Active energy ray curable resin composition, cured coating film, and laminate

Abstract

To provide an active energy ray-curable resin composition that contains a (co)polymer of specific urethane (meth)acrylate and a (meth)acrylic monomer, which achieves hardness, elongation and adhesion when being coated onto an isosorbide-containing base material.SOLUTION: A coating material that is coated onto an isosorbide-containing base material contains a (co)polymer (B) of urethane (meth)acrylate (A) having a structure derived from the following (a1) and (a2), and a (meth)acrylic monomer, and a photopolymerization initiator (C). (a1) Isocyanate compound having at least two isocyanate groups. (a2) Hydroxyl group-containing monofunctional (meth)acrylate.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a coating material to be applied to an isosorbide-containing substrate.

Background Art

[0002] Plastic materials such as polycarbonate, polyester, polymethyl methacrylate, triacetyl cellulose, polystyrene, and polyvinyl chloride are used in various applications such as display members, electrical and electronic components, automotive parts, building materials, lenses, containers, and packaging materials. Among them, for example, polycarbonate is one of the resins having excellent impact resistance and heat resistance and a wide range of applications.

[0003] Many plastic products, including polycarbonate, are generally manufactured using materials derived from petroleum resources. However, since it leads to the depletion of petroleum resources, there is a demand for providing plastic products using plant-derived raw materials. In addition, global warming caused by an increase in carbon dioxide emissions is also cited as an issue, and from the perspective of carbon neutrality, it is required to use plant-derived raw materials.

[0004]

[0005]

Prior Art Documents

[0006]

Patent Documents

[0005] [Patent Document 1] Japanese Patent Publication No. 2016-079321 [Overview of the project] [Problems that the invention aims to solve]

[0006] This invention relates to a specific urethane (meth)acrylate and a (meth)acrylic monomer (co By making an active energy ray curable resin composition containing a polymer, the isosorbide-containing group An active energy ray curable resin composition exhibiting excellent hardness, elongation, and adhesion when applied to a material. A cured coating film made of the active energy ray curable resin composition, and the active energy ray curable resin composition. The objective is to provide a laminate having a layer made of a chemical resin composition. [Means for solving the problem]

[0007] The present invention has the following aspects. In other words, the above objectives of the present invention can be achieved by the following means [1] to [7]. [1] A coating material to be applied to an isosorbide-containing substrate, A urethane (meth)acrylate (A) synthesized from (a1) and (a2) below, and (Me (T) Active energy containing an acrylic monomer (co)polymer (B) and a photopolymerization initiator (C) A ghee wire-curing type resin composition. (a1) An isocyanate compound having at least two isocyanate groups. (a2) Hydroxyl group-containing monofunctional (meth)acrylate [2] The amount of urethane (meth)acrylate (A) added to the active energy ray curing resin compound The active ingredient described in [1] is present in an amount of 5% by mass or more and 80% by mass or less relative to the total amount of solids in the product. Energy ray curable resin composition. [3] The base material is a polycarbonate base material having isosorbide as a structural unit, [1 The active energy ray-curable resin composition according to [1 [4] The blending amount of the (co)polymer (B) of the (meth)acrylic monomer is 5% by mass or more and 60% by mass or less with respect to the total amount of the solid content of the active energy ray-curable resin composition, [1] ~[3] The active energy ray-curable resin composition according to [5] Further containing a compound (D) having a quaternary ammonium base, [1]~[4] described in active energy ray-curable resin composition. [6] The cured coating film of the active energy ray-curable resin composition according to [1]~[5]. [7] An active energy ray-curable resin composition containing urethane (meth)acrylate (A) and a (co)polymer (B) of the (meth)acrylic monomer and a photoinitiator (C), The cured product obtained by curing the active energy ray-curable resin composition has an elongation at 80 °C of 20% or more, the active energy ray-curable resin composition. [8] Urethane (meth)acrylate (A) synthesized from the following (a1) and (a2) and , A laminate obtained by coating an active energy ray-curable resin composition containing a (co)polymer (B) of a (meth)acrylic monomer and a photoinitiator (C) on a base material containing isosorbide. (a1) An isocyanate compound having at least two isocyanate groups (a2) A hydroxyl group-containing monofunctional (meth)acrylate [Advantages of the Invention]

[0008] According to the present invention, when coated on a base material containing isosorbide, an active energy ray-curable resin composition having excellent hardness, elongation, and adhesion properties, the active energy ray-curable resin composition ​A cured coating film comprising the same, and a laminate having a layer comprising the active energy ray-curable resin composition can be provided.

Mode for Carrying Out the Invention

[0009] <Active Energy Ray Resin Composition> The active energy ray-curable resin composition of the present invention (hereinafter referred to as this composition) is obtained by reacting a compound (a1) and a compound (a2) described later urethane (meth) acrylate ( A) [referred to as component (A)], a (co) polymer (B) of a (meth) acrylic monomer [component ( B)].], and a photopolymerization initiator (C) [referred to as component (C)]. It is an active energy ray-curable resin composition.

[0010] [Component A] Component (A) blended in this composition is urethane (meth) acrylate having a structure derived from compound (a1) and compound (a2). As component (A), for example, compound (a 1), urethane (meth) acrylate obtained by reacting compound (a2) can be mentioned . Component (A) contributes to the toughness of the cured coating film (hereinafter simply referred to as the cured coating film) obtained by curing this composition. .

[0011] [Compound (a1)] Compound (a1) is an isocyanate compound having at least two isocyanate groups . Compound (a1) contributes to the flexibility of the coating film. As compound (a1), for example, those conventionally used in the production of urethane (meth) acrylate can be used. As compound (a1), for example, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate , Nate, 2,6-Tolylene diisocyanate, 2,4-Diphenylmethane diisocyanate Aromatic polyisocyanates such as 4,4'-diphenylmethane diisocyanate; ethyl Diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhex Shark methyl diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate aliphatic polyisocyanates such as lysine diisocyanate and lysine triisocyanate; Isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, Alicyclic polyisocyanates such as methylcyclohexylene diisocyanate; xylene diisocyanate Aromatic aliphatic polyisocyanates such as sorbyanates and tetramethylxylylene diisocyanate Examples include biuret compounds, allophanates, isocyanurates, etc. . Among these, 1,3-phenylenediiso is chosen because it can impart excellent toughness to the coating film. Cyanates, 1,4-phenylenediisocyanate, 2,4-tolylenediisocyanate , 2,6-tolide diisocyanate, 2,4-diphenylmethane diisocyanate, 4 ,4'-diphenylmethane diisocyanate, isophorone diisocyanate, bis(4- Isocyanatocyclohexyl methane, 1,2-hydrogenated xylylene diisocyanate, 1,4 - Hydrogenated xylylene diisocyanate, hydrogenated tetramethylxylylene diisocyanate, no Ruborane diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, Diisocyanates with aliphatic skeletons, such as 2,2,4-trimethylhexamethylene diisocyanate T is preferable. For the synthesis of component (A), one compound alone or two or more compounds may be used as compound (a1). Compounds can be used in combination.

