Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L57/00—Compositions of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C08L57/02—Copolymers of mineral oil hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L93/00—Compositions of natural resins; Compositions of derivatives thereof
  • C08L93/04—Rosin
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
  • C09J133/04—Homopolymers or copolymers of esters

Definitions

• the present invention relates to a curable composition containing a polymer having a reactive silicon group and a cured product thereof.
• An organic polymer having a hydroxyl group or a hydrolyzable group on a silicon atom and having a silicon group capable of forming a siloxane bond by a hydrolysis/condensation reaction (hereinafter also referred to as a "reactive silicon group”) can be used even at room temperature. Reacts with moisture, etc. It is known that a rubber-like cured product can be obtained by cross-linking such an organic polymer through a siloxane condensation reaction of reactive silicon groups.
• the polyoxyalkylene polymer having a reactive silicon group has a relatively low viscosity, so it is excellent in workability when preparing or using a blended composition.
• the resulting cured product has a good balance of performance such as mechanical properties, weather resistance, and dynamic durability, it is widely used for applications such as sealants, adhesives, and paints (see Patent Document 1).
• Patent Document 3 for the purpose of eliminating the drawback that the curing speed of one-component moisture-curable adhesives using modified silicone or acrylic-modified silicone is slow, a curing agent having a high curing speed and excellent adhesiveness is disclosed.
• Group-containing graft copolymers are described.
• Curable compositions such as adhesives or pressure-sensitive adhesives containing an organic polymer having a reactive silicon group have a high viscosity in a relatively low temperature range and good fixability to the adherend, while being heated to a high temperature.
• curable compositions such as adhesives or pressure-sensitive adhesives containing an organic polymer having a reactive silicon group have a high viscosity in a relatively low temperature range and good fixability to the adherend, while being heated to a high temperature.
• there is a demand for physical properties such that the viscosity decreases and workability such as application to a base material is improved.
• the present invention provides a curable composition containing an organic polymer having a reactive silicon group, which has a high viscosity at a relatively low temperature, but the viscosity is significantly reduced at a relatively high temperature.
• An object of the present invention is to provide a curable composition capable of
• a reactive silicon group-containing (meth)acrylic acid ester polymer is composed of a specific monomer and a chain transfer agent, and a tackifier
• the inventors have found that the above problems can be solved by using a resin together, and have completed the present invention.
• the present invention contains a (meth)acrylic acid ester copolymer (A) having a reactive silicon group represented by the following general formula (1), and a tackifying resin (B),
• the monomer component constituting the (meth)acrylic acid ester copolymer (A) is (meth) acrylic acid ester (a1), A polymer (a2) having more than one (meth)acryloyl group in the molecule, and containing a chain transfer agent (a3) having a mercapto group
• the monomer component further contains a monomer (a4) having a reactive silicon group and a polymerizable unsaturated group, and/or the chain transfer agent (a3) having a mercapto group is a reactive silicon It relates to a curable composition further comprising groups.
• R 1 represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms
• X represents a hydroxyl group or a hydrolyzable group
• a is 2 or 3.
• the present invention also relates to a cured product obtained by curing the curable composition.
• a curable composition containing an organic polymer having a reactive silicon group which has a high viscosity at a relatively low temperature, can be cured so that the viscosity can be remarkably reduced at a relatively high temperature.
• a sexual composition can be provided.
• the curable composition according to the present invention can be suitably used as a hot-melt curable composition or an adhesive composition.
• the curable composition according to this embodiment contains at least a (meth)acrylic acid ester copolymer (A) having a reactive silicon group and a tackifying resin (B).
• the (meth)acrylic ester-based copolymer (A) has a reactive silicon group represented by the following general formula (1) at the molecular chain terminal and/or side chain (non-terminal site).
• —SiR 1 3-a X a (1) (Wherein, R 1 represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms; X represents a hydroxyl group or a hydrolyzable group; a represents 2 or 3.)
• the number of carbon atoms in the hydrocarbon group of R 1 is preferably 1-10, more preferably 1-5, even more preferably 1-3.
• Specific examples of R 1 include methyl group, ethyl group, chloromethyl group, methoxymethyl group and N,N-diethylaminomethyl group. Preferred are methyl group, ethyl group, chloromethyl group and methoxymethyl group, and more preferred are methyl group and methoxymethyl group.
• Examples of X include halogen, alkoxy group, acyloxy group, ketoximate group, amino group, amide group, acid amide group, aminooxy group, mercapto group and alkenyloxy group.
• an alkoxy group is more preferable, and a methoxy group and an ethoxy group are particularly preferable, since they are moderately hydrolyzable and easy to handle.
• Specific examples of the reactive silicon group possessed by the (meth)acrylate copolymer (A) include a trimethoxysilyl group, a triethoxysilyl group, a tris(2-propenyloxy)silyl group, and a triacetoxysilyl group.
• dimethoxymethylsilyl group diethoxymethylsilyl group, dimethoxyethylsilyl group, (chloromethyl)dimethoxysilyl group, (chloromethyl)diethoxysilyl group, (methoxymethyl)dimethoxysilyl group, (methoxymethyl)diethoxysilyl group (N,N-diethylaminomethyl)dimethoxysilyl group, (N,N-diethylaminomethyl)diethoxysilyl group, and the like.
• methyldimethoxysilyl, trimethoxysilyl, triethoxysilyl, (chloromethyl)dimethoxysilyl, (methoxymethyl)dimethoxysilyl, (methoxymethyl)diethoxysilyl, (N,N- Diethylaminomethyl)dimethoxysilyl group is preferred because it exhibits high activity and gives a cured product with good mechanical properties, and a trimethoxysilyl group and a triethoxysilyl group are more preferred because a cured product with a high Young's modulus is obtained. , and a trimethoxysilyl group are more preferred.
• the reactive silicon group equivalent of the (meth)acrylate copolymer (A) is not particularly limited, but is preferably 0.2 mmol/g or more, more preferably 0.5 mmol/g or more, and 0.6 mmol/g. The above is more preferable.
• the reactive silicon group equivalent is preferably 2.0 mmol/g or less, and more preferably 1.0 mmol/g or less from the viewpoint of suppressing a decrease in elongation of the cured product.
• the reactive silicon group equivalent is particularly preferably 0.5 mmol/g or more and 1.0 mmol/g or less.
• the (meth)acrylic acid ester-based copolymer (A) includes at least a (meth)acrylic acid ester (a1), a polymer (a2) having more than one (meth)acryloyl group in the molecule, and a mercapto It is a polymer formed by copolymerizing a monomer component containing a chain transfer agent (a3) having a group.
• “(meth)acryl” means "acryl and/or methacryl”.
• the (meth)acrylic ester-based copolymer (A) has reactive silicon groups by satisfying either one or both of the following two conditions.
• Condition 1 The monomer component further contains a monomer (a4) having a reactive silicon group and a polymerizable unsaturated group.
• Condition 2 The chain transfer agent (a3) having a mercapto group further has a reactive silicon group.
• a curable composition containing a reactive silicon group-containing (meth)acrylic acid ester copolymer (A) that satisfies the above requirements has a high viscosity at a relatively low temperature, but can be cured at a relatively high temperature. Then the viscosity can be significantly reduced.
• the number of reactive silicon groups introduced under Condition 2 is greater than the number of reactive silicon groups introduced under Condition 1.
• the reactive silicon group equivalent introduced under Condition 1 is preferably 0.01 mmol/g or more, more preferably 0.03 mmol/g or more, and even more preferably 0.05 mmol/g or more.
• the reactive silicon group equivalent introduced under Condition 1 is preferably 1.0 mmol/g or less, more preferably 0.5 mmol/g or less.
• the reactive silicon group equivalent introduced under Condition 2 is preferably 0.2 mmol/g or more, more preferably 0.3 mmol/g or more, and even more preferably 0.5 mmol/g or more.
• the reactive silicon group equivalent introduced under Condition 2 is preferably 1.5 mmol/g or less, more preferably 1.0 mmol/g or less.
• the reactive silicon group equivalent introduced under Condition 1 is preferably 0.1 mmol/g or more, more preferably 0.2 mmol/g or more, and even more preferably 0.3 mmol/g or more. Further, the reactive silicon group equivalent introduced under Condition 1 is preferably 1.8 mmol/g or less, more preferably 1.0 mmol/g or less.
• the reactive silicon group equivalent introduced under Condition 2 is preferably 0.1 mmol/g or more, more preferably 0.2 mmol/g or more, and even more preferably 0.3 mmol/g or more. In addition, the reactive silicon group equivalent introduced under Condition 2 is preferably 1.5 mmol/g or less, more preferably 1.0 mmol/g or less.
• the (meth)acrylic acid ester (a1) is not particularly limited, and examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, (meth) ) n-butyl acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) ) n-heptyl acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, (meth)
• the content of the (meth)acrylic acid ester (a1) is 30% relative to the total amount of the monomer components constituting the (meth)acrylic acid ester copolymer (A). It is preferably at least 40% by weight, even more preferably at least 45% by weight.
• the upper limit is preferably 80% by weight or less, more preferably 70% by weight or less, and even more preferably 65% by weight or less.
