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
  • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
  • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
• • 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
  • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
• • 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
  • C08F290/06—Polymers provided for in subclass C08G
  • C08F290/062—Polyethers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds

Definitions

• the present invention relates to a (meth)acrylic acid ester-based copolymer having a reactive silicon group, a method for producing the same, and a curable composition containing the copolymer.
• 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 a curable resin having a high curing speed and excellent adhesiveness is used 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.
• an oligomer having a polyether skeleton and having double bonds at both ends, a vinyl monomer such as (meth)acrylic acid ester, and a chain transfer agent are radically polymerized to synthesize a reactive silicon group-containing Graft copolymers are described.
• Polymers having reactive silicon groups are desired to have low viscosity so that they can be easily handled before curing, while exhibiting good physical properties after curing.
• the reactive silicon group-containing graft copolymer described in Patent Document 3 does not have sufficient physical properties after curing, and needs to be improved.
• the present invention provides a reactive silicon group-containing (meth)acrylic acid ester copolymer that exhibits good physical properties after curing while having a low viscosity, and a curable composition containing the same. intended to
• the present inventors have conducted intensive studies to solve the above problems, and found that a specific monomer and a chain transfer agent are used as monomer components constituting a reactive silicon group-containing (meth)acrylic acid ester polymer.
• the inventors have found that the above problems can be solved by using a specific ratio, and completed the present invention.
• the first present invention is a (meth)acrylic acid ester copolymer (A) having a reactive silicon group represented by the following formula (1), wherein the monomer component constituting the copolymer is , (meth)acrylic acid ester (a1), polyoxyalkylene polymer (a2) having more than one (meth)acryloyl group in the molecule, and chain transfer agent (a3) having a mercapto group,
• the molar ratio of the polyoxyalkylene polymer (a2)/chain transfer agent (a3) having a mercapto group is 0.06 or more
• the monomer component contains a reactive silicon group and a polymerizable Further containing a monomer (a4) having a saturated group, and / or a (meth) acrylic acid ester copolymer ( A).
• R 1 represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms
• X represents a hydroxyl group or a hydrolyzable group
• c is 0 or 1.
• the value calculated by the formula: (weight average molecular weight of copolymer (A))/(weight average molecular weight of polyoxyalkylene polymer (a2)) is 0.65 or more.
• the polyoxyalkylene polymer (a2) accounts for 0.08 mol % or more and 6.0 mol % or less in the monomer component.
• the chain transfer agent (a3) having a mercapto group accounts for 0.4 mol % or more and 15 mol % or less in the monomer component.
• the polyoxyalkylene polymer (a2) has a number average molecular weight of 50,000 or less.
• the content of the polyoxyalkylene polymer (a2) is 60% by weight or less in the monomer component.
• the weight average molecular weight of copolymer (A) is 80,000 or less.
• the copolymer (A) has a molecular weight distribution of 3.0 or more and 11.0 or less.
• c in the formula (1) is 0.
• the (meth)acrylic acid ester (a1) is at least one monomer selected from the group consisting of methacrylic acid esters, isobornyl acrylate, dicyclopentenyl acrylate, and dicyclopentanyl acrylate. contains Preferably, among the total amount of the monomer components excluding the polyoxyalkylene-based polymer (a2), the (meth)acrylic acid ester (a1) component, methacrylic acid ester, isobornyl acrylate, and dicyclopentenyl acrylate and at least one monomer selected from the group consisting of dicyclopentanyl acrylate accounts for 60% by weight or more.
• the sulfur atom concentration in the (meth)acrylate copolymer (A) is 700 ppm or more and 20,000 ppm or less.
• the second aspect of the present invention is a (meth)acrylic acid ester copolymer (A) having reactive silicon represented by the following formula (1), wherein the copolymer has two first molecular chains, including a structure bonded via one second molecular chain, both ends of the second molecular chain are respectively bonded to non-terminal sites of the first molecular chain, and the first molecular chain is (meth)acrylic It is composed of a molecular chain of an acid ester polymer, the second molecular chain is composed of a polyoxyalkylene polymer molecular chain, the reactive silicon group is bonded to the first molecular chain, and the first molecular chain is , a structure represented by —SR 3 (wherein S represents a sulfur atom and R 3 represents a hydrocarbon group which may have a reactive silicon group) at either end and the
• the third aspect of the present invention relates to a curable composition containing the (meth)acrylate copolymer (A) or a cured product of the curable composition.
• the fourth aspect of the present invention is a method for producing a (meth)acrylic acid ester copolymer (A) having a reactive silicon group represented by the following formula (1), comprising a step of copolymerizing a monomer component Including, the monomer component includes (meth) acrylic acid ester (a1), polyoxyalkylene polymer (a2) having more than one (meth) acryloyl group in the molecule, and a chain having a mercapto group a transfer agent (a3), wherein the molar ratio of the polyoxyalkylene polymer (a2)/chain transfer agent (a3) having a mercapto group is 0.06 or more, and the monomer component comprises Further containing a monomer (a4) having a reactive silicon group and a polymerizable unsaturated group, and/or the chain transfer agent (a3) having a mercapto group further has a reactive silicon group, (meth) It relates to a method for producing an acrylate copolymer (A).
