CN115466551A - Inorganic fine particle dispersion, active energy ray-curable composition, cured product, laminate, and article - Google Patents

Inorganic fine particle dispersion, active energy ray-curable composition, cured product, laminate, and article Download PDF

Info

Publication number
CN115466551A
CN115466551A CN202210649159.0A CN202210649159A CN115466551A CN 115466551 A CN115466551 A CN 115466551A CN 202210649159 A CN202210649159 A CN 202210649159A CN 115466551 A CN115466551 A CN 115466551A
Authority
CN
China
Prior art keywords
meth
inorganic fine
acrylate
mass
active energy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202210649159.0A
Other languages
Chinese (zh)
Inventor
井上直人
伊藤正广
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DIC Corp
Original Assignee
DIC Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by DIC Corp filed Critical DIC Corp
Publication of CN115466551A publication Critical patent/CN115466551A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • 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
    • C09D135/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D135/02—Homopolymers or copolymers of esters
    • 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
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • 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
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • 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
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2345/00—Characterised by the use of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2435/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
    • C08J2435/02—Characterised by the use of homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymerisation Methods In General (AREA)
  • Graft Or Block Polymers (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)

Abstract

The invention provides an inorganic fine particle dispersion, an active energy ray-curable composition, a cured product, a laminate, and an article. An inorganic fine particle dispersion comprising inorganic fine particles (A), a (meth) acrylate compound (B) having 2 or more (meth) acryloyl groups in one molecule, and a wetting dispersant (C), wherein the inorganic fine particles (A) have an average primary particle diameter in the range of 1 to 50nm, the content of the inorganic fine particles (A) is in the range of 40 to 90 mass% in the total mass of the inorganic fine particles (A), the compound (B), and the wetting dispersant (C) has an acid value and/or an amine value. Thus, an inorganic fine particle dispersion having excellent adhesion and a cured product having excellent scratch resistance can be obtained.