• the (meth)acrylic acid ester (a1) preferably contains a (meth)acrylic acid alkyl ester in which the alkyl has 1 to 4 carbon atoms, since a cured product with high strength can be obtained.
• the (meth)acrylic acid alkyl ester in which the alkyl has 1 to 4 carbon atoms is contained in an amount of 30% by weight or more based on the total amount of the monomer components constituting the (meth)acrylic acid ester-based copolymer (A). 35% by weight or more is more preferable, and 40% by weight or more is even more preferable.
• the upper limit is preferably 70% by weight or less, more preferably 60% by weight or less, and even more preferably 55% by weight or less.
• (Meth)acrylic acid ester (a1) can form a hard polymer chain to obtain a cured product with high strength. It preferably contains at least one monomer selected from the group consisting of dicyclopentanyl. In particular, among the total amount of the monomer components excluding the polymer (a2), at least one selected from the group consisting of methacrylate, isobornyl acrylate, dicyclopentenyl acrylate, and dicyclopentanyl acrylate The proportion of the seed monomer is preferably 60% by weight or more, more preferably 70% by weight or more.
• Polymer (a2) having more than one (meth)acryloyl group in the molecule is itself a polymer, it is one of the monomers constituting the (meth)acrylate copolymer (A). Since the polymer (a2) has a (meth)acryloyl group, it can be copolymerized with other monomers such as (meth)acrylic acid ester (a1). Moreover, since the polymer (a2) has more than one (meth)acryloyl group in one molecule, it can function as a so-called polyfunctional macromonomer.
• the main chain skeleton (second molecular chain described later) of the polymer (a2) is mainly composed of the (meth)acrylic acid ester (a1) in the (meth)acrylic acid ester-based copolymer (A) 2 It can form a structure that crosslinks the molecular chains (the first molecular chain described later).
• the polymer (a2) is also referred to as polyfunctional macromonomer (a2).
• the (meth)acryloyl group possessed by the polyfunctional macromonomer (a2) is preferably represented by the following formula (4).
• CH2 C( R7 )-COO-Z (4)
• R 7 represents hydrogen or a methyl group.
• Z represents the main chain skeleton of the polyfunctional macromonomer (a2).
• the polyfunctional macromonomer (a2) has an average of more than one (meth)acryloyl group in one molecule.
• the average number of (meth)acryloyl groups per molecule of the polyfunctional macromonomer (a2) is preferably 1.1-5, more preferably 1.3-4, and 1.6-2. 5 is more preferred, and 1.8 to 2.0 is particularly preferred.
• the polyfunctional macromonomer (a2) may have only an acryloyl group, may have only a methacryloyl group, or may have both an acryloyl group and a methacryloyl group. You may
• the polyfunctional macromonomer (a2) can have (meth)acryloyl groups at either or both of the molecular chain terminals and side chains of the polymer. From the standpoint of excellent mechanical properties, it is preferred to have it at the end of the molecular chain. In particular, it is particularly preferred that the polyfunctional macromonomer (a2) has a linear main chain skeleton and (meth)acryloyl groups at both ends of the molecular chain.
• the main chain skeleton of the polyfunctional macromonomer (a2) is preferably a (meth)acrylate polymer or a polyoxyalkylene polymer.
• the polyfunctional macromonomer (a2) whose main chain skeleton is a (meth)acrylic acid ester polymer is denoted as (a2′), and the main chain skeleton is a polyoxyalkylene polymer.
• Macromonomer (a2) is denoted as (a2′′).
• the monomer constituting the main chain skeleton of the polyfunctional macromonomer (a2') is not particularly limited, and various (meth)acrylic monomers can be used.
• (meth)acrylic monomers include (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, ( meth) n-butyl acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, ( meth)n-heptyl acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)
• monomers that are copolymerizable with the (meth)acrylic monomer may be used in combination.
• Other monomers include, for example, styrene-based monomers such as styrene, vinyltoluene, ⁇ -methylstyrene, chlorostyrene, and styrenesulfonic acid; fluorine-containing vinyls such as perfluoroethylene, perfluoropropylene, and vinylidene fluoride; Monomer; Maleic acid and its derivatives such as maleic acid, maleic anhydride, maleic acid monoalkyl ester, and maleic acid dialkyl ester; Fumaric acid and its derivatives such as fumaric acid, fumaric acid monoalkyl ester, and fumaric acid dialkyl ester; Maleimide-based monomers such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, o
• the main chain skeleton of the polyfunctional macromonomer (a2') is preferably composed of a soft polymer.
• the monomer component forming the main chain skeleton of the polyfunctional macromonomer (a2′) is an acrylate ester (however, isobornyl acrylate, dicyclopentenyl acrylate, and dicyclopentaacrylate excluding nil) is preferably 60% by weight or more, more preferably 70% by weight or more. The upper limit may be 100% by weight.
• the method for synthesizing the polyfunctional macromonomer (a2') is not particularly limited, for example, the method shown below can be used. The following methods may be used in combination.
• a copolymer obtained by copolymerizing a monomer having a reactive functional group (V group) e.g., acrylic acid, 2-hydroxyethyl acrylate
• V group e.g., acrylic acid, 2-hydroxyethyl acrylate
• a compound having a functional group and (meth)acryloyl group that reacts with group V eg, 2-isocyanatoethyl (meth)acrylate.
• (ii) A method of polymerizing a (meth)acrylic monomer by a living radical polymerization method and then introducing (meth)acryloyl groups to the ends of the molecular chain (preferably both ends of the molecular chain).
• a living radical polymerization method uses a cobalt porphyrin complex as shown, for example, in J. Am. Chem. Soc., 1994, 116, 7943.
• Atom Transfer Radical Polymerization using a transition metal complex as a catalyst, and the like. Atom transfer radical polymerization is most preferred because it facilitates the introduction of (meth)acryloyl groups to the ends of the molecular chains.
• the polyoxyalkylene polymer that is the main chain skeleton of the polyfunctional macromonomer (a2′′) is not particularly limited, and examples include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, and polyoxyethylene. -polyoxypropylene copolymer, polyoxypropylene-polyoxybutylene copolymer, etc. Among them, polyoxypropylene is preferred.
• the main chain skeleton of the polyoxyalkylene polymer may be linear or branched, but is preferably linear.
• the method for synthesizing the polyfunctional macromonomer (a2′′) is not particularly limited, for example, a polyoxyalkylene polymer having more than one hydroxyl group in the molecule (preferably, a linear A method of preparing a polyoxyalkylene-based polymer) and introducing a (meth)acryloyl group using the hydroxyl group.
• a polyoxyalkylene polymer having a hydroxyl group is reacted with a compound having an isocyanate group and a (meth)acryloyl group to form a urethane bond.
• a compound having an isocyanate group and a (meth)acryloyl group can introduce a (meth)acryloyl group.
• Specific examples of the compound having an isocyanate group and a (meth)acryloyl group include isocyanatoethyl (meth)acrylate, isocyanatopropyl (meth)acrylate, isocyanatobutyl (meth)acrylate, isocyanatohexyl (meth)acrylate, and the like. be done.
• a polyoxyalkylene polymer having a hydroxyl group is reacted with a diisocyanate compound to introduce an isocyanate group into the polymer, and then the hydroxyl group and ( A (meth)acryloyl group can also be introduced by reacting a compound having a meth)acryloyl group.
• the diisocyanate compound include tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate, and the like.
• the compound having a hydroxyl group and a (meth)acryloyl group include, for example, hydroxybutyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxyethyl (meth)acrylate, polyethylene glycol mono(meth)acryl acid esters, polypropylene glycol mono(meth)acrylic acid esters, and the like.
• a polyoxyalkylene polymer having a hydroxyl group is reacted with an acid anhydride to introduce a carboxyl group into the polymer, followed by epoxy
• a (meth)acryloyl group can also be introduced by reacting the group with a compound having a (meth)acryloyl group.
• the acid anhydride include succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, and methyl anhydride.
• Specific examples of the compound having an epoxy group and a (meth)acryloyl group include glycidyl (meth)acrylate.
• Still another example of the method for synthesizing the polyfunctional macromonomer (a2′′) is a method of dehydration condensation of methacrylic acid and acrylic acid on a polyoxyalkylene polymer having a hydroxyl group.
• methacrylic acid chloride, methacrylic acid bromide, methacrylic acid iodide, acrylic acid chloride, acrylic acid bromide, acrylic acid iodide, etc. are reacted with a polyoxyalkylene polymer having a hydroxyl group. There is a way.
• the number average molecular weight of the polyfunctional macromonomer (a2) is not particularly limited, but is preferably 500 or more from the viewpoint of achieving both the mechanical properties and adhesiveness exhibited by the cured product and the ease of handling of (a2). ,000 or more is more preferable, and 2,000 or more is even more preferable. Also, it is preferably 100,000 or less, more preferably 50,000 or less, even more preferably 40,000 or less, and particularly preferably 30,000 or less.
• the weight average molecular weight of the polyfunctional macromonomer (a2) is not particularly limited, but is preferably 500 or more from the viewpoint of achieving both the mechanical properties and adhesive properties exhibited by the cured product and the ease of handling of (a2). ,000 or more is preferable, and 2,500 or more is more preferable. Also, it is preferably 130,000 or less, more preferably 65,000 or less, even more preferably 60,000 or less, and even more preferably 30,000 or less.
