength of the cured product to the adherend and thus preventing the cured product from peeling off from the adherend.
• reaction (4) caps the thiol groups contained in the polyfunctional thiol compound, thereby suppressing the formation of new crosslinks. As a result, reaction (4) does not increase the crosslink density of the cured product.
• the epoxy resin is a polyfunctional epoxy resin, the reaction (4) can theoretically form new crosslinks.
• UV curing treatment forms a polymer, which restricts the movement of the (b2) epoxy resin in the system, making it difficult to form new crosslinks.
• the curable resin composition of the present invention may contain optional components other than the above components (A) to (D), such as those described below.
• the curable resin composition of the present invention may further contain (E) a heat curing accelerator, if desired.
• a heat curing accelerator By including a thermosetting accelerator, the curable resin composition of the present invention can be cured in a short time even under low temperature conditions.
• the thermosetting accelerator used in the present invention is not particularly limited as long as it is a curing catalyst for epoxy resins, and known ones can be used.
• the thermal accelerator is a basic substance.
• the thermal curing accelerator is a latent curing catalyst.
• a latent curing catalyst is a compound that is inactive at room temperature and is activated by heating to function as a curing catalyst.
• an imidazole compound that is solid at room temperature a solid-dispersed amine adduct-based latent curing catalyst such as a compound (amine-epoxy adduct system); a reaction product of an amine compound and an isocyanate compound or a urea compound (urea adduct system);
• Typical examples of commercially available latent curing catalysts include "Amicure PN-23” (trade name, manufactured by Ajinomoto Fine-Techno Co., Inc.) and “Amicure PN-40” as amine-epoxy adduct system (amine adduct system).
• Urea adducts include "Fujicure FXE-1000" (trade name, manufactured by T&K TOKA Co., Ltd.), “Fujicure FXR-1030” (trade name, manufactured by T&K TOKA Co., Ltd.), but are not limited to these. Absent.
• the thermosetting accelerator may be used alone or in combination of two or more.
• the heat curing accelerator is preferably a solid-dispersed amine adduct latent curing catalyst.
• the amount of the heat curing accelerator is preferably 0.1 to 20% by mass of the curable resin composition, more preferably 0.5 to 15% by mass, and 1 to 10% by mass. More preferred.
• thermosetting accelerators are provided in the form of a dispersion dispersed in a polyfunctional epoxy resin.
• the amount of the polyfunctional epoxy resin in which it is dispersed is also included in the amount of the (b2) epoxy resin in the curable resin composition of the present invention. Be careful.
• the curable resin composition of the present invention may contain fillers, particularly silica fillers and/or talc fillers, if desired.
• a filler can be added to improve the thermal cycle resistance of the cured product obtained by curing the curable resin composition of the present invention.
• the reason why the thermal cycle resistance is improved by adding a filler is that the coefficient of linear expansion of the cured product is reduced, that is, expansion and contraction of the cured product due to thermal cycles are suppressed. In addition, shrinkage during curing is also suppressed.
• the average particle size is preferably 0.1 to 10 ⁇ m.
• the average particle diameter refers to a volume-based median diameter (d50) measured by a laser diffraction method in accordance with ISO-13320 (2009), unless otherwise specified.
• a filler When a filler is used, its content is preferably 1 to 70% by mass, more preferably 5 to 60% by mass, relative to the total mass of the curable resin composition.
• a filler may be used independently and may be used in combination of 2 or more type.
• Specific examples of fillers other than silica fillers and talc fillers include alumina fillers, calcium carbonate fillers, polytetrafluoroethylene (PTFE) fillers, silicone fillers, acrylic fillers, styrene fillers, etc., but are limited to these. not.
• the filler may be surface-treated.
• the curable resin composition of the present invention may contain a stabilizer, if desired.
• a stabilizer can be added to the curable resin composition of the present invention in order to improve its storage stability and prolong its pot life.
• Various stabilizers known in the art can be used as stabilizers for one-liquid type adhesives. At least one selected is preferred.
