WO2013011943A1 - Composition de résine durcissable, revêtement, et article portant un film obtenu par durcissage dudit revêtement - Google Patents

Composition de résine durcissable, revêtement, et article portant un film obtenu par durcissage dudit revêtement Download PDF

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WO2013011943A1
WO2013011943A1 PCT/JP2012/067931 JP2012067931W WO2013011943A1 WO 2013011943 A1 WO2013011943 A1 WO 2013011943A1 JP 2012067931 W JP2012067931 W JP 2012067931W WO 2013011943 A1 WO2013011943 A1 WO 2013011943A1
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group
composite resin
vinyl polymer
segment
polymer segment
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PCT/JP2012/067931
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English (en)
Japanese (ja)
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幸司 植村
直人 矢木
高田　泰廣
伸一 工藤
博 松沢
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Dic株式会社
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Publication of WO2013011943A1 publication Critical patent/WO2013011943A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6295—Polymers of silicium containing compounds having carbon-to-carbon double bonds
    • 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
    • C08F275/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers containing phosphorus, selenium, tellurium or a metal as defined in group C08F30/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/10—Block or graft copolymers containing polysiloxane sequences
    • 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
    • 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
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences

Definitions

  • the present invention relates to a curable composition that can be cured at room temperature, has excellent transparency, and has excellent weather resistance after curing, a paint containing the curable resin composition, and an article having a cured coating film of the paint.
  • polyester resins such as polyethylene terephthalate (PET), acrylic resins, ABS resins, polycarbonate resins and plastics such as fiber reinforced plastic (FRP) have been used for exterior construction in terms of lightness, impact resistance, workability and recyclability. Widely used in parts and automotive exterior parts. However, it has been pointed out that these synthetic resins suffer from yellowing and cracking due to long-term outdoor use.
  • PET polyethylene terephthalate
  • acrylic resins acrylic resins
  • ABS resins polycarbonate resins
  • plastics such as fiber reinforced plastic (FRP)
  • curable resin compositions for use in polysiloxane-based paints the inventors previously described polymers having functional groups other than hydrolyzable silyl groups and hydrolyzable silyl groups, silanol groups and / or hydrolyzable silyls.
  • a curable resin composition containing a resin obtained by condensation reaction of a polysiloxane having a group and a curing agent has been invented and disclosed (for example, see Patent Document 1).
  • the cured coating film obtained from the curable resin composition is excellent in weather resistance and scratch resistance.
  • the curable resin composition is a resin that is cured by heat, and particularly when it is cured by heat, heating at a high temperature of 140 ° C.
  • Patent Document 1 see Example 1
  • Patent Document 1 Japanese Patent Document 1
  • the construction is difficult when the construction is performed outdoors such as a wall surface of a building, and a high weather resistance resin that can be cured at room temperature is demanded.
  • Patent Document 2 a resin obtained by further modifying a fatty acid-modified acrylic resin with a silicon resin as a resin that has good storage stability and can be cured at room temperature, and an epoxy group is introduced into the resin.
  • a resin in which an epoxy group is opened and reacted during resin synthesis is disclosed. Although the resin can be cured at room temperature, since the produced resin is brown, there is a great problem in using it as an exterior paint.
  • the problem to be solved by the present invention is a two-component curable resin composition that has excellent storage stability in a one-component state, can be cured at room temperature, and has excellent transparency, and contains the curable resin composition. It is to provide an article having a paint and a cured coating of the paint.
  • a curable resin which is a resin composition, wherein the mass ratio of the polysiloxane segment in the composite resin, the epoxy equivalent of the composite resin, the amount of hydroxyl groups in the vinyl polymer segment, and the mass ratio of the polyisocyanate are within a specific range
  • the composition is excellent in long-term storage stability in a one-liquid state before adding a curing agent, and in a two-liquid state in which a curing agent is added, a cured coating having excellent curability and weather resistance after curing at room temperature and transparency.
  • the present invention provides a polysiloxane segment (a1) having a structural unit represented by the general formula (1) and / or the general formula (2), a silanol group and / or a hydrolyzable silyl group, and an epoxy group.
  • Resin composition containing a composite resin (A) in which a vinyl polymer segment (a2) having an alcoholic hydroxyl group is bonded by a bond represented by the general formula (3), and a polyisocyanate (B)
  • the mass ratio of the polysiloxane segment (a1) in the solid content of the composite resin (A) is 20 to 70% by mass, and the epoxy equivalent of the solid content of the composite resin (A) is 900 to 17,000 g / eq, the hydroxyl value of the vinyl polymer segment (a2) is 55 to 200 mgKOH / g, and the mass ratio of the polyisocyanate (B) Providing a curable resin composition which is a 5 to 50% by weight of the total solids.
  • R 1 , R 2 and R 3 each independently represent —R 4 —CH ⁇ CH 2 , —R 4 —C (CH 3 ) ⁇ CH 2 , — A group having one polymerizable double bond selected from the group consisting of R 4 —O—CO—C (CH 3 ) ⁇ CH 2 and —R 4 —O—CO—CH ⁇ CH 2 (provided that R 4 Represents a single bond or an alkylene group having 1 to 6 carbon atoms.), An alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group, or 7 carbon atoms. Represents an aralkyl group of ⁇ 12.
  • the present invention is to provide an article characterized by having a paint containing the curable resin composition and a coating film formed using the paint.
  • the curable resin composition of the present invention is excellent in curability even at room temperature curing, it is difficult to cure by active energy rays or heat, it is particularly useful as a cured coating for outdoor enforcement or large buildings, cured products Is particularly useful as a coating for exterior building because it has long-term weather resistance outdoors.
  • the curable resin composition of this invention is a 2 liquid type, the storage stability in the state of 1 liquid before mixing is also favorable, and it is excellent in the usefulness as a coating material.
  • the curable resin composition and paint of the present invention are colorless, it can be suitably used as a top coat, undercoat, clear paint or enamel paint.
  • the curable resin composition of the present invention has a structural unit represented by the general formula (1) and / or the general formula (2), a silanol group and / or a hydrolyzable silyl group, and an epoxy group.
  • a composite resin (A) in which a polysiloxane segment (a1) and a vinyl polymer segment (a2) having an alcoholic hydroxyl group are bonded by a bond represented by the general formula (3); and a polyisocyanate (B) A curable resin composition containing, wherein the mass ratio of the polysiloxane segment (a1) in the solid content of the composite resin (A) is 20 to 70% by mass, and the solid content of the composite resin (A)
  • the epoxy equivalent is 900 to 17000 g / eq, the hydroxyl value of the vinyl polymer segment (a2) is 55 to 200 mg KOH / g, and the polyisocyanate Weight ratio of bets (B) are those from 5 to 50% by weight of the total solids.