• the molecular weight distribution (weight average molecular weight (Mw)/number average molecular weight (Mn)) of the polyfunctional macromonomer (a2) is not particularly limited, but is preferably narrow, specifically less than 2.0. 6 or less is more preferable, 1.5 or less is more preferable, 1.4 or less is even more preferable, 1.3 or less is particularly preferable, and 1.2 or less is most preferable.
• the number average molecular weight (Mn) and weight average molecular weight (Mw) of the polyfunctional macromonomer (a2) are values measured by GPC (converted to polystyrene), and detailed measurement methods are described in Examples.
• the (meth)acrylic acid ester-based copolymer (A) has a molecular chain mainly composed of the (meth)acrylic acid ester (a1) and a molecule derived from the main chain skeleton of the polyfunctional macromonomer (a2). have chains. Since the polyfunctional macromonomer (a2) has more than one (meth)acryloyl group in one molecule, which is a polymerizable group, the (meth)acrylic acid ester copolymer (A) is a polyfunctional macro It may have a structure in which more than one molecular chain mainly composed of the (meth)acrylic acid ester (a1) is bonded to one molecular chain derived from the main chain skeleton of the monomer (a2).
• the molecular chain derived from the main chain skeleton of the polyfunctional macromonomer (a2) is introduced into either the terminal or the side chain (non-terminal portion) of the molecular chain mainly composed of the (meth)acrylic acid ester (a1). However, from the viewpoint of adhesiveness, it is preferably introduced into the side chain.
• an H-type structure can be formed in which molecular chains composed mainly of (meth)acrylic acid ester (a1) are bonded.
• the molecular chain derived from the main chain skeleton of the polyfunctional macromonomer (a2) corresponds to the horizontal bar of H, and the molecular chain mainly composed of the (meth)acrylic acid ester (a1) Corresponds to the two vertical bars included.
• the H-shaped structure will be described later.
• the content of the polyfunctional macromonomer (a2) is preferably 1% by weight or more and 70% by weight or less with respect to the total amount of the monomer components constituting the (meth)acrylate copolymer (A). , 5 wt % or more and 60 wt % or less, more preferably 10 wt % or more and 50 wt % or less, and particularly preferably 15 wt % or more and 45 wt % or less.
• the content of the polyfunctional macromonomer (a2) is preferably less than 35% by weight.
• the content of the polyfunctional macromonomer (a2) is preferably 35% by weight or more.
• the content of the polyfunctional macromonomer (a2) is 0.05 mol% or more and 6.0 mol% or less in the monomer components constituting the (meth)acrylate copolymer (A). It preferably accounts for 0.1 mol % or more and 2.3 mol % or less, and even more preferably 0.2 mol % or more and 1.5 mol % or less. Within the above range, the effect of using the polyfunctional macromonomer (a2) can be achieved while suppressing gelation during the synthesis of the (meth)acrylate copolymer (A).
• the average number of polyfunctional macromonomers (a2) per molecule of (meth)acrylic acid ester copolymer (A) is 0.05 or more and 2.0 or less from the viewpoint of the strength of the resulting cured product. is preferred.
• the lower limit is more preferably 0.07 or more, and even more preferably 0.08 or more.
• the upper limit is more preferably 1.5 or less, even more preferably 1.0 or less.
• the average number can be calculated by the following formula.
• a polyfunctional macromonomer (a2) is used by including a chain transfer agent (a3) having a mercapto group in the monomer component constituting the (meth)acrylate copolymer (A). Nevertheless, the molecular weight distribution of the (meth)acrylic acid ester copolymer (A) is relatively narrowed, and gelation is suppressed when synthesizing the (meth)acrylic acid ester copolymer (A). can do. In addition, it becomes possible to preferentially synthesize a polymer molecule in which one molecule of the polyfunctional macromonomer (a2) is introduced into one molecule of the (meth)acrylate copolymer (A).
• the chain transfer agent (a3) having a mercapto group may not have a reactive silicon group, but preferably has a reactive silicon group.
• the reactive silicon group is a reactive silicon group represented by formula (1) described above.
• a reactive silicon group can be introduced at the end of the molecular chain mainly composed of the (meth)acrylic acid ester (a1). .
• chain transfer agent (a3) having a mercapto group is not particularly limited, examples thereof include 3-mercaptopropyldimethoxymethylsilane, 3-mercaptopropyltrimethoxysilane, (mercaptomethyl)dimethoxymethylsilane, (mercaptomethyl)trimethoxysilane. , n-dodecylmercaptan, tert-dodecylmercaptan, laurylmercaptan and the like.
• the content of the chain transfer agent (a3) having a mercapto group is 1% by weight or more and 15% by weight or less with respect to the total amount of the monomer components constituting the (meth)acrylate copolymer (A). is preferred, more preferably 2 wt % or more and 10 wt % or less, and more preferably 3 wt % or more and 8 wt % or less.
• the content of the chain transfer agent (a3) having a mercapto group accounts for 0.1 mol% or more and 20 mol% or less of the monomer components constituting the (meth)acrylate copolymer (A). preferably 0.4 mol% or more and 15 mol% or less, more preferably 0.5 mol% or more and 10 mol% or less, and 0.6 mol% or more and 8 mol% or less is particularly preferred. Within the above range, the effect of using the chain transfer agent (a3) having a mercapto group can be achieved.
• the content of the polyfunctional macromonomer (a2) and the content of the chain transfer agent (a3) having a mercapto group improve the strength of the resulting cured product, so that the polyfunctional macromonomer (a2)/mercapto group
• the molar ratio of the chain transfer agent (a3) to have is preferably 0.03 or more, more preferably 0.05 or more, still more preferably 0.09 or more, and particularly preferably 0.1 or more.
• the upper limit of the molar ratio is not particularly limited, it is preferably 1 or less, more preferably 0.5 or less, and even more preferably 0.3 or less.
• the (meth)acrylic acid ester copolymer (A) may have a substituent derived from the chain transfer agent (a3) having a mercapto group (structure represented by -SR 8 described later). Therefore, it may contain sulfur atoms.
• the sulfur atom concentration in the (meth)acrylate copolymer (A) is preferably 700 ppm or more and 20,000 ppm or less, more preferably 1,000 ppm or more and 15,000 ppm or less.
• the method for measuring the sulfur atom concentration is not particularly limited. It can be measured by known elemental analysis methods such as organic elemental analysis and fluorescent X-ray analysis. Further, the sulfur atom concentration is calculated from the total amount of the monomer components used in the production of the (meth)acrylate copolymer (A) and the amount (a3) of the chain transfer agent having a mercapto group. It may be a theoretical value.
• the monomer (a4) having a reactive silicon group and a polymerizable unsaturated group is an arbitrary monomer and may not be used, but is preferably used.
• the reactive silicon group possessed by the monomer (a4) is the reactive silicon group represented by formula (1) described above.
• Examples of the monomer (a4) having a reactive silicon group and a polymerizable unsaturated group include 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-( Compounds having a (meth)acryloxy group and a reactive silicon group, such as meth)acryloxypropyldimethoxymethylsilane, (meth)acryloxymethyltrimethoxysilane, and (meth)acryloxymethyldimethoxymethylsilane; vinyltrimethoxysilane, vinyl Examples include compounds having a vinyl group and a reactive silicon group such as triethoxysilane. These compounds may use only 1 type and may use 2 or more types together.
• the content of the monomer (a4) is 0.1 weight with respect to the total amount of the monomer components constituting the (meth)acrylic acid ester copolymer (A) % or more and 50 wt % or less, more preferably 0.5 wt % or more and 30 wt % or less, even more preferably 1 wt % or more and 20 wt % or less, and particularly preferably 2 wt % or more and 15 wt % or less.
• the content of the monomer (a4) is preferably 10% by weight or less from the viewpoint of improving the thixotropy of the curable composition and obtaining a cured product with high elongation.
• the monomer component constituting the (meth)acrylic acid ester-based copolymer (A) contains another monomer (b5) that does not correspond to any of (a1) to (a4) detailed above. It may contain, or may not contain.
• Other monomers (b5) include (meth)acrylic esters (a1) and monomers (a4) having a reactive silicon group and a polymerizable unsaturated group (meth)acrylic monomers and monomers other than the (meth)acrylic monomer. Specifically, other monomers described above for multifunctional macromonomer (a2') can be used.
• the number average molecular weight of the (meth)acrylic acid ester copolymer (A) is not particularly limited, but is preferably 500 or more and 50,000 or less, preferably 500 or more and 30,000 or less, in terms of polystyrene equivalent molecular weight by GPC measurement. More preferably, 1,000 or more and 10,000 or less are particularly preferable. Among them, the number average molecular weight is preferably 7,000 or less because a (meth)acrylate copolymer (A) having a low viscosity can be obtained. In addition, the number average molecular weight is preferably 3,500 or less because good adhesiveness can be exhibited with low viscosity.
• the weight average molecular weight of the (meth)acrylic acid ester copolymer (A) is not particularly limited, but the polystyrene equivalent molecular weight by GPC measurement is preferably 500 or more and 80,000 or less, and 3,000 or more and 70,000. The following are more preferable, and 5,000 or more and 65,000 or less are particularly preferable. Among them, the weight-average molecular weight is preferably 20,000 or less because a cured product having a low viscosity and a high strength can be obtained.
