WO2019189131A1 - Composition de résine durcissable - Google Patents

Composition de résine durcissable Download PDF

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Publication number
WO2019189131A1
WO2019189131A1 PCT/JP2019/012783 JP2019012783W WO2019189131A1 WO 2019189131 A1 WO2019189131 A1 WO 2019189131A1 JP 2019012783 W JP2019012783 W JP 2019012783W WO 2019189131 A1 WO2019189131 A1 WO 2019189131A1
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WIPO (PCT)
Prior art keywords
meth
acrylate
resin composition
curable resin
resin
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PCT/JP2019/012783
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English (en)
Japanese (ja)
Inventor
鈴木悠介
大下徹
Original Assignee
ダイセル・オルネクス株式会社
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Application filed by ダイセル・オルネクス株式会社 filed Critical ダイセル・オルネクス株式会社
Priority to CN201980021799.3A priority Critical patent/CN111902481B/zh
Priority to KR1020207030730A priority patent/KR20200140295A/ko
Publication of WO2019189131A1 publication Critical patent/WO2019189131A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of 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
    • C09D133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; 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
    • C09D133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • 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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Definitions

  • the present invention relates to a curable resin composition and a cured product thereof.
  • This application claims the priority of Japanese Patent Application No. 2018-066687 for which it applied to Japan on March 30, 2018, and uses the content here.
  • thermoplastic resin such as an acrylic resin, a polycarbonate resin, an ABS resin, a urethane resin, or polyethylene is widely used as a coating agent from the viewpoint of light weight, excellent impact resistance, transparency, and easy molding.
  • molded articles of these thermoplastic resins are easily damaged by friction or the like, and have problems such as a decrease in transparency and a loss of appearance. Therefore, attempts have been made to improve the wear resistance, scratch resistance, surface hardness and the like by applying a surface coating to the molded product.
  • Patent Document 1 describes a technique for imparting abrasion resistance and scratch resistance to a cured product by blending a thermoplastic resin with a compound having a specific (meth) acryloyl group.
  • the coating film (uncured product) obtained by applying and drying the composition described in Patent Document 1 on a substrate has a problem that the surface is sticky, that is, tackiness is generated.
  • the composition having low tackiness is, for example, that the coating film is not easily broken even if the hand or object comes into contact after the coating film is dried, and even when the coating films are stacked, these do not stick. Even when cured after a certain period of time, since the surface is not dusty, there is an advantage that a slip sheet is unnecessary, and there is an advantage that workability is excellent.
  • even when the composition is used as a printing layer it is possible to form a coating film repeatedly, and finally, it is possible to cure all at once by irradiation with active energy rays or heating. There is. For this reason, it can be said that it is an important characteristic that tackiness after coating film drying is low (it is excellent in tack-free property).
  • the object of the present invention is that the obtained cured product not only has good abrasion resistance and scratch resistance and high surface hardness, but also has low tackiness after drying the coating (excellent tackiness) ) To provide a curable resin composition. Moreover, it is providing the hardened
  • the present inventors have found that a curable resin composition containing at least a specific amount of a thermoplastic resin and a resin having 5 or more (meth) acryloyl groups is obtained after the coating film is dried.
  • the present invention has been completed by finding that it has a low tackiness and gives a useful cured product when cured.
  • the present invention is a curable resin composition
  • a curable resin composition comprising a thermoplastic resin (A) and a resin (B) having 5 or more (meth) acryloyl groups
  • a curable resin composition wherein the content of the thermoplastic resin (A) is 42% by weight or more based on the total resin content of the curable resin composition.
  • the glass transition temperature of the thermoplastic resin (A) is preferably 60 to 140 ° C.
  • thermoplastic resin (A) is an acrylic resin and / or a polyester resin.
  • the acrylic resin preferably contains at least a (meth) acrylic acid alkyl ester as a monomer unit.
  • the (meth) acrylic acid alkyl ester is preferably methyl (meth) acrylate.
  • the resin (B) having 5 or more (meth) acryloyl groups preferably contains dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate.
  • the curable resin composition of the present invention is preferably used as a coating agent.
  • the present invention also provides a cured product of the curable resin composition.