• liquid borate compounds include 2,2′-oxybis(5,5′-dimethyl-1,3,2-oxaborinane), trimethylborate, triethylborate, tri-n-propylborate, triisopropylborate, tri-n-butylborate, tripentylborate, triallylborate, trihexylborate, tricyclohexylborate, trioctylborate, trinonylborate, tridecylborate, tridodecylborate, trihexadecylborate, trioctadecylborate, tris( 2-ethylhexyloxy)borane, bis(1,4,7,10-tetraoxaundecyl)(1,4,7,10,13-pentoxatetradecyl)(1,4,7-trioxaundecyl) ) borane, tribenzylborate, triphenylborate, tri-
• liquid borate ester compound is liquid at room temperature (25° C.), it is preferable because the viscosity of the formulation can be kept low.
• aluminum chelate for example, aluminum chelate A (manufactured by Kawaken Fine Chemicals Co., Ltd.) can be used.
• organic acid for example, barbituric acid can be used.
• the amount of the stabilizer is 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount of components (A) to (D). It is preferably from 0.05 to 5 parts by mass, and even more preferably from 0.1 to 3 parts by mass.
• the curable resin composition of the present invention may contain a coupling agent, if desired.
• Addition of a coupling agent, particularly a silane coupling agent, is preferable from the viewpoint of improving adhesive strength.
• a silane coupling agent is an organosilicon compound having two or more different functional groups in its molecule, including a functional group that can chemically bond with an inorganic material and a functional group that can chemically bond with an organic material.
• a functional group capable of chemically bonding with an inorganic material is a hydrolyzable silyl group, and an alkoxy group, especially a silyl group containing a methoxy group and/or an ethoxy group is used as this functional group.
• silane coupling agents As functional groups capable of chemically bonding with organic materials, vinyl groups, epoxy groups, (meth)acrylic groups, styryl groups, unsubstituted or substituted amino groups, mercapto groups, ureido groups, isocyanate groups and the like are used.
• the coupling agent various silane coupling agents having the above functional groups can be used. Specific examples of silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, vinyltrimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene).
• silane coupling agents may be used alone or in combination of two or more.
• silane coupling agent including those used for surface treatment of the filler
• silane coupling agents are not included in components (A) to (D).
• the amount of the coupling agent is 0.01 with respect to 100 parts by mass of the total amount of components (A) to (D) from the viewpoint of improving adhesive strength. It is preferably from 10 parts by mass, more preferably from 0.1 to 5 parts by mass.
• the curable resin composition of the present invention may contain a thixotropic agent, if desired.
• the thixotropic agent used in the present invention is not particularly limited, and known ones can be used.
• Examples of thixotropic agents for use in the present invention include, but are not limited to, silica and the like.
• Silica may be natural silica (silica stone, quartz, etc.) or synthetic silica. Synthetic silica can be synthesized by any method, including dry and wet methods.
• the thixotropic agent may also be surface treated with a surface treatment agent (eg, polydimethylsiloxane). In the present invention, at least part of the thixotropic agent is preferably surface-treated.
• the average particle size of the primary particles of the thixotropic agent is preferably 5 to 50 nm.
• the curable resin composition of the present invention preferably contains 0.1 to 30% by mass, more preferably 1 to 20% by mass, of the thixotropic agent relative to the total mass of the curable resin composition. It is particularly preferable to contain ⁇ 15% by mass.
• the curable resin composition of the present invention may contain other additives, such as carbon black, titanium black, ion trapping agents, leveling agents, if desired, within the scope of the present invention.
• additives such as carbon black, titanium black, ion trapping agents, leveling agents, if desired, within the scope of the present invention.
• Antioxidants, antifoaming agents, viscosity modifiers, flame retardants, colorants, solvents and the like can be added.
• the type and amount of each additive are as per conventional methods.
• the method for producing the curable resin composition of the present invention is not particularly limited.
• components (A) to (D) and, if desired, additives are simultaneously or separately introduced into a suitable mixer and mixed by stirring while melting by heating if necessary to obtain a homogeneous mixture.
• the curable resin composition of the present invention can be obtained.
• the mixer is not particularly limited, but a Raikai machine equipped with a stirring device and a heating device, a Henschel mixer, a three-roll mill, a ball mill, a planetary mixer, a bead mill, or the like can be used. Also, these devices may be used in combination as appropriate.