• the value calculated by the following formula is 1.1 or more. is preferred.
• the fact that the value calculated by the above formula is 1.1 or more means that the average number of introduction of the polyfunctional macromonomer (a2) in one molecule of the (meth)acrylic acid ester copolymer (A) is large. It means that the strength of the resulting cured product can be further improved.
• the value calculated by the above formula is preferably 1.1 or more, more preferably 1.2 or more, and even more preferably 1.3 or more.
• the upper limit is not particularly limited, it is preferably 10 or less, more preferably 5 or less.
• the molecular weight distribution of the (meth)acrylic acid ester copolymer (A) is not particularly limited, but from the viewpoint of making the (meth)acrylic acid ester copolymer (A) low in viscosity, it is 3.0 to 11.0. The following is preferable, 3.2 to 10.0 is more preferable, and 3.4 to 8.0 is even more preferable.
• the molecular weight distribution of the (meth)acrylate copolymer (A) can be determined from the number average molecular weight and weight average molecular weight obtained by GPC measurement.
• the (meth)acrylate copolymer (A) may contain a triblock copolymer.
• the triblock copolymer comprises a structure in which two first molecular chains are linked via one second molecular chain.
• the first molecular chain is mainly composed of a molecular chain obtained by polymerizing the (meth)acrylic acid ester (a1), and the second molecular chain is composed of the main chain skeleton of the polyfunctional macromonomer (a2). .
• the first molecular chain is a molecular chain formed by copolymerization of (a1), (meth)acryloyl groups in (a2), (a3), optional (a4), and optional other monomers. .
• a reactive silicon group is attached to this first molecular chain.
• the chain transfer agent (a3) having a mercapto group has a reactive silicon group
• a reactive silicon group is bonded to the end of the first molecular chain, and a monomer having a reactive silicon group and a polymerizable unsaturated group
• a4 is used, a reactive silicon group is attached to the non-terminal portion of the first molecular chain.
• the second molecular chain corresponds to the main chain skeleton of the (meth)acrylate polymer or polyoxyalkylene polymer in the polyfunctional macromonomer (a2).
• the bonding method of two first molecular chains and one second molecular chain is different from that of ordinary ABA-type triblock copolymers, and both ends of the second molecular chain are respectively non-terminal sites of the first molecular chain.
• the triblock copolymer comprises an H-type structure, where two vertical bars in H correspond to two first molecular chains and one horizontal bar in H corresponds to one second molecular chain. It corresponds to a molecular chain.
• the (meth)acrylic acid ester-based copolymer (A) is not limited to a triblock copolymer with an H-type structure, and in addition to a triblock copolymer with an H-type structure, It may contain a block copolymer having Block copolymers having such other structures include, for example, block copolymers having a structure in which three first molecular chains are bonded via two second molecular chains.
• the first molecular chain and the second molecular chain have an ester bond derived from the (meth)acryloyl group in the polyfunctional macromonomer (a2) (that is, an ester bond corresponding to the ester bond in the formula (4)). are connected through
• the first molecular chain is composed of a hard polymer and the second molecular chain is composed of a soft polymer, it is preferable because a cured product with high strength and high elongation can be obtained.
• a hard polymer refers to a polymer with a high glass transition temperature.
• a soft polymer refers to a polymer with a low glass transition temperature.
• the monomer components constituting the first molecular chain are methacrylic acid esters, It preferably contains at least one monomer selected from the group consisting of isobornyl acrylate, dicyclopentenyl acrylate, and dicyclopentanyl acrylate.
• the ratio of the monomers to the total amount of monomer components constituting the first molecular chain is preferably 60% by weight or more, more preferably 70% by weight or more. The upper limit may be 100% by weight.
• the second molecular chain when the second molecular chain is composed of a soft polymer, the second molecular chain may be the main chain skeleton of a polyoxyalkylene-based polymer, or a (meth)acrylic acid ester-based polymer.
• the monomer component constituting the second molecular chain (the monomer component forming the main chain skeleton of (a2′)) is an acrylate ester (however, isobornyl acrylate, dicycloacrylate excluding pentenyl and dicyclopentanyl acrylate).
• the acrylic acid ester accounts for preferably 60% by weight or more, more preferably 70% by weight or more, of the monomer components constituting the second molecular chain.
• the upper limit may be 100% by weight.
• the first molecular chain is a molecular chain formed by reacting the chain transfer agent (a3) having a mercapto group, at either end of the first molecular chain, as a substituent derived from (a3) , —SR 8 .
• S represents a sulfur atom
• R8 represents a hydrocarbon group which may have a reactive silicon group.
• the hydrocarbon group includes an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and the like.
• the said reactive silicon group is a reactive silicon group represented by Formula (1) mentioned above.
• Specific examples of R 8 include reactive silicon group-containing methyl group, reactive silicon group-containing propyl group, n-dodecyl group, tert-dodecyl group, lauryl group and the like.
• the molar ratio of the main chain skeleton of the polyfunctional macromonomer (a2) to the -SR 8 is preferably 0.03 or more, more preferably 0.05 or more, and 0.05 or more. 09 or more is more preferable, and 0.1 or more is particularly preferable.
• the upper limit of the molar ratio is not particularly limited, it is preferably 1 or less, more preferably 0.5 or less, and even more preferably 0.3 or less.
• the (meth)acrylate copolymer (A) can be produced by polymerizing the above monomer components.
• the polymerization method is not particularly limited, but may be general free radical polymerization. According to the present embodiment, although it is a free radical polymerization, the polymerization can be controlled, and the (meth)acrylic acid ester copolymer (A), which is a block copolymer, can be produced. , its molecular weight distribution can be relatively narrow.
• Polymerization initiators that can be used in the free radical polymerization include, for example, 2,2′-azobis(2-methylbutyronitrile), dimethyl 2,2′-azobis(2-methylpropionate), 2,2 '-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis [N- (2-propenyl) -2- methyl propionamide], 1,1'-azobis (cyclohexane-1-carbonitrile) and other azo compounds; benzoyl peroxide, isobutyryl peroxide, isononanoyl peroxide, decanoyl peroxide, lauroyl peroxide, para diacyl peroxides such as chlorobenzoyl peroxide and di(3,5,5-trimethylhexanoyl) peroxide; diisopropyl purge carbonate, di-sec-butyl purge carbonate, di-2
• solvents that can be used in the free radical polymerization include aromatic solvents such as toluene, xylene, styrene, ethylbenzene, paradichlorobenzene, di-2-ethylhexyl phthalate, and di-n-butyl phthalate; hexane, Aliphatic hydrocarbon solvents such as heptane, octane, cyclohexane, and methylcyclohexane; carboxylic acid ester compounds such as butyl acetate, n-propyl acetate, and isopropyl acetate; ketone compounds such as methyl isobutyl ketone and methyl ethyl ketone; dimethyl carbonate, diethyl carbonate, etc.
• aromatic solvents such as toluene, xylene, styrene, ethylbenzene, paradichlorobenzene, di-2-eth
• alcohol compounds such as n-propanol, 2-propanol, n-butanol, 2-butanol, isobutanol, tert-butanol, and amyl alcohol; Among them, alcohol compounds are preferable because they have a narrow molecular weight distribution.
• Aromatic solvents are preferred because of their high dissolving power.
• Aliphatic hydrocarbon solvents are preferred because of their low odor.
• the molecular weight distribution of the (meth)acrylate copolymer (A) is affected by the amount of the chain transfer agent (a3) added and the solvent. When the amount of chain transfer agent (a3) added is 3% by weight or less, it is greatly affected by the type of solvent. When it is desired to obtain a (meth)acrylate copolymer (A) with a narrow molecular weight distribution, isobutanol is preferably used as the solvent.
• the (meth)acrylic acid ester copolymer (A) uses a monomer (a4) having a reactive silicon group and a polymerizable unsaturated group, or reacts in addition to a mercapto group By using a chain transfer agent (a3) having a reactive silicon group, it will have a reactive silicon group. Both methods may be used in combination.
• a monomer (a4) having a reactive silicon group and a polymerizable unsaturated group reactive silicon is randomly added to the side chains of the molecular chain mainly composed of the (meth)acrylic acid ester (a1) groups can be introduced.
• a chain transfer agent (a3) having a reactive silicon group in addition to a mercapto group a reactive silicon group is added to the end of the molecular chain mainly composed of the (meth)acrylic acid ester (a1). can be introduced.
• a method of reacting an isocyanate silane compound having a reactive silicon group, or after copolymerizing glycidyl acrylate, an aminosilane compound having a reactive silicon group is used.
• a reaction method and the like can be exemplified.
• a (meth)acrylic ester copolymer obtained by a living radical polymerization method is easy to introduce a functional group into the terminal of the polymer, and by modifying this, a reactive silicon group can be introduced into the terminal of the polymer.
• Examples of the compound having a reactive silicon group and a functional group that reacts with group V used in method (iii) include 3-isocyanatopropyldimethoxymethylsilane, 3-isocyanatopropyltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane.
• any modification reaction can be used.