[0012] [Compound (a2)] Compound (a2) contains one hydroxyl group and one (meth)acryloyloxy group It is a compound having. Compound (a2) has a hydroxyl group that is the same as compound (a1) or compound (a1 The isocyanate group of the intermediate compound having an isocyanate group obtained from ) and the urethane bond Any compound that can form a compound and introduce a (meth)acryloyloxy group into component (A) is acceptable. . Examples of compound (a2) include 2-hydroxyethyl (meth)acrylate, 2- Hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate , 6-hydroxyhexyl (meth)acrylate, cyclohexanedimethanol mono(meth)acrylate Examples include acrylates and caprolactone adducts of these (meth)acrylates. . Among these, since a component with low viscosity (A) can be obtained, 2-hydroxyethyl ( Meth)acrylate, 2-hydroxypropyl(meth)acrylate, 4-hydroxypropyl Chill (meth)acrylate is preferred. (A) For the synthesis of component (a2), one compound alone or two or more compounds are used as compound (a2). They can be used together.

[0013] For the synthesis of component (A), in addition to compounds (a1) and (a2), polyol (a3) ​​is used. They can also be used in combination. Examples of polyols include neopentyl glycol and ethylene Glycol, diethylene glycol, propylene glycol, 1,6-hexanediol Lu, 1,4-butanediol, 1,9-nonanediol, 1,10-decanediol, 3- Methylpentanediol, 2,4-diethylpentanediol, tricyclodecanediol Nol, 1,4-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 1 ,3-Cyclohexanedimethanol, cyclohexanediol, hydrogenated bisphenol A, Polyols such as trimethylolpropane and pentaerythritol; these polyhydric alcohols in addition, alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide Polyether-modified polyols with added phosphate groups; these polyhydric alcohols and ε-capro Lactones, including γ-butyrolactone, γ-valerolactone, and δ-valerolactone. Polycaprolactone polyols obtained by reaction with these polyhydric alcohols and Polybasic acids, ε-caprolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone Caprolactone-modified polyester polymer obtained by reaction with lactones such as loractone. All; 1,6-Hexanediol, 3-Methylpentanediol, 2,4-Diethylpentane Tanediol, trimethylhexanediol, 1,4-butanediol, 1,5-pentane Diols such as 1,4-cyclohexanediol and ethylene carbonate, Dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, diiso Propyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl Polycarbonates obtained by transesterification reaction with carbonate esters such as nyl carbonates Todiol, polybutadiene glycol, polyether polyol, polyester polyol Examples include ol and amide diol. Among these, neopentyl glycol and ethyl acetate are used because they result in good curability for this composition. ethylene glycol, diethylene glycol, propylene glycol, 1,6-hexanediol 1,4-butanediol, 1,9-nonanediol, 1,10-decanediol, 3 -Methylpentanediol, 2,4-diethylpentanediol, tricyclodecanediol Tanol, 1,4-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 1,3-Cyclohexanedimethanol, cyclohexanediol, hydrogenated bisphenol A Polyols such as trimethylolpropane and pentaerythritol are preferred. (A) For the synthesis of component (a3), one compound alone or two or more compounds are used as compound (a3). They may be used in combination.

[0014] The molecular weight of (a3) ​​is preferably 500 or more and less than 3,000. The moisture resistance of the coating film is improved, and the appearance of the coating film is good as long as it is below the upper limit.

[0015] [Synthesis method for component (A)] The synthesis method for component (A) is, for example, the conventionally known urethane (meth)acrylate synthesis. The method can be used. A specific synthesis method is, for example, to put compound (a1) into a flask and add 2 ml 1 molar charge, then mix in a known catalyst such as dibutyltin dilaurate, and the temperature inside the flask is... While maintaining the temperature at 40-80°C, add 1 mole of compound (a3) ​​dropwise using a dropping funnel. Then, a urethane prepolymer having isocyanate groups at the terminals is obtained. Subsequently, the obtained urethane A compound having an equivalent amount of hydroxyl group in the isocyanate group remaining at the end of the tanprepolymer (a2 Add 2 mol dropwise and combine with the isocyanate group of the urethane prepolymer at 60-85°C. Component (A) can be synthesized by an addition reaction with the hydroxyl group of substance (a2). The reaction endpoint can be determined by quantifying the remaining isocyanate groups. The reaction rate at the endpoint is: Preferably 97% or more, more preferably 99% or more.

[0016] [Proportion of ingredient (A)] The proportion of component (A) in this composition is determined from the viewpoint of balancing hardness and elongation, with respect to the active energy. Preferably, the solid content of the wire-curable resin composition is 5% to 80% by mass, relative to the total amount of solids. 7% by mass or more and 70% by mass or less is more preferable, and even more preferably 10% by mass or more and 60% by mass The amount is less than %. (A) The proportion of component should be above the lower limit to achieve a good balance between hardness and elongation. Above the upper limit, and below the upper limit, it exhibits excellent adhesion.

[0017] [Component (B)] Component (B) is a (co)polymer of (meth)acrylic monomers. Method for producing component (B) As a legal measure, for example, one or more radical polymerization initiators are used in the presence of conventionally known radical polymerization initiators. The (meth)acrylic monomer is polymerized by methods such as solution polymerization, bulk polymerization, and emulsion polymerization. Several methods can be listed.

[0018] Examples of vinyl monomers used as raw materials for component (B) include methyl (meth)acrylate. Ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth) Acrylate, t-butyl (meth)acrylate, isobutyl (meth)acrylate, 2 -Ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, cyclohexyl Sil(meth)acrylate, benzyl(meth)acrylate, dicyclopentanyl(meth)acrylate ) Acrylate, dicyclopentenyl (meth)acrylate, 2-dicyclopentenoxy Ethyl (meth)acrylate, isobornyl (meth)acrylate, methoxyethyl (meth)acrylate Acrylate, ethoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate Relate, Methoxyethoxyethyl (meth)acrylate, Ethoxyethoxyethyl (meth)acrylate Acrylates such as tetrahydrofurfuryl (meth)acrylate and other hydroxyl-free acrylates. (meth)acrylate; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl Ropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-Hydropropyl Hydroxyalkyl (meth)acrylates such as roxybutyl (meth)acrylate; 2- 2-hydroxyethyl(meth)acrylate and ethylene oxide adduct, Adducts of methyl(meth)acrylate and propylene oxide, 2-hydroxyethyl(meth)acrylate ) 2-hydroxyethyl (meth)acrylate such as an adduct of acrylate and ε-caprolactone Hydroxyl group-containing vinyl monomers such as adducts of rates and alkylene oxides or organic lactones; Styrene, α-methylstyrene, PT-butylstyrene, vinyltoluene, etc. or styrene derivatives; N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide (T) Acrylamides such as acrylamide; (meth)acrylic acid, itaconic acid, maleic acid , unsaturated carboxylic acids such as fumaric acid; unsaturated nitriles such as (meth)acrylonitrile; male Diethyl ioate, dibutyl maleate, dibutyl fumarate, diethyl itaconate, Itako Dibutyl carboxylate and other unsaturated carboxylic acid esters; vinyl acetate, vinyl propionate and other vinyl compounds Esters are one example. Among these, in terms of hardness, methyl (meth)acrylate and ethyl (meth)acrylate are the most popular. Rate, propyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth) Acrylates and isobornyl (meth)acrylates are preferred. Component (B) may consist of one (co)polymer alone, or two or more (co)polymers combined. It can be used in this way.