• the curable resin composition thus obtained is, as described above, It can be converted into a cured product by subjecting it to a UV curing treatment by ultraviolet (UV) irradiation and optionally a thermal curing treatment by heating.
• UV ultraviolet
• the UV curing treatment can be performed by causing the curable resin composition of the present invention to receive a sufficient cumulative amount of ultraviolet rays at room temperature.
• the irradiation intensity is preferably 100-10000 mW/cm 2 , more preferably 1000-9000 mW/cm 2 .
• the wavelength of the ultraviolet rays is preferably 315-450 nm, more preferably 340-430 nm, and particularly preferably 350-380 nm.
• the ultraviolet light source is not particularly limited, and a gallium nitride UV-LED or the like can be used.
• the integrated amount of ultraviolet light received by the curable resin composition of the present invention is preferably 200 mJ/cm 2 or more, more preferably 500 mJ/cm 2 or more, still more preferably 1000 mJ/cm 2 or more, and particularly It is preferably 2000 mJ/cm 2 or more.
• the integrated amount of ultraviolet light can be measured using a measuring instrument commonly used in the relevant field, such as an integrated ultraviolet light meter and a light receiver.
• the integrated amount of light in the ultraviolet wavelength region (310 to 390 nm) with a center wavelength of 365 nm can be measured using an ultraviolet integrating photometer (Ushio Inc., UIT-250) and a light receiver (Ushio Inc., UVD-S365). ) can be measured using
• heat curing treatment can optionally be performed by heating the curable resin composition of the present invention after UV curing treatment under appropriate conditions.
• This heating is preferably carried out at 60 to 120°C, more preferably 60 to 100°C, particularly preferably 70 to 90°C.
• This heating is preferably carried out for 5 to 180 minutes, more preferably for 10 to 120 minutes, particularly preferably for 20 to 70 minutes.
• the curable resin composition of the present invention When the curable resin composition of the present invention is subjected to UV curing treatment as described above, it gives a flexible cured product with a lower crosslink density than conventional cured products. Therefore, when two parts (adherends) are joined using the curable resin composition of the present invention, even if the resulting assembly is deformed due to changes in temperature after UV curing, the The cured product provided by the curable resin composition is difficult to separate from the adherend.
• the curable resin composition of the present invention can be used, for example, as a semiconductor device including various electronic parts, an adhesive for bonding parts constituting electronic parts, or a raw material thereof.
• the present invention also provides an adhesive containing the curable resin composition of the present invention.
• the adhesive of the present invention is suitable, for example, for fixing modules and electronic components.
• the present invention also provides a cured product obtained by curing the curable resin composition or adhesive of the present invention.
• the present invention further provides a semiconductor device containing the cured product of the present invention.
• the present invention further provides a sensor module including the semiconductor device of the present invention.
• Examples 1-36, Comparative Examples 1-8 A curable resin composition was prepared according to the formulation shown in Table 1 by mixing predetermined amounts of each component using a three-roll mill. In Table 1, the amount of each component is expressed in parts by mass (unit: g).
• A Polyfunctional (meth)acrylate compound
• the compounds used as the polyfunctional (meth)acrylate compounds are as follows.
• (B) Modifier (b1) Monofunctional (meth)acrylate compound In the examples and comparative examples, the compounds used as the monofunctional (meth)acrylate compounds are as follows. (B-1): Isobornyl acrylate (trade name: Light Acrylate IBXA, manufactured by Kyoeisha Chemical Co., Ltd., (meth)acrylate equivalent: 208) (B-2): Phenoxyethyl acrylate (trade name: Light Acrylate PO-A, manufactured by Kyoeisha Chemical Co., Ltd., (meth)acrylate equivalent: 192) (B-3): 4-tert-butylcyclohexyl acrylate (trade name: TBCHA, manufactured by KJ Chemicals, (meth)acrylate equivalent: 210) (B-4): Dicyclopentanyl acrylate (trade name: FA513AS, manufactured by Showa Denko Materials Co., Ltd., (meth)acrylate equivalent: 206) (B-5): 3-phenoxybenzyl acrylate (trade name
• (b2) Epoxy Resins Having No Reactive Unsaturated Double Bonds
• (B-9) Bisphenol A type epoxy resin (trade name: JER834, manufactured by Mitsubishi Chemical Holdings Corporation, epoxy equivalent: 250)
• (B') Epoxy Resin Having Reactive Unsaturated Double Bonds Compounds used as epoxy resins having reactive unsaturated double bonds in Examples and Comparative Examples are as follows.