• the curable composition according to the present embodiment has a high viscosity at a relatively low temperature, but the viscosity decreases at a relatively high temperature. While the fixability to the body is good, heating to a high temperature can provide the advantage of good workability such as application to a substrate. In addition, the adhesiveness and adhesion of the curable composition to the substrate can be enhanced by blending the tackifier resin (B).
• a general tackifying resin can be used as the tackifying resin (B).
• terpene resins such as terpene resins, aromatic modified terpene resins, hydrogenated terpene resins, terpene-phenol resins; phenol resins, alkylphenol resins, modified phenol resins (e.g., cashew oil-modified phenol resin , tall oil-modified phenol resin, etc.), xylene-phenol resin, cyclopentadiene-phenol resin, coumarone-indene resin; gum rosin, tall oil rosin, wood rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, maleated rosin, rosin ⁇ Rosin resins such as glycerin ester, hydrogenated rosin/glycerin ester; aromatic hydrocarbon resins such as xylene resin, low molecular weight polystyrene resin, styrene copo
• rosin-based resins have good compatibility with the (meth)acrylic acid ester-based copolymer (A) and are excellent in the effect of achieving both improved fixability at low temperatures and improved workability by heating.
• Terpene-based resins petroleum-based resins, alkylphenol resins, or aromatic hydrocarbon resins are preferred.
• rosin-based resins and terpene-based resins are particularly preferred because they have a good effect of increasing stickiness and adhesiveness.
• the rosin-based resin When using a rosin-based resin as the tackifying resin (B), the rosin-based resin preferably has an acid value of 160 KOHmg/g or less.
• the acid value is preferably 100 mg KOH/g or less, more preferably 70 mg KOH/g or less, and even more preferably 35 mg KOH/g or less.
• the acid value refers to the weight (mg) of potassium hydroxide required to neutralize the carboxyl groups contained in 1 g of the tackifier resin (B).
• the amount of the tackifier resin (B) is, from the viewpoint of achieving both improvement in fixability at low temperatures and improvement in workability by heating, relative to 100 parts by weight of the (meth)acrylic acid ester copolymer (A), 1 to 100 parts by weight is preferred, 3 to 80 parts by weight is more preferred, 5 to 60 parts by weight is even more preferred, and 10 to 50 parts by weight is particularly preferred.
• the polyoxyalkylene polymer (C) has a reactive silicon group represented by formula (1) described above.
• the reactive silicon group of the polyoxyalkylene polymer (C) may be the same as or different from the reactive silicon group of the (meth)acrylate copolymer (A).
• Specific examples of the reactive silicon group possessed by the polyoxyalkylene polymer (C) include a trimethoxysilyl group, a triethoxysilyl group, a tris(2-propenyloxy)silyl group, a triacetoxysilyl group, and dimethoxymethyl silyl group, diethoxymethylsilyl group, dimethoxyethylsilyl group, (chloromethyl)dimethoxysilyl group, (chloromethyl)diethoxysilyl group, (methoxymethyl)dimethoxysilyl group, (methoxymethyl)diethoxysilyl group, (N ,N-diethylaminomethyl)dimethoxysilyl group, (N,N-diethylaminomethyl)diethoxysilyl group, and the like, but are not limited thereto.
• methyldimethoxysilyl trimethoxysilyl, triethoxysilyl, (chloromethyl)dimethoxysilyl, (methoxymethyl)dimethoxysilyl, (methoxymethyl)diethoxysilyl, (N,N- diethylaminomethyl)dimethoxysilyl group is preferred because it exhibits high activity and gives a cured product with good mechanical properties; A trimethoxysilyl group is more preferred.
• the polyoxyalkylene polymer (C) may have an average of 1 or less reactive silicon groups at one terminal site, or an average of more than 1 reactive silicon group at one terminal site may have a silicon group.
• having more than one reactive silicon group on average at one terminal site means that the polyoxyalkylene polymer (C) has two or more reactive silicon groups at one terminal site. It shows that polyoxyalkylene is included.
• a terminal site having two or more reactive silicon groups can be represented, for example, by the following general formula (2).
• R 2 and R 4 each independently represent a divalent C 1-6 bonding group, and the atoms bonded to the respective carbon atoms adjacent to R 2 and R 4 are carbon, oxygen, nitrogen
• Each of R 3 and R 5 independently represents hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, n is an integer of 1 to 10.
• R 1 , X, and a represent the above formula (1) is as described above.
• R 2 and R 4 may be a divalent organic group having 1 to 6 carbon atoms, or may be a hydrocarbon group which may contain an oxygen atom.
• the number of carbon atoms in the hydrocarbon group is preferably 1-4, more preferably 1-3, even more preferably 1-2.
• Specific examples of R 2 include -CH 2 OCH 2 -, -CH 2 O- and -CH 2 -, preferably -CH 2 OCH 2 -.
• R 4 include -CH 2 - and -CH 2 CH 2 -, preferably -CH 2 -.
• the number of carbon atoms in the hydrocarbon groups of R 3 and R 5 is preferably 1-5, more preferably 1-3, even more preferably 1-2.
• Specific examples of R 3 and R 5 include a hydrogen atom, a methyl group and an ethyl group, preferably a hydrogen atom and a methyl group, more preferably a hydrogen atom.
• the terminal portion represented by the general formula (2) is such that R 2 is —CH 2 OCH 2 —, R 4 is —CH 2 —, and R 3 and R 5 are each hydrogen atoms.
• n is preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and even more preferably 1 or 2.
• n is not limited to one value, and may be a mixture of multiple values.
• the polyoxyalkylene polymer (C) may have an average of 1.0 or less reactive silicon groups at one terminal site.
• the average number is preferably 0.4 or more, more preferably 0.5 or more, even more preferably 0.6 or more.
• the polyoxyalkylene polymer (C) may have an average of more than 1.0 reactive silicon groups at one terminal site.
• the average number is more preferably 1.1 or more, still more preferably 1.5 or more, and even more preferably 2.0 or more.
• the average number is preferably 5 or less, more preferably 3 or less.
• the polyoxyalkylene polymer (C) may have reactive silicon groups in addition to the terminal sites, but if it has only the terminal sites, a rubber-like cured product exhibiting high elongation and low elastic modulus can be obtained. It is preferable because it becomes easy to be
• the average number of reactive silicon groups per molecule of the polyoxyalkylene polymer (C) is preferably more than 1.0, more preferably 1.2 or more, from the viewpoint of the strength of the cured product. , is more preferably 1.3 or more, even more preferably 1.5 or more, and particularly preferably 1.7 or more.
• the average number may be 2.0 or less, or may be more than 2.0. From the viewpoint of elongation of the cured product, the number is preferably 6.0 or less, more preferably 5.5 or less, and most preferably 5.0 or less.
• the main chain skeleton of the polyoxyalkylene polymer (C) is not particularly limited, and examples include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, Examples include polyoxypropylene-polyoxybutylene copolymers. Among them, polyoxypropylene is preferred.
• the main chain structure of the polyoxyalkylene polymer (C) may be linear or branched.
• the number average molecular weight of the polyoxyalkylene polymer (C) is preferably 3,000 or more and 100,000 or less, more preferably 3,000 or more and 50,000 or less, and particularly preferably It is 3,000 or more and 30,000 or less.
• the molecular weight distribution (Mw/Mn) of the polyoxyalkylene polymer (C) is not particularly limited, it is preferably narrow, specifically less than 2.0, more preferably 1.6 or less. 5 or less is more preferable, and 1.4 or less is particularly preferable. Moreover, from the viewpoint of improving various mechanical properties such as improving the durability and elongation of the cured product, it is preferably 1.2 or less.
• the molecular weight distribution of the polyoxyalkylene polymer (C) can be obtained from the number average molecular weight and weight average molecular weight obtained by GPC measurement.
• the method for synthesizing the polyoxyalkylene polymer (C) is not particularly limited.
• an initiator having a hydroxyl group is polymerized with an epoxy compound to obtain a hydroxyl group-terminated polymer.
• an alkali metal salt for example, sodium methoxide
• a halogenated hydrocarbon compound having a carbon-carbon unsaturated bond for example, allyl chloride
• a reactive silicon group-containing hydrosilane compound eg, dimethoxymethylsilane, trimethoxysilane
• a reactive silicon group-containing polyoxyalkylene polymer (C) can be obtained.
• a polyoxyalkylene polymer (C) having an average of more than 1.0 reactive silicon groups at one terminal site which is a preferred embodiment, can be obtained as follows. After reacting the hydroxyl group of the hydroxyl-terminated polymer with the alkali metal salt in the same manner as described above, an epoxy compound having a carbon-carbon unsaturated bond (eg, allyl glycidyl ether) is first reacted, and then the carbon-carbon unsaturated bond is reacted. Two or more carbon-carbon unsaturated bonds are introduced at one end by reacting a halogenated hydrocarbon compound having a saturated bond (eg, allyl chloride). After that, a reactive silicon group-containing hydrosilane compound may be reacted.
• an epoxy compound having a carbon-carbon unsaturated bond eg, allyl glycidyl ether
• Two or more carbon-carbon unsaturated bonds are introduced at one end by reacting a halogenated hydrocarbon compound having a saturated bond (eg,
• a cured product obtained from a curable composition containing a polyoxyalkylene polymer (C) containing an ester bond or an amide segment may have high hardness and strength due to the action of hydrogen bonds and the like.