[0019] [Proportion of ingredient (B)] The proportion of component (B) is determined by the total amount of solids in the active energy ray-curable resin composition. Preferably 5% by mass or more and 60% by mass or less, more preferably 6% by mass or more and 55% by mass or less. More preferably, the amount is 8% by mass or more and 50% by mass or less. The blending ratio of component (B) is above the lower limit. If the value is below the upper limit, the hardness will be even better, and if it is below the upper limit, the hardness will be superior.

[0020] The molecular weight of component (B) is preferably 3,000 to 150,000, and preferably 4,000 to 1 40,000 is more preferable, and 5,000 to 130,000 is even more preferable. If it is above the lower limit, the toughness of the coating film is improved and the hardness is improved, and if it is below the upper limit, the coating film The smoothness is improved. The glass transition temperature (Tg) of component (B) is preferably 30 to 150°C, and 40 to 14 0°C is more preferable, and 50-130°C is even more preferable. The glass transition temperature is above the lower limit. If present, the toughness and hardness of the coating film are improved; if below the upper limit, the processability of the coating film is improved. do.

[0021] [Component (C)] Component (C) is a photopolymerization initiator, which cures the composition by irradiation with active energy rays. It is a component. Component (C) can be, for example, benzophenone type, anthraquinone type, or Cylphenone type, thioxanthone type, acylphosphine oxide type, phenylglio Xylate-type photopolymerization initiators are one example.

[0022] Component (C) may include, for example, benzophenone, 4-methylbenzophenone, 2,4, 6-Trimethylbenzophenone, methyl orthobenzoylbenzoate, and 4-phenyl Benzophenones such as benzophenone; t-butylanthraquinone and 2-ethyl anthraquinone. Anthraquinone types such as raquinone; 2-hydroxy-2-methyl-1-phenylpropane 1-ONE, oligo{2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phen [nyl]propanone, benzyldimethyl ketal, 1-hydroxycyclohexylphenic acid Luketone, benzoin methyl ether, 2-methyl-[4-(methylthio)phenyl]- 2-Molfolino-1-propanone and 2-hydroxy-1-{4-[4-(2-hydroxy C-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one, Alkylphenone types such as 2,2-dimethoxy-1,2-diphenylethane-1-one; 2 -benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, di Thioxanthone types such as ethylthioxanthone and isopropylthioxanthone; 2,4, 6-Trimethylbenzoyldiphenylphosphine oxide, bis(2,6-dimethoxy) Benzoyl)-2,4,4-trimethylpentylphosphine oxide and bis(2,4 Acylphosphines such as 6-trimethylbenzoyl)-phenylphosphine oxide Oxide type; phenylglyoxylic acid methyl esters and other phenylglyoxylic acid esters Examples include silate-type photopolymerization initiators. Among these, benzophenone and 2-ethyl ant are selected in terms of the dry-to-the-touch properties of this composition. Laquinone, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-1,2 -Diphenylethane-1-one is preferred. Component (C) can be a single compound or a combination of two or more compounds.

[0023] [Amount of ingredient (C)] The amount of component (C) included is, relative to the total amount of solids in the active energy ray curable resin composition, Preferably 0.1% by mass or more and 15% by mass or less, and more preferably 1% by mass or more and 10% by mass or less. The higher the amount of component (C) added, the better the curing properties of this composition in an air atmosphere. The less the hardened coating film contains, the less the amount of component (C) remaining in the hardened coating tends to be.

[0024] [Component (D)] Component (D) is a compound having a quaternary ammonium base (however, (meth)acrylic (Excluding (B)) a (co)polymer of ru-type monomers. Component (D) is, for example, a quaternary ammonium salt. Monomers containing a group or monomers containing a quaternary ammonium base, either as monomers alone or as other monomers Examples include polymers obtained by copolymerization with a compound.

[0025] Examples of quaternary ammonium base-containing monomers that can be used as component (D) include ammonium bases. (Meth)acrylic acid esters of alcohols, specifically N,N-dimethylaminoethyl N,N-(meth)acrylate, N,N-diethylaminoethyl(meth)acrylate, N,N -dimethylaminopropyl (meth)acrylate, N,N-diethylaminopropyl (meth)acrylate (T) Acrylate, N,N-dimethylaminobutyl (meth)acrylate, N,N-Dimethylaminobutyl (meth)acrylate, N,N-Dimethylaminobutyl Tylaminobutyl (meth)acrylate, N,N-dihydroxyethylaminoethyl (meth)acrylate Examples include acrylates, particularly N,N-dimethylaminoethyl (meth)acrylate. The following is preferably used. The two alkyl groups of the N,N-dialkylamino group may be different. good. Examples of quaternary ammonium salts containing N,N-dialkylamino groups include commercially available products. Quaternary compounds of N,N-dimethylaminoethyl methacrylate by methyl chloride [Example] For example, the product name is "Light Ester (registered trademark) DQ-100," manufactured by Kyoeisha Chemical Co., Ltd. Examples include: Quaternary ammonium salts of monomers containing N,N-dialkylamino groups, It can also be produced by the quaternization reaction of (meth)acrylic acid esters of no alcohols. .

[0026] The polymer contains polymerizable monomer units other than monomers having a quaternary ammonium base. Common examples of such polymerizable monomers include methyl (meth)acrylate and ethyl acetate. propyl(meth)acrylate, butyl(meth)acrylate , 2-ethylhexyl (meth)acrylate, stearyl (meth)acrylate, lauric acid Alkyl(meth)acrylates such as tridecyl(meth)acrylates Rate; (meth)acrylic acid ester of the above amino alcohol; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl(meth)acrylate, hydroxybutyl Hydroxyalkyl(meth)acrylates such as methacrylate; benzyl(meth)acrylate ) Acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate Dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate Acrylate, ethoxyethyl (meth)acrylate, ethyl carbitol (meth) Acrylate, butoxyethyl (meth)acrylate, cyanoethyl (meth)acrylate Various (meth)acrylates such as glycidyl (meth)acrylate, styrene, methyl Examples include styrene. These may be used individually or in combination of two or more. This is also good. Among these, polymerizable monomers having highly hydrophobic long-chain alkyl groups are good polymers. It is preferable because it can be segregated at the air interface of the cured layer, thereby improving the antistatic properties of the cured layer. Such polymerizable monomers having long-chain alkyl groups include stearyl(meth) Examples include acrylate, lauryl (meth)acrylate, and tridecyl (meth)acrylate. It can be done.

[0027] [Amount of ingredient (D)] The proportion of quaternary ammonium base-containing monomer units in the polymer is preferably 10-90% by weight. 20-70% by weight is more preferable. The higher this percentage, the higher the antistatic properties. The transparency of the hardened layer tends to improve as the hardening progresses. The weight-average molecular weight of the polymer is preferably 800 to 120,000, and 2,000 to 60. 000 is preferable.

[0028] The polymer can be produced by a radical polymerization reaction using the above-mentioned raw material monomers. Radical polymerization reactions are preferably carried out in organic solvents in the presence of a radical polymerization initiator. stomach. Examples of organic solvents used in radical polymerization reactions include acetone and methyl ethyl ketone. Ketone solvents such as (MEK); ethanol, methanol, isopropyl alcohol (IP A) Alcohol-based solvents such as isobutanol; ethylene glycol dimethyl ether, p ether solvents such as propyl glycol monomethyl ether; ethyl acetate, propylene glycol Ester compounds such as monomethyl ether acetate and 2-ethoxyethyl acetate Solvents include aromatic hydrocarbon solvents such as toluene. Only one of these organic solvents may be used. You may use one type or a combination of two or more types.