• C- 1 Pentaerythritol tetrakis(3-mercaptopropionate) (trade name: PEMP, manufactured by SC Organic Chemical Co., Ltd., thiol equivalent: 122)
• C-2) Pentaerythritol trippropanethiol (trade name: PEPT, manufactured by SC Organic Chemical Co., Ltd., thiol equivalent: 124)
• C-3) 1,3,4,6-tetrakis(2-mercaptopropyl)glycoluril (trade name: C3 TS-G, manufactured by Shikoku Kasei Co., Ltd., thiol equivalent: 114)
• (D) Photoradical Initiator Compounds used as photoradical initiators in Examples and Comparative Examples are as follows.
• E Heat Curing Accelerator Compounds used as heat curing accelerators in Examples and Comparative Examples are as follows.
• E-1) Amine adduct latent curing catalyst 1 (trade name: Fujicure FXR1121, manufactured by T&K TOKA Co., Ltd.)
• E-2) Amine adduct-based latent curing catalyst 2 (trade name: Amicure PN-23, manufactured by Ajinomoto Fine-Techno Co., Inc.)
• the glass plate coated with the curable resin composition is placed on the PBT plate with the surface coated with the curable resin composition facing down so that the curable resin composition is positioned between the two spacers. Then, the curable resin composition and the spacer were put on the glass plate and the PBT plate so as to be sandwiched between the glass plate and the PBT plate.
• the curable resin composition between the PBT plate and the glass plate was irradiated with a UV LED irradiation device AC475 manufactured by Excelitas Technologies, Inc., with an integrated light amount of 2000 mJ / cm 2 (Ushio Inc. UIT-250 (receiver UVD-365). connection)) and cured by UV irradiation.
• the spacer was removed, and the UV-cured curable resin composition was heated at 80° C. for 60 minutes in a blower dryer.
• the obtained cured product between the PBT plate and the glass plate was allowed to stand at room temperature (20° C.) for 2 hours, and then the degree of peeling of the cured product from the glass plate and/or the PBT plate was evaluated by visual observation.
• the cured product prepared above is observed from the glass plate side, the cured product adhering to both the glass plate and the PBT plate is perceived as a transparent area, and the cured product peeled off from the glass plate and/or the PBT plate. is perceived as a white area.
• the degree of peeling of the cured product was evaluated based on the approximate ratio (%) of the area of the white region to the total area of the clear region and the white region.
• Table 1 shows the results.
• the symbol “ ⁇ ” in the table indicates that the above ratio was substantially 0% in all four tests.
• the symbol “O” in the table indicates that the above ratio was more than 0% and 50% or less in all four tests.
• the symbol “ ⁇ ” in the table indicates that the ratio was more than 0% and 50% or less in 2 or 3 tests out of 4 tests, and the ratio was more than 50% in 1 or 2 tests.
• the curable resin compositions of Examples 1 to 36 containing appropriate amounts of (A) a polyfunctional (meth)acrylate compound, (B) a modifier and (C) a polyfunctional thiol compound. can be cured in a short time by UV irradiation. Further, the resulting cured product is less likely to separate from the adherend even if it is cooled after being heated. Incidentally, the adhesion reliability of the curable resin composition of Example 36 using (A) a polyfunctional (meth) acrylate compound having a poly (alkylene glycol) skeleton is inferior to those of Examples 1 to 35, It was better than Comparative Examples 1-7.
• the curable resin composition of Comparative Example 8 which contains (B′) an epoxy resin having a reactive unsaturated double bond instead of (B) the modifier, can be cured by UV irradiation, but the It can be seen that the cured product is separated from the adherend when it is cooled following heating.
• the curable resin composition of the present invention gives a flexible cured product with a lower crosslink density than conventional ones.
• the curable resin composition of the present invention is not easily peeled off from the adherend even when the ambient temperature changes in the heating and/or cooling process described above after UV curing. useful for

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Epoxy Resins (AREA)
• Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

Priority Applications (3)

Applications Claiming Priority (2)

Publications (1)

Family

ID=84919389

Family Applications (1)

Country Status (4)

Cited By (1)

Citations (9)

Family Cites Families (2)

• 2022
  • 2022-07-08 WO PCT/JP2022/027059 patent/WO2023286699A1/ja not_active Ceased
  • 2022-07-08 JP JP2023534768A patent/JP7828657B2/ja active Active
  • 2022-07-08 KR KR1020247004296A patent/KR20240032947A/ko active Pending
  • 2022-07-08 CN CN202280046568.XA patent/CN117616067A/zh active Pending

Patent Citations (9)

Also Published As

Similar Documents

Legal Events