WO2018207828A1 - Composition durcissable - Google Patents

Composition durcissable Download PDF

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Publication number
WO2018207828A1
WO2018207828A1 PCT/JP2018/017955 JP2018017955W WO2018207828A1 WO 2018207828 A1 WO2018207828 A1 WO 2018207828A1 JP 2018017955 W JP2018017955 W JP 2018017955W WO 2018207828 A1 WO2018207828 A1 WO 2018207828A1
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Prior art keywords
component
group
meth
ethylenically unsaturated
compound
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PCT/JP2018/017955
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English (en)
Japanese (ja)
Inventor
佐内　康之
橋本　直樹
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東亞合成株式会社
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Priority to JP2019517666A priority Critical patent/JP7255480B2/ja
Publication of WO2018207828A1 publication Critical patent/WO2018207828A1/fr

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    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • 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
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives

Definitions

  • the present invention relates to a curable composition, and preferably to an active energy ray curable composition.
  • the cured film of the composition of the present invention has excellent adhesion to a plastic substrate and is preferably used as a coating agent for the purpose of preventing the anti-fogging of the plastic surface (anti-fogging coating agent) and preventing adhesion of dust to the plastic.
  • acrylate and / or methacrylate is represented as (meth) acrylate
  • acryloyl group and / or methacryloyl group is represented as (meth) acryloyl group
  • acrylic acid and / or methacrylic acid is represented by (meth) acrylic acid.
  • an allyl group and / or a methallyl group is represented as a (meth) allyl group.
  • Active energy ray-curable compositions can be cured by irradiating active energy rays such as ultraviolet rays, visible rays, and electron beams for a very short time, and are widely used as inks and coatings for various substrates because of their high productivity. It has been.
  • the surface of plastic substrates such as plastic plates and plastic films is protected with a hard coat agent for the purpose of preventing scratches on the surface, and active energy ray-curable compositions are also used for such applications.
  • Plastic substrates are highly transparent, so they are used for protective glasses, goggles, bathroom inner walls, and head lamp covers and rear lamp covers for automobiles and motorcycles. When used in a location, condensation may occur on the surface, resulting in cloudiness and loss of transparency.
  • a method of applying an antifogging composition comprising a non-reactive surfactant to the surface of a substrate has been performed. Although the anti-fogging effect is exhibited in the initial stage, once the treated surface is wiped, the anti-fogging property is lowered, that is, the anti-fogging sustainability is lacking.
  • an antifogging composition comprising a hydrophilic polymer diluted with an organic solvent to the surface of the substrate, but the cured film hardness is insufficient and the solvent resistance is insufficient. Besides, anti-fogging property was not satisfactory.
  • an antifogging composition composed of a hydrophilic group-containing UV curable resin and a hydrophilic group-free UV curable resin, a hydrophilic polymer and various hydrophilic (meth) acrylates.
  • An antifogging composition comprising the following has been proposed (Patent Document 2).
  • Patent Document 1 An antifogging composition comprising the following has been proposed (Patent Document 2).
  • Patent Document 2 An antifogging composition comprising the following has been proposed (Patent Document 2).
  • these compositions have a problem that antifogging properties are not exhibited in an environment under high humidity.
  • Patent Document 3 an antifogging composition comprising a hydrophilic monomer and a non-reactive surfactant has been proposed (Patent Document 3), the antifogging property is reduced if the cured film surface is wiped off. As a result, the antifogging sustainability was lacking.
  • Patent Document 4 a composition in which a specific (meth) acrylate and a surfactant having reactivity with the (meth) acrylate are combined is excellent in surface hardness and antifogging durability.
  • the (meth) acrylate used in the composition is an oligomer having a relatively large molecular weight
  • the surface hardness is insufficient due to the relatively low molar fraction of (meth) acryloyl groups in the entire molecule.
  • the hydrophilicity of (meth) acrylate was insufficient, and it was necessary to improve antifogging properties.
  • the amount of the surfactant must be increased, and it is difficult to achieve both hard coat properties.
  • the inventors of the present invention have a cured film obtained that has excellent adhesion to a substrate, in particular, adhesion to a plastic substrate, has a good surface hardness and can be preferably used as a hard coating agent, and is excellent even under high humidity.
  • intensive studies were conducted.
  • the inventors of the present invention include a compound having an ethylenically unsaturated group and an ionic group and a compound having a hydrophilic ethylenically unsaturated group, and an ethylenically unsaturated group such as an alcohol solvent.
  • the present invention was completed by finding that a composition containing almost no hydroxyl group-containing compound having no saturated group forms a cured film having excellent surface hardness, excellent antifogging properties and durability.
  • the present invention will be described in detail.
  • the formed cured film has good adhesion to a plastic substrate, high surface hardness, and good antifogging durability. Therefore, the composition of the present invention can be preferably applied to coatings for protective glasses, goggles and the like that require these performances for cured films, and coating agents for headlamps and rear lamp covers of automobiles and motorcycles.
  • the present invention includes the following component (A), component (B) and component (C) and does not include component (D) below, or the sum of component (A), component (B) and component (C).
  • the present invention relates to a curable composition containing 3 parts by weight or less of the following component (D) with respect to 100 parts by weight (hereinafter sometimes simply referred to as “composition”).
  • (A) Component Compound having an ethylenically unsaturated group and an ionic group
  • B Component: Compound having a hydrophilic group and an ethylenically unsaturated group
  • C Component
  • the compound (D) component having two or more ethylenically unsaturated groups a hydroxyl group-containing compound having no ethylenically unsaturated group
  • the components (A) to (C), which are essential components, may be contained in small amounts.
  • the good (D) component, other components, and usage methods will be described.
  • Component (A) is a compound having an ethylenically unsaturated group and an ionic group.
  • component is a component which gives the low surface resistance required for favorable anti-fogging property and dust adhesion prevention to a cured film by hardening a composition.
  • Component (A) maintains excellent anti-fogging properties even when the cured film surface is wetted or wiped by chemically bonding an ionic group in the cured film by reacting with an ethylenically unsaturated group. It can be repeated and excellent in antifogging properties.
  • various compounds can be used as long as they are compounds having an ethylenically unsaturated group and an ionic group.
  • the ethylenically unsaturated group include a (meth) acryloyl group, a (meth) allyl group, a vinyl group, and a styryl group.
  • the compound (G) having one ethylenically unsaturated group other than the components (B) and (C) and the components (A) and (B) described later [G]
  • the (meth) acryloyl group is preferable, and the acryloyl group is more preferable, because the reactivity with “(G) component” is good and the curability is excellent.
  • the component (A) has an ionic group, so that the anti-fogging property and low surface resistance can be obtained without impairing the hard coat property inherent to the cured film of the composition, and a smaller content ratio.
  • the ionic group include salts of strong acids. Specifically, sulfonates such as ammonium sulfonate, sodium sulfonate, and potassium sulfonate, ammonium alkyl sulfate, sodium alkyl sulfate, and potassium alkyl sulfate. And alkyl sulfates such as ammonium carboxylate, sodium carboxylate and potassium carboxylate.
  • the ionic group of the component (A) is preferably a salt of a sulfonic acid group or a salt of an alkyl sulfate group because a desired effect can be obtained even when the content of the component (A) is made smaller.
  • examples of the counter cation constituting the sulfonate include secondary ammonium ions, tertiary ammonium ions, and quaternary ammonium ions.
  • secondary ammonium ions include dimethylamine, diethylamine, di-1-propylamine, di-2-propylamine, di-n-butylamine, di-2-butylamine, di-1-pentylamine.