[0029] Examples of radical polymerization initiators used in radical polymerization reactions include benzoyl peroxide. Organic peroxides such as di-t-butyl peroxide; 2,2'-azobisbutyronite Ryl, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis( Examples include azo compounds such as 4-methoxy-2,4-dimethylvaleronitrile. The radical polymerization initiator may be used alone or in combination of two or more. The CAL polymerization initiator is added in an amount of 0.01 to 5 parts by weight per 100 parts by weight of the total amount of raw material monomers. It is preferable to use it.

[0030] Furthermore, during radical polymerization reactions, chain transfer is used to control the weight-average molecular weight of the polymer. A chain transfer agent can be used. Examples of chain transfer agents include butanethiol and octanthiol. Decanethiol, dodecanethiol, hexadecanthiol, octadecanethiol 2-Methodyl mercaptan, cyclohexyl mercaptan, thiophenol, octyl thioglycolate, 2-methionine Octyl lucaptopropionate, octyl 3-mercaptopropionate, mercaptopropionate 2-ethylhexyl pionic acid, 2-ethylhexyl thioglycolate, butyl- 3-Mercaptopropionate, mercaptopropyltrimethoxysilane, methyl-3- Mercaptopropionate, 2,2-(ethylenedioxy)diethanethiol, ethane All, 4-methylbenzenethiol, 2-mercaptoethyl octanoate, 1, 8-Dimercapto-3,6-Dioxaoctane, Decantrichol, Dodecylmercap Tan, diphenyl sulfoxide, dibenzyl sulfide, 2,3-dimethylcapto-1- Propanol, mercaptoethanol, thiosalicylic acid, thioglycerol, thioglycol 3-Mercaptopropionic acid, 3-Mercaptopropionic acid, Thiomalic acid, Mercaptoacetic acid, Mercapto amber Examples include acids and thiol compounds such as 2-mercaptoethanesulfonic acid. You may use only one type or a combination of two or more types.

[0031] The amount of chain transfer agent used is 0.1 to 25 parts by weight per 100 parts by weight of the total raw material monomers. Preferably, 0.5 to 20 parts by weight, more preferably, and even more preferably 1.0 to 15 parts by weight.

[0032] The reaction time for the radical polymerization reaction is preferably 1 to 20 hours, and more preferably 3 to 12 hours. Furthermore, the reaction temperature is preferably 40 to 120°C, and more preferably 50 to 100°C.

[0033] [Amount of ingredient (D)] The amount of component (D) included is, relative to the total amount of solids in the active energy ray curable resin composition, Preferably, the amount is 3% by mass or more and 30% by mass or less, and more preferably 5% by mass or more and 20% by mass or less. The higher the amount of component (D) added, the lower the surface resistivity and the better the antistatic performance; the lower the amount added, the better the antistatic performance. The transparency of the coating tends to improve.

[0034] [Other ingredients] Other components that can be added include various (meth)acrylate compounds. For example... Examples of monomers having four or more (meth)acryloyl groups include dipentaerythrocytes. Thritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate Rate, caprolactone-modified dipentaerythritol penta(meth)acrylate, and , caprolactone-modified dipentaerythritol hexa(meth)acrylate, pentaerythritol Thritol tetra (meth)acrylate, ethoxylated pentaerythritol tetra Poly(meth)acrylates, such as la(meth)acrylates, which have a pentaerythritol skeleton. Trimethylolpropane such as ditrimethylolpropanetetra(meth)acrylate Poly(meth)acrylate with a skeleton, polyester poly(meth)acrylate, urethane Examples include tan(meth)acrylate.

[0035] Other polyester poly(meth)acrylates that can be used as components include, for example, , phthalates, succinates, hexahydrophthalates, tetrahydrophthalates, terephthalates, Polybasic acids such as azelaic acid and adipic acid, and ethylene glycol, hexanediol, and poly(P) Esterification reaction with polyols such as ethylene glycol and polytetramethylene glycol. The polyester polyol obtained in response reacts with (meth)acrylic acid or its derivatives. The resulting compounds are listed below.

[0036] Other urethane (meth)acrylates that can be used as components include, for example, isopropyl alcohol. Polyisocyanates such as long diisocyanates and compound hydroxyl groups such as pentaerythritol Urethane obtained by urethane reaction with a compound having a number of (meth)acryloyl groups (T) Acrylates are an example.

[0037] This composition may optionally contain a photosensitizer. Examples of photosensitizers include: Methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethyl Examples of known photosensitizers include amyl aminobenzoate and 4-dimethylaminoacetophenone. It is possible.

[0038] This composition may contain, as needed, UV absorbers, light stabilizers, leveling agents, antioxidants, and yellow Various types of anti-deterioration agents, bluing agents, pigments, dyes, defoaming agents, thickeners, anti-settling agents, anti-fogging agents, etc. The following additives may be used.

[0039] [Organic solvents] This composition may contain organic solvents as needed for purposes such as adjusting viscosity. Yes, it is possible. Organic solvents include water, aromatic solvents such as toluene and xylene, and methyl ethyl acetate. Ketone solvents such as acetone, methyl isobutyl ketone, and cyclohexanone; Lu ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glyco Dimethyl ether, ethylene glycol diethyl ether, diethylene glycol diethyl ether Methyl ether, diethylene glycol diethyl ether, propylene glycol monomer Ether-based solvents such as ethyl ether, anisole, and phenethole; ethyl acetate, butyl acetate ester solvents such as isopropyl acetate and ethylene glycol diacetate; dimethyl phosphate Amide solvents such as methyl amide, diethylformamide, and N-methylpyrrolidone; methyl Cellosolve-based solvents such as cellosolve, ethyl cellosolve, and butyl cellosolve; methanol, ethyl cellosolve; Alcohol-based solvents such as butanol, propanol, isopropanol, and butanol; dichloro Examples include halogenated solvents such as molethane and chloroform; etc. These organic solvents are type 1 They may be used alone or in combination of two or more. Of these organic solvents, the one used for application is... Ester-based solvents, ether-based solvents, and alcohol-based solvents are good choices because they make it easier to improve workability. And ketone solvents are preferred.

[0040] <Cured coating> The cured coating film of the active energy ray curable resin composition is an active energy ray curable resin composition Apply to the surface of a substrate or article to form a coating film, and after drying as necessary, activate the coating film. It can be formed by irradiation with energy rays. The formation of the cured coating film is done by conventionally known methods. It can be used, and in addition to coating, other examples include transfer, but with fewer steps, Furthermore, a coating method is preferred from the standpoint of being easy to apply. A cured coating film is formed. The application methods used include gravure coating, reverse roll coating, die coating, and air coating. Doctor's coat, blade coat, rod coat, bar coat, curtain coat, knife Coat, transfer coat, squeeze coat, impregnation coat, kiss coat, spray Known coatings such as o-coat, calendula coat, extruded coat, dip coat, spin coat, etc. A ting method can be used.