• R 1 represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms
• X represents a hydroxyl group or a hydrolyzable group
• c is 0 or 1.
• a reactive silicon group-containing (meth)acrylic acid ester copolymer that exhibits good physical properties (e.g., elongation, strength, etc.) after curing while having a low viscosity, and a curability containing the same A composition can be provided.
• the reactive silicon group-containing (meth)acrylic acid ester copolymer according to the present invention contains a block copolymer and can have a relatively low viscosity even if it has a large weight average molecular weight.
• the (meth)acrylic ester-based copolymer (A) has a reactive silicon group represented by the following formula (1) at the molecular chain terminal and/or side chain (non-terminal site).
• —SiR 1 c X 3-c (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; c is 0 or 1.)
• 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, N,N-diethylaminomethyl group and the like, preferably methyl group and ethyl group.
• Examples of X include hydroxyl group, hydrogen, halogen, alkoxy group, acyloxy group, ketoximate group, amino group, amide group, acid amide group, aminooxy group, mercapto group, and alkenyloxy group.
• alkoxy groups such as methoxy and ethoxy groups are more preferred, and methoxy and ethoxy groups are particularly preferred, since they are moderately hydrolyzable and easy to handle.
• c is 0 or 1; 0 is preferable because a cured product having a high Young's modulus can be obtained.
• 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- A 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 can be 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 0.06 mmol/g or more, more preferably 0.08 mmol/g or more, and 0.1 mmol/g. The above is more preferable.
• the reactive silicon group equivalent is preferably 1.0 mmol/g or less, more preferably 0.5 mmol/g or less, and particularly preferably 0.3 mmol/g or less from the viewpoint of suppressing a decrease in elongation of the cured product.
• the (meth)acrylate copolymer (A) comprises at least (meth)acrylate (a1) and a polyoxyalkylene polymer (a2) having more than one (meth)acryloyl group in the molecule. and a chain transfer agent (a3) having a mercapto group are copolymerized to form a monomer component.
• (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.
• 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 40% relative to the total amount of the monomer components constituting the (meth)acrylic acid ester copolymer (A). It is preferably at least 45% by weight, more preferably at least 50% by weight, still more preferably at least 55% by weight, and even more preferably at least 60% by weight. Further, from the viewpoint of durable adhesion, it is preferably 50% by weight or more, more preferably 55% by weight or more, relative to the total amount of the monomer components constituting the (meth)acrylic acid ester copolymer (A). , more preferably 60% by weight or more.
• an alkyl (meth)acrylic acid ester in which the alkyl has 1 to 4 carbon atoms is preferable because a hardened 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 40% by weight or more based on the total amount of the monomer components constituting the (meth)acrylic acid ester-based copolymer (A). preferably 45% by weight or more, and even more preferably 50% by weight or more.
• (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.
• the (meth)acrylate (a1) component methacrylate, isobornyl acrylate, dicyclopentenyl acrylate,
• the proportion of at least one monomer selected from the group consisting of dicyclopentanyl acrylate is preferably 60% by weight or more, more preferably 70% by weight or more.
• Polyoxyalkylene polymer (a2) having more than one (meth)acryloyl group in the molecule The polyoxyalkylene polymer (a2) itself is a polymer, but it is one of the monomers constituting the (meth)acrylate copolymer (A). Since the polyoxyalkylene polymer (a2) has a (meth)acryloyl group, it can be copolymerized with other monomers such as (meth)acrylic acid ester (a1). Moreover, since the polyoxyalkylene 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 polyoxyalkylene-based polymer (a2) is the (meth)acrylic acid ester-based copolymer (A), the (meth)acrylic acid ester (a1), etc. It can form a structure that bridges two molecular chains (first molecular chain to be described later) composed of coalescence.
• the polyoxyalkylene polymer (a2) is also referred to as polyfunctional macromonomer (a2).
• the main chain skeleton of the polyfunctional macromonomer (a2) is a polyoxyalkylene polymer.
• the main chain skeleton of the polyfunctional macromonomer (a2) is not particularly limited, and examples thereof include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, poly Oxypropylene-polyoxybutylene copolymer and the like are included. Among them, polyoxypropylene is preferred.
• the main chain skeleton of the polyoxyalkylene polymer may be linear or branched, but is preferably linear.
• the (meth)acryloyl group possessed by the polyfunctional macromonomer (a2) is preferably represented by the following formula (2).
• CH2 C( R2 )-COO-Z (2)
• R 2 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 polyoxyalkylene 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 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 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.
• (meth)acryloyl groups can be introduced.