  • Examples include ions in which amine and ethylethanolamine are protonated, respectively.
  • Tertiary ammonium ions include trimethylamine, triethylamine, tri-1-propylamine, tri-2-propylamine, tri-n-butylamine, tri-2-butylamine, tri-1-pentylamine, and tri-2-pentyl.
  • Examples include ions obtained by protonating amine, diethylethanolamine, lauryldiethanolamine and bis (2-methoxyethyl) methylamine.
  • methylethanolamine, ethylethanolamine, dimethylethanolamine, diethylethanolamine, or lauryldiethanolamine are preferably protonated ions, and methylethanolamine, ethylethanolamine, or lauryldiethanolamine are respectively protonated.
  • the ions are protonated ions, more preferably methylethanolamine, dimethylethanolamine, or ethylethanolamine are each protonated ions, and particularly preferably ethylethanolamine is a protonated ion. preferable.
  • the ionic group of component (A) is preferably bonded to an ethylenically unsaturated group via an alkyl group, an alkylbenzene group, an alkylene oxide group, or the like.
  • component (A) examples include the following components (A-1) and (A-2), and any of them can be used.
  • Component (A-1) Compound comprising a cation having an ethylenically unsaturated group in one molecule and an anion (A-2)
  • Component From an anion having an ethylenically unsaturated group in a molecule and a cation Compound
  • Component (A-1) is a compound comprising a cation having an ethylenically unsaturated group in one molecule and an anion.
  • the cationic group in the cation having an ethylenically unsaturated group in one molecule include ammonium ion, imidazolium ion, pyridinium ion, pyrrolidinium ion, pyrrolium ion, piperidinium ion, pyrazinium ion, and pyrimidinium ion.
  • Triazolium ion triazinium ion, quinolinium ion, isoquinolinium ion, indolinium ion, quinoxalinium ion, piperazinium ion, oxazolinium ion, thiazolinium ion, and morpholinium ion
  • Triazolium ion triazinium ion, quinolinium ion, isoquinolinium ion, indolinium ion, quinoxalinium ion, piperazinium ion, oxazolinium ion, thiazolinium ion, and morpholinium ion
  • Triazolium ion triazinium ion
  • quinolinium ion isoquinolinium ion
  • indolinium ion quinoxalinium ion
  • piperazinium ion oxazolinium ion
  • thiazolinium ion morpholinium i
  • ethylammonium dimethylmono (meth) acrylate [quaternary ammonium ion of dimethylaminoethyl (meth) acrylate] and diethylmono (meth) acrylic.
  • Dialkyl mono (meth) acrylate alkyl ammonium ions such as ethyl ammonium ion [quaternary ammonium ion of diethylaminoethyl (meth) acrylate], and 1,2,2,6,6-pentamethyl-4- (meth) acrylate pipette Lizinium ions and the like can be mentioned as suitable ones.
  • ammonium ion descriptions such as “N—” and “N, N—” indicating a substituent on a nitrogen atom are omitted.
  • the anion constituting the component (A-1) examples include halogen-based anions such as sulfonic acid derivatives, bromide ions and triflate, boron-based anions such as tetraphenylborate, and phosphorus-based anions such as hexafluorophosphate.
  • a sulfonic acid derivative is preferable.
  • Specific examples of the sulfonic acid derivatives include anions of sulfonic acids having polyoxyalkylene units such as anions of alkoxy polyethylene glycol sulfonic acids, and anions of alkyl group-containing aromatic sulfonic acids such as anions of isopropylbenzene sulfonic acid. It is done.
  • the component (A-1) is preferably a compound comprising an alkylammonium dialkylmono (meth) acrylate and an anion of sulfonic acid.
  • the anion of sulfonic acid is preferably an anion of sulfonic acid having a polyoxyalkylene unit.
  • the compound represented by following formula (1) is preferable.
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents an optionally branched alkylene group having 1 to 12 carbon atoms
  • R 3 and R 4 are each independently and represents an alkyl group branched 1 carbon atoms which may have ⁇ 10
  • X - is an alkylsulfate ion, polyoxyalkylene alkyl ether sulfate, polyoxyalkylene alkyl phenyl ether sulfate, alkyl sulfonate ion or Represents an alkylbenzene sulfonate ion.
  • R 3 and R 4 are an alkylene group having 1 to 12 carbon atoms which may be branched. Specific examples thereof include a methylene group, an ethylene group, a propylene group, and a butylene group. R 3 and R 4 are each independently a C 1-10 alkyl group which may be branched. Specific examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group.
  • X ⁇ represents an alkyl sulfate ion, a polyoxyalkylene alkyl ether sulfate ion, a polyoxyalkylene alkyl phenyl ether sulfate ion, an alkyl sulfonate ion or an alkyl benzene sulfonate ion.
  • the component (A) needs to be present in the vicinity of the cured film surface, but generally a highly hydrophobic component is oriented on the coating film surface after coating the composition It's easy to do.
  • the alkyl group in these groups is preferably an alkyl group having 6 or more carbon atoms, and an alkyl group having 6 to 20 carbon atoms is preferable so as to increase hydrophobicity.
  • polyoxyalkylene units in these groups include polyoxyethylene units, polyoxypropylene units, and polyoxytetramethylene units.
  • a commercially available product can be used as the component (A-1).
  • a compound having a cation containing a (meth) acryloyl group and ammonium ion in the molecule and an anion trade names “IL-MA1”, “IL-MA2” and “IL- MA3 ";
  • a compound having a cation containing an acryloyl group and an ammonium ion and an anion trade names “JI-62C01” and “JI-63F01” manufactured by Nippon Emulsifier Co., Ltd .
  • a cation containing a methacryloyl group and an ammonium ion Examples of the compound having alkylsulfuric acid as “JNA-04006” manufactured by Nippon Emulsifier Co., Ltd.
  • Component (A-2) is a compound comprising an anion having an ethylenically unsaturated group in one molecule and a cation.
  • Specific examples of the component (A-2) include the following examples in which the anionic group is a sulfonate ion.
  • polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate ammonium salt polyoxyethylene nonylpropenyl phenyl ether sulfate ammonium salt, ⁇ -sulfo- ⁇ - (1- (alkoxy ) Methyl-2- (2-propenyloxy) ethoxy) -poly (oxy-1,2-ethanediyl) ammonium salt, bis (polyoxyethylene polycyclic phenyl ether) methacrylate sulfate ammonium salt, 2-sodium sulfoethyl methacrylate, alkyl allyl sulfosuccinic acid sodium salt, (meth) acryloyl polyoxyalkylene sulfate sodium salt, bis (polyoxyethylene polycyclic phenyl ether) methacrylate sulfate sodium salt, etc. whose cation is sodium ion Can be mentioned.
  • component (A-2) commercially available products can be used. Specific examples thereof include polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate ammonium salt, trade names “AQUALON KH-10” and “AQUALON KH-1025” manufactured by Daiichi Kogyo Seiyaku Co., Ltd. , “AQUALON KH-05”; Examples of the polyoxyethylene nonylpropenyl phenyl ether ammonium sulfate salt are trade names “AQUALON HS-10”, “AQUALON HS-1025”, “AQUALON BC-0515”, “AQUALON BC-10” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
  • ⁇ -sulfo- ⁇ - (1- (alkoxy) methyl-2- (2-propenyloxy) ethoxy) -poly (oxy-1,2-ethanediyl) ammonium salt is a product name “ADEKA” manufactured by ADEKA Corporation.