[0041] There are no particular limitations regarding the drying and curing conditions when forming a cured coating film. Regarding the drying of the organic solvents and other media used in the coating solution, the temperature is usually 30-200°C, or preferably... The temperature range is 50-150°C, more preferably 70-120°C. The drying time is 0 A duration of 0.01 to 30 minutes is preferable, and 0.1 to 10 minutes is more preferable.

[0042] In the case of curing using active energy rays, the active energy rays used are ultraviolet rays. Examples include electron beams, visible light, infrared rays, and X-rays. Among these, curing properties and resin degradation prevention are important. From the perspective of stopping, ultraviolet light and electron beams are preferred, and ultraviolet light is more preferred. Also, the active energy The radiation dose can be appropriately selected according to the activated energy radiation being irradiated.

[0043] For example, when using ultraviolet light, the integrated light intensity of the irradiation is 20 to 5,000 mJ / cm². 2 is preferred Furthermore, 50-3,000 mJ / cm² 2 More preferably, 100-2,000 mJ / cm² 2 This is even more preferable. Furthermore, the illuminance is preferably 50-600 mW / cm, and 75-4 50 mW / cm is more preferable, and 100-300 mW / cm is even more preferable. For example, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, electrodeless lamps, metal halide lamps, Alternatively, high-pressure mercury lamps, ultra-high-pressure mercury lamps, etc., using scanning or curtain-type electron beam accelerators, etc. Mercury lamps, etc., can be used.

[0044] Furthermore, when curing by electron beam irradiation, various electron beam irradiation devices can be used. The electron beam irradiation dose (Mrad) is preferably 0.5 to 20 Mrad, and the present invention is active From the perspectives of curability of energy ray-curable compositions, flexibility of cured products, and prevention of damage to substrates, More preferably, it is 1 to 15 mad.

[0045] The thickness of the cured coating film is preferably 0.01 to 20 μm, more preferably 0.05 to 10 μm. m, more preferably in the range of 0.1 to 7 μm. This makes it easier to achieve the desired hardness.

[0046] <Laminate> The laminate of the present invention comprises a substrate and a cured coating film of an active energy ray curable resin composition. The laminate may also have a functional layer provided on top of the cured coating film of the present invention. Examples of layers include conventionally known types, such as anti-reflective layers, low-reflection layers, high-reflection layers, and anti- Examples include glare layers, anti-blocking layers, anti-fouling layers, anti-fogging layers, and adhesive layers. Furthermore, the base material It is also possible to provide various functional layers on the side opposite to the side with the cured coating. It is also possible to apply a hardened coating film.

[0047] [Base material] Any substrate containing a compound with an isosorbide structure can be used. This is possible. In particular, isosorbide can be used as a dihydroxy component in polycarbonate resins and poly One form is to incorporate it into an ester resin, which allows for the inclusion of many isosorbide structures. This allows for a higher amount of plant-derived ingredients, making it a desirable form.

[0048] When using polycarbonate resin with isosorbide as the dihydroxy component as the base material In addition, diester carbonates used as raw materials for polycarbonate resins are conventionally known materials. This can be done. For example, phenyl carbonate such as diphenyl carbonate and dityl carbonate. Bonates, dimethyl carbonate, diethyl carbonate, di-t-butyl carbonate Examples include alkyl carbonates such as t. Among these, phenyl carbonates... These are preferred, and diphenyl carbonate is particularly preferred. These diester carbonates are used individually. You may use one type, or you may use two or more types in combination.

[0049] Furthermore, it is preferable to use compounds other than isosorbide as the dihydroxy component. It is also a copolymerized polycarbonate used as a copolymerizing component of isosorbide. It is preferable that it be a resin. As for the dihydroxy component, for example, an aliphatic dihydroxylated Compounds, alicyclic dihydroxy compounds, aromatic bisphenol compounds, or isosorbide compounds A preferred compound is an ether group-containing dihydroxy compound, such as isosorbide. By introducing a more flexible molecular structure than the existing structure, the toughness of polycarbonate resin can be improved. It can be made possible. Also, from the perspective of further improving impact resistance, aliphatic dihydroxy Use of compounds, alicyclic dihydroxy compounds, or aromatic bisphenol compounds. This is preferable. Furthermore, from the viewpoint of improving weather resistance, having an aromatic ring structure within the molecular structure is preferable. Compounds that do not undergo this process, i.e., aliphatic dihydroxy compounds or alicyclic dihydroxy compounds. It is more preferable to have a certain type, and if further improvement in heat resistance is also considered, an alicyclic dihydroxy compound This is even more preferable. These dihydroxy components may be one type or a combination of two or more types. It can also be used in combination with other structures. Furthermore, it is not limited to dihydroxy structures, but also trihydroxy and tetrahydroxy structures. Compounds with three or more hydroxyl groups, such as trahydroxy, can also be used. ru.

[0050] Examples of alicyclic dihydroxy compounds include 1,4-cyclohexanedimethanol and tricyclic dihydroxy compounds. Rodecanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol , 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, penta Cyclopentadecane dimethanol, 2,6-decalingimethanol, 1,5-decalingimethanol Methanol, 2,3-decalingimethanol, 2,3-norbornanedimethyl, 2, Examples include 5-norbornanedimethanol, 1,3-adamantanedimethanol, and limonene. This is possible. Among these, the balance between impact resistance and flexibility, as well as ease of manufacturing, should be considered. 1,4-cyclohexanedimethanol or tricyclodecanedimethanol is preferred. Furthermore, in applications where flexibility is particularly important, 1,4-cyclohexanedimethanol is even more suitable. It is preferable.

[0051] The aliphatic dihydroxy compound may be a linear aliphatic or a branched aliphatic. Aliphatic dihydroxy compounds include, specifically, ethylene glycol and 1,3-propane. 1,2-propanediol, 1,4-butanediol, 1,3-butanediol 1,2-butanediol, 1,5-heptanediol, 1,6-hexanediol , 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1 ,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol These are some examples.

[0052] Examples of aromatic bisphenol compounds include 2,2-bis(4-hydroxyphenyl)pro Pan(bisphenol A), 2,2-bis(4-hydroxy-3,5-dimethylphenyl ) Propane, 2,2-bis(4-hydroxy-3,5-diethylphenyl)propane, 2 ,2-bis(4-hydroxy-(3,5-diphenyl)phenyl)propane, 2,2-bi Su(4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4-hydro Xyphenyl)pentane, 2,4'-dihydroxy-diphenylmethane, bis(4-Hyd Roxyphenyl)methane, bis(4-hydroxy-5-nitrophenyl)methane, 1,1 -Bis(4-hydroxyphenyl)ethane, 3,3-bis(4-hydroxyphenyl)ethane 1,1-Bis(4-hydroxyphenyl)cyclohexane, Bis(4-hydroxy 2,4'-Dihydroxydiphenyl sulfone, bis(4-hydro Xyphenyl) sulfide, 4,4'-dihydroxydiphenyl ether, 4,4'-di Hydroxy-3,3'-dichlorodiphenyl ether, 9,9-bis(4-(2-hydro Xyethoxy-2-methyl)phenyl)fluorene, 9,9-bis(4-hydroxyphenyl Nyl fluorene, 9,9-bis(4-hydroxy-2-methylphenyl)fluorene These can be listed. Among these, bisphenol A is preferred when considering the balance of performance. stomach.