  • the present invention also provides a coat layer that is the cured product.
  • the obtained cured product has not only good abrasion resistance and scratch resistance and high surface hardness, but also low tackiness after drying the coating film.
  • the cured product of the curable resin composition has good wear resistance and scratch resistance, and high surface hardness.
  • the curable resin composition of the present invention includes a thermoplastic resin (A) and a resin (B) having 5 or more (meth) acryloyl groups, and the content of the thermoplastic resin (A) is that of the curable resin composition. It is characterized by being 42% by weight or more with respect to the total resin content. Moreover, the curable resin composition of this invention may contain the photoinitiator (C) and the volatile solvent (D) besides the said resin. Examples of the resin component include, but are not limited to, a thermoplastic resin (A), a resin (B) having 5 or more (meth) acryloyl groups, and other resins described later.
  • the thermoplastic resin (A) is not particularly limited as long as it is a resin polymer that is softened by heating.
  • the glass transition temperature of the thermoplastic resin (A) is not particularly limited, but the lower limit is, for example, preferably ⁇ 120 ° C., more preferably 60 ° C., further preferably 100 ° C., and the upper limit is, for example, 200 ° C is preferred, more preferably 140 ° C, and even more preferably 110 ° C.
  • the lower limit is in the above range, the tack-free property after drying the coating tends to be excellent.
  • the glass transition temperature is measured by a differential scanning calorimeter (DSC) method.
  • the weight average molecular weight of the thermoplastic resin (A) is not particularly limited, but the lower limit is, for example, preferably 1000, more preferably 5000, and still more preferably 10,000. Moreover, 250,000 are preferable, for example, as for an upper limit, More preferably, it is 140000, More preferably, it is 130,000. There exists a tendency for adhesiveness with a base material to be excellent because a lower limit is the said range. When the upper limit is in the above range, the surface hardness of the cured product tends to be excellent.
  • the weight average molecular weight is measured by a gel permeation chromatograph (GPC) method using polystyrene as a standard substance.
  • thermoplastic resin (A) is not particularly limited.
  • the thermoplastic resin (A) does not include those corresponding to a resin (B) having 5 or more (meth) acryloyl groups described later.
  • the thermoplastic resin (A) may have a light or thermosetting group (for example, a (meth) acryloyl group, a vinyl group, an epoxy group, a glycidyl group, or an oxetanyl group), but preferably does not have it.
  • a thermoplastic resin (A) can be suitably selected and used according to adhesiveness with a base material. Moreover, these can also be used individually by 1 type and can also be used in combination of 2 or more type.
  • the acrylic resin means a resin mainly containing (meth) acrylic acid ester as a monomer unit.
  • the acrylic resin for example, [1] a resin containing only one kind of (meth) acrylic acid ester as a monomer unit (that is, a homopolymer of (meth) acrylic acid ester), and [2] two kinds of monomeric units.
  • (meth) acrylic acid ester that is, a copolymer of two or more (meth) acrylic acid esters), [3] (meth) acrylic acid ester and (meth) acrylic acid as monomer units
  • a resin containing a monomer other than an ester a copolymer of a (meth) acrylic acid ester and a monomer other than a (meth) acrylic acid ester
  • (meth) acrylic acid ester means acrylic acid ester and / or methacrylic acid ester.
  • the thermoplastic resin (A) preferably contains an acrylic resin from the viewpoint of improving the adhesion to the substrate, and more preferably an acrylic resin containing a (meth) acrylic acid alkyl ester as a monomer unit.
  • the proportion of the (meth) acrylic acid alkyl ester in the acrylic resin is preferably 30% by weight or more (for example, 30 to 99.9% by weight), more preferably 60% by weight or more, based on the total amount of monomer units of the acrylic resin. More preferably, it is 80% by weight or more, and most preferably 95% by weight or more.
  • the (meth) acrylic acid alkyl ester is not particularly limited, and examples thereof include (meth) acrylic acid alkyl esters having a linear or branched alkyl group having 1 to 20 carbon atoms.
  • Examples of the (meth) acrylic acid alkyl ester having an alkyl group having 1 to 20 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, Butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, (meth) acryl Hexyl acid, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhex
  • Examples of (meth) acrylic acid esters other than (meth) acrylic acid alkyl esters include alicyclic hydrocarbon groups such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate (meth).