• 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 hydroxyl groups is reacted with a diisocyanate compound to introduce isocyanate groups into the polymer, and then the hydroxyl groups and (meth ) A (meth)acryloyl group can also be introduced by reacting a compound having an 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 an epoxy group.
• a (meth)acryloyl group can also be introduced by reacting 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.
• Another example of a method for synthesizing the polyfunctional macromonomer (a2) is a method of dehydration condensation of methacrylic acid and acrylic acid on a polyoxyalkylene polymer having hydroxyl groups.
• methacrylic chloride, methacrylic bromide, methacrylic iodide, acrylic acid chloride, acrylic acid bromide, acrylic acid There is a method of reacting iodide or the like.
• 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, even more preferably 30,000 or less, particularly preferably 15,000 or less, and most preferably 10,000 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, even more preferably 20,000 or less, and most preferably 13,000 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 still more preferable, and 1.3 or less is particularly 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 copolymer (A) is a (meth)acrylic acid ester polymer molecular chain composed of a polymer such as (meth)acrylic acid ester (a1), and a polyfunctional macro It has a polyoxyalkylene polymer molecular chain derived from the monomer (a2).
• the (meth)acrylic acid ester copolymer (A) is a polyoxyalkylene-based It may have a structure in which more than one molecular chain of the (meth)acrylic acid ester-based polymer is bonded to one molecular chain of the polymer.
• the molecular chain of the polyoxyalkylene polymer may be introduced into either the terminal or the side chain (non-terminal portion) of the molecular chain of the (meth)acrylic acid ester polymer. It is preferably introduced into a side chain.
• the polyfunctional macromonomer (a2) has (meth)acryloyl groups at both ends of the molecular chain of the polyoxyalkylene polymer, at both ends of the molecular chain of the polyoxyalkylene polymer, ( An H-type structure in which the molecular chains of the meth)acrylic acid ester-based polymer are bonded can be formed.
• the molecular chain of the polyoxyalkylene-based polymer corresponds to the horizontal bar of H
• the molecular chain of the (meth)acrylic acid ester-based polymer corresponds to the two vertical bars included in H.
• 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). , more preferably 5 wt % or more and 60 wt % or less, and even more preferably 10 wt % or more and 50 wt % or less.
• the content of the polyfunctional macromonomer (a2) is preferably 60% by weight or less, more preferably 50% by weight or less, and even more preferably 35% by weight or less.
• the content of the polyfunctional macromonomer (a2) is preferably more than 35% by weight.
• the content of the polyfunctional macromonomer (a2) is 0.08 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 5.0 mol % or less, and more preferably 0.15 mol % or more and 2.3 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 the (meth)acrylic ester copolymer (A) is obtained by curing the (meth)acrylic ester copolymer (A). From the viewpoint of product strength, it is preferably 0.03 or more and 2.0 or less.
• the lower limit is more preferably 0.04 or more, more preferably 0.05 or more, even more preferably 0.07 or more, and particularly 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.
• a reactive silicon group can be introduced to the terminal of the molecular chain of the (meth)acrylic acid ester polymer.
• 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 0.1% by weight or more and 11% by weight or less with respect to the total amount of the monomer components constituting the (meth)acrylate copolymer (A). It is preferably 0.1% by weight or more and 10% by weight or less, more preferably 0.3% by weight or more and 7% by weight or less, and even more preferably 0.5% by weight or more and 5% by weight 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 determine the strength of the cured product obtained by curing the (meth)acrylate copolymer (A). is improved, the molar ratio of polyoxyalkylene polymer (a2)/chain transfer agent (a3) having a mercapto group is adjusted to satisfy 0.06 or more. If the molar ratio is less than 0.06, the weight average molecular weight of the (meth)acrylic acid ester copolymer (A) will not be sufficiently large, and the resulting cured product will have insufficient strength.
• the molar ratio is preferably 0.08 or more, more preferably 0.1 or more, still more preferably 0.12 or more, and particularly preferably 0.15 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.
• 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 3 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. By using the monomer (a4), a reactive silicon group can be introduced into the side chain (non-terminal portion) of the molecular chain of the (meth)acrylate polymer.
• 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 0.3 wt % or more and 30 wt % or less, and even more preferably 0.5 wt % or more and 20 wt % or less.
• the content of the monomer (a4) is preferably 10% by weight or less, and 5% by weight or less. More preferably, 3% by weight or less is even more preferable.
• the monomer component constituting the (meth)acrylic acid ester copolymer (A) contains another monomer (a5) that does not correspond to any of (a1) to (a4) detailed above. It may contain, or may not contain.
• Other monomers (a5) 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.