  • the composite resin (A) used in the present invention comprises a structural unit represented by the general formula (1) and / or the general formula (2), a silanol group and / or a hydrolyzable silyl group, an epoxy group, A polysiloxane segment (a1) having the following (hereinafter simply referred to as polysiloxane segment (a1)), a vinyl polymer segment (a2) having an alcoholic hydroxyl group (hereinafter simply referred to as vinyl polymer segment (a2)), and Is a composite resin bonded by a bond represented by the general formula (3).
  • the bond represented by the general formula (3) is generated. Accordingly, in the general formula (3), carbon atoms constitute a part of the vinyl polymer segment (a2), and silicon atoms bonded only to oxygen atoms constitute a part of the polysiloxane segment (a1).
  • the form of the composite resin (A) is, for example, a composite resin having a graft structure in which the polysiloxane segment (a1) is chemically bonded as a side chain of the polymer segment (a2), or the polymer segment (a2). And a composite resin having a block structure in which the polysiloxane segment (a1) is chemically bonded.
  • the polysiloxane segment (a1) in the present invention comprises a structural unit represented by the general formula (1) and / or the general formula (2), a silanol group and / or a hydrolyzable silyl group, and an epoxy group. It has a segment.
  • R 1 , R 2 and R 3 in the general formulas (1) and (2) are each independently —R 4 —CH ⁇ CH 2 , —R 4 —C (CH 3 ) ⁇ A group having one polymerizable double bond selected from the group consisting of CH 2 , —R 4 —O—CO—C (CH 3 ) ⁇ CH 2 , and R 4 —O—CO—CH ⁇ CH 2 (provided that R 4 represents a single bond or an alkylene group having 1 to 6 carbon atoms.), An alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group, or 7 to 7 carbon atoms. 12 aralkyl groups are represented.
  • alkylene group having 1 to 6 carbon atoms in R 4 examples include methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, sec-butylene group, tert-butylene group, and pentylene.
  • R 4 is preferably a single bond or an alkylene group having 2 to 4 carbon atoms because of easy availability of raw materials.
  • alkyl group having 1 to 6 carbon atoms examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, and isopentyl.
  • Examples of the cycloalkyl group having 3 to 8 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
  • Examples of the aryl group include a phenyl group, a naphthyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 4-vinylphenyl group, and a 3-isopropylphenyl group.
  • Examples of the aralkyl group having 7 to 12 carbon atoms include a benzyl group, a diphenylmethyl group, and a naphthylmethyl group.
  • R 1 , R 2 and R 3 when at least one of R 1 , R 2 and R 3 is a group having the polymerizable double bond, it can be cured by an active energy ray or the like, an active energy ray, and a silanol group and / or
  • the two curing mechanisms of improving the crosslinking density of the coating film by the condensation reaction of hydrolyzable silyl groups can form a cured coating film with better wear resistance, acid resistance, alkali resistance and solvent resistance, It is difficult to use a curable resin composition, and it can be suitably used for a base material that easily undergoes thermal deformation, such as paints for exterior buildings and plastics.
  • Two or more groups having a polymerizable double bond are present in the polysiloxane segment (a1), preferably 3 to 200, more preferably 3 to 50, A coating film with more excellent wear resistance can be obtained.
  • the content of polymerizable double bonds in the polysiloxane segment (a1) is 3 to 35% by mass, desired wear resistance can be obtained.
  • the polymerizable double bond here is a general term for groups capable of performing a growth reaction by free radicals among vinyl group, vinylidene group or vinylene group.
  • the content rate of a polymerizable double bond shows the mass% in the polysiloxane segment of the said vinyl group, vinylidene group, or vinylene group.
  • —R 4 —C (CH 3 ) The (meth) acryloyl group represented by CH 2 or —R 4 —O—CO—C (CH 3 ) ⁇ CH 2 is rich in reactivity at the time of ultraviolet curing, and the vinyl polymer segment (described later) Good compatibility with a2).
  • the structural unit represented by the general formula (1) and / or the general formula (2) is a three-dimensional network-like polysiloxane structural unit in which two or three of the silicon bonds are involved in crosslinking. Since a three-dimensional network structure is formed but a dense network structure is not formed, gelation or the like is not caused and storage stability is also improved.
  • the polysiloxane segment (a1) constituting the composite resin (A) in the present invention has an epoxy group, and the epoxy equivalent of the solid content of the composite resin (A) is 900 to 17000 g / eq.
  • the range of 2500 to 6000 g / eq is particularly preferable because of excellent long-term storage stability and room temperature curability when a curable resin composition is obtained.
  • the epoxy equivalent of solid content is larger than 17000 g / eq, the composite resin (A) is easily gelled and cannot be stored for a long time.
  • it is a case where it is less than 900 g / eq when it mixes with a polyisocyanate (B) and it is set as a curable resin composition, it becomes impossible to cure at normal temperature.
  • Epoxy group-containing silane compounds include ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxyethoxysilane, ⁇ -glycidoxypropyltriacetoxysilane, ⁇ -(3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltriethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxyethoxysilane, ⁇ - (3, 4-epoxycyclohexyl) ethyltriacetoxysilane, ⁇ -g
  • the silanol group is a silicon-containing group having a hydroxyl group directly bonded to a silicon atom.
  • the silanol group is a silanol group formed by combining an oxygen atom having a bond with a hydrogen atom in the structural unit represented by the general formula (1) and / or the general formula (2). Preferably there is.
  • the hydrolyzable silyl group is a silicon-containing group having a hydrolyzable group directly bonded to a silicon atom, and specifically includes, for example, a group represented by the general formula (4). .
  • R 5 is a monovalent organic group such as an alkyl group, an aryl group or an aralkyl group
  • R 6 is a halogen atom, an alkoxy group, an acyloxy group, a phenoxy group, an aryloxy group, a mercapto group
  • a hydrolyzable group selected from the group consisting of an amino group, an amide group, an aminooxy group, an iminooxy group, and an alkenyloxy group
  • b is an integer of 0 to 2.
  • Examples of the alkyl group in R 5 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, and a tert group.
  • -Pentyl group 1-methylbutyl group, 2-methylbutyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, hexyl group, isohexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl Group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 2,2-dimethylbutyl group, 1-ethylbutyl group, 1,1,2-trimethylpropyl group, 1,2,2-trimethylpropyl group 1-ethyl-2-methylpropyl group, 1-ethyl-1-methylpropyl group and the like.
  • Examples of the group include a phenyl group, a naphthyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 4-vinylphenyl group, and a 3-isopropylphenyl group.
  • Examples of the aralkyl group include a benzyl group, a diphenylmethyl group, and a naphthylmethyl group.
  • examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a tert-butoxy group, and a sec-butoxy group.
  • acyloxy group examples include formyloxy group, acetoxy group, propanoyloxy group, butanoyloxy group, pivaloyloxy group, pentanoyloxy group, phenylacetoxy group, acetoacetoxy group, benzoyloxy group, naphthoyloxy group, etc. Is mentioned.
  • aryloxy group examples include a phenyloxy group and a naphthyloxy group.