  • the acrylic resin contains a monomer other than the (meth) acrylic acid ester (hereinafter, simply referred to as “other monomer component”) as necessary for the purpose of modifying the surface hardness and the like. May be.
  • Examples of other monomer components include carboxyl group-containing monomers such as (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid; Hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxyoctyl (meth) acrylate, hydroxydecyl (meth) acrylate, (meta ) Hydroxyl group-containing monomers such as hydroxyalkyl (meth) acrylates such as hydroxylauryl acrylate and (4-hydroxymethylcyclohexyl) methyl methacrylate; acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride; Styrene, butadiene
  • thermoplastic resin (A) A commercially available product can be used as the thermoplastic resin (A), and examples thereof include a product name “Paraloid A-21” (acrylic resin (homopolymer of methyl methacrylate), manufactured by Dow Chemical Co., Ltd.).
  • the content of the thermoplastic resin (A) with respect to the total resin content of the curable resin composition is not particularly limited as long as it is 42% by weight or more, but is preferably 44 to 95% by weight, particularly preferably 47 to 90% by weight. Most preferably, it is 48 to 80% by weight.
  • the thermoplastic resin (A) is in the above range, the adhesion to the substrate is improved, and the tackiness after drying of the coating film tends to be improved.
  • the content of the thermoplastic resin (A) with respect to the total nonvolatile content of the curable resin composition is not particularly limited, but is preferably 42% by weight or more, more preferably 44 to 95% by weight, particularly preferably 47 to 90% by weight. %, Most preferably 48 to 80% by weight.
  • the thermoplastic resin (A) is in the above range, the adhesion to the substrate is improved, and the tackiness after drying of the coating film tends to be improved.
  • resin (B) having 5 or more (meth) acryloyl groups Although it does not specifically limit as resin (B) which has five or more (meth) acryloyl groups, For example, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol penta (meth) acrylate, tri Low molecular weight compounds (for example, having a molecular weight of 200 to 800) having 5 or more (meth) acryloyl groups such as pentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, and tripentaerythritol octa (meth) acrylate, Examples include silicone (meth) acrylate having 5 or more (meth) acryloyl groups and urethane (meth) acrylate having 5
  • the silicone (meth) acrylate having 5 or more (meth) acryloyl groups for example, 5 or more (meth) acryloyl groups and an organosiloxane unit [—Si (—R) 2 —O—] (R represents an organic group) ).
  • the silicone (meth) acrylate may be a silicone (meth) acrylate having an average (meth) acryloyl group number of 5 or more.
  • the R is not particularly limited as long as it is an organic group, and examples thereof include a C 1-6 alkyl group and a C 1-6 alkoxy group.
  • the number of Si atoms (or organosiloxane units) in one molecule of the silicone (meth) acrylate is, for example, 1 to 30, preferably 1 to 20, and more preferably 1 to 15.
  • the number of (meth) acryloyl groups (or the average number of (meth) acryloyl groups) in the silicone (meth) acrylate is not particularly limited as long as it is 5 or more. For example, 5 to 20, preferably 5 to 15, and more preferably 5 ⁇ 10.
  • the “average (meth) acryloyl group number” can be defined as an average value of the number of (meth) acryloyl groups per molecule of silicone (meth) acrylate.
  • a dialkyl dialkoxysilane or a polymer thereof with a mixture of an alkoxysilane having two (meth) acryloyl groups and an alkoxysilane having three (meth) acryloyl groups (molar ratio is 1: 1).
  • the average number of (meth) acryloyl groups in the resulting silicone (meth) acrylate is 5.
  • the silicone (meth) acrylate may be a mixture of two or more of the same or different average functional group numbers.
  • the urethane (meth) acrylate having 5 or more (meth) acryloyl groups specifically refers to a urethane (meth) acrylate having an average (meth) acryloyl group number of 5 or more.
  • the urethane (meth) acrylate is obtained by reacting, for example, polyol (X), polyisocyanate (Y), and hydroxy group-containing (meth) acrylate (Z) (that is, these reactants). May be.