• (meth)acrylic acid styrene-based monomers such as styrene, vinyltoluene, ⁇ -methylstyrene, chlorostyrene, and styrenesulfonic acid; fluorine-containing compounds such as perfluoroethylene, perfluoropropylene, and vinylidene fluoride Vinyl monomers; maleic acid and its derivatives such as maleic acid, maleic anhydride, maleic acid monoalkyl esters and maleic acid dialkyl esters; fumaric acid and its derivatives such as fumaric acid, fumaric acid monoalkyl esters and fumaric acid dialkyl esters; Maleimide-based monomers such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide
• 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)acrylic acid ester copolymer (A) having a low viscosity can be obtained.
• 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. Above all, it is preferably 30,000 or more because good mechanical properties are exhibited.
• the value calculated by the following formula is 0.65 or more. is preferred.
• the fact that the value calculated by the above formula is 0.65 or more means that the average number of introduction of the polyoxyalkylene polymer (a2) in one molecule of the (meth)acrylic acid ester copolymer (A) is large.
• the strength of the cured product obtained by curing the (meth)acrylic acid ester copolymer (A) can be further improved.
• the value calculated by the above formula is more preferably 0.8 or more, more preferably 1.0 or more, even more preferably 1.1 or more, and 1.2 or more. It is particularly preferred, and 1.3 or more is most preferred.
• 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 composed of a (meth)acrylic ester-based polymer molecular chain
• the second molecular chain is composed of a polyoxyalkylene-based polymer molecular chain.
• 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 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 (2)). are connected through
• 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 include methacrylate, isobornyl acrylate, dicyclopentenyl acrylate, and , 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 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 3 .
• S represents a sulfur atom
• R3 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 reactive silicon group is a reactive silicon group represented by formula (1) described above. Specific examples of R 3 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 polyoxyalkylene polymer to the —SR 3 is 0.06 or more. If the molar ratio is less than 0.06, the weight average molecular weight of the (meth)acrylic acid ester copolymer (A) will not be sufficiently large, and the resulting cured product will have insufficient strength.
• the molar ratio is preferably 0.08 or more, more preferably 0.1 or more, still more preferably 0.12 or more, and particularly preferably 0.15 or more. Although the upper limit of the molar ratio is not particularly limited, it is preferably 1 or less, more preferably 0.5 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, 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-ethy
• alcohol compounds such as n-propanol, 2-propanol, n-butanol, 2-butanol, isobutanol, tert-butanol, and amyl alcohol.
• 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 the chain transfer agent (a3) added is 2% by weight or less, it is greatly affected by the type of solvent.
• isobutanol is preferably used as the solvent.
• an aromatic hydrocarbon solvent it is preferable to use an aromatic hydrocarbon solvent 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
• a chain transfer agent (a3) which additionally has reactive silicon groups, it will have reactive silicon groups. Both methods may be used in combination.
• a monomer (a4) having a reactive silicon group and a polymerizable unsaturated group a reactive silicon group is randomly introduced into the side chain of the molecular chain of the (meth)acrylic acid ester polymer. can be done.
• a chain transfer agent (a3) further having a reactive silicon group in addition to a mercapto group it is possible to introduce a reactive silicon group to the end of the molecular chain of the (meth)acrylate polymer. can.
• the following methods can be used in combination.
• a method of reacting a compound having a silicon group is used.
• a reaction method and the like can be exemplified.
• (ii) A method of modifying terminal functional groups of a (meth)acrylic acid ester-based copolymer synthesized by a living radical polymerization method to introduce a reactive silicon group.
• a (meth)acrylic acid ester-based copolymer obtained by a living radical polymerization method is easy to introduce a functional group to the polymer terminal, and by modifying this, a reactive silicon group can be introduced to the polymer terminal.
• Examples of the compound having a functional group that reacts with group V and a reactive silicon group used in method (i) include 3-isocyanatopropyldimethoxymethylsilane, 3-isocyanatopropyltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane.
• any modification reaction can be used.
• This embodiment also relates to a curable composition containing a (meth)acrylate copolymer (A).
• the curable composition may contain only the (meth)acrylic acid ester copolymer (A) as the reactive silicon group-containing polymer, or may contain the (meth)acrylic acid ester copolymer (A).
• other reactive silicon group-containing polymers may be contained.
• the curable composition according to the present embodiment promotes the reaction of condensing the reactive silicon groups of the (meth)acrylic acid ester-based copolymer (A), and for the purpose of chain extension or crosslinking of the polymer, silanol condensation It preferably contains a catalyst.
• 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, stearylamine; pyridine, 1,8-diazabicyclo[5,4,0]undecene-7 (DBU), 1, Nitrogen-containing heterocyclic compounds such as 5-diazabicyclo[4,3,0]nonene-5 (DBN); guanidines such as guanidine, phenylguanidine and diphenylguanidine; biguanides such as phenyl biguanide; amino group-containing silane coupling agents; ketimine 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), diisopropoxy aluminum ethylacetate
• titanium compounds such as tetrabutyl titanate, titanium tetrakis (acetylacetonate), diisopropoxytitanium bis (ethylacetonate), aluminum tris (acetylacetonate), diisopropoxy aluminum 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 preferably 0.001 to 20 parts by weight with respect to 100 parts by weight of the (meth) acrylic acid ester copolymer (A), and 0.01 to 15 parts by weight is more preferred, and 0.01 to 10 parts by weight is particularly preferred.