• the polyoxyalkylene polymer (C) containing amide segments and the like may be cleaved by heat or the like.
• a curable composition containing a polyoxyalkylene polymer (C) containing an amide segment or the like tends to have a high viscosity.
• polyoxyalkylene polymer (C) a polyoxyalkylene containing an amide segment or the like may be used, or a polyoxyalkylene containing no amide segment or the like may be used. You may
• Examples of the amide segment represented by the general formula (3) include the reaction between an isocyanate group and a hydroxyl group, the reaction between an amino group and a carbonate, the reaction between an isocyanate group and an amino group, and the reaction between an isocyanate group and a mercapto group. and the like.
• the amide segment represented by the general formula (3) also includes those formed by the reaction of the amide segment containing an active hydrogen atom with an isocyanate group.
• a polyoxyalkylene having an active hydrogen-containing group at its terminal is reacted with a polyisocyanate compound to produce a polymer having an isocyanate group at its terminal.
• a compound having both a functional group for example, a hydroxyl group, a carboxyl group, a mercapto group, a primary amino group or a secondary amino group
• a method of reacting is mentioned.
• Another example is a method of reacting a polyoxyalkylene having an active hydrogen-containing group at its end with a reactive silicon group-containing isocyanate compound.
• the number (average value) of amide segments per molecule of the polyoxyalkylene polymer (C) is preferably 1 to 10, and 1.5 to 5. is more preferred, and 2 to 3 are particularly preferred. If this number is less than 1, the curability may not be sufficient, and conversely if it is greater than 10, the polyoxyalkylene polymer (C) will have a high viscosity and may be difficult to handle. There is In order to lower the viscosity of the curable composition and improve workability, the polyoxyalkylene polymer (C) preferably does not contain an amide segment.
• a method of blending a (meth)acrylic acid ester copolymer (A) and a polyoxyalkylene polymer (C) is disclosed in JP-A-59-122541, JP-A-63-112642, and JP-A-6. -172631, Japanese Patent Application Laid-Open No. 11-116763, and the like.
• a method of polymerizing a (meth)acrylic acid ester-based monomer in the presence of a polyoxypropylene-based polymer having a reactive silicon group can be used.
• the weight ratio (C):(A) is 95:5 to 10:90, that is, The proportion of (C) is preferably 10% by weight or more and 95% by weight or less. Within this range, a cured product exhibiting flexibility and high shear adhesive strength can be obtained. Furthermore, from the viewpoint of achieving both high strength and flexibility, (C):(A) is preferably 80:20 to 10:90, more preferably 70:30 to 20:80. The upper limit may be 50:50. Furthermore, from the viewpoint of placing emphasis on improving the final adhesive strength of the cured product, the ratio is preferably 50:50 to 10:90, more preferably 45:55 to 20:80.
• silanol condensation catalyst is an optional component, it can promote the condensation reaction of the reactive silicon groups of the (meth)acrylic acid ester copolymer (A) and the polyoxyalkylene polymer (C). , is preferably blended.
• silanol condensation catalysts examples include organic tin compounds, carboxylic acid metal salts, amine compounds, carboxylic acids, and alkoxy metals.
• organotin compounds include dibutyltin dilaurate, dibutyltin dioctanoate, dibutyltin bis(butyl maleate), dibutyltin diacetate, dibutyltin oxide, dibutyltin bis(acetylacetonate), dibutyltin oxide and silicate compounds.
• reaction product with dibutyltin oxide and phthalate ester dioctyltin diacetate, dioctyltin dilaurate, dioctyltin bis(ethyl maleate), dioctyltin bis(octyl maleate), dioctyltin bis(acetylacetonate) phosphate), dioctyltin distearate, dioctyltin oxide, a reaction product of dioctyltin oxide and a silicate compound, and the like.
• carboxylate metal salts include tin carboxylate, bismuth carboxylate, titanium carboxylate, zirconium carboxylate, iron carboxylate, potassium carboxylate, and calcium carboxylate.
• carboxylic acid metal salt the following carboxylic acid and various metals can be combined.
• amine compounds include amines such as octylamine, 2-ethylhexylamine, laurylamine, and stearylamine; pyridine, 1,8-diazabicyclo[5,4,0]undecene-7 (DBU), 1,5 - nitrogen-containing heterocyclic compounds such as diazabicyclo[4,3,0]nonene-5(DBN); guanidines such as guanidine, phenylguanidine and diphenylguanidine; butylbiguanide, 1-o-tolylbiguanide and 1-phenylbiguanide biguanides such as; amino group-containing silane coupling agents; and ketimine compounds.
• amines such as octylamine, 2-ethylhexylamine, laurylamine, and stearylamine
• pyridine 1,8-diazabicyclo[5,4,0]undecene-7 (DBU), 1,5 - nitrogen-containing heterocyclic compounds
• carboxylic acids include acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, lauric acid, stearic acid, oleic acid, linoleic acid, neodecanoic acid, and versatic acid.
• alkoxy metals include titanium compounds such as tetrabutyl titanate, titanium tetrakis(acetylacetonate), diisopropoxytitanium bis(ethylacetonate), aluminum tris(acetylacetonate), diisopropoxyaluminum ethylacetate.
• titanium compounds such as tetrabutyl titanate, titanium tetrakis(acetylacetonate), diisopropoxytitanium bis(ethylacetonate), aluminum tris(acetylacetonate), diisopropoxyaluminum ethylacetate.
• Aluminum compounds such as acetate, zirconium compounds such as zirconium tetrakis (acetylacetonate), and the like.
• fluorine anion-containing compounds As other silanol condensation catalysts, fluorine anion-containing compounds, photoacid generators, and photobase generators can also be used.
• the silanol condensation catalyst may be used in combination of two or more different catalysts.
• the combined use of the amine compound and carboxylic acid, or the combined use of the amine compound and alkoxy metal has the effect of improving reactivity. may be obtained.
• the amount used is 100 parts by weight of the (meth)acrylic acid ester copolymer (A) from the viewpoint of promoting the condensation reaction of the reactive silicon group [however, polyoxyalkylene polymer When coalescence (C) is contained, a total of 100 parts by weight of the (meth)acrylate copolymer (A) and the polyoxyalkylene polymer (C). hereinafter the same], it is preferably 0.001 to 20 parts by weight, more preferably 0.01 to 15 parts by weight, and even more preferably 0.01 to 10 parts by weight.
• the curable composition according to the present embodiment includes a (meth)acrylate copolymer (A), a tackifier resin (B), a polyoxyalkylene polymer (C), and a silanol condensation catalyst.
• a (meth)acrylate copolymer A
• a tackifier resin B
• a polyoxyalkylene polymer C
• silanol condensation catalyst a silanol condensation catalyst.
• plasticizers, fillers, adhesion imparting agents, dehydrating agents, rheology control agents, antioxidants, light stabilizers, ultraviolet absorbers, and other resins may be added.
• additives may be added to the curable composition according to the present embodiment as necessary for the purpose of adjusting various physical properties of the curable composition or cured product.
• additives include solvents, diluents, photo-curing substances, oxygen-curing substances, surface property modifiers, silicates, curability modifiers, radical inhibitors, metal deactivators, ozone Degradation inhibitors, phosphorus-based peroxide decomposers, lubricants, pigments, antifungal agents, flame retardants, foaming agents and the like.
• the curable composition may contain a plasticizer. By blending the plasticizer, the viscosity of the curable composition can be lowered and handling becomes easier.
• plasticizers include, but are not limited to, dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di(2-ethylhexyl) phthalate, diisodecyl phthalate (DIDP), and phthalate compounds such as butylbenzyl phthalate; (2-ethylhexyl)-1,4-benzenedicarboxylate and other terephthalic acid ester compounds; 1,2-cyclohexanedicarboxylic acid diisononyl ester and other non-phthalic acid ester compounds; dioctyl adipate, dioctyl sebacate, dibutyl sebacate, Aliphatic polyvalent carboxylic acid ester compounds such as diisodecyl succinate and acetyl tributyl citrate; unsaturated fatty acid ester compounds such as butyl oleate and methyl acetylricinole
• Polymeric plasticizers can also be used as plasticizers.
• polymeric plasticizers include vinyl polymers; polyester plasticizers; polyether polyols such as polyethylene glycol and polypropylene glycol having a number average molecular weight of 500 or more; polyether plasticizers such as derivatives converted to polystyrenes; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene and the like.
• polymer plasticizers are preferred, polyether plasticizers are more preferred, and polypropylene glycol is particularly preferred.
• the plasticizer only one type may be used, or two or more types may be used in combination.
• the blending amount of the plasticizer is preferably 5 to 150 parts by weight, more preferably 10 to 120 parts by weight, more preferably 20 to 100 parts by weight with respect to 100 parts by weight of the (meth)acrylic acid ester copolymer (A). Parts by weight are particularly preferred.
• a filler can be blended into the curable composition.
• the strength of the cured product can be improved by adding a filler.