  • alkenyloxy group examples include vinyloxy group, allyloxy group, 1-propenyloxy group, isopropenyloxy group, 2-butenyloxy group, 3-butenyloxy group, 2-petenyloxy group, 3-methyl-3-butenyloxy group, 2 -Hexenyloxy group and the like.
  • the hydrolyzable silyl group represented by the general formula (4) becomes a silanol group.
  • a methoxy group and an ethoxy group are preferable because of excellent hydrolyzability.
  • the hydrolyzable silyl group specifically includes an oxygen atom having a bond in the structural unit represented by the general formula (1) and / or the general formula (2) bonded to the hydrolyzable group. Or it is preferable that it is the hydrolyzable silyl group substituted.
  • the silanol group or the hydrolyzable silyl group undergoes a hydrolytic condensation reaction between the hydroxyl group in the silanol group or the hydrolyzable group in the hydrolyzable silyl group, the polysiloxane structure of the resulting coating film The crosslink density increases, and a coating film excellent in solvent resistance can be formed. Further, the polysiloxane segment (a1) containing the silanol group or the hydrolyzable silyl group is bonded to the vinyl polymer segment (a2) described later via the bond represented by the general formula (3). Use when.
  • examples of the structure in which at least one of R 1 , R 2, and R 3 is a group having the polymerizable double bond as the polysiloxane segment (a1) include the following structures.
  • the mass ratio of the polysiloxane segment (a1) in the solid content of the composite resin (A) is 20 to 70% by mass, whereby the curable resin composition has a normal temperature. It becomes possible to achieve both curability and weather resistance.
  • the vinyl polymer segment (a2) in the present invention is a vinyl polymer segment such as an acrylic polymer, a fluoroolefin polymer, a vinyl ester polymer, an aromatic vinyl polymer, and a polyolefin polymer. . These are preferably selected appropriately depending on the application.
  • the acrylic polymerizable segment is obtained by polymerizing or copolymerizing a general-purpose (meth) acrylic monomer.
  • the (meth) acrylic monomer is not particularly limited, and vinyl monomers can also be copolymerized.
  • Fluoroolefins alkyl vinyl ethers such as ethyl vinyl ether and n-butyl vinyl ether; cycloalkyl vinyl ethers such as cyclopentyl vinyl ether and cyclohexyl vinyl ether; N, N-dimethyl (meth) Acrylamide, N- (meth) acryloyl morpholine, N- (meth) acryloyl pyrrolidine, tertiary amide group-containing monomers such as N- vinylpyrrolidone and the like.
  • the polymerization method the solvent, or the polymerization initiator for copolymerizing the monomers
  • the vinyl polymer segment (a2) can be obtained by a known method.
  • 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4-) can be obtained by various polymerization methods such as bulk radical polymerization, solution radical polymerization, and non-aqueous dispersion radical polymerization.
  • the vinyl polymer segment (a2) can be obtained by using a polymerization initiator such as tert-butyl peroxide, cumene hydroperoxide, diisopropyl peroxycarbonate or the like.
  • the number average molecular weight of the vinyl polymer segment (a2) is preferably in the range of 500 to 200,000 in terms of number average molecular weight (hereinafter abbreviated as “Mn”). It is possible to prevent thickening and gelation during the production of A) and is excellent in durability. In particular, Mn is more preferably in the range of 700 to 100,000, and more preferably in the range of 1,000 to 50,000, because a good film can be formed when a layer is formed on the substrate.
  • the vinyl polymer segment (a2) is a vinyl polymer segment (A1) in order to form a composite resin (A) bonded to the polysiloxane segment (a1) by a bond represented by the general formula (3). It has a silanol group and / or a hydrolyzable silyl group directly bonded to the carbon atom in a2). Since these silanol groups and / or hydrolyzable silyl groups become bonds represented by the general formula (3) in the production of the composite resin (A) described later, the composite resin ( Almost no vinyl polymer segment (a2) in A).
  • the vinyl polymer segment (a2) having a silanol group and / or a hydrolyzable silyl group directly bonded to a carbon atom includes the general-purpose monomer, the silanol group directly bonded to the carbon bond, and / or It is obtained by copolymerizing a vinyl monomer containing a hydrolyzable silyl group.
  • vinyl monomers containing a silanol group and / or a hydrolyzable silyl group directly bonded to a carbon atom include vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, and vinyltri (2-methoxyethoxy) silane.
  • the vinyl polymer segment (a2) contains an alcoholic hydroxyl group. It is important that the hydroxyl group value of the vinyl polymer segment (a2) is 55 to 200 mgKOH / g because it reacts with the polyisocyanate (B) and cures at room temperature, preferably in the range of 90 to 200 mgKOH / g. .
  • the hydroxyl value is less than 55 mgKOH / g, it is difficult to react with the polyisocyanate (B), so it does not cure at room temperature, and when the hydroxyl value is more than 200 mgKOH / g, gelation occurs when the composite resin (A) is synthesized. Is not preferable.
  • the vinyl polymer segment (a2) having an alcoholic hydroxyl group can be obtained by copolymerizing a (meth) acryl monomer having an alcohol hydroxyl group.
  • the (meth) acrylic monomer having an alcohol hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) ) Acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, di-2-hydroxyethyl fumarate, mono-2-hydroxyethyl mono Butyl fumarate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, “Placcel FM” or “Placcel FA” (both caprolactone addition monomers manufactured by Daicel Chemical Industries, Ltd.) Various alpha,
  • the composite resin (A) used in the present invention is produced by the methods shown in the following (Method 1) to (Method 3).
  • Method 1 The general-purpose (meth) acrylic monomer and the like, and a vinyl monomer containing a silanol group and / or a hydrolyzable silyl group directly bonded to the carbon bond are copolymerized and directly bonded to the carbon bond.
  • a vinyl polymer segment (a2) containing a silanol group and / or a hydrolyzable silyl group is obtained.
  • This and a silane compound are mixed and hydrolytic condensation reaction is carried out.
  • an epoxy group-containing silane compound having both a silanol group and / or a hydrolyzable silyl group is simultaneously used in order to introduce an epoxy group into the resulting polysiloxane.
  • a silane compound having the group to be introduced is used in combination.
  • a silane compound having both a group and a silanol group and / or a hydrolyzable silyl group may be appropriately used in combination.
  • a silane compound having both a group having a polymerizable double bond and a silanol group and / or a hydrolyzable silyl group may be used in combination.
  • a composite resin (A) in which (a2) is combined with the bond represented by the general formula (3) is obtained.
  • Method 2 In the same manner as in Method 1, a vinyl polymer segment (a2) containing a silanol group and / or a hydrolyzable silyl group directly bonded to a carbon bond is obtained.
  • a silane compound in order to introduce an epoxy group, an epoxy group-containing silane compound having both a silanol group and / or a hydrolyzable silyl group is used. If there is another group to be introduced, the group to be introduced is selected.