• the curable composition according to the present embodiment includes a (meth) acrylic acid ester copolymer (A), and an optional silanol condensation catalyst, as additives, a filler, an adhesion imparting agent, and an anti-sagging agents, antioxidants, light stabilizers, UV absorbers, and other resins.
• the curable composition according to the present embodiment may contain various additives as necessary for the purpose of adjusting various physical properties of the composition or its cured product.
• additives examples include plasticizers, solvents, diluents, photo-curing substances, oxygen-curing substances, surface property modifiers, silicates, curability modifiers, radical inhibitors, metal deactivators, agents, antiozonants, phosphorus peroxide decomposers, lubricants, pigments, antifungal agents, flame retardants, foaming agents, and the like.
• the curable composition according to this embodiment can contain a filler.
• Such fillers include ground calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, clay, talc, titanium oxide, fumed silica, precipitated silica, crystalline silica, fused silica, wet silica, anhydrous silica. Acid, hydrous silicic acid, alumina, carbon black, ferric oxide, fine aluminum powder, zinc oxide, activated zinc white, PVC powder, PMMA powder, glass fiber, filament and the like.
• the amount of the filler used is preferably 1 to 300 parts by weight, more preferably 10 to 250 parts by weight, per 100 parts by weight of the (meth)acrylate copolymer (A).
• Organic balloons and inorganic balloons may be added for the purpose of weight reduction (lower specific gravity) of the composition.
• the curable composition according to this embodiment can contain an adhesion imparting agent.
• a silane coupling agent or a reactant of the silane coupling agent can be used 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 adhesiveness-imparting agent may be used alone or in combination of two or more.
• the amount of the silane coupling agent used 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).
• plasticizer can be added to the curable composition according to the present embodiment.
• plasticizers include dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di(2-ethylhexyl) phthalate, diisodecyl phthalate (DIDP), phthalate compounds such as butylbenzyl phthalate; bis(2-ethylhexyl )-terephthalate compounds such as 1,4-benzenedicarboxylate; non-phthalate compounds such as 1,2-cyclohexanedicarboxylic acid diisononyl ester; dioctyl adipate, dioctyl sebacate, dibutyl sebacate, diisodecyl succinate, Aliphatic polyvalent carboxylic acid ester compounds such as tributyl acetylcitrate; unsaturated fatty acid ester compounds such as butyl ole
• polymer plasticizer can be used.
• 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; polyethers such as derivatives converted to polystyrenes; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene and the like.
• a plasticizer may be used individually and may use 2 or more types together.
• the amount of the plasticizer used is preferably 5 to 150 parts by weight, more preferably 10 to 120 parts by weight, and more preferably 20 to 100 parts by weight with respect to 100 parts by weight of the (meth)acrylate copolymer (A). More preferred.
• Solvents and diluents that can be used include, but are not limited to, aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, alcohols, esters, ketones, and ethers.
• the boiling point of the solvent is preferably 150° C. or higher, more preferably 200° C. or higher, and particularly preferably 250° C. or higher, because of the problem of air pollution when the composition is used indoors. .
• the above solvents or diluents may be used alone or in combination of two or more.
• the curable composition according to the present embodiment may contain an anti-sagging agent as necessary to prevent sagging and improve workability.
• the anti-sagging agent is not particularly limited, but examples thereof include polyamide waxes; hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate and barium stearate. These anti-sagging agents may be used alone or in combination of two or more.
• the amount of anti-sagging agent used is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the (meth)acrylate copolymer (A).
• the curable composition according to this embodiment can contain an antioxidant (antiaging agent).
• 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 amount of the antioxidant used 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).
• the curable composition according to this embodiment can contain a light stabilizer.
• a light stabilizer can prevent photo-oxidative deterioration of the cured product.
• Examples of light stabilizers include benzotriazole-based, hindered amine-based, and benzoate-based compounds, with hindered amine-based compounds being particularly preferred.
• the amount of light stabilizer used 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).
• the curable composition according to this embodiment can contain an ultraviolet absorber.
• 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. Benzotriazoles are particularly preferred. Specific examples include commercial names Tinuvin P, Tinuvin 213, Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 329, and Tinuvin 571 (manufactured by BASF).
• the amount of the ultraviolet absorber used 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 according to the present embodiment, if necessary.
• the physical property modifier is not particularly limited, for example, alkylalkoxysilanes such as phenoxytrimethylsilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and 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).
• a tackifying resin can be added to the curable composition according to the present embodiment for the purpose of enhancing the adhesiveness or adhesion to a substrate, or for other purposes.
• the tackifying resin there is no particular limitation, and those commonly used can be used.