• Fillers include ground calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, clay, talc, titanium oxide, fumed silica, precipitated silica, crystalline silica, fused silica, anhydrous silicic acid, hydrous silicic acid, Alumina, carbon black, ferric oxide, fine aluminum powder, zinc oxide, activated zinc white, PVC powder, PMMA powder, glass fiber and filament, and the like.
• Organic balloons and inorganic balloons may be added for the purpose of weight reduction (lower specific gravity) of the composition. Only one type of filler may be used, or two or more types may be used in combination.
• the amount of the filler compounded is preferably 1 to 300 parts by weight, more preferably 10 to 250 parts by weight, per 100 parts by weight of the (meth)acrylic acid ester copolymer (A).
• the curable composition may contain an adhesive agent.
• a silane coupling agent or a reactant of the silane coupling agent can be added as the adhesion imparting agent.
• silane coupling agents include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropylmethyldimethoxysilane, N- ⁇ -aminoethyl- ⁇ -aminopropyltrimethoxysilane, N- ⁇ -aminoethyl- ⁇ - Amino group-containing silanes such as aminopropylmethyldimethoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxysilane, (2-aminoethyl)aminomethyltrimethoxysilane; ⁇ -isocyanatopropyltrimethoxysilane, ⁇ -isocyanatopropyltrimethoxysilane; isocyanate group-containing silanes such as ethoxysilane, ⁇ -isocyanatopropylmethyldimethoxysilane, ⁇ -isocyanatomethyltrimethoxysilane, ⁇ -isocyan
• Condensates of various silane coupling agents such as condensation products of amino group-containing silanes, condensation products of amino group-containing silanes and other alkoxysilanes; reaction products of amino group-containing silanes and epoxy group-containing silanes; Reaction products of various silane coupling agents, such as reaction products of containing silanes and (meth)acrylic group-containing silanes, can also be used.
• the adhesion imparting agent may be used alone or in combination of two or more.
• the amount of the adhesion-imparting agent is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the (meth)acrylic acid ester copolymer (A).
• a dehydrating agent can be added to the curable composition.
• the dehydrating agent is preferably a compound that can react with water, more preferably a silicon compound that can react with water (excluding compounds corresponding to adhesiveness-imparting agents), and particularly a trialkoxysilane compound. preferable.
• dehydrating agent examples include vinyl group-containing silanes such as methyltrimethoxysilane, phenyltrimethoxysilane, n-propyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane and vinylmethyldimethoxysilane. and the like. Only one type of dehydrating agent may be used, or two or more types may be used.
• the amount of the dehydrating agent is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, and 1 to 10 parts by weight with respect to 100 parts by weight of the (meth)acrylate copolymer (A). 5 parts by weight is more preferred.
• a rheology control agent may be added to the curable composition to prevent sagging and improve workability.
• rheology control agent is not particularly limited, examples thereof include fatty acid amide waxes, hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate, and barium stearate; dry silica, wet silica, and the like. These rheology control agents may be used alone or in combination of two or more.
• the content of the rheology control agent is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the (meth)acrylic acid ester copolymer (A).
• An antioxidant can be used in the curable composition.
• the use of an antioxidant can enhance the weather resistance of the cured product.
• antioxidants include hindered phenols, monophenols, bisphenols, and polyphenols. Specific examples of antioxidants are also described in JP-A-4-283259 and JP-A-9-194731.
• the content of the antioxidant is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, per 100 parts by weight of the (meth)acrylate copolymer (A).
• a light stabilizer can be used in the curable composition.
• the use of a light stabilizer can prevent photo-oxidative deterioration of the cured product.
• Benzotriazole-based, hindered amine-based, and benzoate-based compounds can be exemplified as light stabilizers, and hindered amine-based compounds are particularly preferred.
• the blending amount of the light stabilizer is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, per 100 parts by weight of the (meth)acrylic acid ester copolymer (A).
• a UV absorber can be used in the curable composition.
• the use of an ultraviolet absorber can enhance the surface weather resistance of the cured product.
• UV absorbers include benzophenone-based, benzotriazole-based, salicylate-based, substituted acrylonitrile-based, and metal chelate-based compounds.
• Benzotriazole-based compounds are particularly preferred, and are commercially available under the names Tinuvin P, Tinuvin 213, Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 329, and Tinuvin 571 (manufactured by BASF).
• the blending amount of the ultraviolet absorber is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, per 100 parts by weight of the (meth)acrylate copolymer (A).
• a physical property modifier for adjusting the tensile properties of the resulting cured product may be added to the curable composition, if necessary.
• the physical property modifier is not particularly limited, for example, alkylalkoxysilanes such as phenoxytrimethylsilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, n-propyltrimethoxysilane; diphenyldimethoxysilane, phenyltrimethoxysilane.
• arylalkoxysilanes such as; alkylisopropenoxysilanes such as dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, ⁇ -glycidoxypropylmethyldiisopropenoxysilane; trialkylsilylborates such as silyl)borate; silicone varnishes; polysiloxanes;
• the physical property modifiers may be used alone or in combination of two or more.
• a compound that produces a compound having a monovalent silanol group in its molecule by hydrolysis has the effect of lowering the modulus of the cured product without exacerbating the stickiness of the surface of the cured product.
• Compounds that generate trimethylsilanol are particularly preferred.
• examples of compounds that generate a compound having a monovalent silanol group in the molecule by hydrolysis include alcohol derivatives such as hexanol, octanol, phenol, trimethylolpropane, glycerin, pentaerythritol, and sorbitol, which are hydrolyzed into silane monovalent groups.
• Mention may be made of silicon compounds that produce ols. Specific examples include phenoxytrimethylsilane and tris((trimethylsiloxy)methyl)propane.
• the amount of the physical property modifier used is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, per 100 parts by weight of the (meth)acrylic acid ester copolymer (A).
• the curable composition according to one embodiment of the present invention can be prepared as a one-component type in which all ingredients are pre-blended and stored in a sealed container, and cured by moisture in the air after application.
• the ingredients containing water are dehydrated and dried in advance before use, or dehydrated by decompression or the like during compounding and kneading.
• the curable composition according to one embodiment of the present invention includes a main agent containing a (meth)acrylic acid ester copolymer (A) and a tackifier resin (B), a silanol condensation catalyst, a filler, and a plasticizer. , water, etc., and can be prepared as a two-component type in which the main agent and the curing agent are mixed before use.
• the method for preparing the curable composition according to one embodiment of the present invention is not particularly limited.
• the above components are blended and kneaded at room temperature or under heating using a mixer, roll, kneader, etc., or a small amount of an appropriate solvent is used to dissolve and mix the above components. methods can be employed.
• the curable composition according to one embodiment of the present invention can exhibit good adhesion to various adherends such as plastics, metals and composite materials.
• adherends such as plastics, metals and composite materials.
• non-polar materials such as polypropylene and engineering plastics with rigid molecular chains such as polyphenylene sulfide
• the adherend can be previously surface-treated by known methods. For example, surface treatment techniques such as sanding, flame treatment, corona discharge, arc discharge, plasma treatment, etc. can be used. Plasma treatment is preferred because it causes less damage to the adherend and provides stable adhesion. These surface treatments are also effective for removing release agents used during molding and remaining on the adherend surface.
• the curable composition can be used as an adhesive, a sealing It can be used as a material or an adhesive.
• the curable composition according to one embodiment of the present invention has a high viscosity at a relatively low temperature, but the viscosity can be significantly reduced at a relatively high temperature. It can be suitably used as a mold curable composition or an adhesive composition.
• the curable composition according to one embodiment of the present invention is preferably heated to a high temperature to reduce the viscosity in order to ensure workability when applied to an adherend.
• a high temperature about 70 to 180°C is preferable, 90 to 160°C is more preferable, and 100 to 150°C is even more preferable.
• the heating method is not particularly limited, and conventionally known methods can be used.
• the curable composition according to one embodiment of the present invention can express the desired physical properties by performing a long-term curing (curing) process after bonding the adherends.
• the conditions for the curing (curing) step are not particularly limited, but include, for example, a temperature of 5 to 90° C. and a time of 24 hours to 1 week.
• the curable composition according to one embodiment of the present invention when used as a hot-melt curable composition, it can be used as a reactive hot-melt adhesive.
• This curable composition can be used as an adhesive for joining panels of buses, trailers, trains, etc., as an adhesive for displays and housings in smartphones, tablet terminals, laptop computers, etc.
• -Also suitable for joining dissimilar materials such as composites and aluminum-composites.
• a sealer it is possible to use a polymer having reactive silicon groups as shown in this application.
• the curable composition according to one embodiment of the present invention can be It is preferably used as an adhesive used in various machine parts.
• the curable composition according to one embodiment of the present invention when used as an adhesive composition, it can be used for general office work, paper diapers, PP film adhesion, removability, general packaging, electrical use, and fixing. Can be used for adhesive products.
• Adhesive products containing the adhesive composition according to one embodiment of the present invention include packaging adhesive tapes, office adhesive tapes, paint masking tapes, electrical insulating adhesive tapes, binding adhesive tapes, protective adhesive tapes, identification ⁇ Decorative adhesive tapes and sheets, sports tapes, double-sided adhesive tapes, electromagnetic wave interference countermeasure films and tapes, removable films and tapes, veneer films, semiconductor chip transport tapes, marking films, protective films for deep drawing, glass scattering Prevention films, foamed adhesive tapes, waterproof/water-stopping tapes, anti-corrosion adhesive tapes, surface-protecting adhesive tapes, dicing adhesive tapes, back-grinding adhesive tapes, printing adhesive sheets, adhesive labels, and the like.