  • the components (A-1) and (A-2) may be selected according to the purpose.
  • the component (A) is preferable because it is superior in antifogging durability compared to the component (A-2).
  • the details of the reason why the component (A-1) is superior to the anti-fogging durability are unknown, but if the cation that is a counter ion constituting the component (A-2) is a metal cation such as sodium or potassium, Because of its extremely high property, when it comes into contact with water, these are easily eluted from the cured film, and it is considered that the antifogging property is hardly sustained.
  • anions for example, alkyl sulfonate ions, alkyl benzene sulfonate ions, alkyl naphthalene sulfonate ions, and polyoxyethylene alkyl sulfate ions
  • anions for example, alkyl sulfonate ions, alkyl benzene sulfonate ions, alkyl naphthalene sulfonate ions, and polyoxyethylene alkyl sulfate ions
  • these are counter ions constituting the component (A-1) are slightly hydrophobic.
  • the copolymerization In order to develop stable antifogging properties, the copolymerization must be greatly different from the (B), (C) and (G) components, and the concentration of the (A) component should be locally increased. More specifically, this object can be achieved by using the components (A-1) and (A-2) in combination.
  • the component (A) is often a solid at room temperature, and is preferably diluted with an organic solvent or a reactive diluent from the viewpoint of handling such as ease of incorporation into the composition.
  • an organic solvent it is necessary to use compounds other than the component (D) described later, and examples include ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, and ester solvents such as ethyl acetate and butyl acetate.
  • the reactive diluent include component (B), component (C) and component (G) described later.
  • the component (A) is often a solid compound, and usually a hydroxyl group-containing compound that does not have an ethylenically unsaturated group such as an alcohol solvent in order to facilitate the handling of blending and mixing.
  • Component (D) is often included as an organic solvent.
  • the ionic group of the component (A) is, for example, alkyl sulfuric acid or sulfonic acid
  • the alkyl sulfuric acid or sulfonic acid generated from the component (A) becomes an acidic catalyst, and the ethylenically unsaturated group of (A) and (D )
  • the addition reaction with the hydroxyl group of the component is promoted. Therefore, when the component (D) such as an alcohol solvent is used as the organic solvent of the component (A), the component (A) becomes a compound having almost no ethylenically unsaturated bond (hereinafter referred to as “byproduct A”). -D ").
  • the composition of this invention does not contain (D) component, or (D) component with respect to a total of 100 weight part of (A) component, (B) component, and (C) component. Since it is contained at a ratio of 3 parts by weight or less, there is no such problem.
  • the content ratio of the component (A) may be appropriately set according to the purpose.
  • the component (G) described later is included in the total 100% by weight of the components (A) to (C)
  • the component (A) The total content of the component (C) and the component (G) is preferably 1 to 30% by weight, and more preferably 3 to 20% by weight.
  • the cured film has excellent antifogging properties, and by setting it to 30% by weight or less, sufficient hydrophilicity to impart antifogging properties and long Even when exposed to high temperature and high humidity for a long time, it becomes a cured film that is compatible with water resistance without swelling and peeling due to water absorption.
  • components (A) to (C) or components (A) to (C) and (G) are referred to as “curable components”.
  • the component (B) is a compound having a hydrophilic group and an ethylenically unsaturated group. As described above, when the component (A) and the component (D) are included in the composition, the ethylenically unsaturated group in the component (A) and the hydrophilic group in the component (D) undergo an addition reaction to cause a side reaction. The product AD is produced, and the ethylenically unsaturated group in the component (A) disappears.
  • the component (B) is a side reaction product (hereinafter referred to as “side reaction product AB”) in which the ethylenically unsaturated group in the component (A) and the hydrophilic group in the component (B) are side-reacted. Even if the ethylenically unsaturated group in component (A) disappears by side reaction, side reaction product AB has an ethylenically unsaturated group derived from component (B). As a result, the ionic group derived from the component (A) is incorporated into the cured film by chemical bonding, which brings about an effect on the long-term durability of the antifogging performance.
  • ammonium alkyl sulfate or ammonium sulfonate is used as a raw material, but there is also a reaction in which ammonia generated from them is added to the ethylenically unsaturated bond of the component (A) in the production process. Occurs, and the ethylenically unsaturated group is converted to an amino group (hereinafter referred to as “by-product A-AM”). Therefore, as described above, the by-product A-AM is not chemically bonded in the cured film of the composition, but is washed away by moisture on the surface of the cured film, and the ionicity derived from the component (A) in the cured film.
  • the group disappears and the anti-fogging durability is lowered.
  • the ethylenically unsaturated group of component (B) can react with the amino group of the by-product A-AM. Further, even if the component (B) reacts with the by-product A-AM, since it has an ethylenically unsaturated group derived from the component (B), an ionic group derived from the component (A) is present in the cured film. Can be imported.
  • examples of the hydrophilic group include a hydroxyl group, a carboxyl group, a sulfone group, and a phosphate group, and a hydroxyl group is more preferable in terms of excellent cured film performance.
  • the ethylenically unsaturated group (B) is preferably a (meth) acryloyl group, more preferably an acryloyl group, because the composition has excellent curability.
  • Preferred examples of the component (B) include a compound having a hydroxyl group and one (meth) acryloyl group [hereinafter referred to as “hydroxyl group-containing monofunctional (meth) acrylate”], and a hydroxyl group and two or more (meth) acryloyl groups.
  • hydroxyl-containing polyfunctional (meth) acrylate examples include hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate; Mono (meth) of polyols such as trimethylolpropane mono (meth) acrylate, glycerin mono (meth) acrylate, pentaerythritol mono (meth) acrylate, ditrimethylolpropane mono (meth) acrylate and dipentaerythritol mono (meth) acrylate Acrylates; and mono (meth) acrylates of these polyol alkylene oxide adducts.
  • hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate
  • Examples of hydroxyl group-containing polyfunctional (meth) acrylates include trimethylolpropane di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di- or tri (meth) acrylate, ditrimethylolpropane di- or tri (meth) Poly (meth) acrylates of di-, tri-, tetra- or penta (meth) acrylate polyols of acrylate and dipentaerythritol; Poly (meth) acrylates of these polyol alkylene oxide adducts; And di (meth) acrylate of isocyanuric acid; and di (meth) acrylate of isocyanuric acid alkylene oxide adduct.
  • examples of the alkylene oxide in the alkylene oxide adduct include ethylene oxide, propylene oxide, and tetramethylene oxide.
  • a hydroxyl group-containing polyfunctional (meth) acrylate is preferable in that the cured film is repeatedly excellent in antifogging properties and excellent in surface hardness. Specific examples thereof are as described above. Further, as the hydroxyl group-containing polyfunctional (meth) acrylate, glycerin di (meth) acrylate, di or tri (meth) acrylate of pentaerythritol, and di (meth) acrylate of isocyanuric acid alkylene oxide adduct are preferable.
  • the content ratio of the component (B) may be appropriately set according to the purpose, and is preferably 10 to 97% by weight, more preferably 40 to 80% by weight, in 100% by weight of the curable components.
  • the content ratio of the component (B) may be appropriately set according to the purpose, and is preferably 10 to 97% by weight, more preferably 40 to 80% by weight, in 100% by weight of the curable components.
  • the component (C) is a compound having two or more ethylenically unsaturated groups other than the components (A) and (B).
  • (C) component is a component required in order to make sclerosis
  • the component (A) contains the by-product A-AM.