Description

Inorganic fine particle dispersion, active energy ray-curable composition, cured product, laminate, and article
Technical Field
The present invention relates to an inorganic microparticle dispersion, an active energy ray-curable composition, a cured product, a laminate, and an article.
Background
Resin materials having a (meth) acryloyl group can be easily and instantaneously cured by irradiation with ultraviolet rays or the like, and cured products are excellent in transparency, hardness, and the like, and thus are widely used in the fields of paints, coating agents, and the like. The objects to be coated include optical films, plastic molded articles, and wood products, and the properties required for the objects to be coated are various according to the types and applications of the objects to be coated, and therefore, many resins designed according to the purposes have been proposed.
As a resin material having a (meth) acryloyl group, an active energy ray-curable resin composition containing a (meth) acryloyl group-containing acrylic resin, pentaerythritol tetraacrylate, and pentaerythritol triacrylate is known (for example, see patent document 1). The active energy ray-curable resin composition described in patent document 1 is excellent in the balance between the surface hardness and the low curing shrinkage of the cured product, and is therefore useful as a coating agent for coating a thin plastic film. However, there are problems that the adhesion to the film base material, particularly the adhesion after long-term storage under high-temperature and humid conditions, is low and peeling is likely to occur.
Therefore, a material having excellent adhesion and excellent scratch resistance which can be used as a coating agent is required.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2011-207947
Disclosure of Invention
Problems to be solved by the invention
The present invention addresses the problem of providing an inorganic fine particle dispersion having excellent adhesion and a cured product having excellent scratch resistance, an active energy ray-curable composition, and a cured product, a laminate, and an article each comprising the active energy ray-curable composition.
Means for solving the problems
The present inventors have intensively studied to solve the above problems, and as a result, have found that the above problems can be solved by using an inorganic fine particle dispersion containing specific inorganic fine particles, a (meth) acrylate compound having 2 or more (meth) acryloyl groups in one molecule, and a specific wetting dispersant, and have completed the present invention.
That is, the present invention relates to an inorganic fine particle dispersion containing inorganic fine particles (a), a (meth) acrylate compound (B) having 2 or more (meth) acryloyl groups in one molecule, and a wetting dispersant (C), wherein the average primary particle diameter of the inorganic fine particles (a) is in the range of 1 to 50nm, the content of the inorganic fine particles (a) is in the range of 40 to 90 mass% in the total mass of the inorganic fine particles (a), the compound (B), and the wetting dispersant (C) is a wetting dispersant having an acid value and/or an amine value, an active energy ray-curable composition, a cured product, a laminate, and an article.
ADVANTAGEOUS EFFECTS OF INVENTION
The inorganic fine particle dispersion of the present invention can form a cured product having excellent adhesion to a substrate and excellent abrasion resistance, and therefore, can be used as a coating agent or an adhesive, and can be preferably used as a coating agent in particular.
Detailed Description
The inorganic fine particle dispersion of the present invention is characterized by containing inorganic fine particles (A), a (meth) acrylate compound (B) having 2 or more (meth) acryloyl groups in one molecule, and a wetting dispersant (C).
In the present invention, "(meth) acrylate" means acrylate and/or methacrylate. In addition, "(meth) acryloyl" means acryloyl and/or methacryloyl. Further, "(meth) acryl" means acryl and/or methacryl.
As the inorganic fine particles (A), inorganic fine particles having an average primary particle diameter in the range of 1 to 50nm are used. The average primary particle size can be obtained as follows: the diameter of the plurality of inorganic fine particles is measured by a transmission electron microscope or a scanning electron microscope, and the average value is calculated.
Examples of the inorganic fine particles (a) include zirconium oxide, silica, barium sulfate, zinc oxide, barium titanate, cerium oxide, alumina, titanium oxide, niobium oxide, zinc oxide, tin oxide, tungsten oxide, and antimony. These inorganic fine particles may be used alone, or 2 or more kinds may be used in combination. Among these, silica is preferable, and silica fine particles having a hydrophobized particle surface are more preferable, from the viewpoint of obtaining an inorganic fine particle dispersion that can form a cured product excellent in substrate adhesion and abrasion resistance.
The content of the inorganic fine particles (a) in the total mass of the inorganic fine particles (a), the (meth) acrylate compound (B), and the wetting dispersant (C) is preferably in the range of 40 to 90 mass%, more preferably in the range of 45 to 70 mass% from the viewpoint of obtaining an inorganic fine particle dispersion that can form a cured product excellent in substrate adhesion and abrasion resistance.
As the (meth) acrylate compound (B), a (meth) acrylate compound having 2 or more (meth) acryloyl groups in one molecule is used.
Examples of the compound (B) include: 1, 6-hexanediol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 3-butanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide-modified 1, 6-hexanediol di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, propylene oxide-modified neopentyl glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, ethylene oxide-modified di (meth) acrylate of bisphenol A, propylene oxide-modified di (meth) acrylate of bisphenol A, ethylene oxide-modified di (meth) acrylate of bisphenol F, tricyclodecane dimethanol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, propylene oxide-modified tri (meth) acrylate of glycerin, 2-hydroxy-3-acryloyloxy-propylene glycol di (meth) acrylate, ethylene oxide-modified fluorene di (meth) acrylate, methylene ethylene oxide-ethoxylated (meth) acrylate, triethylene glycol di (meth) acrylate, and ethylene oxide-modified di (meth) acrylate, 2-functional (meth) acrylates such as phenoxyethylene glycol (meth) acrylate, stearyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinate, trifluoroethyl (meth) acrylate, 3-methyl-1, 5-pentanediol di (meth) acrylate, 2,3- [ (meth) acryloyloxymethyl ] norbornane, 2,5- [ (meth) acryloyloxymethyl ] norbornane, 2,6- [ (meth) acryloyloxymethyl ] norbornane, 1, 3-adamantyl di (meth) acrylate, 1, 3-bis [ (meth) acryloyloxymethyl ] adamantane, tris (hydroxyethyl) isocyanurate di (meth) acrylate, 3, 9-bis [1, 1-dimethyl-2- (meth) acryloyloxyethyl ] -2,4,8, 10-tetraoxaspiro [5.5] undecane, trimethylolpropane di (meth) acrylate, pentaerythritol di (meth) acrylate, dipentaerythritol di (meth) acrylate, ditrimethylolpropane di (meth) acrylate and the like;
3-functional (meth) acrylates such as EO-modified glycerol (meth) acrylate, PO-modified glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, EO-modified phosphoric acid tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, caprolactone-modified trimethylolpropane tri (meth) acrylate, HPA-modified trimethylolpropane tri (meth) acrylate, (EO) or (PO) -modified trimethylolpropane tri (meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, tris (acryloyloxyethyl) isocyanurate, and tris (methacryloyloxyethyl) isocyanurate;
4-functional (meth) acrylates such as ditrimethylolpropane tetra (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, and pentaerythritol tetra (meth) acrylate;
5-functional (meth) acrylates such as dipentaerythritol hydroxypenta (meth) acrylate and alkyl-modified dipentaerythritol penta (meth) acrylate;
6-functional (meth) acrylates such as dipentaerythritol hexa (meth) acrylate.
These (meth) acrylate compounds having 2 or more (meth) acryloyl groups in one molecule may be used alone, or 2 or more may be used in combination. Among them, a (meth) acrylate compound having 2 to 4 (meth) acryloyl groups in one molecule is preferable from the viewpoint of obtaining an inorganic fine particle dispersion capable of forming a cured product excellent in substrate adhesion and abrasion resistance.
The wetting and dispersing agent (C) is a wetting and dispersing agent having an acid value and/or an amine value.
Examples of the wetting and dispersing agent (C) include: a urethane resin having a carboxyl group, a phosphoric acid group and/or an amino group; an acrylic resin having a carboxyl group, a phosphoric acid group and/or an amino group; a polyester resin having a carboxyl group, a phosphoric acid group and/or an amino group; amide resins having a carboxyl group, a phosphoric acid group and/or an amino group, and the like. These wetting and dispersing agents may be used alone, or 2 or more kinds may be used in combination. Among these, polyester resins having a carboxyl group and amide resins having an amino group are preferable from the viewpoint of having excellent dispersibility in inorganic particles and maintaining excellent stability.
As a commercially available product of the wetting and dispersing agent (C), examples thereof include "DISPERBYK-102", "DISPERBYK-106", "DISPERBYK-108", "DISPERBYK-109", "DISPERBYK-110/111", "DISPERBYK-118", "DISPERBYK-140", "DISPERBYK-142", "DISPERBYK-145", "DISPERBYK-161", "DISPERBYK-162/163", "DISPERBYK-164", "DISPERBYK-167", "DISPERBYK-168", "DISPERBYK-170", "DISPERBYK-174", "DISPERBYK-180", "DISPERBYK-182", "DISPERBYK-184", "DISPERBYK-185", "DISPERBYK-2000", "DISPERBYK-102" "DISPERBYK-2001", "DISPERBYK-2008", "DISPERBYK-2009", "DISPERBYK-2013", "DISPERBYK-2022", "DISPERBYK-2023", "DISPERBYK-2025v2026", "DISPERBYK-2050", "DISPERBYK-2055", "DISPERBYK-2096", "DISPERBYK-2150", "DISPERBYK-2155", "DISPERBYK-2157", "DISPERBYK-2158", "DISPERBYK-2159", "DISPERBYK-2163", "DISPERBYK-2164", "BYK-9076", "BYK-9077", "BYK-220S", "ANTI-TERRA-U/U100", "ANTI-TERRA-U/U204"; "DISPARLON 1831", "DISPARLON 1850", "DISPARLON 1860", "DISPARLON DA-1401", "DISPARLON DA-1200", "DISPARLON PW36DISPARLON DA-703-50", "DISPARLON DA7301", "DISPARLON DA-325", "DISPARLON DA-375", and "DISPARLON DA234", manufactured by NANOBIAL CHEMICAL CREAM.