[0053] Examples of ether group-containing dihydroxy compounds include diethylene glycol and triethylene glycol. Recall, polyethylene glycol, poly-1,3-propylene glycol, polytetra Examples include methylene glycol. For polyethylene glycol, the molecular weight is, for example... For example, items ranging from 150 to 2,000 can be used.

[0054] When using copolymerized polycarbonate resin as the base material, all dihydroxy compounds are derived from The proportion of structural units derived from isosorbide in 100 mol% of structural units is preferably 1 mol% or more. More preferably 10 mol% or more, even more preferably 30 mol% or more, and particularly preferably 4 The range is 5 mol% or more, most preferably 55 mol% or more. Furthermore, there are no particular restrictions regarding the upper limit. There is no limit, and all structural units may be derived from isosorbide, but preferably 99 mol% or less. Preferably 95 mol% or less, more preferably 90 mol% or less, and especially preferably 85 mol% or less. It is within a range of less than %. Using it within the above range improves heat resistance and rigidity, and also improves molding processes. This makes it easier to adjust the properties to achieve a balanced combination of strength and mechanical strength.

[0055] The copolymerized polycarbonate resin contains structural units other than the dihydroxy compounds mentioned above. It may have. For example, dihydroxy compounds of aromatic hydrocarbons can be cited, but the aroma Compounds containing rings undergo structural degradation when exposed to sunlight or ultraviolet light, due to their absorption of ultraviolet rays. This often results in problems such as yellowing. Therefore, dihydroxy compounds of aromatic hydrocarbons When using such materials, ensure that the required product characteristics, such as formability, weather resistance, and surface properties, are not compromised. It is desirable to use it within a limited range.

[0056] When considering heat resistance and toughness, the glass transition temperature of polycarbonate resin is preferable. The temperature range is 40-180°C, more preferably 60-160°C, and even more preferably 80-150°C. The temperature is particularly preferably in the range of 90 to 140°C.

[0057] Polycarbonate resin is an ester of the aforementioned dihydroxy compound and the aforementioned diester carbonate. It can be synthesized by polycondensation via transesterification. More specifically, by transesterification The polycondensation reaction proceeds by removing the by-product monohydroxy compounds, etc., from the system. This is possible. The transesterification reaction is promoted in the presence of a transesterification catalyst. As catalysts, metal compounds of Group 1 or Group 2 in the long-period periodic table, and basic Boron compounds, basic phosphorus compounds, basic ammonium compounds, or amine compounds, etc. Basic compounds can be used, particularly Group 1 metal compounds or Group 2 metal compounds. It is preferable to use at least one of the following. The amount of catalyst used is the total dihydr subjected to the reaction. Preferably 0.1 to 300 μmol per mole of roxy compound, more preferably 0.5 to It is 100 μmoles, and especially 1 to 50 μmoles.

[0058] The molar ratio of dihydroxy compound to dicarbonate diester is preferably 0.90~ A range of 1.20 is good. In this case, the amount of hydroxyl groups at the end of the polycarbonate resin Because the increase can be suppressed, the thermal stability of the resin can be improved. This can reduce discoloration during the reaction. It also suppresses the decrease in the rate of the transesterification reaction. This allows for the more reliable production of copolymers with the desired molecular weight. Furthermore, in this case, From the perspective of being able to suppress the increase in thermal history during the reaction, polycarbonate resin The discoloration can be reduced. Furthermore, in this case, residual carbon in the polycarbonate resin The amount of acid diester can be reduced, and from this perspective, the discoloration of the resin can be reduced. It is possible. Furthermore, it is possible to avoid or mitigate the generation of odors. These effects can be further enhanced. From this perspective, the mixed molar ratio of dihydroxy compounds to diester carbonates is particularly favorable. The range is 0.95 to 1.10.

[0059] Examples of polymerization reaction methods include batch, continuous, or combinations thereof. In particular, a continuous process carried out in multiple stages using multiple reactors in the presence of the catalyst is possible. This is preferable in terms of productivity and ease of thermal history management.

[0060] Furthermore, the polycarbonate resin used as the base material can also contain various additives. It is possible. Examples of additives include UV absorbers, antioxidants, light stabilizers, catalyst deactivators, Examples include dyes and pigments, flame retardants, flame retardant additives, fillers, impact modifiers, hydrolysis inhibitors, nucleating agents, and plasticizers. It can be done.

[0061] When using a polyester resin with isosorbide as the dihydroxy component as the base material, Examples of acid components used for polymerization include terephthalic acid, isophthalic acid, and 2-chloroterephthalic acid. Dichloroterephthalic acid, 2,5-dichloroterephthalic acid, 2-methylterephthalic acid, 4,4-stilbenzyl Carboxylic acids, 4,4-biphenyldicarboxylic acid, orthophthalic acid, 2,6-naphthalenedi Carboxylic acid, 2,7-naphthalenedicarboxylic acid, bisbenzoic acid, bis(p-carboxyphosphate) Phenyl methane, anthracene dicarboxylic acid, 4,4-diphenyl ether dicarboxylic acid , 4,4-diphenoxyethanedicarboxylic acid, 5-sodium sulfisoisophthalic acid, eth Aromatic dicarboxylic acids such as lenbis-p-benzoic acid, succinic acid, adipic acid, sebacic acid azelaic acid, dodecanediic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclo Derived from aliphatic dicarboxylic acids such as hexanedicarboxylic acid or their ester derivatives. Examples of such compounds include: These acidic components may be present individually or in pairs. It may contain more than one type.

[0062] A homopolymer formed with isosorbide alone as the dihydroxy component is also acceptable, but it is flexible. Considering properties and other factors, copolymer polyester resins using other polyhydroxy components are preferable. It seems so. Examples of polyhydroxy compounds that can be used include ethylene glycol and dieth Lencolyl, 1,4-butanediol, neopentyl glycol, polytetramethyl Glycol, 1,4-cyclohexanedimethanol, spiroglycol, 2,2,4, Examples of compounds include 4-tetramethylcyclobutane-1,3-diol. However, in particular, from the perspective of achieving a balance of various performance characteristics, ethylene glycol and 1,4 -Cyclohexanedimethanol is preferred.

[0063] Resins containing compounds having an isosorbide structure obtained by the above-described methods are conventionally known It can be processed in various ways. It is not limited to the methods listed below, but for example... Then, the resin is introduced into the extruder, mixed while continuously supplying additives, etc., and then passed through a vacuum equipment. By-product gases and low molecular weight volatile components are removed through devolving, and the molten material is extruded in a strand-like manner from the tip of the extruder. One method involves cutting the material into pellets while cooling and solidifying it. The extruder must have sufficient defoliation capacity. A twin-screw extruder equipped with a vacuum device at the vent port is preferable to obtain sufficient force and uniform dispersion of additives. .

[0064] In terms of extruder operating conditions, a lower melt viscosity of the resin is preferable to increase devolatilization efficiency. Furthermore, a higher melt-mixing temperature within the extruder system is preferable. However, if the temperature is too high, discoloration may occur. Because thermal decomposition may occur, it is necessary to process the product at the highest possible and appropriate temperature. Yes, it exists. The appropriate melting temperature depends on the type of resin, the glass transition temperature of the resin, the molecular weight, the melt viscosity, etc. However, considering the temperature at which thermal decomposition begins rapidly, 200°C to 320°C is preferable. In this case, the plasticizing load on the extruder is reduced, which can improve productivity. Both methods can suppress the thermal decomposition of resin, preventing discoloration, a decrease in mechanical strength due to molecular weight reduction, and heat loss. This can further prevent the generation of decomposition gases, etc. From the perspective of further enhancing this effect, The melting temperature is more preferably 210°C to 300°C, and particularly preferably 220°C to 290°C.