• [Item 1] (Meth)acrylic acid ester copolymer (A) having a reactive silicon group represented by the following general formula (1), and Containing a tackifying resin (B),
• the monomer component constituting the (meth)acrylic acid ester copolymer (A) is (meth) acrylic acid ester (a1), A polymer (a2) having more than one (meth)acryloyl group in the molecule, and containing a chain transfer agent (a3) having a mercapto group,
• the monomer component further contains a monomer (a4) having a reactive silicon group and a polymerizable unsaturated group, and/or the chain transfer agent (a3) having a mercapto group is a reactive silicon
• a curable composition further comprising a group.
• the tackifying resin (B) contains at least one resin selected from the group consisting of rosin-based resins, terpene-based resins, petroleum-based resins, alkylphenol resins, and aromatic hydrocarbon resins. 1.
• the polymer (a2) is a (meth)acrylate polymer (a2') having more than one (meth)acryloyl group in the molecule.
• the curable composition according to any one of items 1 to 4 wherein the molar ratio of polymer (a2)/chain transfer agent (a3) having a mercapto group is 0.05 or more.
• the number average molecular weight and weight average molecular weight in the examples are GPC molecular weights measured under the following conditions.
• Liquid delivery system Tosoh HLC-8120GPC
• Column TSK-GEL H type manufactured by Tosoh Solvent: THF
• Molecular weight Polystyrene equivalent Measurement temperature: 40°C
• the terminal group equivalent molecular weights in the examples were obtained by determining the hydroxyl value by the measurement method of JIS K 1557, the iodine value by the measurement method of JIS K 0070, and the structure of the organic polymer (the degree of branching determined by the polymerization initiator used). It is the molecular weight obtained by taking into consideration.
• the average number of carbon-carbon unsaturated bonds introduced per terminal of the polymer shown in the examples was calculated by the following formula.
• (Average introduction number) [Unsaturated group concentration of polymer determined from iodine value (mol/g) - Unsaturated group concentration of precursor polymer determined from iodine value (mol/g)]/[Determined from hydroxyl value Hydroxyl group concentration of precursor polymer (mol/g)]
• sulfur atom concentration is a theoretical value calculated from the total amount of the monomer components used in the production of the (meth)acrylate copolymer (A) and the amount of the chain transfer agent (a3) having a mercapto group. be.
• Synthesis example 1 Polyoxypropylene glycol with a number average molecular weight of about 4,020 (molecular weight as converted to terminal groups: 2,980) is used as an initiator, and propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst to have hydroxyl groups at both ends. , a number average molecular weight of 21,100 (termed molecular weight of terminal groups: 13,600) and a molecular weight distribution Mw/Mn of 1.21.
• a mixed solution dissolved in .3 parts by weight was added dropwise over 5 hours. Further, a mixed solution of 0.3 parts by weight of 2,2'-azobis(2-methylbutyronitrile) dissolved in 9.4 parts by weight of isobutanol was added, and polymerization was carried out at 105°C for 2 hours. 390 and a weight average molecular weight of 29,950 (GPC molecular weight), an isobutanol solution (solid content: 55%) of a reactive silicon group-containing (meth)acrylic acid ester copolymer (A-1) was obtained. The solid content of the solution has a polyfunctional macromonomer equivalent weight of 0.021 mmol/g, a reactive silicon group equivalent weight of 0.30 mmol/g, and a sulfur atom concentration of 4,238 ppm.
• an isobutanol solution (solid content: 55%) of a reactive silicon group-containing (meth)acrylate copolymer (A-2) was obtained.
• the solid content of the solution has a polyfunctional macromonomer equivalent weight of 0.021 mmol/g, a reactive silicon group equivalent weight of 0.17 mmol/g, and a sulfur atom concentration of 4,890 ppm.
• an isobutanol solution (solid content: 55%) of a reactive silicon group-containing (meth)acrylic acid ester copolymer (A-3) was obtained.
• the solid content of the solution has a polyfunctional macromonomer equivalent weight of 0.021 mmol/g, a reactive silicon group equivalent weight of 0.19 mmol/g, and a sulfur atom concentration of 5,320 ppm.
• Example 1 YS Polystar T80 (terpene phenol Resin, manufactured by Yasuhara Chemical Co., Ltd.) was mixed to 30 weight, and the isobutanol was devolatilized by heating to obtain a mixture, and the viscosity of the mixture was measured by the following method. Table 1 shows the results obtained.
• viscosity A parallel disk plate with a diameter of 20 mm was used as a jig, the gap was set to 0.3 mm, the shear rate was set to 1 (1/sec), and the viscosity was measured while increasing the temperature from 60° C. to 150° C. at a rate of 5° C./min. . The viscosity was read at 60°C and 120°C.
• Example 2 A mixture was prepared in the same manner as in Example 1 except that D-6011 (rosin resin, manufactured by Arakawa Chemical Industries, Ltd.) was used as the tackifier resin (B), and the viscosity of the mixture was measured in the same manner as in Example 1. bottom. Table 1 shows the results obtained.
• Example 3 A mixture was prepared in the same manner as in Example 1 except that 50 parts by weight of FTR6125 (aromatic hydrocarbon resin, manufactured by Mitsui Chemicals, Inc.) was blended as the tackifying resin (B), and the viscosity of the mixture was measured in Example 1. was measured in the same manner as Table 1 shows the results obtained.
• FTR6125 aromatic hydrocarbon resin, manufactured by Mitsui Chemicals, Inc.
• Example 4 A mixture was prepared in the same manner as in Example 1 except that Nisseki Neopolymer (aromatic hydrocarbon resin, manufactured by ENEOS) was used as the tackifying resin (B), and the viscosity of the mixture was measured in the same manner as in Example 1. . Table 1 shows the results obtained.
• Nisseki Neopolymer aromatic hydrocarbon resin, manufactured by ENEOS
• the curable compositions of Examples 1 to 4 containing the (meth)acrylic acid ester copolymer (A) and the tackifying resin (B) are the (meth)acrylic acid ester-based compositions of Comparative Example 1. It can be seen that the viscosity at high temperatures (120° C.) is low, although the viscosity at low temperatures (60° C.) is higher than that of copolymer (A). From this, it can be said that the curable compositions of Examples 1 to 4 are suitable for hot melt adhesives.
• Example 5 YS Polystar T80 (terpene phenol Resin, manufactured by Yasuhara Chemical Co., Ltd.) was mixed so as to have a weight of 60, and the isobutanol was heated and devolatilized to obtain a mixture. ) were mixed, and the viscosity of the mixture was measured by the method described above. Table 2 shows the results obtained.
• Example 6 A mixture was prepared in the same manner as in Example 1 except that D-6011 (rosin-based resin, manufactured by Arakawa Chemical Industries, Ltd., acid value: 0) was used as the tackifier resin (B), and the viscosity of the mixture was measured in Examples. Measured in the same manner as in 5. Table 2 shows the results obtained.
• Example 7 D-6011 (rosin-based Resin, manufactured by Arakawa Chemical Industries Co., Ltd.) was mixed to 40 weight, then isobutanol was heated and devolatilized to obtain a mixture. The viscosity of the mixture was measured in the same manner as in Example 5 after mixing N,N-diethyl-1,3-propanediamine as an amine compound. Table 2 shows the results obtained.
• the mixture heated to 150° C. was applied to an aluminum foil having a size of 200 mm ⁇ 25 mm and a thickness of 0.1 mm so as to have a thickness of about 300 ⁇ m.
• the coated aluminum foil was heated at 80° C. for 15 minutes to cure the mixture. After being left under conditions of 23° C. and 50% RH for 1 hour, it was attached to a stainless steel plate (100 mm ⁇ 25 mm ⁇ 1.6 mm). With the aluminum foil surface facing up, a roller of 5 kg was reciprocated 10 times to bring the aluminum foil and the stainless steel plate into close contact with each other, and allowed to stand at 23° C. and 50% RH for 24 hours.
• a tensile test was performed so that the aluminum foil and the stainless steel plate were at 180°, and the peel strength was measured. The state of destruction was visually confirmed with CF representing cohesive failure (destruction at the adhesive portion) and AF representing interfacial failure (separation at the interface between the adhesive and the stainless steel plate).
• the tensile test was performed using an autograph (AGS-X) manufactured by Shimadzu Corporation at a tensile speed of 300 mm/min. Table 2 shows the results.
• the curable compositions of Examples 5 to 7 containing the (meth)acrylic acid ester copolymer (A) and the tackifying resin (B) are the (meth)acrylic acid ester-based compositions of Comparative Example 2. It can be seen that the viscosity at high temperatures (120° C.) is low, although the viscosity at low temperatures (60° C.) is higher than that of copolymer (A). In addition, it can be seen that the curable compositions of Examples 5 to 7 have higher peel strength in the peel test than Comparative Example 2. From the above, it can be said that the curable compositions of Examples 5 to 7 are suitable for adhesives.

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