The acid value of the wetting dispersant (C) is preferably in the range of 0.5 to 180mgKOH/g, more preferably 10 to 80mgKOH/g, from the viewpoint of excellent dispersibility in inorganic fine particles and excellent stability. The amine value of the wetting dispersant (C) is preferably in the range of 0 to 150mgKOH/g, more preferably in the range of 20 to 50mgKOH/g, from the viewpoint of having excellent dispersibility in inorganic particles and maintaining excellent stability. In the present invention, the acid value is a value measured by a neutralization titration method according to JIS K0070 (1992). The amine value is a value calculated according to JIS K2501 (2003).
In the inorganic fine particle dispersion of the present invention, other active energy ray-curable resin components than the compound (B) may be used in combination within a range not impairing the effects of the present invention.
The other active energy ray-curable resin component may be other (meth) acrylate resin (D) than the compound (B). Examples of the other (meth) acrylate resin (D) include a dendrimer-type (meth) acrylate resin (D1), an acrylic- (meth) acrylate resin (D2), and an epoxy (meth) acrylate resin (D3). These other (meth) acrylate resins (D) may be used alone or in combination of 2 or more.
The dendrimer-type (meth) acrylate resin (D1) is a resin having a regular multi-branched structure and having a (meth) acryloyl group at the end of each branch, and is also referred to as a hyperbranched polymer, a star polymer, or the like, in addition to the dendrimer type. Examples of such compounds include those represented by the following structural formulae (1-1) to (1-8), but the compounds are not limited thereto, and any of them can be used as long as they have a regular multi-branched structure and a (meth) acryloyl group at each branched end.
Figure BDA0003685350950000061
Figure BDA0003685350950000071
[ in formulae (1-1) to (1-8), R 1 Is a hydrogen atom or a methyl group, R 2 Is a hydrocarbon group having 1 to 4 carbon atoms.]
Examples of commercially available products of the dendritic polymer-type (meth) acrylate resin (D1) include: "Viscoat #1000" manufactured by Osaka organic Chemicals K.K. [ having a weight average molecular weight (Mw) of 1500 to 2000 and an average (meth) acryloyl group number of each molecule of 14], "Viscoat1020" [ having a weight average molecular weight (Mw) of 1000 to 3000], "SIRIUS501" [ having a weight average molecular weight (Mw) of 15000 to 23000]; "SP-1106" manufactured by MIWON corporation [ having a weight average molecular weight (Mw) of 1630 and an average (meth) acryloyl number per molecule of 18]; "CN2301" and "CN2302" manufactured by SARTOMER corporation [ the average (meth) acryloyl group number per molecule is 16], "CN2303" [ the average (meth) acryloyl group number per molecule is 6], "CN2304" [ the average (meth) acryloyl group number per molecule is 18]; "ESDRIMER HU-22" manufactured by Nissian iron-on-gold chemical Co., ltd.; "A-HBR-5" manufactured by Xinzhongcun chemical Co., ltd.; "NEW FRONTIER R R-1150" manufactured by first Industrial pharmaceutical Co., ltd; "HYPERTECH UR-101" manufactured by Nissan chemical Co., ltd.
The weight average molecular weight (Mw) of the dendritic polymer-type (meth) acrylate resin (D1) is preferably in the range of 1000 to 30000. The average number of (meth) acryloyl groups per molecule is preferably in the range of 5 to 30.
Examples of the acrylic- (meth) acrylate resin (D2) include resins obtained by: a resin obtained by polymerizing a (meth) acrylate compound (α) having a reactive functional group such as a hydroxyl group, a carboxyl group, an isocyanate group, or a glycidyl group as an essential component, and further reacting the obtained acrylic resin intermediate with a (meth) acrylate compound (β) having a reactive functional group capable of reacting with these functional groups to introduce a (meth) acryloyl group.
Examples of the (meth) acrylate compound (α) having a reactive functional group include: hydroxyl group-containing (meth) acrylate monomers such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate; a carboxyl group-containing (meth) acrylate monomer such as (meth) acrylic acid; isocyanate group-containing (meth) acrylate monomers such as 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, and 1, 1-bis (acryloyloxymethyl) ethyl isocyanate; glycidyl group-containing (meth) acrylate monomers such as glycidyl (meth) acrylate and 4-hydroxybutyl acrylate glycidyl ether. These can be used alone, can also be combined with 2 or more.
The acrylic resin intermediate may be copolymerized with other polymerizable unsaturated group-containing compounds as necessary in addition to the (meth) acrylate compound (α). Examples of the other polymerizable unsaturated group-containing compound include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate; alicyclic structure-containing (meth) acrylates such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and the like; aromatic ring-containing (meth) acrylates such as phenyl (meth) acrylate, benzyl (meth) acrylate, and phenoxyethyl acrylate; silyl group-containing (meth) acrylates such as 3-methacryloxypropyltrimethoxysilane; styrene derivatives such as styrene, α -methylstyrene and chlorostyrene. These may be used alone, or 2 or more of them may be used in combination.
The acrylic resin intermediate can be produced by the same method as that for a conventional acrylic resin. As an example of the production conditions, the polymer can be produced by polymerizing various monomers in the presence of a polymerization initiator at a temperature range of 60 ℃ to 150 ℃. Examples of the polymerization method include bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. Examples of the polymerization form include a random copolymer, a block copolymer, and a graft copolymer. In the case of the solution polymerization method, for example, a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone, and a glycol ether solvent such as propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monopropyl ether or propylene glycol monobutyl ether are preferably used.
The (meth) acrylate compound (β) is not particularly limited as long as it is a compound that can react with the reactive functional group of the (meth) acrylate compound (α), and from the viewpoint of reactivity, the following combinations are preferable. That is, when a hydroxyl group-containing (meth) acrylate is used as the (meth) acrylate compound (α), it is preferable to use an isocyanate group-containing (meth) acrylate as the (meth) acrylate compound (β). When a carboxyl group-containing (meth) acrylate is used as the (meth) acrylate compound (. Alpha.), a glycidyl group-containing (meth) acrylate is preferably used as the (meth) acrylate compound (. Beta.). When an isocyanate group-containing (meth) acrylate is used as the (meth) acrylate compound (. Alpha.), a hydroxyl group-containing (meth) acrylate is preferably used as the (meth) acrylate compound (. Beta.). When a glycidyl group-containing (meth) acrylate is used as the (meth) acrylate compound (. Alpha.), a carboxyl group-containing (meth) acrylate is preferably used as the (meth) acrylate compound (. Beta.). The (meth) acrylate compound (. Beta.) may be used alone or in combination of 2 or more.
The reaction between the acrylic resin intermediate and the (meth) acrylate compound (. Beta.) may be carried out, for example, by a method in which an esterification catalyst such as triphenylphosphine is used at a temperature of 60 to 150 ℃ as appropriate in the esterification reaction. In addition, the reaction is a carbamation reaction, and a method of reacting the acrylic resin intermediate while dropping the compound (. Beta.) thereto at a temperature in the range of 50 to 120 ℃ is exemplified. The reaction ratio of both is preferably in the range of 1.0 to 1.1 mol based on 1 mol of the functional group in the acrylic resin intermediate.
Examples of the epoxy (meth) acrylate resin (D3) include resins obtained by reacting an epoxy resin with (meth) acrylic acid or an acid anhydride thereof. Examples of the epoxy resin include diglycidyl ethers of 2-membered phenols such as hydroquinone and catechol; diglycidyl ethers of diphenol compounds such as 3,3 '-diphenol and 4,4' -diphenol; bisphenol epoxy resins such as bisphenol a epoxy resin, bisphenol B epoxy resin, bisphenol F epoxy resin, and bisphenol S epoxy resin; polyglycidyl ether ethers of naphthol compounds such as 1, 4-naphthalenediol, 1, 5-naphthalenediol, 1, 6-naphthalenediol, 2, 7-naphthalenediol, binaphthol, bis (2, 7-dihydroxynaphthyl) methane and the like; triglycidyl ethers such as 4,4',4 ″ -methylenetrisphenol; novolac type epoxy resins such as novolac type epoxy resins and cresol novolac resins; (poly) oxyalkylene modified products in which (poly) oxyalkylene chains such as (poly) oxyethylene chains, (poly) oxypropylene chains, and (poly) oxytetramethylene chains are introduced into the molecular structures of the above epoxy resins; lactone modifications obtained by introducing a (poly) lactone structure into the molecular structure of the above epoxy resins, and the like.
In the active energy ray-curable composition of the present invention, a photopolymerization initiator is preferably used depending on the type of active energy ray used. Examples of the photopolymerization initiator include photoradical polymerization initiators such as 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethyloxy) phenyl ] -2-hydroxy-2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2' -dimethoxy-1, 2-diphenylethane-1-one, diphenyl (2, 4, 6-trimethoxybenzoyl) phosphine oxide, 2,4, 6-trimethylbenzoyl diphenylphosphine oxide, bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone.
Examples of commercially available products of the other photopolymerization initiators include "Omnirad 1173", "Omnirad 184", "Omnirad 127", "Omnirad 2959", "Omnirad 369", "Omnirad 379", "Omnirad 907", "Omnirad 4265", "Omnirad 1000", "Omnirad 651", "Omnirad TPO", "Omnirad 819", "Omnirad 2022", "Omnirad 2100", "Omnirad 754", "Omnirad 784", "Omnirad 500" and "Omnirad 81" (manufactured by IGM Resins); "KAYACURE DETX", "KAYACURE MBP", "KAYACURE DMBI", "KAYACURE EPA", "KAYACURE OA" (manufactured by Kayaku chemical Co., ltd.); "Vicure 10" and "Vicure 55" (manufactured by Stoffa Chemical Co.); "Trigonal P1" (manufactured by Akzo Nobel) and "SANDORAY 1000" (manufactured by SANDOZ); "DEAP" (manufactured by Upjohn Chemical Co., ltd.), "Quantacure PDO", "Quantacure ITX" and "Quantacure EPD" (manufactured by Ward Blenkinson Co., ltd.); "Runtecure 1104" (manufactured by Runtec corporation), and the like. These photopolymerization initiators may be used alone, or 2 or more of them may be used in combination.