• terpene-based resins aromatic modified terpene resins, hydrogenated terpene resins, terpene-phenolic resins, phenolic resins, modified phenolic resins, xylene-phenolic resins, cyclopentadiene-phenolic resins, coumarone-indene resins, rosin-based Resins, rosin ester resins, hydrogenated rosin ester resins, xylene resins, low molecular weight polystyrene resins, styrene copolymer resins, styrene block copolymers and hydrogenated products thereof, petroleum resins (e.g., C5 hydrocarbon resins, C9 hydrocarbon resins, C5C9 hydrocarbon copolymer resins, etc.), hydrogenated petroleum resins, DCPD resins, and the like. These may be used alone or in combination of two or more.
• petroleum resins e.g., C5 hydrocarbon resins, C9 hydrocarbon resins, C
• the amount of the tackifying resin used is preferably 2 to 100 parts by weight, more preferably 5 to 50 parts by weight, more preferably 5 to 30 parts by weight, based on 100 parts by weight of the (meth)acrylate copolymer (A). Parts by weight are more preferred.
• a compound containing an epoxy group can be used in the curable composition according to the present embodiment.
• the use of a compound having an epoxy group can enhance the restorability of the cured product.
• compounds having an epoxy group include epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, epichlorohydrin derivatives, and mixtures thereof.
• the epoxy compound is preferably used in an amount of 0.5 to 50 parts by weight per 100 parts by weight of the (meth)acrylate copolymer (A).
• a photocurable substance can be used in the curable composition according to the present embodiment.
• a photocurable substance When a photocurable substance is used, a film of the photocurable substance is formed on the surface of the cured product, and the stickiness of the cured product and the weather resistance of the cured product can be improved.
• Many compounds such as organic monomers, oligomers, resins, or compositions containing them are known as this type of compound. Unsaturated acrylic compounds, polyvinyl cinnamates, azide resins, etc., which are monomers, oligomers, or mixtures thereof can be used.
• the amount of the photocurable substance used is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the (meth)acrylic acid ester copolymer (A), and more preferably 0.5 to 10 parts by weight. preferable.
• oxygen-curable substance can be used in the curable composition according to this embodiment.
• oxygen-curable substances include unsaturated compounds that can react with oxygen in the air, and react with oxygen in the air to form a hardened film near the surface of the cured product, which causes the surface to become sticky and dust on the surface of the cured product. and prevent the adhesion of dust.
• Specific examples of oxygen-curable substances include drying oils such as paulownia oil and linseed oil, various alkyd resins obtained by modifying these compounds; acrylic polymers modified with drying oils, and epoxy resins.
• silicone resins 1,2-polybutadiene, 1,4-polybutadiene, C5-C8 diene polymers obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, 1,3-pentadiene, etc.
• diene compounds such as butadiene, chloroprene, isoprene, 1,3-pentadiene, etc.
• liquid polymers These may be used alone or in combination of two or more.
• the amount of the oxygen-curable substance used is preferably in the range of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, per 100 parts by weight of the (meth)acrylic acid ester copolymer (A). part is more preferred.
• oxygen-curable substances are preferably used in combination with photo-curable substances.
• Epoxy resin can be used in combination with the curable composition according to the present embodiment.
• a composition containing an epoxy resin is particularly preferred as an adhesive, especially an adhesive for exterior wall tiles.
• epoxy resins include bisphenol A type epoxy resins and novolac type epoxy resins.
• a curing agent that cures the epoxy resin can be used in combination with the curable composition according to the present embodiment.
• the epoxy resin curing agent that can be used is not particularly limited, and generally used epoxy resin curing agents can be used.
• the amount used is preferably in the range of 0.1 to 300 parts by weight with respect to 100 parts by weight of the epoxy resin.
• the curable composition according to the present embodiment is preferably prepared as a one-component type in which all the ingredients are preliminarily blended, sealed and stored, and cured by moisture in the air after application.
• the curable composition is of the one-component type, all ingredients are blended in advance. Therefore, ingredients containing water are dehydrated and dried before use, or dehydrated by decompression during compounding and kneading. is preferred.
• the heat drying method is suitable for solid substances such as powder, and the dehydration method under reduced pressure or the dehydration method using synthetic zeolite, activated alumina, silica gel, quicklime, magnesium oxide, etc. is suitable for liquid substances.
• a small amount of an isocyanate compound may be blended to react the isocyanate groups with water to dehydrate.
• An oxazolidine compound such as 3-ethyl-2-methyl-2-(3-methylbutyl)-1,3-oxazolidine may be blended and reacted with water for dehydration.
• the storage stability can be further improved by adding lower alcohols such as methanol and ethanol, and alkoxysilane compounds.
• alkoxysilane compounds include methyltrimethoxysilane, phenyltrimethoxysilane, n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, ⁇ -mercaptopropylmethyldimethoxysilane, ⁇ -mercaptopropylmethyldimethoxysilane. ethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, and the like.