  • the “average (meth) acryloyl group number” is an average value of the number of (meth) acryloyl groups per molecule of urethane (meth) acrylate.
  • 1 mol of diol (X1) as polyol (X) 2 mol of diisocyanate (Y1) as polyisocyanate (Y), one hydroxy group and one hydroxyl group-containing (meth) acrylate (Z)
  • the number of (meth) acryloyl groups is 4 (the structure of the resulting urethane (meth) acrylate is schematically shown below).
  • the urethane (meth) acrylate may be a mixture of two or more of the same or different average functional groups.
  • Polyol (X) is a compound having two or more hydroxy groups in the molecule. However, polyol (X) does not include a compound corresponding to hydroxy group-containing (meth) acrylate (Z). In addition, polyol (X) can also be used individually by 1 type, and can also be used in combination of 2 or more type.
  • polyol (X) known or commonly used compounds having two or more hydroxy groups in the molecule can be used, and are not particularly limited.
  • Glycerin 1,1,1-tris (hydroxymethyl) propane, D-sorbitol, xylitol, D-mannitol, D-mannitol, diglycerin, polyglycerin, trimethylolethane, trimethylolpropane, pentaerythritol, polyether Polyol, polyester polyol, polycarbonate polyol, acrylic polyol, epoxy polyol, natural oil polyol, silicone polyol, fluorine Polyols include polyols having 3 or more hydroxyl groups in the molecule, such as a polyolefin polyol.
  • a commercially available product can be used as the polyol (X).
  • the product name “TCD alcohol DM” tricyclodecanedimethanol, manufactured by Oxea
  • the product name “isosorbide” isosorbide, manufactured by Toei Chemical Co., Ltd.
  • Product name “PEG-400” polyethylene glycol having a number average molecular weight of 400, manufactured by Sanyo Chemical Industries, Ltd.
  • Polyisocyanate (Y) is a compound having two or more isocyanate groups in the molecule.
  • polyisocyanate (Y) can also be used individually by 1 type as a raw material of urethane (meth) acrylate, and can also be used in combination of 2 or more type.
  • polyisocyanate (Y) examples include aromatic isocyanates, aliphatic isocyanates, cycloaliphatic isocyanates, alicyclic isocyanates, mixtures thereof, adducts of the above isocyanates, modified products of the above isocyanates, and the above isocyanates.
  • isocyanates such as polymers of More specifically, for example, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hydrogenated diphenylmethane diisocyanate (H12MDI), polyphenylmethane isocyanate compound (crude MDI), modified diphenylmethane diisocyanate (modified MDI), xylylene diene
  • TDI tolylene diisocyanate
  • MDI diphenylmethane diisocyanate
  • H12MDI hydrogenated diphenylmethane diisocyanate
  • CAde MDI polyphenylmethane isocyanate compound
  • modified MDI modified MDI
  • xylylene diene Examples include isocyanate (XDI), hydrogenated xylylene diisocyanate (H-XDI), hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMXDI),
  • polyisocyanate (Y) a commercially available product can be used.
  • the product name “Sumijour N3300” (1,6-hexamethylene diisocyanate-derived nurate compound, manufactured by Sumitomo Bayer Urethane Co., Ltd.)
  • the product name “VESTANAT IPDI” (Isophorone diisocyanate, manufactured by Evonik).
  • Hydroxy group-containing (meth) acrylate (Z) is a compound having one or more hydroxy groups in the molecule and one or more (meth) acryloyl groups in the molecule.
  • the hydroxy group containing (meth) acrylate (Z) can also be used individually by 1 type as a raw material of urethane (meth) acrylate, and can also be used in combination of 2 or more type.
  • Examples of the hydroxy group-containing (meth) acrylate (Z) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxy-3-methoxypropyl.
  • Monofunctional (meth) acrylate compounds having hydroxyl groups such as (meth) acrylates and lactone adducts thereof (caprolactone adducts, etc.); pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipenta Polyfunctional (meth) acrylate compounds having hydroxyl groups such as erythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, and lactone adducts thereof (such as caprolactone adducts) It is below. Hydroxyl group containing (meth) acrylate (Z) may be used individually by 1 type, and may be used in combination of 2 or more type.