[0065] It is melted in an extruder, preferably via a gear pump, and filtered as needed. The resin is extruded, for example, in strand form from a die head, and after cooling and solidification, it is processed using a rotary method. The strands are cut into pellets using a cutter or similar tool. Cooling of the strands is typically done by air or water. This is done in various ways, and in the case of air cooling, the air used is filtered to remove foreign matter from the air using a HEPA filter or the like. It is preferable to use clean air to prevent contamination from airborne contaminants. Also, when used in water cooling systems... The water is first treated to remove metal components using ion exchange resin, and then filtered to remove foreign matter from the water. It is preferable to use clean water from which impurities have been removed.

[0066] The resulting pelletized resin can be further processed by conventionally known methods. For example, Methods include processing the film and molding using molds. The following methods are limited to the following: Although it is not something that is done in this way, for example, when making a film, a common manufacturing method is to dissolve the resin. One method involves melting the material, forming it into a sheet, and then stretching it as needed to increase its strength or for other purposes. .

[0067] For example, the aforementioned resin is melt-extruded from a die using an extruder, and the molten film is cooled. The film is cooled and solidified on a roll to obtain an unstretched film. In this case, the flatness of the film is improved. Therefore, it is preferable to improve the adhesion between the molten sheet and the cooling roll, and methods such as electrostatic application adhesion and liquid A body coating and adhesion method can also be used. If the film is to be left as is in its unstretched state, roll temperature Thickness variation can be reduced by adjusting the degree and extrusion speed. Furthermore, production efficiency and thickness It is also possible to stretch the unstretched film obtained for purposes such as reducing runout and roughness. Stretching the film in the longitudinal direction can be achieved by utilizing the difference in peripheral speed of the rolls, and Extension in the lateral direction can be achieved using a tenter-type extension machine, etc. Furthermore, a combination of both can be used. It is also possible to produce a biaxially oriented film. Furthermore, a simultaneous biaxial stretching method can also be used. It is possible. The stretching temperature and stretching ratio vary depending on the type of resin, but preferably 7 The temperature range is 0 to 200°C, more preferably 80 to 160°C, and the stretching ratio is in one direction. The range is 7 times or less, preferably 5 times or less. There is no particular lower limit, but it is 1 time. Depending on the type of resin, it is possible to obtain a stretched film by applying appropriate heat treatment or other methods.

[0068] It is also possible to use various additives at any stage of the resin processing described above. For example, When added before or during melt extrusion, such as when creating a lett or film, It is preferable due to its good dispersion efficiency. Examples of additives include catalyst deactivators and heat stabilizers used in resin manufacturing. Neutralizing agents, UV absorbers, light stabilizers, particles, mold release agents, dyes, pigments, lubricants, plasticizers, and other similar substances. Examples include compatibilizers and flame retardants.

[0069] Any form of substrate can be used, for example, film, sheet Examples include sheets, plates, molded bodies, etc. The thickness is also arbitrary, but for example, if it is a film, handling From the viewpoint of ease of processing, productivity, and workability, the particle size should be 1 to 500 μm, preferably 10 to 300 μm, and more preferably 10 to 300 μm. The thickness is in the range of 20 to 250 μm. Also, if it is a molded product, from the standpoint of weight, 0 In the range of 0.05 to 10 mm, preferably 0.1 to 6 mm, more preferably 0.2 to 4 mm be.

[0070] Furthermore, the substrate improves the coatability of the active energy ray-curable resin composition, Corona treatment and plastic treatment are used to improve the adhesion of linearly curing resin compositions to the cured coating layer, etc. It is also possible to apply a Zuma treatment.

[0071] The laminate of the present invention is particularly excellent in hardness among various applications, making it suitable for display components and electrical equipment. • Suitable for use in electronic components, and offers superior scratch resistance compared to general polycarbonate resins. Due to its excellent adhesion properties, it can be suitably used in automotive parts and various lenses, and similarly in general applications. Compared to typical polycarbonate resins, it offers superior processability, making it suitable for various film applications, for example... It can be suitably used as a display component or for decorative purposes. [Examples]

[0072] The present invention will be described in more detail below with reference to examples, but the present invention will not exceed its gist. The following examples are not limited to those described below. The measurement and evaluation methods used in this invention are as follows.

[0073] (1) Measurement of weight-average molecular weight (Mw) and number-average molecular weight Equipment: Tosoh Corporation's "HLC-8120GPC" Column: TSKgel SuperHZM-M*HZM-M*HZ (manufactured by Tosoh Corporation) 2000, Detector: Differential refractive index detector (RI detector / built-in), Solvent: Tetrahydrofuran, Temperature: 40℃, Flow rate: 0.5mL / min, Injection volume: 10μL, Concentration: 0.2% by mass, Calibration sample: Monodisperse polystyrene, Calibration method: Polystyrene equivalent.

[0074] (2) Measurement of pencil hardness The coated laminate was tested according to JIS K-5600 to measure its pencil hardness. The evaluation criteria are as follows: ◎...Pencil hardness F or higher ○...Pencil hardness B~HB ×...Pencil hardness of 2B or less

[0075] (3) Measurement of elongation The coated laminate was cut out with the substrate together to a size of 10 mm wide and 60 mm long. The sample was tested using an Imada MX2-500N-FA with a chuck distance of 40 mm and tensile strength. A tensile test was performed at a speed of 50 mm / min and an ambient temperature of 80°C, and the yield point value was defined as elongation. The following criteria were used for evaluation. ◎...Elongation of 35% or more ○...Elongation is 20%~34% ×...Elongation is less than 20%

[0076] (4) Measurement of adhesion Cut the coated laminate with a utility knife in a grid pattern at 1mm intervals, reaching the base material. 1mm 2 Create 100 grid squares and stick Nichiban's cellophane tape (registered trademark) onto them. After applying, peel it off rapidly and observe the grid-like pattern of separation between the substrate and the coating layer. Initial adhesion was evaluated according to the following criteria. ◎...The number of remaining squares after cutting the grid is 95 or more. ○...The number of remaining squares after cutting out the grid is 70-94. ×...Cutting out the grid leaves 69 or fewer squares remaining.