  • the ethylenically unsaturated bond of component (C) reacts with the amino group of by-product A-AM, and since the reaction product has an ethylenically unsaturated group, it is derived from component (A) in the cured film. Ionic groups can be incorporated.
  • the (C) component ethylenically unsaturated group is preferably a (meth) acryloyl group, more preferably an acryloyl group, because the composition is excellent in curability.
  • component (C) a compound having two (meth) acryloyl groups (hereinafter referred to as “bifunctional (meth) acrylate”) and a compound having three or more (meth) acryloyl groups (hereinafter referred to as “3”). Functional or more (referred to as “(meth) acrylate”).
  • bifunctional (meth) acrylate examples include di (meth) acrylate of an alkylene oxide adduct of bisphenol A, di (meth) acrylate of an alkylene oxide adduct of bisphenol F, butanediol di (meth) acrylate, Diol di (meth) acrylates such as hexanediol di (meth) acrylate and nonanediol di (meth) acrylate; Examples thereof include di (meth) acrylates of these polyol alkylene oxide adducts.
  • examples of the alkylene oxide in the alkylene oxide adduct include ethylene oxide, propylene oxide, and tetramethylene oxide.
  • tri- or higher functional (meth) acrylates include glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and di Poly (meth) acrylates of polyols such as pentaerythritol hexa (meth) acrylate; Di (meth) acrylates of these polyol alkylene oxide adducts; And tris (2- (meth) acryloyloxyethyl) isocyanurate; and tri (meth) acrylates of isocyanuric acid alkylene oxide adducts.
  • alkylene oxide in the alkylene oxide adduct include ethylene oxide, propylene oxide, and tetramethylene oxide.
  • glycerol tri (meth) acrylate, tetra (meth) acrylate of pentaerythritol, and tri (meth) acrylate of isocyanuric acid alkylene oxide adduct are preferable.
  • These compounds are preferable because they have relatively high hydrophilicity among tri- or higher functional (meth) acrylates, and blending these components can improve the coating film hardness and curability without adversely affecting the antifogging property.
  • the content ratio of the component (C) may be appropriately set according to the purpose, and is preferably 2 to 60% by weight, more preferably 10 to 40% by weight in 100% by weight of the curable components.
  • the cured film has excellent hard coat properties, and by making it 40% by weight or less, the antifogging properties are excellent.
  • Component (D) The composition of the present invention comprises 3 hydroxyl group-containing compounds having no ethylenically unsaturated group as component (D) with respect to 100 parts by weight of the total of components (A), (B) and (C). It is included at a ratio of parts by weight or less.
  • component (D) component what is contained in the ratio of 2 weight part or less is preferable, More preferably, (D) component is not included.
  • the composition containing the component (D) in excess of 3 parts by weight repeatedly deteriorates the antifogging property.
  • the composition contains the component (A) and the component (D)
  • the ethylenically unsaturated group in the component (A) and the hydroxyl group in the component (D) undergo a Michael addition reaction. This is because the side reaction product AD is generated and the ethylenically unsaturated group in the component (A) disappears.
  • component (D) examples include alcohol compounds such as methanol, ethanol, isopropanol and butanol; alkylene glycol monoether compounds such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether; acetone alcohols such as diacetone alcohol; .
  • Water is not included in the component (D). Since water does not cause the Michael addition reaction that causes the above-described repeated deterioration of antifogging properties, water may be contained in the composition in an amount of about several percent, and is preferably 5% by weight or less in the composition.
  • Curable composition The composition of the present invention comprises the component (A), the component (B) and the component (C) as essential components and does not contain the component (D), or the component (A), (B
  • the component (D) is a curable composition containing 3 parts by weight or less with respect to 100 parts by weight of the total of the component (C) and the component (C).
  • the essential components (A) to (C) and other components described later may be stirred and mixed as necessary.
  • the other components described later may contain the component (D) as an organic solvent, and in the present invention, the component (D) introduced from the other components in the composition is not included, or the component (A), It is necessary to make it 3 parts by weight or less with respect to a total of 100 parts by weight of the component (B) and the component (C).
  • the components (A) to (C) and other components described later may be heated and stirred as necessary.
  • the temperature when stirring and mixing by heating is preferably in the range of 40 to 90 ° C.
  • a thermal polymerization initiator described later is blended, it is preferably carried out at 30 ° C. or lower in order to prevent polymerization during the production of the composition.
  • a preferred viscosity is 5 to 10,000 mPa ⁇ s, more preferably 10 to 1,000 mPa ⁇ s.
  • the viscosity means a value measured at 25 ° C. with an E-type viscometer.
  • this invention is a preservation
  • the said (D) component is not included in the said curable composition.
  • composition of the present invention can be used as an active energy ray-curable composition or a thermosetting composition, it can be preferably used as an active energy ray-curable composition.
  • the composition of the present invention comprises the components (A) to (C) as essential components, but various components can be blended depending on the purpose. Specific examples of other components include a photopolymerization initiator (hereinafter referred to as “component (E)”), a thermal polymerization initiator (hereinafter referred to as “component (F)”), and a component (G) ((A). And a compound having one ethylenically unsaturated group other than the component and the component (B)].
  • component (E) photopolymerization initiator
  • component (F) thermal polymerization initiator
  • G component ((A)
  • a compound having one ethylenically unsaturated group other than the component and the component (B) will be described.
  • the other component mentioned later may use only 1 type of the illustrated compound, and may use
  • (E) component When the composition of the present invention is used as an active energy ray curable composition and further used as an electron beam curable composition, the component (E) (photopolymerization initiator) is not included. It is also possible to cure with an electron beam.
  • the component (E) is further added from the viewpoint of ease of curing and cost. It is preferable to contain.
  • the component (E) in the present invention various known photopolymerization initiators can be used.
  • the component (E) is preferably a radical photopolymerization initiator.
  • Specific examples of the component (E) include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopro Pan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, diethoxyacetophenone, oligo ⁇ 2-hydroxy-2-methyl-1- [4- ( 1-methylvinyl) phenyl] propanone ⁇ and 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methylpropionyl
  • an acetophenone compound, a benzophenone compound, and a phosphine oxide compound are preferably mentioned, and good curability can be easily obtained in the air even when the cured film is coated with a thin film of several ⁇ m or less. Therefore, an acetophenone compound is particularly preferable.
  • the content of the component (E) is preferably 0.01 to 10 parts by weight, more preferably 0.5 to 7 parts by weight, with respect to 100 parts by weight of the total amount of the curable components. It is particularly preferred that the amount be ⁇ 5 parts by weight. Within the above range, the composition has excellent curability and the resulting cured film has excellent scratch resistance.
  • the component (F) is a thermal polymerization initiator, and when the composition is used as a thermosetting composition, the component (F) can be blended.
  • the composition of this invention can mix
  • Various compounds can be used as the thermal polymerization initiator, and organic peroxides and azo initiators are preferred.
  • organic peroxide examples include 1,1-bis (t-butylperoxy) 2-methylcyclohexane, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, , 1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, , 2-bis (4,4-di-butylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy) cyclododecane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl 2,5-di (m-
  • azo compound examples include 1,1′-azobis (cyclohexane-1-carbonitrile), 2- (carbamoylazo) isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile. Azodi-t-octane, azodi-t-butane, and the like. These may be used alone or in combination of two or more. Moreover, an organic peroxide can also be made into a redox reaction by combining with a reducing agent.
  • a thermal polymerization initiator When a thermal polymerization initiator is used alone, it may be carried out in accordance with conventional means of normal radical thermal polymerization. For the purpose of improving the temperature, thermosetting can also be performed.