Further, a photosensitizer such as an amine compound, a urea compound, a sulfur compound, a phosphorus compound, a chlorine compound, or a nitrile compound may be used in combination with the photopolymerization initiator.
The amount of the photopolymerization initiator used is preferably in the range of 0.05 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the components other than the organic solvent in the active energy ray-curable composition of the present invention.
The active energy ray-curable composition used in the present invention may further contain other components. Examples of the other components include a silane coupling agent, a phosphate ester compound, a solvent, an ultraviolet absorber, an antioxidant, a silicon additive, a fluorine additive, an antistatic agent, organic beads, quantum Dots (QD), a rheology control agent, a defoaming agent, an antifogging agent, and a colorant.
Examples of the silane coupling agent include (meth) acryloyloxy silane coupling agents such as [ (meth) acryloyloxyalkyl ] trialkylsilane, [ (meth) acryloyloxyalkyl ] dialkylalkoxysilane, [ (meth) acryloyloxyalkyl ] alkyldialkoxysilane, [ (meth) acryloyloxyalkyl ] trialkoxysilane; vinyl silane coupling agents such as trialkylstyrenesilane, dialkylalkoxyvinylsilane, alkyldialkoxyvinylsilane, trialkoxyvinylsilane, trialkylallylsilane, dialkylalkoxyallylsilane, alkyldialkoxyallylsilane, trialkoxyallylsilane, and the like; styrene-based silane coupling agents such as styryl trialkylsilane, styryl dialkylalkoxysilane, styryl alkyldialkoxysilane, styryl trialkoxysilane, and the like; epoxy-based silane coupling agents such as (glycidoxyalkyl) trialkylsilane, (glycidoxyalkyl) dialkylalkoxysilane, (glycidoxyalkyl) alkyldialkoxysilane, (glycidoxyalkyl) trialkoxysilane, [ (3, 4-epoxycyclohexyl) alkyl ] trimethoxysilane, [ (3, 4-epoxycyclohexyl) alkyl ] trialkylsilane, [ (3, 4-epoxycyclohexyl) alkyl ] dialkylalkoxysilane, [ (3, 4-epoxycyclohexyl) alkyl ] alkyldialkoxysilane, [ (3, 4-epoxycyclohexyl) alkyl ] trialkoxysilane; isocyanate-based silane coupling agents such as (isocyanatoalkyl) trialkylsilane, (isocyanatoalkyl) dialkylalkoxysilane, (isocyanatoalkyl) alkyldialkoxysilane, and (isocyanatoalkyl) trialkoxysilane. These silane coupling agents may be used alone or in combination of 2 or more.
Examples of the commercially available phosphate compounds include "KAYAMER PM-2" and "KAYAMER PM-21" manufactured by KAYAMER CHEMICAL CO., LTD., having a (meth) acryloyl group in the molecular structure, "LIGHT ESTER P-1M", "LIGHT ESTER P-2M", "LIGHT ACRYLATE P-1A (N)" manufactured by KORON CHEMICAL CO., LTD., SIPHOER PAM 100"," SIPHOR PAM 200"," SIPHOR PAM 300"," SIPHOR PAM 4000 "manufactured by SOLVAY CORPORATION, viscoat #3PA", "Viscoat #3PMA" manufactured by Osaka ORGAN CHEMICAL, and "NEW FRONTER S-23A" manufactured by NIGHT CHEMICAL CO., LTD., LTD.; "sipome PAM 5000" manufactured by SOLVAY corporation as a phosphate ester compound having an allyl ether group in a molecular structure.
The solvent is added for the purpose of adjusting the coating viscosity of the active energy ray-curable composition, and the type and the amount of the solvent are appropriately adjusted according to the desired performance. Usually, the nonvolatile content of the active energy ray-curable composition is used in a range of 10 to 90% by mass. Specific examples of the solvent include: ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; esters such as methyl acetate, ethyl acetate, and butyl acetate; aromatic solvents such as toluene and xylene; alicyclic solvents such as cyclohexane and methylcyclohexane; alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, propylene glycol monomethyl ether, and the like; glycol ether solvents such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monopropyl ether. These solvents may be used alone, or 2 or more of them may be used in combination.
Examples of the ultraviolet absorber include: triazine derivatives such as 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 and the like; 2- (2 '-xanthenecarboxy-5' -methylphenyl) benzotriazole, 2- (2 '-o-nitrobenzyloxy-5' -methylphenyl) benzotriazole, 2-xanthenecarboxy-4-dodecyloxybenzophenone, 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone, and the like. These ultraviolet absorbers may be used alone, or 2 or more of them may be used in combination.
Examples of the antioxidant include hindered phenol antioxidants, hindered amine antioxidants, organic sulfur antioxidants, and phosphate antioxidants. These antioxidants may be used alone, or two or more of them may be used in combination.
Examples of the silicon-based additive include: polyorganosiloxanes having alkyl groups and phenyl groups, such as dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic dimethylpolysiloxanes, methylhydropolysiloxanes, polyether-modified dimethylpolysiloxane copolymers, polyester-modified dimethylpolysiloxane copolymers, fluorine-modified dimethylpolysiloxane copolymers, and amino-modified dimethylpolysiloxane copolymers; polydimethylsiloxanes having polyether-modified acryloyl groups, polydimethylsiloxanes having polyester-modified acryloyl groups, and the like. These silicon-based additives may be used alone, or 2 or more of them may be used in combination.
Examples of commercially available fluorine-containing additives include "Megaface" series manufactured by DIC. These fluorine-containing additives may be used alone or in combination of 2 or more.
Examples of the antistatic agent include pyridinium, imidazolium, phosphonium, ammonium, and lithium salts of bis (trifluoromethanesulfonyl) imide and bis (fluorosulfonyl) imide. These antistatic agents may be used alone, or 2 or more of them may be used in combination.
Examples of the organic beads include polymethyl methacrylate beads, polycarbonate beads, polystyrene beads, polyacrylic-styrene beads, silicone columns, glass beads, acrylic beads, benzoguanamine resin beads, melamine resin beads, polyolefin resin beads, polyester resin beads, polyamide resin beads, polyimide resin beads, polyvinyl fluoride resin beads, and polyethylene resin beads. These organic beads may be used alone, or 2 or more kinds may be used in combination. The average particle diameter of these organic beads is preferably in the range of 1 to 10 μm.
Examples of the Quantum Dots (QD) include group II-V semiconductor compounds, group II-VI semiconductor compounds, group III-IV semiconductor compounds, group III-V semiconductor compounds, group III-VI semiconductor compounds, group IV-VI semiconductor compounds, group I-III-VI semiconductor compounds, group II-IV-V semiconductor compounds, group I-II-IV-VI semiconductor compounds, group IV elements, and compounds containing these compounds. Examples of the group II-VI semiconductor compound include: znO, znS, znSe, znTe, cdS, and CdSe, cdTe, hgS,Binary compounds such as HgSe and HgTe; ternary compounds such as ZnSeS, znSeTe, znSTe, cdZnS, cdZnSe, cdZnTe, cdSeS, cdSeTe, cdSTe, cdHgS, cdHgSe, cdHgTe, hgSeS, hgSeTe, hgSTe, hgZnS, hgZnSe, and HgZnTe; and quaternary compounds such as CdZnSeS, cdZnSeTe, cdZnSTe, cdHgSeS, cdHgSeTe, cdHgSTe, cdHgZnTe, hgZnSeS, hgZnSeTe, and HgZnSTe. Examples of the group III-IV semiconductor compound include B 4 C 3 、Al 4 C 3 、Ga 4 C 3 And the like. Examples of the group III-V semiconductor compound include: binary compounds such as BP, BN, alN, alP, alAs, alSb, gaN, gaP, gaAs, gaSb, inN, inP, inAs, and InSb; ternary compounds such as GaNP, gaNAs, gaNSb, gaGaAs, gaPSb, alNP, alNAs, alNSb, alPAs, alPSb, inNP, inNAs, inNSb, inPAs, inPSb, and GaAlNP; quaternary compounds such as GaAlNAs, gaAlNSb, gaAlPAs, gaAlPSb, gaInNP, gaInNAs, gaInNSb, gaInPAs, gaInPSb, inAlNP, inAlNAs, inAlNSb, inAlPAs, and InAlPSb. Examples of the group III-VI semiconductor compound include: al (Al) 2 S 3 、Al 2 Se 3 、Al 2 Te 3 、Ga 2 S 3 、Ga 2 Se 3 、Ga 2 Te 3 、GaTe、In 2 S 3 、In 2 Se 3 、In 2 Te 3 And InTe. Examples of the group IV-VI semiconductor compound include: binary compounds such as SnS, snSe, snTe, pbS, pbSe, pbTe and the like; ternary compounds such as SnSeS, snSeTe, snSTe, pbSeS, pbSeTe, pbSTe, snPbS, snPbSe, snPbTe and the like; quaternary compounds such as SnPbSSe, snPbSeTe, snPbSTe, etc. Examples of the group I-III-VI semiconductor compound include: cuInS 2 、CuInSe 2 、CuInTe 2 、CuGaS 2 、CuGaSe 2 、CuGaSe 2 、AgInS 2 、AgInSe 2 、AgInTe 2 、AgGaSe 2 、AgGaS 2 、AgGaTe 2 And the like. Examples of the group IV element or the compound containing the element include C, si, ge, siC, and SiGe. The quantum dot may be composed of a single semiconductor compound, or may have a core-shell structure composed of a plurality of semiconductor compounds. In addition, canThe surface of which is modified with an organic compound.
The various additives can be added in any amount depending on the desired performance and the like, and are generally used in a range of 0.01 to 40 parts by mass based on 100 parts by mass of the total of the components other than the solvent in the active energy ray-curable composition.
The active energy ray-curable composition used in the present invention can be produced by mixing the above-described respective compounding ingredients. The mixing method is not particularly limited, and a paint shaker, a disperser, a roll mill, a bead mill, a ball mill, an attritor, a sand mill, a bead mill, or the like can be used.
The cured product of the present invention can be obtained by irradiating the active energy ray-curable composition with an active energy ray. Examples of the active energy rays include ionizing radiation rays such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. In the case of using ultraviolet rays as the active energy rays, the curing reaction by ultraviolet rays is efficiently performed, and the irradiation may be performed in an inert gas atmosphere such as nitrogen gas or in an air atmosphere.
As the ultraviolet ray generating source, an ultraviolet lamp is generally used from the viewpoint of practicality and economy. Specific examples thereof include a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a gallium lamp, a metal halide lamp, sunlight, and an LED.
The cumulative amount of the active energy rays is not particularly limited, but is preferably 0.1 to 50kJ/m 2 More preferably 0.5 to 10kJ/m 2 . If the accumulated light amount is within the above range, the generation of uncured portions can be prevented or suppressed, and thus it is preferable.
The irradiation with the active energy ray may be performed in one stage, or may be performed in two or more stages.