  • the polysiloxane segment (a1) having an epoxy group is obtained by hydrolytic condensation reaction.
  • silanol group and / or hydrolyzable silyl group of the vinyl polymer segment (a2) and the silanol group and / or hydrolyzable silyl group of the polysiloxane segment (a1) having an epoxy group are hydrolyzed.
  • a decomposition condensation reaction is performed.
  • Method 3 In the same manner as in Method 1, a vinyl polymer segment (a2) containing a silanol group and / or a hydrolyzable silyl group directly bonded to a carbon bond is obtained.
  • the polysiloxane segment (a1) which may or may not have an epoxy group is obtained in the same manner as in Method 2.
  • a silane compound having a group to be introduced is mixed and subjected to a hydrolysis condensation reaction.
  • silane compound having both a group having a polymerizable double bond and a silanol group and / or a hydrolyzable silyl group used when introducing a group having a polymerizable double bond
  • Other general-purpose silane compounds used in the (Method 1) to (Method 3) include, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, n- Various nolganotrialkoxysilanes such as propyltrimethoxysilane, iso-butyltrimethoxysilane, cyclohexyltrimethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-butoxysilane, diethyldimethoxysilane, methylcyclohexyldimethoxysilane Or various diorganodialkoxysilanes such as methyltrichlorosilane, ethyltrichlorosilane, vinyltrichlorosilane, dimethyldichlorosilane, diethyldich
  • a tetrafunctional alkoxysilane compound such as tetramethoxysilane, tetraethoxysilane or tetra n-propoxysilane or a partial hydrolysis condensate of the tetrafunctional alkoxysilane compound may be used in combination as long as the effects of the present invention are not impaired. it can.
  • the tetrafunctional alkoxysilane compound or a partially hydrolyzed condensate thereof is used in combination, the silicon atoms of the tetrafunctional alkoxysilane compound are 20 with respect to the total silicon atoms constituting the polysiloxane segment (a1). It is preferable to use together so that it may become the range which does not exceed mol%.
  • a metal alkoxide compound other than a silicon atom such as boron, titanium, zirconium, or aluminum can be used in combination with the silane compound as long as the effects of the present invention are not impaired.
  • a metal alkoxide compound in combination within a range not exceeding 25 mol% with respect to all silicon atoms constituting the polysiloxane segment (a1).
  • hydrolysis condensation reaction in the (Method 1) to (Method 3), a part of the hydrolyzable group is hydrolyzed under the influence of water or the like to form a hydroxyl group, and then the hydroxyl groups or the hydroxyl group and the hydrolysis group are hydrolyzed.
  • This refers to a proceeding condensation reaction that proceeds with a functional group.
  • the hydrolysis-condensation reaction can be performed by a known method, but a method in which the reaction is advanced by supplying water and a catalyst in the production process is simple and preferable.
  • the catalyst used examples include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid; organic acids such as p-toluenesulfonic acid, monoisopropyl phosphate and acetic acid; inorganic bases such as sodium hydroxide and potassium hydroxide; tetraisopropyl titanate , Titanic acid esters such as tetrabutyl titanate; 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), 1,5-diazabicyclo [4.3.0] nonene-5 (DBN), 1 Compounds containing various basic nitrogen atoms such as 1,4-diazabicyclo [2.2.2] octane (DABCO), tri-n-butylamine, dimethylbenzylamine, monoethanolamine, imidazole, 1-methylimidazole; Tetramethylammonium salt, tetrabutylammonium salt, dilauryldimethylammoni Various quaternary
  • the addition amount of the catalyst is not particularly limited, but generally it is preferably used in the range of 0.0001 to 10% by mass with respect to the total amount of each compound having the silanol group or hydrolyzable silyl group. , More preferably in the range of 0.0005 to 3% by mass, and particularly preferably in the range of 0.001 to 1% by mass.
  • the amount of water to be supplied is preferably 0.05 mol or more with respect to 1 mol of the silanol group or hydrolyzable silyl group of each compound having the silanol group or hydrolyzable silyl group, The above is more preferable, and particularly preferably 0.5 mol or more.
  • These catalyst and water may be supplied collectively or sequentially, or may be supplied by previously mixing the catalyst and water.
  • the reaction temperature for carrying out the hydrolysis condensation reaction in the above (Method 1) to (Method 3) is suitably in the range of 0 ° C. to 150 ° C., and preferably in the range of 20 ° C. to 100 ° C.
  • the reaction can be carried out under any conditions of normal pressure, increased pressure, or reduced pressure. Moreover, you may remove the alcohol and water which are the by-products which can be produced
  • the charging ratio of each compound in the above (Method 1) to (Method 3) is appropriately selected depending on the desired structure of the composite resin (A) used in the present invention. Among them, since the durability of the obtained coating film is excellent, it is important to obtain the composite resin (A) so that the content of the polysiloxane segment (a1) is 20 to 70% by mass, and 30 to 70% by mass. Is preferred.
  • the silanol group and the above-described silanol group may be added to only one or both ends of the polymer chain.
  • a silane compound is mixed with the vinyl polymer segment, and a hydrolyzable silyl group-containing vinyl polymer segment is used as an intermediate. The method of carrying out decomposition condensation reaction is mentioned.
  • the main chain of the vinyl polymer segment is The vinyl polymer segment having a structure in which silanol groups and / or hydrolyzable silyl groups are randomly distributed is used as an intermediate.
  • the vinyl polymer segment is Examples thereof include a method of subjecting the silanol group and / or hydrolyzable silyl group and the silane compound to a hydrolytic condensation reaction.
  • the curable resin composition in the present invention contains the composite resin (A) and the polyisocyanate (B). At this time, it is important that the hydroxyl value of the vinyl polymer segment (a2) constituting the composite resin (A) is 55 to 200 mgKOH / g. Further, it is important that the mass ratio of the polyisocyanate (B) is 5 to 50% by mass in the total solid content of the curable resin composition of the present invention.
  • a coating film having particularly excellent long-term weather resistance (specifically, crack resistance) outdoors can be obtained.
  • the polyisocyanate (B) to be used is not particularly limited and known ones can be used, but aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane-4,4′-diisocyanate, meta-xylylene diisocyanate, Polyisocyanates mainly composed of aralkyl diisocyanates such as ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethyl-meta-xylylene diisocyanate have the problem that the cured coating film yellows when exposed to long-term outdoor exposure. It is preferable to minimize the amount used.
  • the polyisocyanate (B) used in the present invention is preferably an aliphatic polyisocyanate containing an aliphatic diisocyanate as a main raw material.
  • the aliphatic diisocyanate include tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate (hereinafter abbreviated as “HDI”), 2,2,4- (or 2,4,4).
  • HDI is particularly suitable from the viewpoint of crack resistance and cost.
  • Examples of the aliphatic polyisocyanate obtained from the aliphatic diisocyanate include allophanate type polyisocyanate, biuret type polyisocyanate, adduct type polyisocyanate, and isocyanurate type polyisocyanate, and any of them can be suitably used.
  • blocked polyisocyanate compounds blocked with various blocking agents can be used.
  • the blocking agent include alcohols such as methanol, ethanol and lactic acid esters; phenolic hydroxyl group-containing compounds such as phenol and salicylic acid esters; amides such as ⁇ -caprolactam and 2-pyrrolidone; oximes such as acetone oxime and methyl ethyl ketoxime Active methylene compounds such as methyl acetoacetate, ethyl acetoacetate and acetylacetone can be used.
  • the isocyanate group in the polyisocyanate is preferably 5 to 50% by mass from the viewpoint of crack resistance of a cured coating film obtained when used as a paint.
  • the isocyanate group in the polyisocyanate exceeds 50%, the molecular weight of the polyisocyanate becomes small, and crack resistance due to stress relaxation may not be exhibited.
  • the reaction between the polyisocyanate and a hydroxyl group in the system (this is a hydroxyl group in the active energy ray-curable monomer having a hydroxyl group of the vinyl polymer segment (a2) or an alcoholic hydroxyl group described later), in particular, There is no need for heating, etc., and the reaction proceeds gradually by leaving it at room temperature.
  • the reaction between the alcoholic hydroxyl group and the isocyanate may be promoted by heating at 80 ° C. for several minutes to several hours (20 minutes to 4 hours). In that case, you may use a well-known urethanation catalyst as needed.
  • the urethanization catalyst is appropriately selected according to the desired reaction temperature.
  • the mass ratio of the polysiloxane segment (a1) in the solid content of the composite resin (A) is 20 to 70% by mass, and the solid content of the composite resin (A) is The epoxy equivalent is 900 to 17000 g / eq, the hydroxyl value of the vinyl polymer segment (a2) is 55 to 200 mgKOH / g, and the mass ratio of the polyisocyanate (B) is 5 to 50 in the total solid content.
  • the storage stability of only the composite resin (A) before curing in the state of one liquid, and the two liquids of the composite resin (A) and the polyisocyanate (B) as a curing agent are mixed. It is possible to provide a resin that is compatible with later room temperature curability and is transparent and excellent in weather resistance.
  • the long-term storage stability of the composite resin (A) in the state of one liquid before curing is considered to be a result of the epoxy group suppressing the condensation reaction between silanol groups.
  • the presence of epoxy groups in the polysiloxane captures silanol residues located nearby by protonated epoxy groups under acidic conditions and prevents their condensation. .
  • the epoxy equivalent of the solid content of the composite resin (A) is less than 900 g / eq, the effect of suppressing the condensation reaction between silanol groups by the epoxy group-containing silane compound becomes too large, so long-term storage before curing. Although stability is maintained, the progress of crosslinking after film formation becomes insufficient, and the cured film does not have sufficiently high weather resistance.
  • the epoxy equivalent of the solid content is larger than 17000 g / eq, the effect of suppressing the condensation reaction between silanol groups by the epoxy group-containing silane compound is too small, and thus long-term storage stability before curing is not maintained. .
  • the hydroxyl value of the vinyl polymer segment (a2) is smaller than 55 mgKOH / g, the crosslinking density when the cured film is formed becomes insufficient, and the cured film has sufficiently high curability and high cured film. Does not have weather resistance.
  • the hydroxyl value of the vinyl polymer segment (a2) is larger than 200 mgKOH / g, gelation occurs during the polymerization of the vinyl polymer segment (a2), and a composite resin cannot be obtained.
  • the epoxy equivalent of the solid content is in the range of 900 to 17000 g / eq
  • the effect of suppressing the condensation reaction between silanol groups by the epoxy group-containing silane compound and the progress of the crosslinking reaction when a cured film is formed. Since the balance is optimized, long-term storage stability before curing, a certain level of curability and high weather resistance of the cured film can be obtained.
  • the hydroxyl group value of the vinyl polymer segment (a2) is in the range of 55 to 200 mgKOH / g, the crosslinked density when the cured film is formed is sufficient, and the cured film has sufficiently high curability and curing. The film has high weather resistance.
  • the curable resin composition of the present invention can be cured at room temperature by mixing the composite resin (A) and the polyisocyanate (B), it is preferably about 5 to 10 days at room temperature, more preferably 7 A cured film having high practicality can be obtained by allowing it to stand for about 10 days to dry.
  • a highly practical cured film can be obtained by performing baking within a temperature range of about 80 to 250 ° C. for about 30 seconds to 2 hours. Is possible. In this case, depending on the baking conditions, it is also possible to obtain a cured film having higher hardness, higher gel fraction, and higher weather resistance than the room temperature cured film.
  • the curable resin composition of the present invention may use a dispersion medium for the purpose of adjusting the solid content and viscosity of the dispersion.
  • a dispersion medium for the purpose of adjusting the solid content and viscosity of the dispersion.
  • Any liquid medium that does not impair the effects of the present invention may be used, and examples thereof include the above organic solvents and liquid organic polymers.
  • the curable composition of the present invention can be cured at room temperature, but various catalysts may be added to perform thermal curing. It is preferable to select each catalyst in consideration of the reaction temperature, reaction time, etc. of the urethanization reaction between an alcoholic hydroxyl group and an isocyanate. Moreover, it is also possible to use a thermosetting resin together.
  • the thermosetting resin include vinyl resins, unsaturated polyester resins, polyurethane resins, epoxy resins, epoxy ester resins, acrylic resins, phenol resins, petroleum resins, ketone resins, silicon resins, and modified resins thereof.
  • inorganic pigments organic pigments, extender pigments, clay minerals, waxes, surfactants, stabilizers, flow regulators, dyes, leveling agents, rheology control agents, UV absorbers, antioxidants, or as necessary
  • Various additives such as a plasticizer can also be used.
  • the curable resin composition of the present invention can be used as it is as a curable coating. Moreover, you may add additives, such as an above described organic pigment and an inorganic pigment.
  • the film thickness of the coating film formed using the curable resin composition or paint of the present invention is not particularly limited, but from the viewpoint that a cured coating film having long-term weather resistance outdoors can be formed, It is preferably 0.1 to 300 ⁇ m.
  • the thickness of the cured coating film is less than 0.1 ⁇ m, discoloration of the plastic material and generation of cracks cannot be prevented, and when the film thickness exceeds 300 ⁇ m, the volatilization of the solvent does not proceed completely, and Care should be taken because residual solvent will remain in the film, which may cause poor curing.
  • the base material various materials can be used.
  • a metal base material an inorganic base material, a plastic base material, paper, a woody base material and the like can be used.
  • inorganic base material examples include glass, concrete, gypsum board, asphalt, and the like, and can be suitably used as a paint for building / civil engineering materials.
  • plastic substrate examples include polyolefins such as polyethylene, polypropylene, and ethylene-propylene copolymer; polyesters such as polyethylene isophthalate, polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate; nylon 1, nylon 11, and nylon 6, Polyamides such as nylon 66, nylon MX-D; styrene polymers such as polystyrene, styrene-butadiene block copolymer, styrene-acrylonitrile copolymer, styrene-butadiene-acrylonitrile copolymer (ABS resin); Acrylic polymers such as polymethyl methacrylate and methyl methacrylate / ethyl acrylate copolymer; polycarbonate and the like can be used.
  • the plastic substrate may have a single layer or a laminated structure of two or more layers. Moreover, these plastic base materials may be unstretched, uniaxially stretched, or
  • the plastic substrate may be subjected to a known surface treatment on the surface of the substrate in order to further improve the adhesion with the paint of the present invention.
  • a surface treatment include corona discharge treatment, plasma, and the like. Examples thereof include a process, a flame plasma process, an electron beam irradiation process, and an ultraviolet irradiation process, and a process combining one or more of these may be performed.
  • the composite resin (A), the polyisocyanate (B), and various additives are mixed to prepare a paint containing a curable composition, and after applying the paint on the substrate surface, The cured product having excellent weather resistance can be obtained by allowing to stand and drying for about 7 to 10 days.
  • the curable composition and the coating material be used by appropriately diluting the solvent by adding a solvent in addition to the additive.
  • the solvent is not particularly limited, but it is preferable to avoid the use of aromatic hydrocarbons such as toluene and xylene in consideration of the working environment during construction.
  • the film thickness after coating is not particularly limited, but is preferably 0.1 to 300 ⁇ m from the viewpoint that a cured coating film having long-term weather resistance outdoors can be formed.
  • the film thickness of the cured coating film is less than 0.1 ⁇ m, discoloration and cracking of the plastic material cannot be prevented, and when the film thickness exceeds 300 ⁇ m, the volatilization of the solvent does not proceed completely, Care should be taken because residual solvent will remain in the coating film, which may cause poor curing.
  • the above-described base material may be a known antistatic agent, antifogging agent, antiblocking agent, ultraviolet absorber, antioxidant, light stabilizer, crystal, and the like, as long as the effects of the present invention are not impaired.
  • Known additives such as nucleating agents and lubricants may be contained.
  • the shape of the base material is not particularly limited, and may be, for example, a sheet shape, a plate shape, a spherical shape, a film shape, or a large structure, or an assembly or molded product having a complicated shape. Further, the surface of the base material may be previously coated with an undercoat paint or the like, and even if the coated portion is deteriorated, the paint of the present invention can be applied.
  • the undercoat paint known water-soluble or water-dispersed paints, organic solvent-type or organic solvent-dispersed paints, powder paints, and the like can be used. Specifically, acrylic resin-based paint, polyester resin-based paint, alkyd resin-based paint, epoxy resin-based paint, fatty acid-modified epoxy resin-based paint, silicon resin-based paint, polyurethane resin-based paint, fluoroolefin-based paint, or amine-modified epoxy resin Various types such as resin paints can be used.
  • the undercoat paint may be a clear paint containing no pigment, or an enamel paint containing the pigment or a metallic paint containing aluminum flakes.
  • Examples of the method for applying the paint of the present invention to the substrate include a brush coating method, a roller coating method, a spray coating method, a dip coating method, a flow coater coating method, a roll coater coating method or an electrodeposition coating method. It is possible to apply a known and commonly used coating method.
  • An article having a cured coating film having excellent long-term weather resistance outdoors by applying the paint of the present invention to the surface of the substrate by the coating method and then allowing it to stand at room temperature for about 7 to 10 days to dry. Can be obtained.
  • Examples of articles that can be coated with the paint of the present invention include housings for home appliances such as televisions, refrigerators, washing machines, and air conditioners; housings for electronic devices such as personal computers, smartphones, mobile phones, digital cameras, and game machines.
  • Body Housing for OA equipment such as printers, facsimiles, etc .;
  • Various plastic parts such as various parts used for interior materials of various vehicles such as automobiles and railway vehicles; Woodwork materials such as furniture, artificial and synthetic leather; FRP bathtubs It is done.
  • Interior and exterior materials for buildings such as exterior walls, roofs, glass, and decorative panels; civil engineering members such as soundproof walls and drainage grooves; galvanized steel sheets used for household appliances, industrial machinery, automotive parts, and aluminum-zinc Metal members such as plated steel plates such as alloy steel plates, aluminum plates, aluminum alloy plates, electromagnetic steel plates, copper plates, and stainless steel plates are also included.
  • the “active ingredient” is a value obtained by dividing the theoretical yield (parts by mass) when all the methoxy groups of the silane monomer used undergo hydrolysis condensation reaction by the actual yield (parts by mass) after hydrolysis condensation reaction, That is, it is calculated by the formula (theoretical yield when all the methoxy groups of the silane monomer undergo hydrolysis hydrolysis reaction (mass part) / actual yield after hydrolysis condensation reaction (mass part)).
  • the number average molecular weight was calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • Shodex GPC SYSTEM-21 manufactured by Showa Denko KK
  • Shodex Asahipak GF-7M HQ manufactured by Showa Denko KK
  • 20 mM LiBr dimethylformamide solution is used as the GPC solvent It was.
  • Table 1 shows the compositions and properties of the polysiloxanes (a-1-1) to (a-1-7) obtained above.
  • GPDMMS ⁇ -glycidoxypropylmethyldimethoxysilane
  • EpCHETMS ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane
  • Synthesis Example 8 Synthesis of vinyl polymer (a-2-1)
  • PTMS phenyltrimethoxysilane
  • DDMS dimethyldimethoxysilane
  • n-acetate -348.8 parts of butyl was added as an initial solvent, and the temperature was raised to 95 ° C while stirring under aeration of nitrogen gas.
  • MMA methyl methacrylate
  • BMA n-butyl methacrylate
  • MMA n-butyl acrylate
  • MAA methacrylic acid
  • MPTMS 3-methacryloyloxypropyltrimethoxysilane
  • HEMA 2-hydroxyethyl methacrylate
  • TPOEH tert-butylperoxy-2-ethylhexanoate
  • the hydroxyl value of the vinyl polymer segment of the reaction product was estimated to be 100 mgKOH / g from the content of HEMA with respect to the total amount of monomers used.
  • the hydroxyl value of the vinyl polymer segment of the reaction product that resulted in gelation was estimated to be 220 mgKOH / g from the content of HEMA with respect to the total amount of monomers used.
  • Table 2 shows the composition and property values of the vinyl polymers (a-2-1) to (a-2-5) obtained above.
  • PGMAC propylene glycol monomethyl ether acetate
  • the epoxy equivalent (the molecular weight (g / eq) of the sample per epoxy group) of the obtained composite resin (A-1) was measured according to the following procedure in accordance with JIS K7236. First, a 5.0 g sample was weighed in a 100 cc beaker, and 10 ml of chloroform was added and dissolved by stirring. Thereafter, 20 ml of acetic acid and 10 ml of tetraammonium bromide acetic acid solution were added at room temperature, and about 2-3 drops of crystal violet was used as an indicator with an automatic titrator AUT-701 (manufactured by Toa DKK Corporation).
  • the equivalence point is automatically determined, and the epoxy equivalent (from the titration difference between the sample and blank test and the potential change) The calculated value of g / eq) was obtained.
  • the tetraammonium bromide acetic acid solution was prepared by dissolving 100 g of tetraammonium bromide in 400 ml of acetic acid. This revealed that the epoxy equivalent of the solid content of the composite resin (A-1) was 8800 g / eq.
  • the hydroxyl value of the vinyl polymer segment (a-2-1) in the obtained composite resin (A-1) was measured by the following procedure. First, 2.5 g of the composite resin (A-1) was weighed into a 200 ml Meyer flask, and an acetylating agent obtained by mixing acetic anhydride and pyridine at a volume ratio of 1:19 was added with a whole pipette. Next, it was placed in a heating bath with a condenser tube adjusted to 115 ° C., and reacted for 1 hour while shaking water through the condenser tube.
  • the flask was removed from the heating bath, and about 5 cc of ion exchange water was added from the top of the condenser tube with a graduated cylinder and shaken. After allowing to cool to room temperature, several drops of phenolphthalein indicator were added, and a 0.5N potassium hydroxide-ethanol solution was titrated. The point where the pale red color lasted for 30 seconds was taken as the end point, and the dripping amount at that time was read. At the same time, a blank test was also performed. The hydroxyl value of the vinyl polymer segment in the composite resin (A-1) was calculated from the following two formulas.
  • the hydroxyl value of the vinyl polymer segment in the composite resin (A-1) was calculated to be 100 mgKOH / g, and the vinyl polymer segment estimated from the HEMA content relative to the total amount of the monomers used was calculated. It was confirmed that the hydroxyl value coincided with the calculated value from the actual measurement value.
  • Table 3 shows the composition and property values of the composite resins (A-1) to (A-5) obtained above.
  • a comparative composite resin (R-1) composed of a polysiloxane segment having a nonvolatile content of 55.0% and a vinyl polymer segment.
  • Synthesis Example 24 Synthesis of composite resin (R-7)
  • Synthesis Example 1 In the same reaction vessel as in Synthesis Example 1, 497.4 parts of the vinyl polymer (a-2-1) obtained in Synthesis Example 8 and polysiloxane (a-1-5) obtained in Synthesis Example 5 106. 7 parts and “4HBAGE” (4-hydroxybutyl acrylate glycidyl ether manufactured by Nippon Kasei Co., Ltd.), an epoxy compound having no hydrolyzable silyl group, for comparison with an epoxy group-containing silane compound After adding 5 parts and stirring for 5 minutes, 36.9 parts of deionized water was added and stirred at 80 ° C.
  • 4HBAGE 4-hydroxybutyl acrylate glycidyl ether manufactured by Nippon Kasei Co., Ltd.
  • Table 4 shows the composition and property values of the composite resins (R-1) to (R-7) obtained above.
  • turbidity of the obtained resin was determined in accordance with JIS K0101, using a precision photoelectric turbidimeter T-2600S (manufactured by Tokyo Denshoku), integrating sphere scattering photometry (change in forward scattered light due to formation of aggregates). , Measured using an integrating sphere, and measured under optical conditions according to a method for comparing the ratio with transmitted light intensity). The smaller the turbidity, the higher the transparency. The turbidity was determined to be a highly transparent resin having a turbidity of 0.5 or less and no turbidity.
  • ⁇ Storage stability> The storage stability of the obtained resin was evaluated based on the viscosity ratio with the viscosity (so-called viscosity with time) of what was stored at 40 ° C. for 30 days as the numerator and the initial viscosity as the denominator. The viscosity was measured at 30 ° C. using an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd.). The sample was stored by placing the obtained resin in a glass tube and allowing it to stand at 40 ° C. for 1 month. The closer this viscosity ratio is to 1, the better the storage stability, and the more excellent the storage stability with a viscosity ratio of 0.9 to 1.1. It was judged that there was.
  • the composite resins (A-1) to (A-5) obtained in Synthesis Examples 13 to 17 and the composite resins (R-1) to (R-2) obtained in Synthesis Examples 18 to 19 were obtained.
  • the composite resins (R-3) to (R-4) obtained in Synthesis Examples 20 to 21 are examples in which the epoxy equivalent of the composite resin is larger than 17000 g / eq, but it was found that the storage stability was inferior. did.
  • the composite resins (R-5) to (R-7) obtained in Synthesis Examples 22 to 24 are examples in which polysiloxane does not have an epoxy group, but it has been found that the storage stability is poor.
  • Example 1 25.0 parts by mass of composite resin (A-1) obtained in Synthesis Example 1, Barnock DN-980 (manufactured by Polyisocyanate DIC Corporation, the diluent solvent is ethyl acetate, and the non-volatile content is 75.3% by mass Further, by mixing 4.5 parts by mass of NCO% of varnish (16.0% by mass) and 18.9 parts by mass of ethyl acetate, a curable resin composition having a nonvolatile content of 55.0% by mass is obtained. The curable resin composition was designated as a clear paint (1).
  • Example 2-5 and Comparative Examples 1-2 Based on the formulation shown in Table 5 below, clear paints (2) to (5) and comparative clear paints (R1) to (R2) were prepared in the same manner as in Example 1.
  • the clear paints (1) to (5) and the comparative clear paints (R1) to (R2) obtained in Examples 1 to 5 and Comparative Examples 1 and 2 were evaluated as follows. That is, the “color tone” of the clear coating, the cured coating film X or Y for evaluation, the “gel fraction” serving as an index of room temperature curability of the cured coating film, and the “gloss retention ratio” serving as an index of weather resistance. evaluated.
  • the obtained clear paint has a Gardner color number (measured by the color test method for chemical products specified in JIS K 0071-2) and is visually color-matched with a standard sample specified in JIS K 0071-2. Was determined. The smaller the Gardner color number, the lighter the coloration, and it was determined that the Gardner color number was 1 or less and the resin was colorless.
  • ⁇ Gel fraction> The cured coating film X for evaluation was peeled off from the PP base material, and the coating film residual amount (mg) after immersion in acetone for 24 hours was divided by the mass (mg) of the cured coating film before immersion in acetone. The value multiplied by 100 was displayed as the gel fraction (%). The closer the gel fraction was to 100%, the better the room temperature curability, and it was determined that the cured coating film had sufficient room temperature curability when the gel fraction was 80% or more.
  • the clear paints (1) to (5) evaluated in Examples 1 to 5 were all colorless, had good gel fraction and gloss retention after curing, and were excellent in room temperature curability and weather resistance. A coating film was obtained.
  • the clear paint (R1) evaluated in Comparative Example 1 is an example in which the epoxy equivalent of the composite resin is too small, but it has been found that room temperature curability and weather resistance are poor.
  • the clear paint (R2) evaluated in Comparative Example 2 is an example in which the hydroxyl value of the vinyl polymer segment is too small, but it has been found that the room temperature curability and weather resistance are poor.
  • Example 6 25.0 parts by mass of the composite resin (A-1) obtained in Synthesis Example 1, 4.5 parts by mass of Bernock DN-980, CR-97 (rutile titanium oxide manufactured by Ishihara Sangyo Co., Ltd.), 9.2 parts by mass, Enamel paint (1) was obtained by mixing 28.3 parts by mass of ethyl acetate.
  • Example 7 Based on the formulation shown in Table 6, enamel paint (2) and comparative enamel paints (R1) to (R2) were prepared in the same manner as in Example 6.
  • the enamel paints (1) to (2) and the comparative enamel paints (R1) to (R2) obtained in Examples 6 to 7 and Comparative Examples 3 to 4 were evaluated as follows. That is, the cured coating film X or Y for evaluation was used to evaluate the “gel fraction” that is an index of room temperature curability of the cured coating film and the “gloss retention ratio” that is an index of weather resistance.
  • ⁇ Gel fraction> The cured coating film X for evaluation was peeled off from the PP base material, and the coating film residual amount (mg) after immersion in acetone for 24 hours was divided by the mass (mg) of the cured coating film before immersion in acetone. The value multiplied by 100 was displayed as the gel fraction (%). The closer the gel fraction was to 100%, the better the room temperature curability, and it was determined that the cured coating film had sufficient room temperature curability when the gel fraction was 80% or more. However, the pigment solid content is not a curing component and is excluded from the calculation.
  • each of the enamel paints (1) to (2) evaluated in Examples 6 to 7 had a good gel fraction and gloss retention, and a coating film excellent in weather resistance was obtained.
  • the enamel paint (R1) evaluated in Comparative Example 3 is an example in which the epoxy equivalent of the composite resin (A) is too small, but it has been found that the room temperature curability and weather resistance are poor.
  • the enamel paint (R2) evaluated in Comparative Example 4 is an example in which the hydroxyl value of the vinyl polymer segment (a-2) is too small, but it has been found that the room temperature curability and weather resistance are poor.
  • the two-component transparent room-temperature curable resin composition in the present invention has both storage stability in a one-component state and good curability at room temperature, and can provide a cured product having excellent weather resistance.
  • the paint containing the curable resin composition can be used for metal substrates, inorganic substrates, plastic substrates, paper, wood-based substrates, etc., exterior building members, automobile exterior members, civil engineering applications, electronic members It can be used in various industrial fields such as leisure goods.

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Abstract

Cette invention concerne une composition de résine durcissable bi-liquide contenant : une résine composite (A) comprenant un segment polysiloxane et un segment polymère de vinyle liés ensemble par des liaisons spécifiques, ledit segment polysiloxane contenant un groupe époxy ; et un durcisseur polyisocyanate (B). Le pourcentage en poids de la résine composite (A) constitué par le segment polysiloxane, le poids équivalent en époxy de la résine composite (A), le poids équivalent en hydroxyle du segment polymère de vinyle, et le rapport en poids du durcisseur polyisocyanate (B) s'inscrivent tous dans des plages spécifiques. La composition de résine durcissable obtenue manifeste une excellente stabilité au stockage à long terme à l'état monoliquide, quand le durcisseur n'a pas encore été ajouté, et peut être utilisée à titre de revêtement à l'état bi-liquide une fois que le durcisseur a été ajouté. Ledit revêtement durcit bien à température ambiante, formant un film durci qui manifeste une excellente résistance aux intempéries et transparence.
PCT/JP2012/067931 2011-07-19 2012-07-13 Composition de résine durcissable, revêtement, et article portant un film obtenu par durcissage dudit revêtement WO2013011943A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013125574A1 (fr) * 2012-02-21 2013-08-29 Dic株式会社 Base de verre et stratifié de verre
JP2014051549A (ja) * 2012-09-05 2014-03-20 Dic Corp 金属用表面処理剤及び該表面処理剤で処理された金属材
JP2020128486A (ja) * 2019-02-08 2020-08-27 Ｄｉｃグラフィックス株式会社 コーティング組成物、及びこれを用いた化粧シート

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JPH0925455A (ja) * 1995-05-09 1997-01-28 Dainippon Ink & Chem Inc 塗膜の形成方法
JP2000129073A (ja) * 1998-10-26 2000-05-09 Toyo Ink Mfg Co Ltd 常温硬化性樹脂組成物および該樹脂組成物を塗工した基材
JP2000281971A (ja) * 1999-03-29 2000-10-10 Shin Etsu Chem Co Ltd シリコーン樹脂含有エマルジョン塗料組成物及びこの組成物の硬化被膜が形成された物品
JP2006328354A (ja) * 2005-03-08 2006-12-07 Dainippon Ink & Chem Inc 紫外線硬化性樹脂組成物、紫外線硬化性塗料及び塗装物。
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07238260A (ja) * 1994-03-01 1995-09-12 Showa Denko Kk 耐汚染性コーティング組成物
JPH07292313A (ja) * 1994-04-27 1995-11-07 Showa Denko Kk 自動車用コーティング剤組成物
JPH0925455A (ja) * 1995-05-09 1997-01-28 Dainippon Ink & Chem Inc 塗膜の形成方法
JPH0924577A (ja) * 1995-07-10 1997-01-28 Nkk Corp 耐汚染性、耐傷つき性および耐久性に優れたプレコート金属板
JP2000129073A (ja) * 1998-10-26 2000-05-09 Toyo Ink Mfg Co Ltd 常温硬化性樹脂組成物および該樹脂組成物を塗工した基材
JP2000281971A (ja) * 1999-03-29 2000-10-10 Shin Etsu Chem Co Ltd シリコーン樹脂含有エマルジョン塗料組成物及びこの組成物の硬化被膜が形成された物品
JP2006328354A (ja) * 2005-03-08 2006-12-07 Dainippon Ink & Chem Inc 紫外線硬化性樹脂組成物、紫外線硬化性塗料及び塗装物。
WO2010067742A1 (fr) * 2008-12-11 2010-06-17 Dic株式会社 Composition de résine durcissable, peinture et produit moulé en matière plastique produit par sa stratification

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013125574A1 (fr) * 2012-02-21 2013-08-29 Dic株式会社 Base de verre et stratifié de verre
JP2014051549A (ja) * 2012-09-05 2014-03-20 Dic Corp 金属用表面処理剤及び該表面処理剤で処理された金属材
JP2020128486A (ja) * 2019-02-08 2020-08-27 Ｄｉｃグラフィックス株式会社 コーティング組成物、及びこれを用いた化粧シート

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