  • the component (G) is a compound having one ethylenically unsaturated group other than the components (A) and (B).
  • the component (G) is an arbitrary component used for adjusting the viscosity and other physical properties of the composition, and various components can be used.
  • Examples of the component (G) include (meth) acrylate having one (meth) acryloyl group (hereinafter referred to as “monofunctional (meth) acrylate”) and one (meth) acryloyl group (meta ) Acrylamide compounds [hereinafter referred to as “monofunctional (meth) acrylamide”] and the like.
  • monofunctional (meth) acrylate Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, lauryl ( Alkyl (meth) acrylates such as (meth) acrylate and stearyl (meth) acrylate; Cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, etc.
  • the monofunctional (meth) acrylamide examples include N-methyl (meth) acrylamide, Nn-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nn-butyl (meth) acrylamide, N-alkyl (meth) acrylamides such as N-sec-butyl (meth) acrylamide, Nt-butyl (meth) acrylamide, Nn-hexyl (meth) acrylamide; N such as N-hydroxyethyl (meth) acrylamide -Hydroxyalkyl (meth) acrylamide; and N, N-dimethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meta) ) Acrylamide, N, N-di-n-propi N, N-dial
  • the content of the component (G) is preferably 1 to 30 parts by weight, more preferably 5 to 25 parts by weight, with respect to 100 parts by weight of the total amount of the curable components. More preferably. Within the above range, the physical properties can be adjusted without impairing the excellent substrate adhesion characteristic of the composition of the present invention.
  • organic solvents examples thereof include an antioxidant, a surface modifier, a hydrophilic polymer, a filler, a silane coupling agent, an acid generator, a pigment, a dye, a tackifier, and a polymerization inhibitor.
  • organic solvent, an antifogging modifier, an ultraviolet absorber, a light stabilizer, an acidic substance, an antioxidant, a surface modifier, a hydrophilic polymer, and a filler will be described.
  • the composition of the present invention can be used without a solvent, but various organic solvents can be used for the purpose of adjusting coating viscosity and film thickness.
  • organic solvent it is necessary to use a compound not corresponding to the component (D), specifically, aromatic compounds such as benzene, toluene and xylene; propylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, etc. Ester compounds; ketone compounds such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ether compounds such as dibutyl ether; and N-methylpyrrolidone.
  • (D) component can also be mix
  • Specific examples in this case include the aforementioned compounds.
  • the content of the organic solvent is preferably 0.01 to 200 parts by weight, more preferably 10 to 150 parts by weight, more preferably 20 to 100 parts by weight based on 100 parts by weight of the total amount of the curable components. More preferably, it is part by weight.
  • the cured film is excellent in repeated antifogging properties, but for the purpose of further improving the initial antifogging property, the antifogging modification is performed within a range that does not adversely affect the repeated antifogging properties of the present invention.
  • a quality agent can be added.
  • the antifogging modifier include ionic surfactants having no ethylenically unsaturated group.
  • the ionic surfactant having no ethylenically unsaturated group known ones can be used, and examples thereof include anionic surfactants, cationic surfactants, and zwitterionic surfactants. .
  • Anionic surfactants include dialkyl sulfosuccinates such as di (2-ethylhexyl) sodium sulfosuccinate and di (2-ethylhexyl) ammonium sulfosuccinate; fatty acid salts such as sodium oleate and potassium oleate; lauryl Higher alcohol sulfates such as sodium sulfate and ammonium lauryl sulfate; alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate; alkyl naphthalene sulfonates of sodium alkyl naphthalene sulfonate; naphthalene sulfonate formalin condensates; dialkyl phosphate salts; and polyoxy Polyoxyethylene sulfate salts such as ethylene alkylphenyl ether sodium sulfate are used.
  • dialkylsulfosuccinate is preferable because it is superior in initial antifogging property.
  • Dialkyl sulfosuccinate is commercially available, and commercially available products can be used.
  • the sodium salt of sulfosuccinic acid di (2-ethylhexyl) include Rikasurf P-10 (solution of the same compound), M-30 (solution of the same compound) and G-30 (propylene glycol of the same compound) manufactured by Shin Nippon Rika Co., Ltd. / Rapidol A30, A70, A80, and A90 manufactured by NOF Corporation.
  • Examples of the di (2-ethylhexyl) ammonium salt of sulfosuccinic acid include Rikasurf G-600 [Propylene glycol / water mixed solution of the same compound] manufactured by Shin Nippon Rika Co., Ltd.
  • Cationic surfactants include amine salts such as ethanolamines, laurylamine acetate, triethanolamine monoformate, stearamide ethyl diethylamine acetate, lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, dilauryldimethylammonium chloride. And quaternary ammonium salts such as distearyldimethylammonium chloride, lauryldimethylbenzylammonium chloride, and stearyldimethylbenzylammonium chloride.
  • amine salts such as ethanolamines, laurylamine acetate, triethanolamine monoformate, stearamide ethyl diethylamine acetate, lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, dilauryldimethylammonium chloride.
  • quaternary ammonium salts such as distearyldimethylammonium chloride,
  • zwitterionic surfactants include fatty acid type zwitterionic surfactants such as dimethylalkyl lauryl betaine and dimethylalkyl stearyl betaine, sulfonic acid type zwitterionic surfactants such as dimethylalkylsulfobetaine, and alkylglycine. Can be mentioned.
  • anionic surfactants having no ethylenically unsaturated group
  • anionic surfactants are preferable in view of excellent initial antifogging property
  • dialkylsulfosuccinate is more preferable as described above.
  • the content of the antifogging modifier is preferably 0.1 to 10% by weight in 100% by weight of the total amount of the composition of the present invention.
  • the content ratio of the antifogging modifier is within the above range, the initial antifogging property can be excellent without impairing the repeated antifogging property of the cured film.
  • UV absorber examples include 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl)- 1,3,5-triazine, 2- [4-[(2-hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine, 2- [4-[(2-hydroxy-3- (2-ethylhexyloxy) propyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) 1,3,5-triazine, 2,4-bis (2-hydroxy-4-butyroxyphenyl) -6- (2,4-bisbutyroxyphenyl) -1,3,5-triazine, 2- ( 2-hydroxy-4- 1-octyl
  • Ultraviolet absorbers are used for the purpose of suppressing discoloration of plastic substrates that are prone to yellowing when irradiated with active energy rays. Used to prevent deterioration.
  • the content of the ultraviolet absorber is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, with respect to 100 parts by weight of the total amount of the curable components. More preferably, it is 1 to 2 parts by weight.
  • a known light stabilizer can be used.
  • a hindered amine light stabilizer HALS
  • Specific examples of hindered amine light stabilizers include bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate and methyl (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate.
  • the content ratio of the light stabilizer is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 2 parts by weight, with respect to 100 parts by weight of the total amount of the curable components. More preferably, it is 1 to 1 part by weight.
  • the composition of this invention is excellent in the adhesive material to base materials, such as a plastics, adhesiveness can be improved further by adding an acidic substance.
  • the acidic substance include a photoacid generator that generates an acid upon irradiation with active energy rays, an inorganic acid, and an organic acid.
  • the inorganic acid include sulfuric acid, nitric acid, hydrochloric acid, and phosphoric acid.
  • the organic acid include p-toluenesulfonic acid and organic sulfonic acid compounds such as methanesulfonic acid.