• the amount of the dehydrating agent, particularly the alkoxysilane compound used, is preferably 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, relative to 100 parts by weight of the (meth)acrylate copolymer (A). more preferred.
• the method for preparing the curable composition according to this embodiment is not particularly limited.
• the above components are blended and kneaded at room temperature or under heat 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 the present embodiment includes sealing materials for buildings, ships, automobiles, roads, etc., adhesives, molding agents, vibration-proof materials, vibration-damping materials, sound-proof materials, foam materials, paints, spraying materials, It can be used as a coating film waterproofing agent.
• the curable composition is a sealant or an adhesive. It is more preferable to use as
• the curable composition according to the present embodiment includes electrical and electronic component materials such as solar cell backside sealing materials, electrical insulating materials such as insulating coating materials for electric wires and cables, elastic adhesives, contact adhesives, and spray seals. materials, crack repair materials, adhesives for tiling, powder coatings, casting materials, medical rubber materials, medical adhesives, sealing materials for medical equipment, food packaging materials, joint sealing materials for exterior materials such as sizing boards , coating materials, primers, conductive materials for shielding electromagnetic waves, thermally conductive materials, hot-melt materials, potting agents for electrical and electronic devices, films, gaskets, various molding materials, rust prevention of wire glass and laminated glass edge faces (cut parts) ⁇ It can be used for various purposes such as waterproof sealing materials, liquid sealants used in automotive parts, electrical parts, and various machine parts.
• electrical and electronic component materials such as solar cell backside sealing materials, electrical insulating materials such as insulating coating materials for electric wires and cables, elastic adhesives, contact adhesives, and spray seals. materials, crack repair
• the cured product of the curable composition according to the present embodiment can adhere to a wide range of substrates such as glass, porcelain, wood, metal, and resin moldings by using alone or in combination with a primer.
• the article can also be used as a sealing composition or adhesive composition.
• the curable composition according to the present embodiment is an adhesive for interior panels, an adhesive for exterior panels, an adhesive for tiling, an adhesive for masonry, an adhesive for ceiling finishing, an adhesive for floor finishing, and an adhesive for wall finishing.
• Adhesives, vehicle panel adhesives, electrical/electronic/precision equipment assembly adhesives, direct glazing sealing materials, double glazing sealing materials, SSG construction method sealing materials, or building working joint sealing materials is also available.
• 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-8220GPC
• Column TSK-GEL H type manufactured by Tosoh Solvent: THF
• Molecular weight Polystyrene equivalent Measurement temperature: 40°C
• 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.
• a polymer having acryloyl groups at both ends (that is, having about two acryloyl groups in one polymer molecule), having a number average molecular weight of 4,020 and a weight average molecular weight of 4,860
• An oxyalkylene polymer (a2-1) was obtained.
• Synthesis example 2 Polyoxypropylene glycol with a number average molecular weight of about 4,020 (molecular weight as converted to terminal group: 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.
• the solution was added dropwise over 5 hours. Furthermore, a mixed solution of 0.7 parts by weight of 2,2'-azobis(2-methylbutyronitrile) dissolved in 8.1 parts by weight of isobutanol was added, and polymerization was carried out at 105°C for 2 hours.
• An isobutanol solution (solid content: 60%) of a reactive silicon group-containing (meth)acrylic acid ester copolymer (A-1) having a molecular weight of 470 (GPC) was obtained.
• the solid content of the solution has a polyfunctional macromonomer equivalent weight of 0.070 mmol/g, a reactive silicon group equivalent weight of 0.42 mmol/g, and a sulfur atom concentration of 10,941 ppm.
• an isobutanol solution (solid content: 60%) of the reactive silicon group-containing (meth)acrylic acid ester copolymer (A-2) was obtained.
• the solid content of the solution has a polyfunctional macromonomer equivalent weight of 0.12 mmol/g, a reactive silicon group equivalent weight of 0.34 mmol/g, and a sulfur atom concentration of 10,291 ppm.
• the solution was added dropwise over 5 hours. Further, a mixed solution of 0.7 parts by weight of 2,2'-azobis(2-methylbutyronitrile) dissolved in 8.1 parts by weight of isobutanol was added, and polymerization was carried out at 105°C for 2 hours.
• An isobutanol solution (solid content: 60%) of a reactive silicon group-containing (meth)acrylate copolymer (A-3) having a molecular weight of 910 (GPC) was obtained.
• the solid content of the solution has a polyfunctional macromonomer equivalent weight of 0.094 mmol/g, a reactive silicon group equivalent weight of 0.53 mmol/g, and a sulfur atom concentration of 15,961 ppm.
• a mixed solution dissolved in .9 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 9.5 parts by weight of isobutanol was added, and polymerization was carried out at 105°C for 2 hours.
• An isobutanol solution (solid content: 60%) of a reactive silicon group-containing (meth)acrylate copolymer (A-5) having a molecular weight of 120 (GPC) was obtained.