The laminate of the present invention has a cured coating film of the active energy ray-curable composition on one surface or both surfaces of a substrate, and can be obtained by applying the active energy ray-curable composition on the substrate and curing the composition by irradiation with active energy rays.
Examples of the substrate include a cycloolefin-based substrate and a linear olefin-based substrate. The substrate may be in the form of a film.
Examples of the method for forming the cured coating film include a coating method, a transfer method, and a sheet adhesion method.
The coating method is a method of spraying the coating material or coating a top coat layer on a molded product using a printing apparatus such as a curtain coater, a roll coater, or a gravure coater, and then irradiating an active energy ray to cure the top coat layer.
The transfer method is a method comprising: a method in which a transfer material obtained by applying the active energy ray-curable composition to a substrate sheet having releasability is bonded to the surface of a molded article, the substrate sheet is peeled off to transfer a top coat layer to the surface of the molded article, and then the substrate sheet is irradiated with an active energy ray to cure the top coat layer; or a method in which the transfer material is adhered to the surface of a molded article, then irradiated with active energy rays to be cured, and then the base sheet is peeled off to transfer the top coat to the surface of the molded article.
The sheet adhesion method is a method of forming a protective layer on the surface of a molded article by adhering a protective sheet having a coating film formed of the curable composition on a base sheet or a protective sheet having a coating film and a decorative layer formed of a curable composition on a base sheet to a plastic molded article.
The sheet bonding method may specifically be a method comprising: a method (post-bonding method) in which a base sheet of a protective layer-forming sheet prepared in advance is bonded to a molded article, and then thermally cured by heating to crosslink and cure a b-staged resin layer; a method (simultaneous molding and bonding method) in which the protective layer forming sheet is inserted into a molding die, a resin is injected into the cavity to fill the cavity, the surface of the resin molded article is bonded to the protective layer forming sheet while obtaining a resin molded article, and then the resin layer is crosslinked and cured by heating and heat curing.
Here, when a film-like cycloolefin substrate or a linear olefin substrate is used as the substrate, the amount of application of the active energy ray-curable composition of the present invention to the film-like cycloolefin substrate or the linear olefin substrate is preferably adjusted so that the film thickness after curing is in the range of 1 to 100 μm. Examples of the coating method include bar coater coating, die coating, spray coating, curtain coating, meyer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, and screen printing. When the active energy ray-curable composition of the present invention contains an organic solvent, it is preferable that the active energy ray-curable composition is cured by heating at 80 to 150 ℃ for several tens of seconds to several minutes after application to volatilize the organic solvent and then irradiating with an active energy ray.
The laminate of the present invention may have another layer structure in addition to the cured coating film formed from the active energy ray-curable composition. The method for forming these various layer structures is not particularly limited, and for example, the layers may be formed by directly applying a resin material, or may be formed into a sheet by bonding a layer previously formed into a sheet with an adhesive.
The article of the present invention is an article having the laminate on the surface. Examples of the above-mentioned articles include cellular phones, home electric appliances, automotive interior and exterior materials, and plastic molded articles such as OA equipment.
Examples
The present invention will be specifically described below with reference to examples and comparative examples. The present invention is not limited to the examples described below.
In the present example, the weight average molecular weight (Mw) was measured by Gel Permeation Chromatography (GPC) under the following conditions.
A measuring device: HLC-8220 available from Tosoh corporation "
A chromatographic column: "guard post H" manufactured by Tosoh corporation XL -H”
+ TSKgel G5000HXL manufactured by Tosoh corporation "
+ TSKgel G4000HXL manufactured by Tosoh corporation "
+ TSKgel G3000HXL manufactured by Tosoh corporation "
"TSKgel G2000HXL", manufactured by Tosoh corporation "
A detector: RI (differential refractometer)
Data processing: SC-8010 manufactured by Tosoh corporation "
The measurement conditions were as follows: column temperature 40 deg.C
Solvent tetrahydrofuran
Flow rate 1.0 ml/min
And (3) standard: polystyrene
Sample preparation: a tetrahydrofuran solution (0.4 mass% in terms of resin solid content) was filtered through a microfilter to obtain a sample (100. Mu.l)
Example 1 production of inorganic Fine particle Dispersion (1)
Silica fine particles (NIPPON AEROSIL CO., manufactured by LTD., "AEROSIL 8200", primary average particle diameter: 12 nm) 208.8 parts by mass, trimethylolpropane triacrylate ("ARONIX M-309", manufactured by Toyo chemical Co., ltd.), 25.2 parts by mass, 1, 9-nonanediol diacrylate ("Viscoat #260", manufactured by Osaka organic chemical industry), 72 parts by mass, a wetting dispersant ("ANTI-TERRA-U100", manufactured by BYK PAN JAKK), 18 parts by mass, a composition (LUMICROURE DPA-600, manufactured by Toyo chemical Co., ltd.) containing dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate in a molar ratio of 40/60, 36 parts by mass, and 840 parts by mass were mixed and dispersed by a wet ball mill ("MILL", manufactured by Aszawa Fiech Ltd., LMNet 015", manufactured by Toyo chemical Ltd., to obtain a dispersion of inorganic fine particles having a nonvolatile content of 30% by mass (1% by mass). The average particle diameter of the resulting dispersion was measured by a particle diameter measuring apparatus ("ELSZ-2" manufactured by Otsuka Denshi Co., ltd.). The average particle diameter (D50) was 105nm. In the present invention, the conditions for dispersion by the wet ball mill are as follows.
Medium: zirconia beads having a median particle size of 100 μm
Filling ratio of resin composition to inner volume of mill: 70% by volume
Peripheral speed of the leading end of the paddle: 11 m/s
Flow rate of resin composition: 200 ml/min
Dispersing time: 50 minutes
Example 2 production of inorganic Fine particle Dispersion (2)
Silica fine particles (NIPPON AEROSIL CO., LTD. "AEROSIL 9200", primary average particle diameter: 12 nm) 208.8 parts by mass, trimethylolpropane triacrylate ("ARONIX M-309", manufactured by Toyo chemical Co., ltd.), 25.2 parts by mass, 1, 9-nonanediol diacrylate ("Viscoat #260", manufactured by Osaka organic chemical industry), 72 parts by mass, a wetting dispersant ("ANTI-TERRA-U100", manufactured by BYK Japan KK), 18 parts by mass, a composition (LUMICROMETE DPA-600, manufactured by Toyo chemical Co., ltd.) containing dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate at a molar ratio of 40/60 in a composition of 36 parts by mass, and 840 parts by mass were mixed and dispersed to obtain a methyl ethyl ketone slurry having a nonvolatile content of 30% by mass, and a fine particle dispersion having a nonvolatile content of 30% by mass was obtained by mixing and dispersing the resulting mixture in a wet ball mill ("MILMZ" 015% by Ashizawa Fiech Ltd. (nonvolatile Co., LTD. "2 nm). The average particle diameter of the resulting dispersion was measured using a particle diameter measuring apparatus ("ELSZ-2" manufactured by Otsuka Denshi Co., ltd.). The average particle diameter (D50) was 124nm.
Example 3 production of inorganic Fine particle Dispersion (3)
Silica fine particles (NIPPON AEROSIL CO., LTD. "AEROSIL #200", primary average particle diameter: 12 nm) 208.8 parts by mass, trimethylolpropane triacrylate ("ARONIX M-309", manufactured by Toyo chemical Co., ltd.), 25.2 parts by mass, 1, 9-nonanediol diacrylate ("VISCOAT #260", manufactured by Osaka organic chemical industry), 72 parts by mass, a wetting and dispersing agent ("JAANTI-TERRA-U100", manufactured by BYK PAN KK) 18 parts by mass, a composition containing dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate at a molar ratio of 40/60 ("LUURE DPA-600", manufactured by Toyo chemical Co., ltd.), 36 parts by mass and 840 parts by mass were mixed and dispersed to prepare a slurry having a nonvolatile component of 30% by mass, and this slurry was subjected to a wet ball mill ("MILMZ 015" manufactured by Asazawa Fiech Ltd.) to obtain an inorganic fine particle dispersion having a nonvolatile component of 30% by mass (3% by mass). The average particle diameter of the resulting dispersion was measured using a particle diameter measuring apparatus ("ELSZ-2" manufactured by Otsuka Denshi Co., ltd.). The average particle diameter (D50) was 132nm.
Example 4 production of inorganic Fine particle Dispersion (4)
Silica fine particles (PGM-ST manufactured by Nissan chemical Co., ltd.; sol-gel silica, primary average particle diameter: 12 nm) 50 parts by mass, trimethylolpropane triacrylate (ARONIX M-309 manufactured by east Asia synthetic Co., ltd.) (13.5 parts by mass), a wetting dispersant (ANTI-TERRA-U100 manufactured by BYK JAPAN KK.) (1.5 parts by mass), and methyl ethyl ketone (35 parts by mass) were mixed to obtain an inorganic fine particle dispersion (4) having a nonvolatile content of 30% by mass.
Example 5 production of inorganic Fine particle Dispersion (5)
Silica fine particles (MEK-ST-40, manufactured by Nissan chemical Co., ltd.; sol-gel silica, primary average particle diameter: 12 nm) 37.5 parts by mass, trimethylolpropane triacrylate (ARONIX M-309, manufactured by Toyo chemical Co., ltd.) (13.5 parts by mass), a wetting dispersant (ANTI-TERRA-U100, manufactured by BYK JAPAN KK) (1.5 parts by mass), and methyl ethyl ketone (47.5 parts by mass) were mixed to obtain an inorganic fine particle dispersion (5) having a nonvolatile content of 30% by mass.
Example 6 production of inorganic Fine particle Dispersion (6)