  • inorganic acids or organic acids are preferable, organic sulfonic acid compounds that are organic acids are more preferable, aromatic sulfonic acid compounds are more preferable, and p-toluenesulfonic acid is particularly preferable.
  • the content ratio of the acidic substance is preferably 0.0001 to 5 parts by weight, more preferably 0.0001 to 1 part by weight, and more preferably 0.0005 to 100 parts by weight of the total amount of the curable components. More preferably, it is 0.5 parts by weight. When the content ratio of the acidic substance is in the above range, the cured film is more excellent in adhesion to the base material, and problems such as corrosion of the base material and decomposition of other components can be prevented.
  • the composition of the present invention may further contain an antioxidant for the purpose of improving the heat resistance and weather resistance of the cured film.
  • an antioxidant for the purpose of improving the heat resistance and weather resistance of the cured film.
  • examples of the antioxidant used in the present invention include phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants.
  • Preferred examples of the phenolic antioxidant include hindered phenols such as di-t-butylhydroxytoluene.
  • Examples of commercially available products include AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, and AO-80 manufactured by Adeka Corporation.
  • phosphorus antioxidant examples include phosphines such as trialkylphosphine and triarylphosphine, trialkyl phosphite, triaryl phosphite, and the like.
  • examples of commercially available products of these derivatives include Adeka Co., Ltd., ADK STAB PEP-4C, PEP-8, PEP-24G, PEP-36, HP-10, 260, 522A, 329K, 1178, 1500, 135A, 3010.
  • Etc examples of the sulfur-based antioxidant include thioether-based compounds, and commercially available products include AO-23, AO-412S, and AO-503A manufactured by Adeka Corporation.
  • the content ratio of the antioxidant is preferably 0.01 to 5% by weight, more preferably 0.1 to 1% by weight in the total amount of 100% by weight of the composition of the present invention.
  • the content of the antioxidant is within the above range, the composition is excellent in stability, and curability and adhesive strength are good.
  • a surface modifier may be added for the purpose of increasing the leveling property at the time of coating, the purpose of increasing the slipping property of the cured film and improving the scratch resistance, and the like.
  • surface modifiers include surface modifiers, surfactants other than those described above, leveling agents, antifoaming agents, slipperiness imparting agents, and antifouling imparting agents, and the use of known surface modifiers. Can do. Of these, silicone-based surface modifiers and fluorine-based surface modifiers are preferred.
  • silicone polymers and oligomers having a silicone chain and a polyalkylene oxide chain silicone polymers and oligomers having a silicone chain and a polyester chain
  • fluorine polymers having a perfluoroalkyl group and a polyalkylene oxide chain a fluorine-based polymer and an oligomer having a perfluoroalkyl ether chain and a polyalkylene oxide chain.
  • a surface modifier having an ethylenically unsaturated group, preferably a (meth) acryloyl group, in the molecule may be used.
  • the content of the surface modifier is preferably 0.01 to 1.0% by weight in the total amount of 100% by weight of the composition of the present invention.
  • the content ratio of the surface modifier is in the above range, the surface smoothness of the cured film is excellent.
  • hydrophilic polymer examples include a polymer having a hydrophilic group.
  • hydrophilic groups include acidic groups and hydroxyl groups, with acidic groups being preferred.
  • the acidic group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. A carboxyl group or a sulfonic acid group is preferable, and a carboxyl group is more preferable.
  • acidic group-containing polymer a neutralized salt in which a part or all of the acidic group is neutralized is preferable.
  • a method for producing a neutralized salt of the acidic group-containing polymer As a method for producing a neutralized salt of the acidic group-containing polymer, a method of using a neutralized salt as a raw material vinyl monomer and a method for producing an acidic group-containing polymer are followed by neutralization treatment. The manufacturing method etc. are mentioned.
  • the hydrophilic polymer is preferably a polymer having a vinyl monomer having a hydrophilic group as an essential constituent monomer unit.
  • the vinyl monomer having a hydrophilic group include a vinyl monomer having an acidic group and a vinyl monomer having a hydroxyl group.
  • Examples of the vinyl monomer having an acidic group include an ethylenically unsaturated compound having a carboxyl group, an ethylenically unsaturated compound having a sulfonic acid group, and an ethylenically unsaturated compound having a phosphoric acid group.
  • Examples of the ethylenically unsaturated compound having a carboxyl group include (meth) acrylic acid, maleic acid, itaconic acid, crotonic acid, and salts of these compounds.
  • Examples of the ethylenically unsaturated compound having a sulfonic acid group include acrylamide 2-methylpropane sulfonic acid, styrene sulfonic acid, and (meth) allyl sulfonic acid.
  • Examples of the ethylenically unsaturated compound having a phosphoric acid group include phosphoric acid group-containing (meth) acrylates such as esterified products of phosphoric acid and (meth) acrylic acid.
  • the acidic group-containing polymer is a neutralized salt in which some or all of the acidic groups are neutralized, it is preferable to use a neutralized salt as the vinyl monomer having an acidic group.
  • Alkali compounds for forming neutralized salts of vinyl monomers having acidic groups include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide; ammonia; and triethylamine and triethanol. Examples thereof include amine compounds such as amines.
  • vinyl monomer having a hydroxyl group examples include hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate.
  • the hydrophilic polymer may be a copolymer of a vinyl monomer other than a vinyl monomer having a hydrophilic group (hereinafter referred to as “other monomer”).
  • Other monomers include alkyl (meth) acrylate, alkylaminoalkyl (meth) acrylate, styrene, alkyl vinyl ether, vinylidene chloride, (meth) acrylamide, N-vinylformamide, N-vinylacetamide, vinyl acetate, vinylpyrrolidone, (Meth) acrylonitrile, (meth) acryloylmorpholine, etc. are mentioned.
  • Alkyl (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) ) Acrylate and decyl (meth) acrylate.
  • Examples of the dialkylaminoalkyl (meth) acrylate include dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate.
  • the weight average molecular weight (hereinafter referred to as “Mw”) of the hydrophilic polymer is preferably 5,000 to 100,000, and more preferably 7,000 to 30,000.
  • the Mw of the hydrophilic polymer means a value obtained by gel permeation chromatography (hereinafter referred to as “GPC”) using standard polystyrene as a calibration curve, and the acid component is carboxylic acid or the like. It is the value measured before neutralizing the acidic group.
  • hydrophilic polymer those produced according to conventional polymerization using the aforementioned monomers can be used.
  • a radical polymerization method, a living anion polymerization method, a living radical polymerization method and the like can be mentioned.
  • polymerization forms include solution polymerization, emulsion polymerization, suspension polymerization, and bulk polymerization.
  • the cured film tends to be colored by irradiation with active energy rays, and when a polymer using a large amount of polymerization initiator is used, the storage stability of the composition is increased. Tends to decrease. For this reason, the polymer manufactured by the high temperature polymerization which does not require a lot of chain transfer agents and polymerization initiators is preferable.
  • the temperature of the high temperature polymerization is preferably 160 to 350 ° C, more preferably 180 to 300 ° C.
  • the form of the hydrophilic polymer may be selected according to the purpose, and examples thereof include a hydrophilic polymer solution, a hydrophilic polymer dispersion, and a powder.
  • a hydrophilic polymer solution a hydrophilic polymer dispersion
  • a powder a powder
  • an organic solvent solution of a hydrophilic polymer, an aqueous solution or aqueous dispersion of a hydrophilic polymer, a mixed solution or water dispersion of an organic solvent and water of a hydrophilic polymer, a powder, and the like can be given.