• the solid content of the solution has a polyfunctional macromonomer equivalent weight of 0.012 mmol/g, a reactive silicon group equivalent weight of 0.12 mmol/g, and a sulfur atom concentration of 2,402 ppm.
• a mixed solution of 0.2 parts by weight of 2,2′-azobis(2-methylbutyronitrile) dissolved in 5.3 parts by weight of SOLVESSO 100 was added and polymerized at 110° C. for 2 hours to obtain a number average molecular weight of 5,360.
• a solution (solid content: 60%) of reactive silicon group-containing (meth)acrylic acid ester copolymer (A-9) having (GPC molecular weight) was obtained.
• the solid content of the solution has a polyfunctional macromonomer equivalent weight of 0.0091 mmol/g, a reactive silicon group equivalent weight of 0.18 mmol/g, and a sulfur atom concentration of 3,912 ppm.
• the dissolved mixed solution was added dropwise over 5 hours. Further, a mixed solution of 0.7 parts by weight of 2,2'-azobis(2-methylbutyronitrile) dissolved in 8.1 parts by weight of isobutanol was added, and polymerization was carried out at 105°C for 2 hours.
• An isobutanol solution (60% solid content) of a reactive silicon group-containing (meth)acrylic acid ester copolymer (P-3) having a molecular weight of 980 (GPC) was obtained.
• the solid content of the solution has a reactive silicon group equivalent of 0.72 mmol/g and a sulfur atom concentration of 10,948 ppm.
• An isobutanol solution (solid content: 60%) of a reactive silicon group-containing (meth)acrylic acid ester copolymer (P-6) having a GPC molecular weight of 770 was obtained.
• the solid content of the solution has a reactive silicon group equivalent of 0.20 mmol/g and a sulfur atom concentration of 5,716 ppm.
• a polyfunctional macromonomer (a2) which is a polyoxyalkylene polymer having more than one (meth)acryloyl group in one molecule, and a mercapto group
• Reactive silicon group-containing (meth)acrylic acid ester copolymers (A-1) to (A-3) could be synthesized by copolymerizing both chain transfer agents (a3) possessed.
• These copolymers (A-1) to (A-3) include block copolymers formed by copolymerizing the polyfunctional macromonomer (a2) with butyl acrylate or the like.
• the (meth)acrylate copolymer (P-2) of Comparative Example 2 was synthesized without using the polyfunctional macromonomer (a2) and is a random copolymer. From Table 1, the (meth) acrylic ester copolymers (A-1) to (A-3) have a weight average molecular weight compared to the (meth) acrylic ester copolymer (P-2). It can be seen that the viscosity relative to (Mw) is low. For example, (A-3) has a viscosity of about 1/4 that of (P-2), although it has a weight average molecular weight slightly higher than that of (P-2). In addition, although (A-2) has a weight average molecular weight as high as about three times that of (P-2), its viscosity is almost the same.
• the (meth)acrylate copolymer (P-3) of Comparative Example 3 is an allyl group-containing polyoxyalkylene polymer (p -1), judging from its weight average molecular weight (Mw), copolymerization of (p-1) hardly progressed. That is, the (meth)acrylic acid ester copolymers (A-1) to (A-3) have low viscosities despite the progress of copolymerization of the polyfunctional macromonomer (a2). I understand.
• Neostan U-20 dibutyltin dibutylmalate manufactured by Nitto Kasei Co., Ltd.
• a sheet of The obtained sheet was subjected to hardening and curing for 2 weeks under conditions of 23° C. and 50% RH.
• a strip test piece of 70 mm ⁇ 10 mm was cut out from the obtained sheet, and the tensile physical properties were measured at 23° C. with the distance between grips set to 40 mm.
• the cured products obtained from the (meth)acrylic acid ester copolymers (A-4) to (A-7) of Examples 4 to 7 were chain transfer agents (a3 ) compared to the cured product obtained from the (meth)acrylic ester-based copolymer (P-4) of Comparative Example 4 in which the ratio of the polyfunctional macromonomer (a2) used is small, 30% modulus (M30) , tensile strength (TB) and Young's modulus.
• the (meth)acrylic acid ester copolymer (P-5) of Comparative Example 5 has a monomer ( The amount of a4) used is increased to increase the reactive silicon group equivalent.
• Comparative Example 5 had slightly higher values of tensile strength and Young's modulus, but significantly lower elongation.
• Examples 4 to 6 have larger values of tensile strength and Young's modulus than Comparative Example 5, and also have larger elongation. From the (meth)acrylic acid ester copolymer (P-6) of Comparative Example 6 synthesized without using the polyfunctional macromonomer (a2), the cured product was too soft and a test piece could not be produced. rice field.
• the cured products obtained from the (meth)acrylate copolymers (A-8) and (A-9) of Examples 8 and 9 have high Young's moduli.

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