  • a commercially available product can be used as the hydroxy group-containing (meth) acrylate (Z).
  • Methanol monoacrylate manufactured by Nippon Kasei Co., Ltd.
  • PETRA a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate, manufactured by Ornex.
  • the resin (B) having 5 or more (meth) acryloyl groups has a low molecular weight (for example, molecular weight) having 5 or more (meth) acryloyl groups from the viewpoint of the abrasion resistance, scratch resistance, and surface hardness of the cured product.
  • a low molecular weight for example, molecular weight
  • dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate is more preferred, and dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are included at the same time It is particularly preferred.
  • dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are simultaneously contained as the resin (B) having 5 or more (meth) acryloyl groups, these ratios are not particularly limited.
  • the content of dipentaerythritol penta (meth) acrylate with respect to the total amount of erythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate is preferably 1 to 90% by weight, more preferably 5 to 80%. % By weight, more preferably 8 to 60% by weight, particularly preferably 10 to 50% by weight.
  • the content of dipentaerythritol penta (meth) acrylate is in the above range, the resulting cured product has improved wear resistance, scratch resistance and surface hardness, and tackiness after drying the coating film is improved. Tend.
  • the resin (B) having 5 or more (meth) acryloyl groups can be used as the resin (B) having 5 or more (meth) acryloyl groups.
  • the product name “KAYATAD DPHA” a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, Nippon Kayaku
  • Product name “Aronix M-403” mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, ratio (content) of dipentaerythritol pentaacrylate is 50 to 60% by weight
  • product name “Aronix” M-400 ” a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, the ratio (content) of dipentaerythritol pentaacrylate is 40 to 50% by weight
  • the content of the resin (B) having 5 or more (meth) acryloyl groups with respect to the total resin content of the curable resin composition is not particularly limited, but is preferably 58% by weight or less, and more preferably 5 to 56, for example. % By weight, particularly preferably 10 to 53% by weight, most preferably 20 to 52% by weight.
  • the resin (B) having 5 or more (meth) acryloyl groups is in the above range, the resulting cured product has improved wear resistance, scratch resistance and surface hardness, and improved tackiness after drying the coating film. Tend to be.
  • the content of the resin (B) having 5 or more (meth) acryloyl groups with respect to the total nonvolatile content of the curable resin composition is not particularly limited, but is preferably 58% by weight or less, and more preferably 5 to 56, for example. % By weight, particularly preferably 10 to 53% by weight, most preferably 20 to 52% by weight.
  • the resin (B) having 5 or more (meth) acryloyl groups is in the above range, the resulting cured product has improved wear resistance, scratch resistance and surface hardness, and improved tackiness after drying the coating film. Tend to be.
  • the content of the resin (B) having 5 or more (meth) acryloyl groups with respect to the total amount of the thermoplastic resin (A) is, for example, preferably 45 to 90% by weight, more preferably 50%. -80% by weight, more preferably 55-75% by weight.
  • the resin (B) having 5 or more (meth) acryloyl groups is in the above range, the resulting cured product has improved wear resistance, scratch resistance and surface hardness, and improved tackiness after drying the coating film. Tend to be.
  • Photopolymerization initiator (C) examples include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, diethoxyacetophenone, and 1- (4-isopropylphenyl) -2.
  • C photopolymerization initiator
  • examples thereof include a product name “IRGACURE184” (1-hydroxycyclohexyl phenyl ketone, manufactured by BASF).
  • the content of the photopolymerization initiator (C) with respect to the total resin content of the curable resin composition is not particularly limited, but is preferably 0.01 to 10% by weight, more preferably 0.1 to 8% by weight, Preferably it is 0.5 to 5% by weight.
  • the volatile solvent (D) is not particularly limited as long as it is a solvent that volatilizes when the curable resin composition is applied to a substrate and dried, and examples thereof include ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone).
  • Etc. ethers (dioxane, tetrahydrofuran, etc.), aliphatic hydrocarbons (hexane, etc.), alicyclic hydrocarbons (cyclohexane, etc.), aromatic hydrocarbons (benzene, etc.), halogenated hydrocarbons (dichloromethane) , Dichloroethane, etc.), esters (ethyl acetate, etc.), alcohols (ethanol, cyclohexanol, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, etc.), cellosolve acetates, amides (dimethylformamide, dimethylacetamide, etc.) Is mentioned. These can also be used individually by 1 type and can also be used in combination of 2 or more type.