  • an aqueous solution or dispersion of a hydrophilic polymer, an organic solvent solution, and a mixed solution or water spray of an organic solvent and water of a hydrophilic polymer are preferable because of excellent solubility in the composition.
  • the solid content of the hydrophilic polymer solution and dispersion is preferably 3 to 70% by weight.
  • the content ratio of the hydrophilic polymer is preferably 0.5 to 50 parts by weight with respect to the total amount of the composition of 100 parts by weight, based on the solid content in any of the aqueous solution and the aqueous dispersion. More preferably, it is 2 to 30 parts by weight.
  • composition of the present invention When the composition of the present invention is applied and cured, deformation and warpage of the substrate can be prevented, and by setting it to 50 parts by weight or less, appearance defects such as white turbidity, streak unevenness, and yuzu skin of the cured film can be prevented. Can be prevented.
  • the composition of the present invention contains an organic solvent
  • the component (B) and / or the component (C) has a low viscosity
  • the composition is organic in the drying step after spray coating or spin coating.
  • the solvent volatilizes, the composition may repel on the substrate, resulting in a poor coating appearance.
  • the coating method as described above is performed using a composition containing an organic solvent, it is preferable to increase the viscosity by blending the composition with a filler in order to prevent repelling after drying.
  • a filler both an inorganic filler and an organic filler can be used, and an organic filler is preferable.
  • the inorganic filler include inorganic compounds such as silica and alumina.
  • the organic filler examples include hydrophobic polymers, such as polyurethane, poly (meth) acrylate, polyamide, polyurea, nylon, polystyrene, polyethylene, and polypropylene, and poly (meth) acrylate is preferable.
  • hydrophobic polymer a polymer having a high average molecular weight is preferable because the number of added parts necessary for thickening can be reduced and a decrease in the antifogging property of the composition can be prevented.
  • the molecular weight is preferably within a range that does not impair the compatibility with the composition, and the weight average molecular weight is preferably 10,000 to 5,000,000, more preferably 100,000 to 2,000,000.
  • the filler is preferably particulate, and the average particle size is preferably 1 to 15 ⁇ m, more preferably 4 to 12 ⁇ m.
  • the average particle diameter in the present invention means a value measured by a laser diffraction method at a wavelength of 680 nm.
  • the content of the filler it is preferable that the viscosity can be increased with a smaller addition amount in consideration of the effect on the antifogging property. Is preferable, and 0.5 to 5 parts by weight is more preferable.
  • Method of Use As a method of using the composition of the present invention, a conventional method may be followed. For example, after apply
  • the active energy ray irradiation method may be a general method known as a conventional curing method.
  • the (E) component (photopolymerization initiator) and the (F) component (thermal polymerization initiator) are used in combination with the composition, and this is irradiated with active energy rays and then heat-cured, thereby adhering to the substrate.
  • a method for improving the property can also be adopted.
  • the curable composition is an active energy ray curable composition
  • the antifogging property when there is a heating step after irradiation with the active energy ray, the antifogging property may be lowered when heated for a long time.
  • a method of heating after supplying an inert gas such as nitrogen gas and irradiating with an active energy ray in an inert gas atmosphere is preferable because the antifogging property can be prevented from being lowered.
  • the substrate to which the composition of the present invention can be applied is applicable to various materials, and examples thereof include inorganic materials, plastics, and paper.
  • inorganic materials include glass, metal, mortar, concrete and stone.
  • metals include steel plates, metals such as aluminum and chromium, metal oxides such as zinc oxide (ZnO) and indium tin oxide (ITO).
  • plastics include polyolefins such as polyethylene and polypropylene, ABS resins, cellulose acetate resins such as polyvinyl alcohol, triacetyl cellulose and diacetyl cellulose, acrylic resins, polyethylene terephthalate, polycarbonate, polyarylate, polyethersulfone, norbornene, etc.
  • cyclic polyolefin resin having a cyclic olefin as a monomer, polyvinyl chloride, epoxy resin and polyurethane resin.
  • the composition of the present invention is excellent in adhesion to plastic among these substrates, it can be preferably applied to plastic. Furthermore, as an inorganic material, it can apply preferably to glass and a metal, and as a plastic, it can apply preferably to a polyethylene terephthalate, a polycarbonate, poly (methyl) methacrylate, and a copolymer which has this as a main component.
  • the method of applying the composition of the present invention to the substrate may be appropriately set according to the purpose, and is a bar coater, applicator, doctor blade, dip coater, roll coater, spin coater, flow coater, knife coater, comma.
  • the coating method include a coater, a reverse roll coater, a die coater, a lip coater, a spray coater, a gravure coater, and a micro gravure coater.
  • the thickness of the cured film may be selected according to the use of the substrate to be used or the substrate having the produced cured film, but is preferably 1 to 100 ⁇ m, more preferably 2 to 40 ⁇ m. .
  • the composition contains an organic solvent
  • the drying temperature is not particularly limited as long as the applied substrate is at a temperature that does not cause a problem such as deformation.
  • a preferable heating temperature is 40 to 100 ° C.
  • the drying time may be appropriately set depending on the substrate to be applied and the heating temperature, and is preferably 0.5 to 20 minutes.
  • examples of the active energy rays for curing include electron beams, ultraviolet rays, and visible rays, but ultraviolet rays or visible rays are preferable, and ultraviolet rays are preferred. Particularly preferred.
  • examples of the ultraviolet irradiation device include a high pressure mercury lamp, a metal halide lamp, an ultraviolet (UV) electrodeless lamp, and a light emitting diode (LED). The irradiation energy should be appropriately set according to the type and composition of the active energy ray.
  • the irradiation energy in the UV-A region is 100 to 8,000 mJ / cm 2 is preferable, and 200 to 3,000 mJ / cm 2 is more preferable.
  • the irradiation energy is 1,000 mJ / cm 2 or more, it is preferable to blend the above-described antifogging modifier from the viewpoint of the antifogging performance of the cured film.
  • the cured film can be obtained by standing the cured film in a heatable dryer or the like. What is necessary is just to set suitably as heating temperature according to the base material to be used and the objective, and 40-180 degreeC is preferable. In the case where the base material is plastic, the base material may be deformed if the temperature is too high.
  • the heating time may be appropriately set depending on the substrate to be applied and the heating temperature, and is preferably 0.5 to 60 minutes.
  • composition of the present invention can be used for various applications, and specifically includes an anti-fogging coating agent, and a coating agent for preventing dust adhesion on plastic substrates and floors.
  • the coating agent include protective glasses, goggles, bathroom inner walls, parts around the kitchen, head lamp covers for automobiles and motorcycles, rear lamp covers such as glass and plastic anti-fogging coating agents, plastic substrates and floor surfaces.
  • the coating agent include a dust adhesion preventing coating agent for preventing dust adhesion.
  • Production example 1-1) Production Example 1 [Production of acrylate containing component (B) and component (C)] In a 3 liter flask equipped with a stirrer, a thermometer, a gas introduction tube, a rectification column, and a cooling tube, glycerin [purified glycerin (trade name) manufactured by Sakamoto Pharmaceutical Co., Ltd.]. Hereinafter, it is referred to as “GLY”.
  • the aluminum silicate is separated by filtration, and the filtrate is put in a flask connected with a stirrer, thermometer, gas introduction pipe, distillation cooling pipe, and decompression pipe, and the temperature is 70 to 100 ° C., pressure
  • the distillate containing unreacted MCA was separated by vacuum distillation for 10 hours while bubbling dry air in the range of 0.001 to 100 mmHg.