Silica fine particles (TOL-ST, manufactured by Nissan chemical Co., ltd.; sol-gel silica, primary average particle diameter: 12 nm) 37.5 parts by mass, trimethylolpropane triacrylate (ARONIX M-309, manufactured by Toyo Synthesis Co., ltd.) (13.5 parts by mass), a wetting and dispersing agent (ANTI-TERRA-U100, manufactured by BYK JAPAN KK) (1.5 parts by mass), and methyl ethyl ketone (47.5 parts by mass) were mixed to obtain an inorganic fine particle dispersion (6) having a nonvolatile content of 30% by mass.
Example 7 production of inorganic Fine particle Dispersion (7)
Silica fine particles (NIPPON AEROSIL CO., LTD. "AEROSIL 9200", primary average particle diameter: 12 nm) "13.92 parts by mass, trimethylolpropane triacrylate (" ARONIX M-309", manufactured by Toyo chemical Co., ltd.), 4.68 parts by mass, 1, 9-nonanediol diacrylate (" VISCOAT #260", manufactured by Osaka organic chemical industry), 1.2 parts by mass, a wetting and dispersing agent (" ANTI-TERRA-U100", manufactured by BYK PAN JAKK"), 2.4 parts by mass, and 63 parts by mass of a composition (LUURE DPA-600, manufactured by Toyo chemical Co., ltd.) containing dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate at a molar ratio of 40/60 to prepare a slurry having a nonvolatile component of 30% by mass, which was further dispersed in a wet ball mill ("MILL", manufactured by Ashi Fizai Town Ltd., MILL 015", manufactured by Hi Hiza Fitdech Ltd.; sol-gel silica, primary average particle diameter 12 nm) 10 parts by mass, thereby obtaining an inorganic fine particle dispersion (7) having a nonvolatile content of 30% by mass.
Example 8 production of inorganic Fine particle Dispersion (8)
Silica fine particles (NIPPON AEROSIL CO., manufactured by LTD. "AEROSIL 8200", primary average particle diameter: 12 nm) 146.2 parts by mass, trimethylolpropane triacrylate ("ARONIX M-309", manufactured by Toyo chemical Co., ltd.), trimethylolpropane triacrylate (125.6 parts by mass), 1, 9-nonanediol diacrylate ("Viscoat #260", manufactured by Osaka organic chemical industry), wetting and dispersing agent ("ANTI-TERRA-U100", manufactured by BYK Japan KK) 12.6 parts by mass, a composition containing dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate ("LUURE DPA-600", manufactured by Toyo chemical Co., ltd.) at a molar ratio of 40/60, 25.2 parts by mass, and 840 parts by mass were mixed to prepare a slurry containing 30% by mass of a non-volatile component, and this was dispersed in a wet ball mill ("MILL Z", manufactured by Ashiza Ltd., MILL, 015% by mass, and was divided into a non-volatile component dispersion (30% by wet ball mill) (LMZ 8). The average particle diameter of the resulting dispersion was measured using a particle diameter measuring apparatus ("ELSZ-2" manufactured by Otsuka Denshi Co., ltd.). The average particle diameter (D50) was 105nm.
Comparative production example 1 production of acrylic resin
184 parts by mass of methyl isobutyl ketone was charged into a reaction apparatus equipped with a stirrer, a condenser, a dropping funnel and a nitrogen gas inlet tube, and the temperature in the system was raised to 110 ℃ with stirring. Subsequently, a mixed solution containing 221 parts by mass of glycidyl methacrylate, 52.5 parts by mass of methyl methacrylate, 2.8 parts by mass of ethyl acrylate, and 16.6 parts by mass of tert-butyl 2-ethylhexanoate peroxide ("PERBUTYL O" manufactured by NIPPON EMULSIFIER CO., LTD.) was added dropwise through a dropping funnel over 3 hours, and the mixture was held at 110 ℃ for 15 hours. Then, after the temperature was decreased to 90 ℃, 0.1 part by mass of hydroquinone monomethyl ether and 76 parts by mass of acrylic acid were added, and 2.0 parts by mass of triphenylphosphine was added to the mixture to react at 100 ℃ for 8 hours or more. After confirming that the acid value of the solution was 4.2mgKOH/g or less, the solution was diluted with methyl isobutyl ketone to obtain 910 parts by mass (50.0% by mass of nonvolatile matter) of a methyl isobutyl ketone solution of an acrylic resin. The weight average molecular weight (Mw) of the acrylic resin was 20000, the theoretical acryloyl equivalent weight in terms of solid content was 250 g/equivalent, and the hydroxyl value was 224mgKOH/g.
Comparative example 1 preparation of inorganic Fine particle Dispersion (R1)
A slurry having a nonvolatile content of 50 mass% was prepared by mixing 53 parts by mass of fine silica particles (fine silica particles having a primary average particle diameter of 12nm, "AEROSIL R7200" manufactured by NIPPON AEROSIL co., ltd., having a (meth) acryloyl group on the particle surface), 12 parts by mass of the acrylic resin (12 parts by mass of the resin solid content) obtained in comparative synthesis example 1, 35 parts by mass of a composition containing dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (lumibure DPA-600 manufactured by tokyo synthesis corporation) in a molar ratio of 40/60, and 188 parts by mass of methyl isobutyl ketone, and was mixed and dispersed using a wet ball mill ("nonvolatile mill z015" manufactured by Ashizawa Finetech ltd., to obtain an inorganic particle dispersion (R1) having a nonvolatile content of 50 mass%.
Comparative example 2 preparation of inorganic Fine particle Dispersion (R2)
Silica fine particles (NIPPON AEROSIL CO., LTD. "MEK-AC 2140Z", primary average particle diameter: 12 nm) 37.5 parts by mass, trimethylolpropane triacrylate ("ARONIX M-309", manufactured by Toyo Seisakusho K.K.) 13.5 parts by mass, and methyl ethyl ketone 47.5 parts by mass were mixed to obtain an inorganic fine particle dispersion (R2) having a nonvolatile content of 30% by mass.
The compositions of the inorganic fine particle dispersions (1) to (8), (R1) and (R2) obtained in examples 1 to 8, comparative example 1 and comparative example 2 are shown in table 1.
[ TABLE 1 ]
Figure BDA0003685350950000221
( Example 9: preparation of active energy ray-curable composition (1) and production of laminate (L1) )
100 parts by mass (30 parts by mass as solids) of the inorganic fine particle dispersion (1) having a nonvolatile content of 30% by mass obtained in example 1 and 0.6 parts by mass of a photopolymerization initiator ("Omnirad-BP Flakes" manufactured by IGM Resins) were mixed to obtain an active energy ray-curable composition (1).
Then, the obtained active energy ray-curable composition (1) was applied to a cycloolefin film (23 μm, "ZeonorFilm ZF-14", manufactured by Nippon Ruiz Co., ltd.) having a thickness of 23 μm by a bar coater, and dried at 90 ℃ for 1 minute. Then, the resultant was irradiated with 5kJ/m of an 80W high-pressure mercury lamp under a nitrogen atmosphere 2 The ultraviolet ray of (4) was used to obtain a laminate (L1) having a cured coating film with a thickness of 5 μm on the cycloolefin film.
( Examples 10 to 17: preparation of active energy ray-curable compositions (2) to (9) and production of laminates (L2) to (L9) )
Active energy ray-curable compositions (2) to (9) were obtained in the same manner as in example 8 at the compounding ratios shown in table 2. Laminates (L2) to (L9) were obtained in the same manner as laminate (L1).
( Comparative examples 3 and 4: preparation of active energy ray-curable compositions (R1) and (R2), and production of laminates (L10) and (L11) )
Active energy ray-curable compositions (R1) and (R2) were obtained in the same manner as in example 8 at the compounding ratios shown in table 2. In addition, laminates (L10) and (L11) were obtained by the same method as laminate (L1).
The laminates (L1) to (L11) obtained in the above examples and comparative examples were used for the following evaluations.
[ method for evaluating scratch resistance ]
A disk-shaped indenter having a diameter of 2.4 cm was wrapped with 0.5g of a STEEL wire ball ("Bon Star #0000" manufactured by ltd.) and a load of 500g was applied to the indenter, and the abrasion test was performed by reciprocating 10 times on the coating surface of the laminate obtained in the examples and comparative examples. Haze values of the laminated films before and after the abrasion Test were measured using "125044012574125\\125671250012512512540\\\12517124792" manufactured by Suga Test co., ltd, using their difference (dH) as follows. The smaller the difference (dH), the higher the resistance to scratching.
A: dH is 1.0% or less
B: dH is more than 1.0-3.0%.
C: dH is more than 3.0-5.0%.
D: dH is more than 5.0-10%.
E: the dH exceeds 10%.
[ method for evaluating adhesion (initial) to substrate ]
The cured coating surfaces of the laminates obtained in examples and comparative examples were scribed with a dicing blade to prepare 100 1mm × 1mm checkerboards, and after a transparent adhesive tape was applied thereto, the number of remaining checkerboards without peeling was counted and evaluated in accordance with the following criteria.
A: the remaining number of the checkerboard is more than 80.
B: the number of the checkerboard residues is 50 or more and less than 80.
C: the number of the checkerboard residues is 30 or more but less than 50.
D: the number of remnants of the checkerboard is less than 30.
[ method for evaluating adhesion to substrate (after light resistance test) ]
The laminates obtained in examples and comparative examples were irradiated with light for 50 hours using a Suga Test Instruments Co., ltd., xenon arc resistance optical machine (Fade Meter) "U48AU" (63 ℃ C., humidity 50%). Thereafter, the adhesion to the substrate (initial) was carried out in the same manner as described above, and the evaluation was carried out according to the following criteria.
A: the number of the remaining checkerboard is more than 80.
B: the number of the checkerboard residues is 50 or more and less than 80.
C: the number of the checkerboard residues is 30 or more and less than 50.
D: the remaining number of the checkerboard is less than 30.
Table 2 shows the compositions of the active energy ray-curable compositions (1) to (8), (R1) and (R2) prepared in examples 9 to 17 and comparative examples 3 and 4, and the evaluation results of the laminates (L1) to (L11) prepared in examples 9 to 17 and comparative examples 3 and 4.
[ TABLE 2 ]
Figure BDA0003685350950000251
Examples 9 to 17 shown in table 2 are examples of laminates using an active energy ray-curable composition containing the inorganic fine particle dispersion of the present invention. It was confirmed that the laminate was excellent in scratch resistance and substrate adhesion.
On the other hand, comparative examples 3 and 4 shown in table 2 are examples of laminates using an active energy ray-curable composition containing an inorganic fine particle dispersion having no wetting dispersion. It was confirmed that the laminate was excellent in scratch resistance, but the substrate adhesion after the light resistance test was significantly insufficient.