  • the concentration of the total amount of resin contained in the curable resin composition is, for example, about 10 to 80% by weight, preferably 20 to 70% by weight, It is preferably used in the range of 30 to 60% by weight. By using in the said range, since the viscosity of curable resin composition shows a moderate value, it exists in the tendency which can form the coating layer of the desired film thickness.
  • the curable resin composition of the present invention contains a resin other than the thermoplastic resin (A) and the resin (B) having 5 or more (meth) acryloyl groups (sometimes referred to as “other resin”). Also good.
  • other resins include resins having 4 or less (meth) acryloyl groups, but the content of other resins relative to the total resin content of the curable resin composition is preferably, for example, 30% by weight or less. It is preferably 10% by weight or less, more preferably 5% by weight or less, particularly preferably 1% by weight or less, and most preferably 0% by weight (not substantially contained).
  • Examples of the resin having 4 or less (meth) acryloyl groups include compounds having one (meth) acryloyl group, compounds having 2 to 4 (meth) acryloyl groups, and the like.
  • Examples of the compound having one (meth) acryloyl group include linear or methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate and the like.
  • Examples of the compound having 2 to 4 (meth) acryloyl groups include 1,6-hexanediol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylolpropane tri Examples include (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra (meth) acrylate.
  • the curable resin composition of the present invention includes a leveling agent, an antioxidant, an ultraviolet absorber, a light-resistant stabilizer, a heat stabilizer, a crystal nucleating agent, a flame retardant, a flame retardant aid, and a filler.
  • additives such as impact resistance improvers, reinforcing agents, dispersants, antistatic agents, foaming agents, antibacterial agents, and coloring agents may be further included.
  • the content (blending amount) of these additives is not particularly limited, and can be appropriately set from the amount usually used in the curable resin composition.
  • the curable resin composition of the present invention can be cured by advancing the polymerization reaction of the resin (B) having 5 or more (meth) acryloyl groups, whereby a cured product can be formed.
  • the curing method can be appropriately selected from well-known methods and is not particularly limited, and examples thereof include irradiation with active energy rays.
  • active energy ray for example, any of infrared rays, visible rays, ultraviolet rays, X-rays, electron beams, ⁇ rays, ⁇ rays, ⁇ rays and the like can be used. Among these, ultraviolet rays are preferable in terms of excellent handleability.
  • Conditions for curing the curable resin composition of the present invention by irradiation with active energy rays depend on the type and energy of the active energy rays to be irradiated, the shape and size of the cured product, and the like. Although it is not particularly limited, it is preferably about 1 to 1000 mJ / cm 2 when irradiating with ultraviolet rays.
  • active energy rays for example, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a carbon arc, a metal halide lamp, sunlight, an LED lamp, a laser, or the like can be used.
  • a heating treatment annealing and aging
  • the curable resin composition of the present invention can be obtained as a coating layer by applying and drying on a substrate to prepare a coating film, and further curing the coating film. That is, the curable resin composition of the present invention can be used as a coating agent (a coating agent composition).
  • a base material for example, a plastic base material, a metal base material, a ceramic base material, a semiconductor base material, a glass base material, a paper base material, a wood base material (wood base material), and the surface is a coating surface
  • a known or commonly used substrate such as a substrate can be used, and is not particularly limited.
  • the coating method is not particularly limited, and can be carried out using known or conventional means such as airless spray, air spray, roll coat, bar coat, gravure coat, and die coat.
  • the drying temperature of the coating film is, for example, preferably 30 to 150 ° C, more preferably 50 to 120 ° C, and more preferably 60 to 100 ° C.
  • the drying time is preferably, for example, 0.1 to 10 minutes, more preferably 0.3 to 5 minutes, and more preferably 0.5 to 2 minutes.
  • Example 1 400 parts by weight of Paraloid A-21, 100 parts by weight of Aronix M-402, and 750 parts by weight of methyl ethyl ketone were mixed, and stirring was continued at 60 ° C. until Paraloid A-21 was dissolved. 6 parts by weight of IRGACURE 184 was added to the obtained solution to prepare a curable resin composition.