  • 5.0 parts of diatomaceous earth [Radiolite (trade name) manufactured by Showa Chemical Industry Co., Ltd.] was added to the kettle liquid, pressure filtration was performed, and the obtained filtrate was used in Examples. The yield was 651 parts. This is called BC-1.
  • HPLC, viscosity, hydroxyl value, GPC and GC were measured under the following conditions.
  • ⁇ HPLC measurement conditions and equipment ACQUITY UPLC manufactured by Waters Co., Ltd.
  • ⁇ Detector UV detector ⁇ Detection wavelength: 210 nm
  • Column Waters Co., Ltd.
  • Viscosity measurement conditions Using an E-type viscometer, the viscosity at 25 ° C was measured.
  • ⁇ Hydroxyl value measurement conditions Add an acetylating reagent to the sample and heat-treat in a warm bath at 92 ° C for 1 hour. After standing to cool, a small amount of water is added and heat-treated in a warm bath at 92 ° C. for 10 minutes. After allowing to cool, the hydroxyl value was determined by titrating the acid with a potassium hydroxide ethanol solution using a phenolphthalein solution as an indicator.
  • GPC measurement conditions and equipment GPC system name manufactured by Waters Co., Ltd. 1515 2414 717P RI -Detector: Differential refractive index (RI) detector-Column: Guard column Shodex KFG (8 ⁇ m 4.6 ⁇ 10 mm) manufactured by Showa Denko K.K., two types of this column Watergel HR 4E THF (7. 8 x 300 mm) + styragel HR 1THF (7.8 x 300 mm) Column temperature: 40 ° C Eluent composition: THF (containing 0.03% sulfur as internal standard), flow rate of 0.75 mL / min. Calibration curve: A calibration curve was prepared using standard polystyrene.
  • detection peaks derived from BC-1 detection peaks derived from monofunctional (meth) acrylates, solvents, and detection peaks with a retention time later than those derived from water are not considered in the calculation of Mw, Mw was calculated by regarding a plurality of other detection peaks as one peak.
  • the pressure in the reaction system is adjusted in the range of 150 to 760 mmHg, and the mixture of MCA and MEL by-produced as the transesterification proceeds is rectified.
  • the reaction system was withdrawn via a tower and a cooling pipe.
  • MCA of the same weight as the extracted liquid was added to the reaction system as needed.
  • MCA containing MEHQ and TEMPOL was added to the reaction system as needed through a rectification column. After 40 hours from the start of heating and stirring, the pressure in the reaction system was returned to normal pressure, and extraction was completed.
  • BC-2 had a viscosity of 26 mPa ⁇ s (25 ° C.) and a hydroxyl value of 16 mgKOH / g. Mw by GPC measurement: 338.
  • a component and (D) component mixture -JI-62C01 propylene glycol monomethyl ether (hereinafter referred to as "A-1-1") having a cation having an acryloyl group and an ammonium ion and an anion (hereinafter referred to as "A-1-1") "PGME”) 50% solution [JI-62C01 manufactured by Nippon Emulsifier Co., Ltd.]
  • a component, B) component and (C) component mixture -JI-64C01 50% solution of A-1 and BC-2 [JI-64C01 manufactured by Nippon Emulsifier Co., Ltd.]
  • Component (A) SR-10 Polyethylene glycol (added mole number 10) A compound having an SO 3 NH 4 group (anionic) at one end and an alkyl group and an allyl group at the other end
  • Component (B) and component mixture (C) MT-3545 70 parts dipentaerythritol pentaacrylate (hereinafter referred to as “DPET-PA”) and 30 parts dipentaerythritol hexaacrylate (hereinafter referred to as “DPET-HA”) Product [Aronix MT-3545 manufactured by Toagosei Co., Ltd.]
  • TPO (2,4,6-trimethylbenzoyl) diphenylphosphine oxide, Irgacure TPO manufactured by BASF Other components
  • G-30 Propylene glycol
  • Pencil Hardness Pencil hardness of the obtained cured film was measured under a load of 750 g according to JIS K5600-5-4.
  • brackets in the column of the composition in Table 1 and Table 2 mean the number of parts of each component, and “-” means not contained.
  • the components (A) to (C) contained in JI-64C01 and JI-64C02 used as raw materials are listed separately, and are included in JI-62C01.
  • (A) component and (D) component are described separately.
  • the composition of the present invention has excellent adhesion to a plastic substrate, surface hardness, antifogging property of a cured film surface and its durability. Met.
  • the composition of Comparative Example 1 contains the component (D) in excess of 3 weights with respect to the total of 100 parts by weight of the component (A), the component (B), and the component (C), the cured film Due to the small amount of component (A) incorporated and incorporated therein, the anti-fogging performance deteriorated when repeatedly exposed to steam.
  • the curable composition of the present invention can be preferably used as a curable composition, and the resulting cured film is excellent in adhesion and scratch resistance to various substrates, and is antifogging and preventing dust adhesion. It also has excellent performance. It can be preferably used as protective glasses, goggles, bathroom inner walls, headlamp covers for automobiles, motorcycles, etc., rear lamp covers, antifogging paints for security camera lenses, etc., and dust adhesion prevention coating agents for plastic films.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne une composition durcissable qui est une composition qui comprend le composant (A), le composant (B), et le composant (C) suivants et qui ne contient pas le composant (D) suivant ou contient le composant (D) suivant dans une quantité de 3 parties en poids ou moins pour 100 parties en poids de la somme des composants (A), (B) et (C). Le composant (A) est un composé ayant un groupe à insaturation éthylénique et un groupe ionique ; le composant (B) est un composé ayant un groupe hydrophile et un groupe à insaturation éthylénique ; le composant (C) est un composé ayant au moins deux groupes à insaturation éthylénique et qui n'est ni le composant (A) ni le composant (B) ; et le composant (D) est un composé hydroxylé ne contenant pas de groupe à insaturation éthylénique.
PCT/JP2018/017955 2017-05-10 2018-05-09 Composition durcissable WO2018207828A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020158680A (ja) * 2019-03-27 2020-10-01 中国塗料株式会社 活性エネルギー線硬化型樹脂組成物およびその用途

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11140109A (ja) * 1997-11-05 1999-05-25 Toagosei Co Ltd 可視光又は活性エネルギー線硬化型防曇性組成物
WO2015133492A1 (fr) * 2014-03-04 2015-09-11 ダイソー株式会社 Liant pour électrodes de batterie, et électrode et batterie utilisant celui-ci
JP2016216635A (ja) * 2015-05-22 2016-12-22 大日精化工業株式会社 ハードコート膜形成用組成物、硬化膜、及び帯電防止性物品

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Publication number Priority date Publication date Assignee Title
JP6919226B2 (ja) * 2017-02-28 2021-08-18 昭和電工マテリアルズ株式会社 感光性樹脂組成物、感光性エレメント及びレジストパターンの形成方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11140109A (ja) * 1997-11-05 1999-05-25 Toagosei Co Ltd 可視光又は活性エネルギー線硬化型防曇性組成物
WO2015133492A1 (fr) * 2014-03-04 2015-09-11 ダイソー株式会社 Liant pour électrodes de batterie, et électrode et batterie utilisant celui-ci
JP2016216635A (ja) * 2015-05-22 2016-12-22 大日精化工業株式会社 ハードコート膜形成用組成物、硬化膜、及び帯電防止性物品

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020158680A (ja) * 2019-03-27 2020-10-01 中国塗料株式会社 活性エネルギー線硬化型樹脂組成物およびその用途

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