[0077] (5) Measurement of antistatic properties The coated laminate is then subjected to an application using Nitto Seiko Analytic High Resta UP. Surface resistivity was measured at a voltage of 500V. Antistatic properties were evaluated according to the following criteria. ◎...Surface resistivity is 1.99E+10 or less ○...Surface resistivity is 2.00E+10 to 9.99E+10 ×...Surface resistivity is 1.00E+11 or higher

[0078] (Manufacturing Example 1) The following was prepared as urethane acrylate A. A four-necked flask equipped with a thermometer, stirrer, water-cooled condenser, and nitrogen gas inlet, Isophorone diisocyanate 37.5g (0.17 mol), polytetramethylene glyco Ludiol 25.5g (Hydroxyl value 167mgKOH / g; Molecular weight calculated from hydroxyl value) 672 (0.04 mol), polyester triol 13.4 g (hydroxyl value 262 mg KO) H / g; molecular weight calculated from hydroxyl value (642; 0.02 mol), dibouti as reaction catalyst. 0.02 g of rustin dilaurate was added and reacted at 80°C. The remaining isocyanate group When the concentration drops below 11%, add 23.6g (0.2 moles) of 2-hydroxyethyl acrylate. ), add 0.04g of methoxyphenol as a polymerization inhibitor and react at 60°C The reaction is terminated when the remaining isocyanate group is 0.3% or less, and the urethane acrylic We obtained compound A (number of functional groups: 2-3, weight-average molecular weight: approximately 3,500).

[0079] (Manufacturing example 2) The following polymer D containing a quaternary ammonium base was prepared. In a reactor equipped with a stirrer, reflux condenser, and thermometer, add DQ100:18 parts by mass, S LMA: 7.5 parts by mass, DMMA: 4.5 parts by mass, Methyl ethyl ketone (MEK): 20 Add parts by mass of isopropyl alcohol (IPA): 50 parts by mass, and after starting to stir, the system The mixture was purged with nitrogen and heated to 55°C. Then, 2,2'-azobis(2,4-dimethylvalero) was added. Nitrile (Wako Pure Chemical Industries, Ltd. "V-65")): 0.6 parts by mass are added, and the system is heated to 65 °C. After raising the temperature to [temperature] and stirring for 3 hours, further heating is performed using 2,2'-azobis(2,4-dimethylvaleroni Trill: 0.6 parts by mass was added and stirred at 65°C for 3 hours. The temperature inside the system was raised to 80°C. After stirring for 2 hours, the mixture was cooled to room temperature to obtain a solution of the polymer containing a quaternary ammonium base. The composition of this solution was polymer / MEK / IPA = 30 / 20 / 50 (by weight). The weight-average molecular weight (Mw) of the combined molecule was 45,200.

[0080] Component (A) is 40 parts by mass of the aforementioned urethane acrylate A, and component (B) is BR -80 (Mitsubishi Chemical Co., Ltd., product name Dianaal BR-80) 20 parts by mass, component (C) and Omn.184 5 parts by mass (made of IGM Resin, product name Omnirad 184) ), 26.7 parts by mass of polymer D having the aforementioned quaternary ammonium base as component (D), Other ingredients include V#300 (20 parts by mass), DPHA (12 parts by mass), and PG (propylene glycol) as an organic solvent. Mix and dissolve 150 parts by mass of M and 150 parts by mass of MEK to form an activated energy ray curable composition. They manufactured it.

[0081] On the film of D7340A (manufactured by Mitsubishi Chemical, product name Duravio D7340A), The above-mentioned active energy ray curable resin composition is applied using a bar coater #16, and 8 After drying at 0°C for 1 minute, irradiate with a high-pressure mercury lamp at an intensity of 120 mW / cm and an integrated light output of 30 mW / cm. 0 mJ / cm 2 A laminate was obtained by irradiating it with ultraviolet light to form a hard coat layer with a thickness of 5 μm.

[0082] [Examples 2-9, Comparative Examples 1-4] Except for the formulation and composition shown in the composition column of Table 1, the activation energy is obtained in the same manner as in Example 1. Linear curing compositions were prepared and evaluated. The results are shown in Table 1.

[0083] [Table 1]

[0084] All numerical values ​​in the table, except for the mixing ratios, are in parts by mass. The abbreviations in Table 1 refer to the following compounds. This indicates. • Urethane acrylate A: As described in Manufacturing Example 1 • Urethane acrylate B: Mitsubishi Chemical Co., Ltd. Diabeam UK-6091 (product name, (Bifunctional urethane acrylate) • Urethane acrylate C: MIWON MIRAMER PU2100 (product name, 2 (Functional urethane acrylate) • BR-80: Mitsubishi Chemical's Dianaal BR-80 (product name, acrylic copolymer) (Mw: 100,000, Tg: 104℃) • MB-7940: Mitsubishi Chemical's Dianaal MB-7940 (product name, acrylic) Copolymer, Mw: 6000, Tg: 82℃) ·Omn.184: Omnirad 184 (product name, 1-hi) made by IGM Resins (Droxycyclohexylphenyl ketone) • Polymer D containing a quaternary ammonium base: Described in Production Example 2 · V#300: Osaka Organic Chemical's Biscote #300 (trade name, pentaerythritol triacrylate) · DPHA: Nippon Kayaku's KAYARAD DPHA (trade name, dipentaerythritol hexaacrylate) · UV-7600B: Mitsubishi Chemical's Violet Light UV-7600B (trade name, 6-functional urethane acrylate) · PGM: Propylene glycol monomethyl ether · MEK: Methyl ethyl ketone

[0085] From the above examples, the cured coating film formed from the active energy ray-curable resin composition of the present invention was excellent in pencil hardness, elongation, and adhesion. On the other hand, the cured coating film formed from the active energy ray-curable resin composition of Comparative Example 1 without blending component (B) had insufficient adhesion, and the cured coating film formed from the active energy ray-curable resin composition of Comparative Example 2 without blending component (A) and component (B) had insufficient elongation. Also, the cured coating film formed from the active energy ray-curable resin composition of Comparative Example 3 without blending component (A) had an insufficient balance between hardness and elongation. ​

Claims

1. A coating material to be applied to an isosorbide-containing substrate, An active energy ray curable resin composition containing a urethane (meth)acrylate (A) having a structure derived from (a1) to (a3) ​​below, a (co)polymer of (meth)acrylic monomers (B), and a photopolymerization initiator (C). (a1) An isocyanate compound having at least two isocyanate groups (a2) Hydroxyl group-containing monofunctional (meth)acrylate (a3) Polyol

2. The active energy ray curable resin composition according to claim 1, wherein the amount of urethane (meth)acrylate (A) blended is 5% by mass or more and 80% by mass or less based on the total amount of solids in the active energy ray curable resin composition.

3. The active energy ray curable resin composition according to claim 1, wherein the substrate is a polycarbonate substrate having isosorbide as a structural unit.

4. The active energy ray curable resin composition according to claim 1, wherein the amount of the (co)polymer (B) of the (meth)acrylic monomer is 5% by mass or more and 60% by mass or less with respect to the total amount of solids of the active energy ray curable resin composition.

5. The active energy ray curable resin composition according to claim 1, further comprising a compound (D) having a quaternary ammonium base (excluding (B) a (co)polymer of (meth)acrylic monomers.

6. A cured coating film of an active energy ray-curable resin composition according to claims 1 to 5.

7. The active energy ray curable resin composition according to claim 1, wherein the cured product obtained by curing the active energy ray curable resin composition has an elongation of 20% or more at 80°C.

8. A urethane (meth)acrylate (A) having a structure derived from (a1) to (a3) ​​below, A laminate having a layer on an isosorbide-containing substrate comprising an active energy ray-curable resin composition containing a (meth)acrylic monomer (co)polymer (B) and a photopolymerization initiator (C). (a1) An isocyanate compound having at least two isocyanate groups (a2) Hydroxyl group-containing monofunctional (meth)acrylate (a3) Polyol

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