  • Examples 2 to 5 Comparative Example 1
  • a curable resin composition was prepared in the same manner as in Example 1 except that the blending amounts described in the table were used.
  • Example 6 A curable resin composition was prepared in the same manner as in Example 1 except that a specific amount of the components described in the table was blended.
  • A-21 Product name “Paraloid A-21”, acrylic resin (homopolymer of methyl methacrylate), weight average molecular weight 120,000, glass transition temperature 105 ° C.
  • M-402 Product name “Aronix M-402”, mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (ratio (content) of dipentaerythritol pentaacrylate is 30 to 40% by weight)
  • M-400 Product name “Aronix M-400”, mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (ratio (content) of dipentaerythritol pentaacrylate is 40 to 50% by weight)
  • M-405 Product name “Aronix M-405”, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (ratio (content) of dipentaerythritol pentaacrylate is 10 to 20% by weight)
  • KRM8452 Product name “K
  • a curable resin composition comprising a thermoplastic resin (A) and a resin (B) having 5 or more (meth) acryloyl groups,
  • the content of the thermoplastic resin (A) is 42% by weight or more based on the total resin content of the curable resin composition.
  • the lower limit of the glass transition temperature of the thermoplastic resin (A) is ⁇ 120 ° C., 60 ° C., or 100 ° C., and the upper limit is 200 ° C., 140 ° C., or 110 ° C. Resin composition.
  • thermoplastic resin (A) is 1000, 5000, or 10,000, and the upper limit value is 250,000, 140000, or 130,000. [1] or [2] object.
  • thermoplastic resin (A) is made of polyethylene, polypropylene, polyvinyl chloride, polystyrene, AS resin, ABS resin, polyethylene terephthalate, acrylic resin, polyvinyl alcohol, polyvinylidene chloride, polycarbonate resin, urethane resin, and polyester resin.
  • the curable resin composition according to any one of [1] to [3], which is at least one selected from the above.
  • thermoplastic resin (A) is an acrylic resin and / or a polyester resin.
  • thermoplastic resin (A) is an acrylic resin
  • acrylic resin includes at least a (meth) acrylic acid alkyl ester as a monomer unit.
  • (meth) acrylic acid alkyl ester is methyl (meth) acrylate.
  • the content of the thermoplastic resin (A) with respect to the total resin content of the curable resin composition is 42% by weight or more, 44 to 95% by weight, 47 to 90% by weight, or 48 to 80% by weight [1] to [7]
  • the content of the thermoplastic resin (A) with respect to the total nonvolatile content of the curable resin composition is 42% by weight or more, 44 to 95% by weight, 47 to 90% by weight, or 48 to 80% by weight [1] to [8]
  • Resin (B) having 5 or more (meth) acryloyl groups is dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate , Low molecular compounds (for example, having a molecular weight of 200 to 800) having 5 or more (meth) acryloyl groups, such as tripentaerythritol hepta (meth) acrylate and tripentaerythritol octa (meth) acrylate, 5 (meth) acryloyl groups Any one of [1] to [9], including at least one selected from the group consisting of silicone (meth) acrylates having the above and urethane (meth) acrylates having 5 or more (meth) acryloyl
  • the resin (B) having 5 or more (meth) acryloyl groups contains dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate at the same time, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa
  • the content of dipentaerythritol penta (meth) acrylate with respect to the total amount of (meth) acrylate is 1 to 90 wt%, 5 to 80 wt%, 8 to 60 wt%, or 10 to 50 wt% [1 ]
  • the curable resin composition according to any one of [11].
  • the content of the resin (B) having 5 or more (meth) acryloyl groups with respect to the total resin content of the curable resin composition is 58 wt% or less, 5 to 56 wt%, 10 to 53 wt%, or 20 to 52 wt%. % Of the curable resin composition according to any one of [1] to [12].
  • the content of the resin (B) having 5 or more (meth) acryloyl groups with respect to the total nonvolatile content of the curable resin composition is 58 wt% or less, 5 to 56 wt%, 10 to 53 wt%, or 20 to 52 wt%. % Of the curable resin composition according to any one of [1] to [13].
  • the content of the resin (B) having 5 or more (meth) acryloyl groups with respect to the total amount of the thermoplastic resin (A) is 45 to 90% by weight, 50 to 80% by weight, or 55 to 75% by weight. % Of the curable resin composition according to any one of [1] to [14].
  • the content of the photopolymerization initiator (C) with respect to the total resin content of the curable resin composition is 0.01 to 10% by weight, 0.1 to 8% by weight, or 0.5 to 5% by weight [1. ]
  • [18] [1] A cured product of the curable resin composition according to any one of [17]. [19] The coat layer which is a hardened
  • the obtained cured product has not only good abrasion resistance and scratch resistance and high surface hardness, but also low tackiness after drying the coating film.
  • the cured product of the curable resin composition has good wear resistance and scratch resistance, and high surface hardness.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (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)
  • Polymerisation Methods In General (AREA)
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Abstract

La présente invention concerne une composition de résine durcissable qui permet d'obtenir un produit durci qui présente non seulement une bonne résistance à l'usure, une bonne résistance aux rayures et une dureté de surface élevée mais également de faibles propriétés collantes (d'excellentes propriétés non collantes) après séchage d'un film de revêtement. La présente invention concerne également un produit durci qui est obtenu à partir de la composition de résine durcissable et présente une bonne résistance à l'usure, une bonne résistance aux rayures et une dureté de surface élevée. Une composition de résine durcissable selon la présente invention contient une résine thermoplastique (A) et une résine (B) qui comprend au moins 5 groupes (méth)acryloyle ; et cette composition de résine durcissable est caractérisée en ce que la teneur en résine thermoplastique (A) est supérieure ou égale à 42 % en poids par rapport à la quantité totale de la teneur en résine de cette composition de résine durcissable.
PCT/JP2019/012783 2018-03-30 2019-03-26 Composition de résine durcissable WO2019189131A1 (fr)

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CN113817086B (zh) * 2021-09-29 2022-11-11 韦尔通(厦门)科技股份有限公司 一种生物基光固化树脂组合物及其制备方法和应用

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JPH03292123A (ja) * 1990-04-09 1991-12-24 Mitsubishi Petrochem Co Ltd ハードコート層を有するプロピレン系樹脂成形品の製造方法
JPH05169862A (ja) * 1991-12-19 1993-07-09 Nippon Kayaku Co Ltd 樹脂組成物及び熱転写記録用シート
JP2014076655A (ja) * 2012-09-21 2014-05-01 Nippon Synthetic Chem Ind Co Ltd:The 積層体及びその用途
JP2014141666A (ja) * 2012-12-27 2014-08-07 Nippon Synthetic Chem Ind Co Ltd:The 活性エネルギー線硬化性樹脂組成物およびコーティング剤組成物
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CN101535347B (zh) * 2006-11-09 2012-06-13 Dic株式会社 活性能量射线固化型水性树脂组合物、活性能量射线固化型涂料、固化涂膜的形成方法及物品
JP5430095B2 (ja) 2008-08-11 2014-02-26 日本カーバイド工業株式会社 硬化性樹脂組成物
TWI650365B (zh) * 2014-02-06 2019-02-11 日商住友化學股份有限公司 熱塑性樹脂薄膜、拉伸薄膜、偏光子保護薄膜及偏光板

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JPH03292123A (ja) * 1990-04-09 1991-12-24 Mitsubishi Petrochem Co Ltd ハードコート層を有するプロピレン系樹脂成形品の製造方法
JPH05169862A (ja) * 1991-12-19 1993-07-09 Nippon Kayaku Co Ltd 樹脂組成物及び熱転写記録用シート
JP2014076655A (ja) * 2012-09-21 2014-05-01 Nippon Synthetic Chem Ind Co Ltd:The 積層体及びその用途
JP2014141666A (ja) * 2012-12-27 2014-08-07 Nippon Synthetic Chem Ind Co Ltd:The 活性エネルギー線硬化性樹脂組成物およびコーティング剤組成物
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TW201942163A (zh) 2019-11-01
CN111902481B (zh) 2022-11-08

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