Claims (9)

1. An inorganic fine particle dispersion comprising inorganic fine particles (A), a (meth) acrylate compound (B) having 2 or more (meth) acryloyl groups in one molecule, and a wetting dispersant (C),
the inorganic fine particles (A) have an average primary particle diameter in the range of 1 to 50nm,
the content of the inorganic fine particles (A) in the total mass of the inorganic fine particles (A), the compound (B) and the wetting and dispersing agent (C) is in the range of 40 to 90% by mass,
the wetting dispersant (C) is a wetting dispersant having an acid value and/or an amine value.
2. The inorganic fine particle dispersion according to claim 1, wherein the compound (B) has 2 to 4 (meth) acryloyl groups in one molecule.
3. The inorganic fine particle dispersion according to claim 1 or 2, wherein the wetting dispersant (C) is a resin having a carboxyl group, a phosphoric acid group and/or an amino group, the resin being 1 or more selected from the group consisting of a urethane resin, an acrylic resin, a polyester resin and an amide resin.
4. An active energy ray-curable composition comprising the inorganic fine particle dispersion according to any one of claims 1 to 3 and a photopolymerization initiator.
5. A cured product of the active energy ray-curable composition according to claim 4.
6. A laminate comprising a substrate and a cured coating film of the active energy ray-curable composition according to claim 4 on one or both surfaces of the substrate.
7. The laminate according to claim 6, wherein the substrate is a cycloolefin-based substrate or a linear olefin-based substrate.
8. The laminate according to claim 6 or 7, wherein the substrate is in the form of a film.
9. An article having the laminate according to any one of claims 6 to 8 on a surface thereof.
CN202210649159.0A 2021-06-10 2022-06-09 Inorganic fine particle dispersion, active energy ray-curable composition, cured product, laminate, and article Pending CN115466551A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2021-097213 2021-06-10
JP2021097213A JP2022188922A (en) 2021-06-10 2021-06-10 Inorganic particulate dispersion, active energy ray curable composition, cured product, laminate and article

Publications (1)

Publication Number Publication Date
CN115466551A true CN115466551A (en) 2022-12-13

Family

ID=84363815

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210649159.0A Pending CN115466551A (en) 2021-06-10 2022-06-09 Inorganic fine particle dispersion, active energy ray-curable composition, cured product, laminate, and article

Country Status (4)

Country Link
JP (1) JP2022188922A (en)
KR (1) KR20220166708A (en)
CN (1) CN115466551A (en)
TW (1) TW202313873A (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004035651A1 (en) * 2002-10-17 2004-04-29 Basf Coatings Ag Coating material which is thermally curable and curable by means of actinic radiation and method for coating microporous surfaces
US20170114233A1 (en) * 2015-10-26 2017-04-27 Tsuyoshi Asami Active energy ray curable composition, stereoscopic modeling material, active energy ray curable ink, inkjet ink, composition storage container, two-dimensional or three-dimensional image forming apparatus, two-dimensional or three-dimensional image forming method, structural body, and processed product
CN110072951A (en) * 2016-12-28 2019-07-30 Dic株式会社 Printing ink composition, light conversion layer and colour filter
US20210054222A1 (en) * 2019-08-21 2021-02-25 Applied Materials, Inc. Additive manufacturing of polishing pads

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5569726B2 (en) 2010-03-29 2014-08-13 Ｄｉｃ株式会社 Active energy ray-curable resin composition and film substrate

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004035651A1 (en) * 2002-10-17 2004-04-29 Basf Coatings Ag Coating material which is thermally curable and curable by means of actinic radiation and method for coating microporous surfaces
US20170114233A1 (en) * 2015-10-26 2017-04-27 Tsuyoshi Asami Active energy ray curable composition, stereoscopic modeling material, active energy ray curable ink, inkjet ink, composition storage container, two-dimensional or three-dimensional image forming apparatus, two-dimensional or three-dimensional image forming method, structural body, and processed product
CN110072951A (en) * 2016-12-28 2019-07-30 Dic株式会社 Printing ink composition, light conversion layer and colour filter
US20210054222A1 (en) * 2019-08-21 2021-02-25 Applied Materials, Inc. Additive manufacturing of polishing pads

Also Published As

Publication number Publication date
KR20220166708A (en) 2022-12-19
JP2022188922A (en) 2022-12-22
TW202313873A (en) 2023-04-01

Similar Documents

Publication Publication Date Title
JP7020016B2 (en) Ink composition, light conversion layer and color filter
JP6927305B2 (en) Ink composition and its manufacturing method, light conversion layer and color filter
CN113661064B (en) Active energy ray-curable resin composition, cured product, laminate, and article
JP7338154B2 (en) Active energy ray-curable resin composition and laminate
JP2017106006A (en) Light emitting composition comprising semiconductor nanoparticle and resin, and molding
CN111149022A (en) Wavelength conversion member, backlight unit, image display device, wavelength conversion resin composition, and wavelength conversion resin cured product
KR20200064073A (en) Wavelength conversion member, backlight unit, image display device, resin composition for wavelength conversion, and cured resin for wavelength conversion
CN116783267A (en) Solvent-free quantum dot composition, preparation method thereof, cured film comprising solvent-free quantum dot composition, color filter comprising solvent-free quantum dot composition, and display device comprising solvent-free quantum dot composition
JP2023143911A (en) Active energy ray curable resin composition, laminated film, producing method thereof, and producing method for decorative film
CN110741025B (en) Curable composition and laminated film
JP7020015B2 (en) Ink composition, light conversion layer and color filter
CN115466551A (en) Inorganic fine particle dispersion, active energy ray-curable composition, cured product, laminate, and article
JP7013705B2 (en) Ink composition and its manufacturing method, light conversion layer and color filter
JP7364098B2 (en) Acrylic (meth)acrylate resin, active energy ray-curable resin composition, cured product and article
JP7346817B2 (en) Laminate and its uses
JP6919308B2 (en) (Meta) Acryloyl group-containing resin and laminated film
JP7495016B2 (en) Active energy ray curable resin composition, cured coating film and article
CN114656767A (en) Active energy ray-curable resin composition, cured product, and article
JP6981082B2 (en) Ink composition and its manufacturing method, light conversion layer and color filter
TW202235517A (en) White ink composition, cured article, light scattering layer and color filter

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination