CN110741025B - Curable composition and laminated film - Google Patents

Curable composition and laminated film Download PDF

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CN110741025B
CN110741025B CN201880039327.6A CN201880039327A CN110741025B CN 110741025 B CN110741025 B CN 110741025B CN 201880039327 A CN201880039327 A CN 201880039327A CN 110741025 B CN110741025 B CN 110741025B
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acrylate
mass
curable composition
dipentaerythritol
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CN110741025A (en
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井上直人
伊藤正广
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DIC Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/12—Polymers provided for in subclasses C08C or C08F

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Paints Or Removers (AREA)

Abstract

The present invention provides a curable composition characterized by containing: a (meth) acryloyl group-containing acrylic resin (A) and a dipentaerythritol (meth) acrylate (B), wherein the hydroxyl value of the dipentaerythritol (meth) acrylate (B) is in the range of 40 to 140 mgKOH/g. The curable composition can form a cured product having excellent properties such as substrate adhesion, surface hardness, low shrinkage, and flexibility.

Description

Curable composition and laminated film
Technical Field
The present invention relates to: a curable composition which gives a cured product having excellent properties such as substrate adhesion, surface hardness, low shrinkage and flexibility, and a coating film and a laminated film each using the curable composition.
Background
Resin materials having a (meth) acryloyl group can be easily and instantly cured by ultraviolet irradiation or the like, and cured products thereof are excellent in transparency, hardness, and the like, and therefore, they are widely used in the fields of paints, coating agents, and the like. The objects to be coated include optical films, plastic molded products, wooden products, and the like, and various performances are required depending on the types, applications, and the like of the objects to be coated, and therefore, a large number of resins designed according to the purposes have been proposed.
An active energy ray-curable resin composition containing: examples of the resin material having a (meth) acryloyl group include (meth) acryloyl group-containing acrylic resins, pentaerythritol tetraacrylate, and pentaerythritol triacrylate (see patent document 1). The active energy ray-curable resin composition described in patent document 1 is excellent in the balance between the surface hardness of the cured product and the low curing shrinkage, and therefore is useful as a coating agent for coating a thin plastic film. However, there are problems as follows: the adhesiveness to the film base material, particularly the adhesiveness after long-term storage under high-temperature and wet conditions, is low, and peeling is likely to occur.
Documents of the prior art
Patent literature
Patent document 1: japanese patent laid-open publication No. 2011-
Disclosure of Invention
Problems to be solved by the invention
Accordingly, an object of the present invention is to provide: a curable composition which gives a cured product having excellent properties such as substrate adhesion, surface hardness, low shrinkage and flexibility, and a coating film and a multilayer film each using the curable composition.
Means for solving the problems
The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that: the present inventors have completed the present invention by finding that a cured product of a curable composition containing a (meth) acryloyl group-containing acrylic resin and a (meth) acrylate of dipentaerythritol, wherein the hydroxyl value of the (meth) acrylate of dipentaerythritol is in the range of 40 to 140mgKOH/g, is excellent in various properties such as substrate adhesion, surface hardness, low shrinkage, and flexibility.
That is, the present invention relates to a curable composition comprising: a (meth) acryloyl group-containing acrylic resin (A) and a dipentaerythritol (meth) acrylate (B), wherein the hydroxyl value of the dipentaerythritol (meth) acrylate (B) is in the range of 40 to 140 mgKOH/g.
The present invention further relates to a coating film formed from the curable composition.
The present invention further relates to a laminated film having a layer comprising the aforementioned coating film.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, there can be provided: a curable composition which gives a cured product having excellent properties such as substrate adhesion, surface hardness, low shrinkage and flexibility, and a coating film and a laminated film each using the curable composition.
Detailed Description
The curable composition of the present invention is characterized by containing: a (meth) acryloyl group-containing acrylic resin (A) and a dipentaerythritol (meth) acrylate (B), wherein the hydroxyl value of the dipentaerythritol (meth) acrylate (B) is in the range of 40 to 140 mgKOH/g.
In the present invention, the (meth) acryloyl group means either or both of an acryloyl group and a methacryloyl group. In addition, (meth) acrylate is a generic term for acrylate and methacrylate.
The (meth) acryloyl acrylic resin (a) may be obtained, for example, as follows: an acrylic resin intermediate obtained by polymerizing a (meth) acrylate monomer (α) having a reactive functional group such as a hydroxyl group, a carboxyl group, an isocyanate group, and a glycidyl group as an essential component is further reacted with a (meth) acrylate monomer (β) having a reactive functional group reactive with the functional group to introduce a (meth) acryloyl group, thereby obtaining the acrylic resin.
Examples of the (meth) acrylate monomer (α) having a reactive functional group include: hydroxyl group-containing (meth) acrylate monomers such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate; carboxyl group-containing (meth) acrylate monomers such as (meth) acrylic acid; isocyanate group-containing (meth) acrylate monomers such as 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, and 1, 1-bis (acryloyloxymethyl) ethyl isocyanate; glycidyl group-containing (meth) acrylate monomers such as glycidyl (meth) acrylate and 4-hydroxybutylacrylate glycidyl ether. These may be used alone, or in combination of 2 or more.
The acrylic resin intermediate may be obtained by copolymerizing, if necessary, other (meth) acrylate monomers, styrene derivatives, and the like, in addition to the (meth) acrylate monomer (α). Examples of the other polymerizable unsaturated group-containing compound include: alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate; alicyclic ring-containing (meth) acrylates such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and the like; aromatic ring-containing (meth) acrylates such as phenyl (meth) acrylate, benzyl (meth) acrylate, and phenoxyethyl acrylate; silyl group-containing (meth) acrylates such as 3-methacryloxypropyltrimethoxysilane; styrene derivatives such as styrene, α -methylstyrene and chlorostyrene. These may be used alone or in combination of two or more. Among these other polymerizable unsaturated group-containing compounds, the alkyl (meth) acrylate is preferably used in view of providing a curable composition having an excellent balance among curl resistance, flexibility, scratch resistance, and the like of a cured coating film. In addition, it is preferable that 80% by mass or more of the reaction raw materials of the (meth) acryloyl acrylic resin (a) be a (meth) acrylate monomer containing no aromatic ring.
In the case where the acrylic resin intermediate is obtained by copolymerizing the (meth) acrylate monomer (α) with the other polymerizable unsaturated group-containing compound, the ratio of the (meth) acrylate monomer (α) to the total amount of the two is preferably 30% by mass or more in terms of the reaction ratio between the two, from the viewpoint of obtaining the (meth) acryloyl group-containing acrylic resin (a) having excellent curability. The ratio of the (meth) acrylate monomer (α) to the total of the (meth) acrylate monomer (α) and the other polymerizable unsaturated group-containing compound is particularly preferably in the range of 30 to 50 mass% in terms of excellent adhesion to a substrate, curl resistance, flexibility and the like of the cured coating film. On the other hand, in terms of excellent scratch resistance and surface hardness of the cured coating film, the ratio of the (meth) acrylate monomer (α) to the total of the (meth) acrylate monomer (α) and the other polymerizable unsaturated group-containing compound is preferably 55 mass% or more.
The acrylic resin intermediate can be produced by the same method as that for a general acrylic resin. As an example of the production conditions, for example, the polymer can be produced by polymerizing various monomers in the presence of a polymerization initiator at a temperature range of 60 to 150 ℃. Examples of the polymerization method include: bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, and the like. Further, examples of the polymerization method include: random copolymers, block copolymers, graft copolymers, and the like. In the case of the solution polymerization method, for example, a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone, or a glycol ether solvent such as propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monopropyl ether, or propylene glycol monobutyl ether can be preferably used.
The (meth) acrylate monomer (β) is not particularly limited as long as it can react with the reactive functional group of the (meth) acrylate monomer (α), and the following combinations are preferred from the viewpoint of reactivity. That is, when the hydroxyl group-containing (meth) acrylate is used as the (meth) acrylate monomer (α), it is preferable to use an isocyanate group-containing (meth) acrylate as the (meth) acrylate monomer (β). When the carboxyl group-containing (meth) acrylate is used as the (meth) acrylate monomer (α), the glycidyl group-containing (meth) acrylate is preferably used as the (meth) acrylate monomer (β). When the isocyanate group-containing (meth) acrylate is used as the (meth) acrylate monomer (α), the hydroxyl group-containing (meth) acrylate is preferably used as the (meth) acrylate monomer (β). When the glycidyl group-containing (meth) acrylate is used as the (meth) acrylate monomer (α), the carboxyl group-containing (meth) acrylate is preferably used as the (meth) acrylate monomer (β).
In the reaction between the acrylic resin intermediate and the (meth) acrylate monomer (β), when the reaction is an esterification reaction, for example, there may be mentioned: a method of using an esterification catalyst such as triphenylphosphine at a temperature of 60 to 150 ℃. In addition, when the reaction is a carbamation reaction, there may be mentioned: and (b) reacting the acrylic resin intermediate with the compound (. beta.) dropwise at a temperature of 50 to 120 ℃. The reaction ratio of the both is preferably 0.95 to 1.05 mol based on 1 mol of the functional group in the acrylic resin intermediate.
The mass average molecular weight (Mw) of the (meth) acryloyl group-containing acrylic resin (A) is preferably in the range of 3000 to 80000, more preferably in the range of 5000 to 30000. The equivalent of (meth) acryloyl group is preferably in the range of 200 to 500 g/equivalent.
In the present invention, the mass average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (Mn/Mw) are values measured by Gel Permeation Chromatography (GPC) under the following conditions.
A measuring device; HLC-8220 made by Tosoh corporation
A column; guard post H made by Tosoh corporationXL-H
+ Tosoh corporation TSKgel G5000HXL
+ Tosoh corporation TSKgel G4000HXL
+ Tosoh corporation TSKgel G3000HXL
+ Tosoh corporation TSKgel G2000HXL
A detector; RI (differential refractometer)
Data processing: SC-8010 manufactured by Tosoh corporation
The measurement conditions were as follows: column temperature 40 deg.C
Solvent tetrahydrofuran
Flow rate 1.0 ml/min
Standard; polystyrene
A sample; the resulting tetrahydrofuran solution (0.4 mass% in terms of resin solid content) was filtered through a microfilter to obtain a filtrate (100. mu.l)
The (meth) acrylate (B) of dipentaerythritol is obtained by (meth) acrylating a part or all of hydroxyl groups of dipentaerythritol, and contains at least one selected from the group consisting of dipentaerythritol mono (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.
In addition, for example, when a (meth) acrylate (B) of dipentaerythritol is produced by a method of esterifying dipentaerythritol with acrylic acid or the like, a high molecular weight component (B') such as an addition reaction product of dipentaerythritol (meth) acrylate may be produced as a by-product other than the (meth) acrylate (B) of dipentaerythritol. The high molecular weight component (B') may be purified and removed, or a crude (meth) acrylate (B) of dipentaerythritol containing the component may be used as it is. In this case, the content of the high molecular weight component (B') in the crude (meth) acrylate (B) of dipentaerythritol is preferably in the range of 1 to 20% by mass.
The (meth) acrylate (B) of dipentaerythritol preferably contains dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate, from the viewpoint of a curable composition which gives a cured product having particularly excellent adhesion to a substrate and surface hardness. The mass ratio of the two is preferably 20/80 to 90/10, and more preferably 40/60 to 85/15. In the case of the curable composition having further excellent adhesion to a substrate, dipentaerythritol tetra (meth) acrylate is preferably further contained, and the content thereof is preferably in the range of 1 to 30% by mass, more preferably in the range of 5 to 20% by mass, based on the total of dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.
In the present invention, the content of each component in the (meth) acrylate (B) of dipentaerythritol or a crude product containing the same, and the ratio of the content of each component are values calculated from the area ratio of the liquid chromatogram measured under the following conditions.
[ measurement conditions ]
The device comprises the following steps: LCMS-2010EV manufactured by Shimadzu corporation "
Data processing: LCMS Solution manufactured by Shimadzu corporation "
Column: ODS-100V (2.0 mmID. times.150 mm, 3 μm) manufactured by Tosoh corporation, 40 deg.C
Eluent: water/acetonitrile, 0.4 mL/min
A detector: PDA, MS
Sample preparation: 1. a sample (50 mg) was dissolved in acetonitrile (for LC) (10 ml)
2. Stirring with Vortex for 30 seconds
3. Standing for 30 minutes
4. The liquid was passed through a 0.2 μm filter to prepare a measurement sample
And (3) calculating the area ratio: calculation at UV wavelength 210nm
The hydroxyl value of the (meth) acrylic acid esterified product (B) of dipentaerythritol is in the range of 40 to 140 mgKOH/g. Further, from the viewpoint of a curable composition which is a cured product and has excellent adhesion to a substrate and further excellent balance among surface hardness, scratch resistance, curl resistance, flexibility, and the like, the range of 40 to 120mgKOH/g is more preferable, and the range of 70 to 120mgKOH/g is particularly preferable. When the (meth) acrylate (B) of dipentaerythritol is produced by a method of esterifying dipentaerythritol with acrylic acid, the hydroxyl value of the crude product containing the high molecular weight component (B') is preferably in the range of 40 to 140mgKOH/g, more preferably in the range of 80 to 140 mgKOH/g. In the present invention, the hydroxyl value of the crude product of (meth) acrylic acid ester (B) of dipentaerythritol is an actual measurement value measured in accordance with JIS K0070, and the hydroxyl value of the crude product of (meth) acrylic acid ester (B) of dipentaerythritol is a calculated value calculated from the composition ratio of the components calculated from the area ratio of the liquid chromatogram.
In the curable composition of the present invention, the mass ratio [ (a)/(B) ] of the (meth) acrylic resin (a) containing a (meth) acryloyl group and the (meth) acrylate (B) of dipentaerythritol is preferably in the range of 30/70 to 99/1 in terms of a curable composition that is a cured product and has excellent substrate adhesion and further excellent balance among surface hardness, scratch resistance, curl resistance, flexibility, and the like. In particular, [ (A)/(B) ] is preferably in the range of 60/40 to 99/1 in view of excellent adhesion to a substrate, curl resistance, flexibility and the like of the cured coating film. On the other hand, [ (A)/(B) ] is preferably in the range of 30/70 to 55/45 in terms of excellent scratch resistance and surface hardness of the cured coating film.
The curable composition of the present invention may contain a (meth) acrylate compound (C) other than the (meth) acryloyl group-containing acrylic resin (a) and the (meth) acrylate compound (B) of dipentaerythritol. Examples of the other (meth) acrylate compound (C) include: a dendrimer-type (meth) acrylate resin (C1), a urethane (meth) acrylate resin (C2), an epoxy (meth) acrylate resin (C3), a mono (meth) acrylate compound and its modified product (C4), an aliphatic hydrocarbon-type poly (meth) acrylate compound and its modified product (C5), an alicyclic poly (meth) acrylate compound and its modified product (C6), an aromatic poly (meth) acrylate compound and its modified product (C7), and the like. These may be used alone, or in combination of 2 or more.
The dendrimer-type (meth) acrylate resin (C1) is a resin having a regular multi-branched structure and having (meth) acryloyl groups at the ends of each branch, and is also referred to as a hyperbranched polymer, a star polymer, or the like, in addition to the dendrimer type. Examples of such compounds include those represented by the following structural formulae (1-1) to (1-8), but the compounds are not limited thereto, and any resin having a regular multi-branched structure and having a (meth) acryloyl group at the end of each branch can be used.
Figure BDA0002314914680000081
Figure BDA0002314914680000091
(in the formula, R1Is a hydrogen atom or a methyl group, R2Is a hydrocarbon group having 1 to 4 carbon atoms. )
As such a dendrimer-type (meth) acrylate resin (C1), there can be used: "Biscoat # 1000" manufactured by Osaka organic Chemicals K.K. "[ mass average molecular weight (Mw) 1500-2000, average (meth) acryloyl number per molecule 14]," Biscoat 1020 "[ mass average molecular weight (Mw) 1000-3000 ]," SIRIUS501 "[ mass average molecular weight (Mw) 15000-23000 ], manufactured by MIWON" SP-1106 "[ mass average molecular weight (Mw)1630, average (meth) acryloyl number per molecule 18], manufactured by SARTOMER" CN2301 "," CN2302 "[ average (meth) acryloyl number per molecule 16]," CN2303 "[ average (meth) acryloyl number per molecule 6]," CN 4 "[ average (meth) acryloyl number per molecule 18], manufactured by Nichikuai iron and gold chemical Co., Ltd." ESDRIMER HU-22 ", manufactured by New chemical Co., Ltd." A-HBR-5 ", manufactured by first Industrial pharmaceutical Co., Ltd." "W-IER 1150 Commercially available products such as "HYPERTECH UR-101" manufactured by Nissan chemical Co., Ltd.
The mass average molecular weight (Mw) of the dendrimer-type (meth) acrylate resin (C1) is preferably in the range of 1000 to 30000. The average number of (meth) acryloyl groups per molecule is preferably in the range of 5 to 30.
Examples of the urethane (meth) acrylate resin (C2) include those obtained by reacting various polyisocyanate compounds, hydroxyl group-containing (meth) acrylate compounds, and, if necessary, various polyol compounds. Examples of the polyisocyanate compound include: aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2, 4-trimethylhexamethylene diisocyanate, and 2,4, 4-trimethylhexamethylene diisocyanate; alicyclic diisocyanate compounds such as norbornane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate; aromatic diisocyanate compounds such as toluene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, and 1, 5-naphthalene diisocyanate; polymethylene polyphenyl polyisocyanate having a repeating structure represented by the following structural formula (2); and isocyanurate, biuret, allophanate modifications thereof. These may be used alone or in combination of 2 or more.
Figure BDA0002314914680000101
[ in the formula, R3Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R4Each independently is an alkyl group having 1 to 4 carbon atoms or a bonding site connecting the structural part represented by the formula (2) through a methylene group denoted by the symbol (x). l is 0 or an integer of 1 to 3, and m is an integer of 1 or more.]
Examples of the hydroxyl group-containing (meth) acrylate compound include: hydroxyl group-containing (meth) acrylate compounds such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and the like; (poly) oxyalkylene modified products obtained by introducing (poly) oxyalkylene chains such as (poly) oxyethylene chains, (poly) oxypropylene chains, and (poly) oxytetramethylene chains into the molecular structures of the various hydroxyl group-containing (meth) acrylate compounds; lactone modifications obtained by introducing a (poly) lactone structure into the molecular structure of the various hydroxyl group-containing (meth) acrylate compounds described above, and the like.
Examples of the polyol compound include: aliphatic polyhydric alcohol compounds such as ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol and the like; aromatic polyhydric alcohol compounds such as biphenol and bisphenol; (poly) oxyalkylene modified products obtained by introducing (poly) oxyalkylene chains such as (poly) oxyethylene chains, (poly) oxypropylene chains, and (poly) oxytetramethylene chains into the molecular structures of the above-mentioned various polyol compounds; lactone modifications obtained by introducing a (poly) lactone structure into the molecular structure of the above-mentioned various polyol compounds, and the like.
Examples of the epoxy (meth) acrylate resin (C3) include those obtained by reacting an epoxy resin with (meth) acrylic acid or its anhydride. Examples of the epoxy resin include: diglycidyl ethers of dihydric phenols such as hydroquinone and catechol; diglycidyl ethers of biphenol compounds such as 3,3 '-biphenyldiol and 4, 4' -biphenyldiol; bisphenol epoxy resins such as bisphenol a epoxy resin, bisphenol B epoxy resin, bisphenol F epoxy resin, and bisphenol S epoxy resin; polyglycidyl ethers of naphthol compounds such as 1, 4-naphthalenediol, 1, 5-naphthalenediol, 1, 6-naphthalenediol, 2, 7-naphthalenediol, binaphthol, and bis (2, 7-dihydroxynaphthyl) methane; triglycidyl ethers such as 4, 4', 4 ″ -methylenetrisphenol; novolac type epoxy resins such as phenol novolac type epoxy resins and cresol novolac resins; (poly) oxyalkylene modified products obtained by introducing (poly) oxyalkylene chains such as (poly) oxyethylene chains, (poly) oxypropylene chains, and (poly) oxytetramethylene chains into the molecular structures of the above epoxy resins; lactone modifications obtained by introducing a (poly) lactone structure into the molecular structure of the above epoxy resins, and the like.
Examples of the mono (meth) acrylate compound and its modified product (C4) include: aliphatic mono (meth) acrylate compounds such as methyl (meth) acrylate, ethyl (meth) acrylate, hydroxyethyl (meth) acrylate, propyl (meth) acrylate, hydroxypropyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate; alicyclic mono (meth) acrylate compounds such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and adamantyl mono (meth) acrylate; heterocyclic mono (meth) acrylate compounds such as glycidyl (meth) acrylate and tetrahydrofurfuryl acrylate; aromatic mono (meth) acrylate compounds such as phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxy ester (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyethoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, phenylphenol ester (meth) acrylate, phenylphenol alkyl (meth) acrylate, phenylbenzyl (meth) acrylate, phenoxybenzyl (meth) acrylate, benzylbenzyl (meth) acrylate, phenylphenoxyethyl (meth) acrylate, and p-cumylphenol (meth) acrylate; a mono (meth) acrylate compound such as a compound represented by the following structural formula (3): (poly) oxyalkylene modifications obtained by introducing (poly) oxyalkylene chains such as (poly) oxyethylene chains, (poly) oxypropylene chains, and (poly) oxytetramethylene chains into the molecular structures of the various mono (meth) acrylate compounds; lactone modifications obtained by introducing a (poly) lactone structure into the molecular structure of the various mono (meth) acrylate compounds described above,
Figure BDA0002314914680000121
(in the formula, R5Is a hydrogen atom or a methyl group. ).
Examples of the aliphatic hydrocarbon type poly (meth) acrylate compound and its modified product (C5) include: aliphatic di (meth) acrylate compounds such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, and neopentyl glycol di (meth) acrylate; aliphatic tri (meth) acrylate compounds such as trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate and the like; aliphatic poly (meth) acrylate compounds having 4 or more functions such as pentaerythritol tetra (meth) acrylate and ditrimethylol propane tetra (meth) acrylate; (poly) oxyalkylene modified products obtained by introducing (poly) oxyalkylene chains such as (poly) oxyethylene chains, (poly) oxypropylene chains, and (poly) oxytetramethylene chains into the molecular structures of the various aliphatic hydrocarbon type poly (meth) acrylate compounds; lactone modifications obtained by introducing a (poly) lactone structure into the molecular structure of the various aliphatic hydrocarbon type poly (meth) acrylate compounds described above, and the like.
Examples of the alicyclic poly (meth) acrylate compound and its modified product (C6) include: alicyclic di (meth) acrylate compounds such as 1, 4-cyclohexanedimethanol di (meth) acrylate, norbornanedimethanol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, and tricyclodecanedimethanol di (meth) acrylate; (poly) oxyalkylene modified products obtained by introducing (poly) oxyalkylene chains such as (poly) oxyethylene chains, (poly) oxypropylene chains, and (poly) oxytetramethylene chains into the molecular structures of the various alicyclic poly (meth) acrylate compounds; lactone modifications obtained by introducing a (poly) lactone structure into the molecular structure of the various alicyclic poly (meth) acrylate compounds described above, and the like.
Examples of the aromatic poly (meth) acrylate compound and its modified product (C7) include: aromatic di (meth) acrylate compounds such as biphenol di (meth) acrylate, bisphenol di (meth) acrylate, a bicarbazole compound represented by the following structural formula (4), and a fluorene compound represented by the following structural formula (5-1) or (5-2);
Figure BDA0002314914680000131
[ in the formula, R6Each independently is any of a (meth) acryloyl group, a (meth) acryloyloxy group, and a (meth) acryloyloxyalkyl group.]
Figure BDA0002314914680000141
[ in the formula, R7Each independently is any of a (meth) acryloyl group, a (meth) acryloyloxy group, and a (meth) acryloyloxyalkyl group.]
(poly) oxyalkylene modified products obtained by introducing (poly) oxyalkylene chains such as (poly) oxyethylene chains, (poly) oxypropylene chains, and (poly) oxytetramethylene chains into the molecular structures of the various aromatic poly (meth) acrylate compounds; lactone modifications obtained by introducing a (poly) lactone structure into the molecular structure of the above-mentioned various aromatic poly (meth) acrylate compounds, and the like.
In the case where these other (meth) acrylate compounds (C) are used, the total amount of the (meth) acryloyl group-containing acrylic resin (a) and the (meth) acrylate compound (B) of dipentaerythritol is preferably 70 mass% or more, more preferably 90 mass% or more, of the total amount of the (meth) acryloyl group-containing compound components contained in the curable composition, from the viewpoint that the effects exhibited by the present invention can be sufficiently exhibited.
In the curable composition of the present invention, the content of (meth) acryloyl groups in the total of the (meth) acryloyl group-containing compound components is preferably in the range of 3.8 to 8.5 mmol/g.
The curable composition of the present invention can be cured by, for example, irradiation with active energy rays. The photopolymerization initiator is preferably used depending on the kind of the active energy ray. Specific examples of the photopolymerization initiator include: alkylphenone-based photopolymerization initiators such as 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, and 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholino) phenyl ] -1-butanone; acylphosphine oxide-based photopolymerization initiators such as 2,4, 6-trimethylbenzoyl-diphenyl-phosphine oxide; and intramolecular hydrogen abstraction type photopolymerization initiators such as benzophenone compounds. These may be used alone or in combination of 2 or more. The photopolymerization initiator can be selected and used as appropriate according to the type of active energy ray to be irradiated.
Examples of commercially available products of the photopolymerization initiator include: "IRGACURE 127", "IRGACURE 184", "IRGACURE 250", "IRGACURE 270", "IRGACURE 290", "IRGACURE 369E", "IRGACURE 379 EG", "IRGACURE 500", "IRGACURE 651", "IRGACURE 754", "IRGACURE 819", "IRGACURE 907", "IRGACURE 1173", "IRGACURE 2959", "IRGACURE MBF", "IRGACURE TPO", "IRGACURE OXE 01", "IRGACURE OXE 02", and "OMNIRAD 184", "OMNIRAD 250", "OMNI 369", "OMNI E", "OMNI 651", "OMNI RAD 82907 FF", "OMNIRAD 1173" manufactured by BASF Corporation.
The amount of the polymerization initiator used is preferably in the range of 0.05 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the components other than the organic solvent in the curable composition.
The curable composition of the present invention may further contain other components. Examples of the other components include: inorganic fine particles, silane coupling agents, phosphate ester compounds, solvents, ultraviolet absorbers, antioxidants, silicon-based additives, fluorine-based additives, antistatic agents, organic beads, Quantum Dots (QD), rheology control agents, defoaming agents, antifogging agents, colorants, and the like.
The inorganic fine particles are added for the purpose of adjusting the hardness, refractive index, and the like of a cured coating film of the curable composition, and various known and commonly used inorganic fine particles can be used. Examples thereof include fine particles of silica, alumina, zirconia, titanium oxide, barium titanate, antimony trioxide, and the like. These may be used alone or in combination of two or more. Among these, silica particles having high versatility include various types such as fumed silica, precipitated silica, wet silica called gel silica, sol-gel silica and the like, and can be used. The surface of the inorganic fine particles may be modified with a silane coupling agent or the like. The particle size of the inorganic fine particles can be suitably adjusted according to desired coating properties and the like, and the measurement value by the dynamic light scattering method is preferably in the range of 10 to 250 nm. When the inorganic fine particles are used, the amount of the inorganic fine particles added is preferably in the range of 0.1 to 60% by mass relative to the total amount of components other than the solvent of the curable composition.
Examples of the silane coupling agent include: (meth) acryloyloxy silane coupling agents such as [ (meth) acryloyloxyalkyl ] trialkylsilane, [ (meth) acryloyloxyalkyl ] dialkylalkoxysilane, [ (meth) acryloyloxyalkyl ] alkyldialkoxysilane, [ (meth) acryloyloxyalkyl ] trialkoxysilane; vinyl silane coupling agents such as trialkylstyrenesilane, dialkylalkoxyvinylsilane, alkyldialkoxyvinylsilane, trialkoxyvinylsilane, trialkylallylsilane, dialkylalkoxyallylsilane, alkyldialkoxyallylsilane, trialkoxyallylsilane, and the like; styrene-based silane coupling agents such as styryl trialkyl, styryl dialkyl alkoxy silane, styryl alkyl dialkoxy silane, and styryl trialkoxy silane; epoxy-based silane coupling agents such as (glycidoxyalkyl) trialkoxysilane, (glycidoxyalkyl) dialkylalkoxysilane, (glycidoxyalkyl) alkyldialkoxysilane, (glycidoxyalkyl) trialkoxysilane, [ (3, 4-epoxycyclohexyl) alkyl ] trimethoxysilane, [ (3, 4-epoxycyclohexyl) alkyl ] trialkoxysilane, [ (3, 4-epoxycyclohexyl) alkyl ] dialkylalkoxysilane, [ (3, 4-epoxycyclohexyl) alkyl ] alkyldialkoxysilane, [ (3, 4-epoxycyclohexyl) alkyl ] trialkoxysilane; isocyanate-based silane coupling agents such as (isocyanatoalkyl) trialkylsilane, (isocyanatoalkyl) dialkylalkoxysilane, (isocyanatoalkyl) alkyldialkoxysilane, and (isocyanatoalkyl) trialkoxysilane. These may be used alone or in combination of 2 or more.
Examples of commercially available products of the phosphate ester compound include: "Kayamer PM-2", "Kayamer PM-21", Kagymer chemical corporation "LIGHT ESTER P-1M", "LIGHT ESTER P-2M", "LIGHT ACRYLATE P-1A (N)", Solvay corporation "SIPOMER PAM 100", "SIPOMER PAM 200", "SIPOMER PAM 300", "SIPOMER PAM 4000", Osaka organic chemical industry corporation "Biscoat #3 PA", "Biscoat #3 PMA", first Industrial pharmaceutical corporation "NEW FRONTER S-23A"; "sipome PAM 5000" manufactured by SOLVAY corporation as a phosphate ester compound having an allyl ether group in its molecular structure, and the like.
The solvent is added for the purpose of adjusting the coating viscosity of the curable composition, and the type and the amount of the solvent added may be appropriately adjusted depending on the desired performance. Generally, the curable composition is used so that the nonvolatile content of the composition falls within the range of 10 to 90 mass%. Specific examples of the solvent include: ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; esters such as methyl acetate, ethyl acetate, and butyl acetate; aromatic solvents such as toluene and xylene; alicyclic solvents such as cyclohexane and methylcyclohexane; alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, propylene glycol monomethyl ether, and the like; glycol ether solvents such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monopropyl ether. These may be used alone or in combination of 2 or more.
Examples of the ultraviolet absorber include: triazine derivatives such as 2- [4- { (2-hydroxy-3-dodecyloxypropyl) oxy } -2-hydroxyphenyl ] -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine, 2- [4- { (2-hydroxy-3-tridecyloxypropyl) oxy } -2-hydroxyphenyl ] -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine, 2- (2 '-xanthenecarboxy-5' -methylphenyl) benzotriazole, 2- (2 '-o-nitrobenzyloxy-5' -methylphenyl) benzotriazole, 2-xanthenecarboxy-4-dodecyloxybenzophenone, and mixtures thereof, 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone, and the like. These may be used alone, or in combination of 2 or more.
Examples of the antioxidant include: hindered phenol antioxidants, hindered amine antioxidants, organic sulfur antioxidants, phosphate antioxidants, and the like. These may be used alone or in combination of 2 or more.
Examples of the silicon-based additive include: and polyorganosiloxanes having alkyl groups and phenyl groups, such as dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic dimethylpolysiloxanes, methylhydrogenpolysiloxanes, polyether-modified dimethylpolysiloxane copolymers, polyester-modified dimethylpolysiloxane copolymers, fluorine-modified dimethylpolysiloxane copolymers, amino-modified dimethylpolysiloxane copolymers, and the like, polydimethylsiloxanes having polyether-modified acryloyl groups, polydimethylsiloxanes having polyester-modified acryloyl groups, and the like. These may be used alone or in combination of 2 or more.
Examples of the fluorine-containing additive include: DIC "MEGAFACE" series, etc. These may be used alone or in combination of 2 or more.
Examples of the antistatic agent include: a pyridinium, imidazolium, phosphonium, ammonium, or lithium salt of a bis (trifluoromethanesulfonyl) imide or a bis (fluorosulfonyl) imide. These may be used alone or in combination of two or more.
Examples of the organic beads include: polymethyl methacrylate beads, polycarbonate beads, polystyrene beads, polyacrylic styrene beads, silicone beads, glass beads, acrylic beads, benzoguanamine resin beads, melamine resin beads, polyolefin resin beads, polyester resin beads, polyamide resin beads, polyimide resin beads, polyvinyl fluoride resin beads, polyethylene resin beads, and the like. These may be used alone or in combination of 2 or more. The average particle diameter of the organic beads is preferably in the range of 1 to 10 μm.
Examples of the Quantum Dots (QDs) include: group II-V semiconductor compounds, group II-VI semiconductor compounds, group III-IV semiconductor compounds, group III-V semiconductor compounds, group III-VI semiconductor compounds, group IV-VI semiconductor compounds, group I-III-VI semiconductor compounds, group II-IV-V semiconductor compounds, group I-II-IV-VI semiconductor compounds, group IV elements, or compounds containing the same, and the like. Examples of the group II-VI semiconductor compound include: binary compounds such as ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgSe, HgTe and the like; ternary compounds such as ZnSeS, ZnSeTe, ZnSTe, CdZnS, CdZnSe, CdZnTe, CdSeS, CdSeTe, CdSTe, CdHgS, CdHgSe, CdHgTe, HgSeS, HgSeTe, HgSTe, HgZnS, HgZnSe, and HgZnTe; and quaternary compounds such as CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, CdHgZnTe, HgZnSeS, HgZnSeTe, and HgZnSTe. Examples of the group III-IV semiconductor compound include: b is4C3、Al4C3、Ga4C3And the like. Examples of the group III-V semiconductor compound include: binary compounds such as BP, BN, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, and InSb; GaNP, GaNAs, GaNSb, GaGaAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNPTernary compounds such as InNAs, InNSb, InPAs, InPSb and GaAlNP; quaternary compounds such as GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, and InAlPSb. Examples of the group III-VI semiconductor compound include: al (Al)2S3、Al2Se3、Al2Te3、Ga2S3、Ga2Se3、Ga2Te3、GaTe、In2S3、In2Se3、In2Te3And InTe, etc. Examples of the group IV-VI semiconductor compound include: binary compounds such as SnS, SnSe, SnTe, PbS, PbSe, PbTe and the like; ternary compounds such as SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe and the like; quaternary compounds such as SnPbSSe, SnPbSeTe, SnPbSTe, etc. Examples of the group I-III-VI semiconductor compound include: CuInS2、CuInSe2、CuInTe2、CuGaS2、CuGaSe2、CuGaSe2、AgInS2、AgInSe2、AgInTe2、AgGaSe2、AgGaS2、AgGaTe2And the like. Examples of the group IV element or a compound containing the same include: C. si, Ge, SiC, SiGe, etc. The quantum dot may be composed of a single semiconductor compound, or may have a core-shell structure composed of a plurality of semiconductor compounds. In addition, the surface of the polymer may be modified with an organic compound.
These various additives may be added in any amount according to desired performance and the like, and are generally used in an amount of preferably 0.01 to 40 parts by mass, based on 100 parts by mass of the total of the components excluding the solvent in the curable composition.
The curable composition of the present invention can be produced by mixing the above-mentioned respective compounding ingredients. The mixing method is not particularly limited, and a paint shaker, a disperser, a roll mill, a bead mill, a ball mill, an attritor, a sand mill, a bead mill, or the like can be used.
The curable composition of the present invention has a low cure shrinkage rate and is excellent in various properties of a cured coating film, such as moist heat resistance, curl resistance, surface hardness, scratch resistance, and flexibility, and therefore, can be suitably used for molded articles, display members, and coating materials for protecting various film materials from scratches.
The curable composition of the present invention can be applied to various substrates and cured by irradiation with active energy rays to form a coating film for protecting the surface of the substrate. The curable composition of the present invention may be used by being applied as it is to a surface-protected member, or may be used as a protective film by being applied to a plastic film. Alternatively, the curable composition of the present invention may be applied to a plastic film to form a coating film, and used as an optical film such as an antireflection film, a diffusion film, and a prism sheet. Further, a layer formed of a coating material other than the curable composition of the present invention may be provided in a stacked manner.
Examples of the plastic film include: triacetyl cellulose film, polyester film, acrylic film, cycloolefin polymer film, polyamide film, polyimide film, polystyrene film, polycarbonate film, polypropylene film, and the like.
Among the above plastic films, triacetyl cellulose film is particularly suitable for a polarizing plate of a liquid crystal display, and has the following characteristics: since the thickness is generally as thin as 40 to 100 μm, even when a hard coat layer is provided, it is difficult to sufficiently improve the scratch resistance, and large curling is likely to occur. Even when a triacetyl cellulose film is used as a substrate, the curable composition of the present invention exhibits the effects of high scratch resistance and transparency, and further excellent curl resistance and toughness, and can be suitably used. When the triacetyl cellulose film is used as a substrate, the coating amount in coating the curable composition of the present invention is preferably such that the film thickness after drying is in the range of 4 to 20 μm, preferably in the range of 6 to 15 μm. Examples of the coating method include: rod coater coating, meyer rod coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, screen printing, and the like.
Among the plastic films, the polyester film is, for example, polyethylene terephthalate, and the thickness thereof is generally about 100 to 300 μm. From the viewpoint of low cost and easy processing, the film is a film that can be used for various applications such as a touch panel display, but has the following characteristics: even when the coating is very soft and provided with a hard coat layer, it is difficult to sufficiently improve the scratch resistance. When the polyethylene film is used as a substrate, the coating amount in coating the curable composition of the present invention is preferably such that the film thickness after drying is in the range of 5 to 100 μm, preferably in the range of 7 to 80 μm, depending on the application. In general, when a coating material is applied at a film thickness of more than 30 μm, a large curl tends to be generated more easily than when the coating material is applied at a thin film thickness, but the curable composition of the present invention is characterized by excellent curl resistance, and therefore, even when the coating material is applied at a high film thickness of more than 30 μm, a curl is not easily generated, and the curable composition can be suitably used. Examples of the coating method include: rod coater coating, meyer rod coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, screen printing, and the like.
Among the plastic films, the polymethyl methacrylate film is generally strong to a thickness of about 100 to 2000 μm, and is therefore suitable for applications such as a front panel of a liquid crystal display, particularly for applications requiring high scratch resistance. When the polymethyl methacrylate film is used as a substrate, the amount of coating in coating the curable composition of the present invention is preferably in the range of 5 to 100 μm, preferably 7 to 80 μm, in thickness after drying, depending on the application. Generally, when a coating material is applied to a thick film such as a polymethyl methacrylate film in a film thickness of more than 30 μm, the resulting film tends to have high abrasion resistance but its transparency is rather low. Examples of the coating method include: rod coater coating, meyer rod coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, screen printing, and the like.
Among the above plastic films, it is known that a cycloolefin polymer film is generally weak against a force from a transverse direction such as a tear and is poor in folding resistance, and that a use area thereof is expanded in recent years from the viewpoint of transparency and heat resistance. The cured coating film obtained from the curable composition of the present invention is excellent in the ability to follow the film itself even in such a fragile film, and has flexibility, and therefore, cracks in the film can be effectively prevented from occurring when the film is bent. From the viewpoint of suitably exhibiting such effects, the thickness of the cured coating film is preferably adjusted within a range of 0.1 to 10 μm. Examples of the coating method include: rod coater coating, meyer rod coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, screen printing, and the like.
Examples of the active energy ray irradiated when the curable composition of the present invention is cured to form a coating film include ultraviolet rays and electron beams. When curing is performed by ultraviolet rays, an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, a metal halide lamp, an LED lamp, or the like as a light source may be used, and the light amount, the arrangement of the light source, and the like may be adjusted as necessary. When a high-pressure mercury lamp is used, it is generally preferable that 1 lamp having a light amount in the range of 80 to 160W/cm is cured at a transport speed in the range of 5 to 50 m/min. On the other hand, when curing is performed by electron beams, it is preferable to perform curing at a transport speed of 5 to 50 m/min by using an electron beam accelerator having an acceleration voltage generally in the range of 10 to 300 kV.
The substrate coated with the curable composition of the present invention can be suitably used not only as a plastic film but also as a surface coating agent for various plastic molded articles, for example, bumpers of cellular phones, household electric appliances, and automobiles. In the above case, examples of the method for forming the coating film include: coating method, transfer method, sheet bonding method, and the like.
The coating method is as follows: the coating is applied by spraying or by coating the molded article in the form of a top coat using a printing apparatus such as a curtain coater, roll coater, gravure coater or the like, and then irradiated with active energy rays to cure the article.
The transfer method may include the following methods: a method in which a transfer material is obtained by applying the curable composition of the present invention to a substrate sheet having releasability, the transfer material obtained is bonded to the surface of a molded article, the substrate sheet is peeled off, a top coat layer is transferred to the surface of the molded article, and then the substrate sheet is cured by irradiation with active energy rays; alternatively, the transfer material is adhered to the surface of a molded article, and then irradiated with active energy rays to be cured, and then the base sheet is peeled off to transfer the top coat layer to the surface of the molded article. On the other hand, the sheet bonding method is a method of: a protective sheet having a coating film formed of the curable composition of the present invention on a base sheet or a protective sheet having a coating film and a decorative layer formed of the curable composition of the present invention on a base sheet is bonded to a plastic molded article to form a protective layer on the surface of the molded article. Among them, the coating material of the present invention can be preferably used for transfer method and sheet adhesion method applications.
In the transfer method, a transfer material is first produced. The transfer material can be produced, for example, as follows: the coating material is applied to a substrate sheet alone or in a mixture with a polyisocyanate compound, and the resultant is heated to semi-cure (B-staging) the coating film. The (meth) acryloyl group-containing resin contained in the curable composition of the present invention is a compound having a hydroxyl group in the molecular structure, and therefore can be used in combination with a polyisocyanate compound for the purpose of more efficiently performing the B-staging step.
To produce a transfer material, the curable composition of the present invention is first applied to a substrate sheet. Examples of the coating method include: coating methods such as gravure coating, roll coating, spray coating, lip coating, and comma coating, printing methods such as gravure printing, and screen printing, and the like. The thickness of the coating film is preferably 0.1 to 30 μm, more preferably 1 to 6 μm, from the viewpoint of improving the abrasion resistance and the like.
After the coating material is applied to the substrate sheet in the above-described manner, the substrate sheet is heated and dried to semi-cure (B-staging) the coating film. The heating is usually 55 to 160 ℃ and preferably 100 to 140 ℃. The heating time is usually 30 seconds to 30 minutes, preferably 1 to 10 minutes, and more preferably 1 to 5 minutes.
The formation of the surface protective layer of the molded article using the transfer material is performed, for example, as follows: the transfer material is prepared by bonding the B-staged resin layer to a molded article, and then irradiating the resin layer with active energy rays to cure the resin layer. Specifically, examples thereof include: a method (transfer method) in which the resin layer is cured by irradiation with active energy rays after the resin layer is B-staged by the transfer material is bonded to the surface of the molded article and then the substrate sheet of the transfer material is peeled off to transfer the resin layer to the surface of the molded article, thereby curing the resin layer by crosslinking; a method (simultaneous molding transfer method) in which the transfer material is held in a molding die, a resin is injected into a cavity and filled with the resin to obtain a resin molded product, the transfer material is bonded to the surface of the resin molded product, the base sheet is peeled off and transferred to the molded product, and then the resin molded product is irradiated with an active energy ray to cure the resin layer by energy ray, thereby crosslinking and curing the resin layer.
Next, specific examples of the sheet adhesion method include: a method (post-bonding method) in which a base sheet of a protective layer-forming sheet prepared in advance is bonded to a molded article, and then the resultant is heated to be thermally cured, thereby crosslinking and curing a resin layer formed by B-staging; a method (simultaneous molding and bonding method) in which the protective layer-forming sheet is held in a molding die, a resin is injected into a cavity and filled to obtain a resin molded product, and the surface of the resin molded product is bonded to the protective layer-forming sheet, and then the resin layer is cured by heating and crosslinking of the resin layer.
Next, the coating film of the present invention is as follows: a coating film formed by applying and curing the curable composition of the present invention on a substrate such as the plastic film; or a coating film formed by applying and curing the curable composition of the present invention as a surface protective agent for a plastic molded article. The laminated film of the present invention is a film obtained by forming the coating film on a base film such as the plastic film. The laminated film of the present invention may have a layer structure other than the coating film formed from the curable composition of the present invention. The method for forming these various layer structures is not particularly limited, and for example, the layers may be formed by directly applying a resin material, or may be formed by bonding a sheet-shaped material formed in advance with an adhesive.
Among the various uses of the film, as described above, a film obtained by applying the curable composition of the present invention to a plastic film and irradiating the film with active energy rays is preferably used as a protective film for a polarizing plate used in a liquid crystal display, a touch panel display, and the like, from the viewpoint of excellent coating film hardness. Specifically, when a film is formed by applying the curable composition of the present invention to a protective film of a polarizing plate used in a liquid crystal display, a touch panel display, or the like and curing the applied film by irradiation with active energy rays, the cured coating film becomes a protective film having both high hardness and high transparency. In the use of the protective film for a polarizing plate, an adhesive layer may be formed on the surface opposite to the coating layer on which the curable composition of the present invention is applied.
The laminated film of the present invention can be suitably used for various applications such as surface protection films, plating substitutes, and coating substitutes for various electronic devices, home appliances, furniture, and the like, in addition to applications to display members, automobile members, and building materials.
Examples
The present invention will be described more specifically below with reference to specific production examples and examples, but the present invention is not limited to these examples. All parts and% in the examples are by mass unless otherwise specified.
In the examples of the present invention, the mass average molecular weight (Mw) is a value measured by Gel Permeation Chromatography (GPC) under the following conditions.
A measuring device; HLC-8220 made by Tosoh corporation
A column; protection column HXL-H manufactured by Tosoh corporation
+ Tosoh corporation TSKgel G5000HXL
+ Tosoh corporation TSKgel G4000HXL
+ Tosoh corporation TSKgel G3000HXL
+ Tosoh corporation TSKgel G2000HXL
A detector; RI (differential refractometer)
Data processing: SC-8010 manufactured by Tosoh corporation
The measurement conditions were as follows: column temperature 40 deg.C
Solvent tetrahydrofuran
Flow rate 1.0 ml/min
Standard; polystyrene
A sample; a tetrahydrofuran solution (0.4 mass% in terms of solid content of resin) was filtered through a microfilter to obtain a filtrate (100. mu.l)
The liquid chromatogram in this example was measured under the following conditions.
[ measurement conditions ]
The device comprises the following steps: LCMS-2010EV manufactured by Shimadzu corporation "
Data processing: LCMS Solution manufactured by Shimadzu corporation "
Column: ODS-100V (2.0 mmID. times.150 mm, 3 μm) manufactured by Tosoh corporation, 40 deg.C
Eluent: water/acetonitrile, 0.4 mL/min
A detector: PDA, MS
Sample preparation: 1. a sample (50 mg) was dissolved in acetonitrile (for LC) (10 ml)
2. Stirring with Vortex for 30 seconds
3. Standing for 30 minutes
4. The liquid was passed through a 0.2 μm filter to prepare a measurement sample
And (3) calculating the area ratio: calculation at UV wavelength 210nm
Production example 1 production of (meth) acryloyl group-containing acrylic resin (A-1)
In a reaction apparatus equipped with a stirrer, a condenser, a dropping funnel and a nitrogen gas inlet tube, 33.3 parts by mass of methyl isobutyl ketone was charged, and the temperature in the system was heated to 110 ℃ while stirring. Subsequently, a mixed solution containing 100 parts by mass of glycidyl methacrylate, 4 parts by mass of t-butylperoxy-2-ethylhexanoate ("Perbutyl O", manufactured by Nichikura oil Co., Ltd.), and 36 parts by mass of methyl isobutyl ketone was added dropwise over 4 hours. After the dropwise addition, the mixture was stirred at 110 ℃ for 10 hours to obtain an acrylic resin intermediate (1) solution containing 60 mass% of nonvolatile components. The epoxy equivalent of the acrylic resin intermediate (1) was 148 g/equivalent.
Then, 173 parts by mass of the acrylic resin intermediate (1) (in terms of resin solid content), 51 parts by mass of acrylic acid, 0.08 parts by mass of p-hydroxyanisole, 0.8 parts by mass of triphenylphosphine, and 87 parts by mass of methyl isobutyl ketone were put into a reaction apparatus equipped with a stirrer, a condenser, a dropping funnel, and an air inlet tube. The reaction mixture was heated to 105 ℃ while bubbling air through the reaction mixture, and reacted for 10 hours to obtain a solution of the (meth) acryloyl group-containing acrylic resin (A-1) having a nonvolatile content of 50.5 mass%. The (meth) acryloyl group-containing acrylic resin (A-1) had an acryloyl equivalent weight of 213 g/equivalent, a number average molecular weight (Mn) of 12000, a mass average molecular weight (Mw) of 22000, and a viscosity of 1200 mPas as measured with an E-type viscometer.
Production example 2 production of (meth) acryloyl group-containing acrylic resin (A-2)
In a reaction apparatus equipped with a stirrer, a condenser, a dropping funnel and a nitrogen gas inlet tube, 33.3 parts by mass of methyl isobutyl ketone was charged, and the temperature in the system was heated to 110 ℃ while stirring. Subsequently, a mixed solution containing 80 parts by mass of glycidyl methacrylate, 20 parts by mass of methyl methacrylate, 4 parts by mass of t-butylperoxy-2-ethylhexanoate ("Perbutyl O" manufactured by Nichikura oil Co., Ltd.) and 36 parts by mass of methyl isobutyl ketone was added dropwise over 4 hours. After the dropwise addition, the mixture was continuously stirred at 110 ℃ for 10 hours to obtain an acrylic resin intermediate (2) solution containing 60 mass% of nonvolatile components. The epoxy equivalent of the acrylic resin intermediate (2) was 185 g/equivalent.
Then, 173 parts by mass (in terms of resin solid content) of the acrylic resin intermediate (2), 41 parts by mass of acrylic acid, 0.07 part by mass of p-hydroxyanisole, 0.7 part by mass of triphenylphosphine, and 76.5 parts by mass of methyl isobutyl ketone were charged into a reaction apparatus equipped with a stirrer, a condenser, a dropping funnel, and an air inlet tube. The reaction mixture was heated to 105 ℃ while bubbling air through the reaction mixture, and reacted for 10 hours to obtain a solution of a (meth) acryloyl group-containing acrylic resin (A-2) having a nonvolatile content of 49.5 mass%. The (meth) acryloyl group-containing acrylic resin (A-2) had an acryloyl equivalent weight of 250 g/equivalent, a number average molecular weight (Mn) of 11000, a mass average molecular weight (Mw) of 20500, and a viscosity of 1080 mPas as measured with an E-type viscometer.
Production example 3 production of (meth) acryloyl group-containing acrylic resin (A-3)
In a reaction apparatus equipped with a stirring device, a condenser tube, a dropping funnel and a nitrogen gas inlet tube, 40 parts by mass of methyl isobutyl ketone was charged, and the temperature in the system was heated to 110 ℃ while stirring. Subsequently, a mixed solution containing 60 parts by mass of glycidyl methacrylate, 40 parts by mass of methyl methacrylate, 8 parts by mass of t-butylperoxy-2-ethylhexanoate ("Perbutyl O" manufactured by Nichikura oil Co., Ltd.) and 32 parts by mass of methyl isobutyl ketone was added dropwise over 4 hours. After the dropwise addition, the mixture was stirred at 110 ℃ for 10 hours to obtain an acrylic resin intermediate (3) solution containing 60 mass% of nonvolatile components. The epoxy equivalent of the acrylic resin intermediate (3) was 256 g/equivalent.
Then, 180 parts by mass (in terms of resin solid content) of the acrylic resin intermediate (3), 30.8 parts by mass of acrylic acid, 0.07 part by mass of p-hydroxyanisole, 0.7 part by mass of triphenylphosphine, and 80.8 parts by mass of methyl isobutyl ketone were put into a reaction apparatus equipped with a stirrer, a condenser, a dropping funnel, and an air inlet tube. The reaction mixture was heated to 105 ℃ while bubbling air through the reaction mixture, and reacted for 10 hours to obtain a solution of a (meth) acryloyl group-containing acrylic resin (A-3) having a nonvolatile content of 49.8 mass%. The (meth) acryloyl group-containing acrylic resin (A-3) had an acryloyl equivalent weight of 313 g/equivalent, a number average molecular weight (Mn) of 4200, a mass average molecular weight (Mw) of 8400, and a viscosity of 360 mPas as measured with an E-type viscometer.
Production example 4 production of (meth) acryloyl group-containing acrylic resin (A-4)
In a reaction apparatus equipped with a stirrer, a condenser, a dropping funnel and a nitrogen gas inlet tube, 46.6 parts by mass of methyl isobutyl ketone was charged, and the temperature in the system was heated to 110 ℃ while stirring. Subsequently, a mixed solution containing 40 parts by mass of glycidyl methacrylate, 60 parts by mass of methyl methacrylate, 2 parts by mass of t-butylperoxy-2-ethylhexanoate ("Perbutyl O" manufactured by Nichikura oil Co., Ltd.) and 18 parts by mass of methyl isobutyl ketone was added dropwise over 4 hours. After the dropwise addition, the mixture was stirred at 110 ℃ for 10 hours to obtain an acrylic resin intermediate (4) solution containing 60 mass% of nonvolatile components. The epoxy equivalent of the acrylic resin intermediate (4) was 362 g/equivalent.
Then, 167 parts by mass of the acrylic resin intermediate (4) (in terms of resin solid content), 41 parts by mass of acrylic acid, 0.06 part by mass of p-hydroxyanisole, 0.6 part by mass of triphenylphosphine, and 55.2 parts by mass of methyl isobutyl ketone were put into a reaction apparatus equipped with a stirrer, a condenser, a dropping funnel, and an air inlet tube. The reaction mixture was heated to 105 ℃ while bubbling air through the reaction mixture, and reacted for 10 hours to obtain a solution of a (meth) acryloyl group-containing acrylic resin (A-4) having a nonvolatile content of 50.2 mass%. The (meth) acryloyl group-containing acrylic resin (A-4) had an acryloyl equivalent weight of 417 g/equivalent, a number average molecular weight (Mn) of 5200, a mass average molecular weight (Mw) of 24700, and a viscosity of 15200 mPas as measured with an E-type viscometer.
Production example 5 production of (meth) acryloyl group-containing acrylic resin (A-5)
In a reaction apparatus equipped with a stirring device, a condenser tube, a dropping funnel and a nitrogen gas inlet tube, 73 parts by mass of methyl isobutyl ketone was charged, and the temperature in the system was heated to 110 ℃ while stirring. Subsequently, a mixed solution containing 50 parts by mass of methacrylic acid, 50 parts by mass of methyl methacrylate, 9 parts by mass of t-butylperoxy-2-ethylhexanoate ("Perbutyl O" manufactured by Nichiyan oil Co., Ltd.) and 35 parts by mass of methyl isobutyl ketone was added dropwise over 4 hours. After the dropwise addition, the mixture was stirred at 110 ℃ for 10 hours to obtain an acrylic resin intermediate (5) solution containing 60 mass% of nonvolatile components. The acid value of the acrylic resin intermediate (5) was 300 mgKOH/g.
Then, 217 parts by mass (in terms of resin solid content) of the acrylic resin intermediate (5), 83.3 parts by mass of glycidyl methacrylate, 0.09 part by mass of p-hydroxyanisole, 0.37 part by mass of triphenylphosphine, and 75.2 parts by mass of methyl isobutyl ketone were put into a reaction apparatus equipped with a stirrer, a condenser, a dropping funnel, and an air inlet tube. The reaction mixture was heated to 105 ℃ while bubbling air through the reaction mixture, and reacted for 10 hours to obtain a solution of a (meth) acryloyl group-containing acrylic resin (A-5) having a nonvolatile content of 49.1 mass%. The (meth) acryloyl group-containing acrylic resin (A-5) had a methacryloyl equivalent weight of 313 g/equivalent, a number average molecular weight (Mn) of 6700, a mass average molecular weight (Mw) of 14000, and a viscosity of 960 mPas as measured with an E-type viscometer.
Production example 6 production of (meth) acrylate (B-1) of dipentaerythritol
In a flask equipped with a thermometer, a stirrer, and a condenser, 400 parts by mass of acrylic acid, 180 parts by mass of dipentaerythritol, 15 parts by mass of sulfuric acid, 1.5 parts by mass of copper chloride, and 300 parts by mass of toluene were charged. The reaction mixture was heated to 105 ℃ with stirring, and reacted at 105 ℃ for 18 hours while refluxing in the system. The amount of water produced in the reaction was 71.8 parts by mass. 425 parts by mass of toluene were added to the reaction mixture, and the solution was washed with 200 parts by mass of distilled water. Further, the reaction mixture was neutralized by adding a 20% aqueous sodium hydroxide solution, and washed with 100 parts by mass of distilled water. Hydroquinone monomethyl ether was added in an amount of 500ppm based on the solid content of the resin, and the toluene was distilled off to obtain a product containing (meth) acrylate (B-1) of dipentaerythritol. The hydroxyl value of the product measured in accordance with JIS K0070 was 42mgKOH/g, the content of dipentaerythritol pentaacrylate calculated from the area ratio of the liquid chromatogram was 40.2%, the content of dipentaerythritol hexaacrylate was 50.7%, and the content of other high-molecular weight components was 9.1%. The hydroxyl value of the (meth) acrylate ester of dipentaerythritol (B-1) calculated from the content ratios of the respective components was 47.9 mgKOH/g.
Production example 7 production of (meth) acrylate (B-2) of dipentaerythritol
In a flask equipped with a thermometer, a stirrer, and a condenser, 300 parts by mass of acrylic acid, 180 parts by mass of dipentaerythritol, 15 parts by mass of sulfuric acid, 1.5 parts by mass of copper chloride, and 300 parts by mass of toluene were charged. The mixture was heated to 105 ℃ with stirring, and reacted at the same temperature for 12 hours while refluxing in the system. 68.5 parts by mass of water produced in the reaction. 425 parts by mass of toluene were added to the reaction mixture, and the solution was washed with 200 parts by mass of distilled water. Further, the reaction mixture was neutralized by adding a 20% aqueous solution of sodium hydroxide, and washed with 100 parts by mass of distilled water. Hydroquinone monomethyl ether was added in an amount of 500ppm based on the solid content of the resin, and the toluene was distilled off to obtain a product containing (meth) acrylate (B-2) of dipentaerythritol. The hydroxyl value of the product measured in accordance with JIS K0070 was 88mgKOH/g, the content of dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate and other high-molecular weight components were 7.2%, 48.3%, 30.7% and 13.8%, respectively, as calculated from the area ratio of the liquid chromatogram. The hydroxyl value of the (meth) acrylate ester of dipentaerythritol (B-2) calculated from the content ratios of the respective components was 79.9 mgKOH/g.
Production example 8 production of (meth) acrylate ester of dipentaerythritol (B-3)
Into a flask equipped with a thermometer, a stirrer, and a condenser, 250 parts by mass of acrylic acid, 180 parts by mass of dipentaerythritol, 15 parts by mass of sulfuric acid, 1.5 parts by mass of copper chloride, and 300 parts by mass of toluene were charged. The reaction mixture was heated to 105 ℃ with stirring, and reacted at 105 ℃ for 9 hours while refluxing in the system. 68.5 parts by mass of water produced in the reaction. 425 parts by mass of toluene were added to the reaction mixture, and the solution was washed with 200 parts by mass of distilled water. Further, the reaction mixture was neutralized by adding a 20% aqueous solution of sodium hydroxide, and washed with 100 parts by mass of distilled water. Hydroquinone monomethyl ether was added in an amount of 500ppm based on the solid content of the resin, and the toluene was distilled off to obtain a product containing (meth) acrylic acid esterified product of dipentaerythritol (B-3). The hydroxyl value of the product measured in accordance with JIS K0070 was 130mgKOH/g, the content of dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate and other high molecular weight components calculated from the area ratio of the liquid chromatogram was 15%, 60%, 15% and 10%, respectively. The hydroxyl value of the (meth) acrylate ester of dipentaerythritol (B-3) calculated from the content ratios of the respective components was 111.2 mgKOH/g.
Examples 1 to 18 and comparative example 1
The respective components were mixed at the ratios shown in tables 1 and 2, and the nonvolatile content was adjusted to 30% by mass with methyl ethyl ketone to obtain a curable composition. Various evaluation tests were carried out on the obtained curable composition in the following manner. The results are shown in tables 1 and 2.
In addition, the components (A-1) to (A-5): (meth) acryloyl group-containing acrylic resins (A-1) to (A-5) obtained in production examples 1 to 5
In addition, the components (B-1) to (B-3): production of (meth) acrylic acid esters of dipentaerythritol (B-1) to (B-3) obtained in production examples 6 to 8
Additionally, PETA: "M-305" manufactured by Toyo Synthesis K.K. contains pentaerythritol triacrylate and pentaerythritol tetraacrylate as an acrylate compound of pentaerythritol in a mass ratio of 6/4
The photopolymerization initiator: irgacure #184 from BASF Corporation "
Calculation of (meth) acryloyl group content
The (meth) acryloyl group content in the total of the (meth) acryloyl group-containing compound components of the curable composition was calculated based on the reaction raw material charge ratio and the blending ratio of each component.
Production of laminated film
The curable composition was applied to a polyethylene terephthalate (PET) film (80 μm in thickness) by a bar coater so that the cured film thickness became 5 μm, and dried at 80 ℃ for 1 minute. Under nitrogen atmosphere, using high-pressure mercury lamp at 200mJ/cm2The irradiation amount of (3) is passed through the substrate and cured to obtain a laminated film.
Evaluation of surface hardness of laminated film
The pencil hardness of the coated film surface side was measured under a load of 500g in accordance with JIS K5600-5-4. The hardness of the cured coating film was measured 5 times for each 1 hardness, and the hardness of the cured coating film was measured 4 or more times without scratching.
A: 2H or more
B: below 2H
Scratch resistance test of laminated film
A disk-shaped indenter having a diameter of 2.4 cm was covered with 0.5g of Steel Wool ("Bon Star # 0000" manufactured by ltd) and subjected to a wear test of 10 times of reciprocation on the coating surface of the laminated film by applying a load of 500g to the indenter. Haze values of the laminated films before and after the abrasion Test were measured by Suga Test Instruments Co., Ltd. "Haze computer HZ-2" manufactured by Ltd. the Haze values were evaluated as a difference value (dH) therebetween.
A: 1.0 or less
B: 3.0 or less
C: less than 10
D: more than 10
Flexibility test
The laminated film was wound around a test rod using a mandrel tester (a "bending tester" manufactured by TP technical research corporation) to perform a test for visually checking whether cracks or peeling occurred, and the minimum diameter of the test rod in which cracks or peeling did not occur was used as an evaluation result. The test rods were used at intervals of 1mm from 2mm in diameter to 10mm in diameter.
Curl resistance test
A 10cm square coating film was cut out from the laminated film to obtain a test piece, and the floating from the horizontal at 4 corners was measured for the test piece to evaluate the average value (mm). The smaller the value, the smaller the curl, and the more excellent the curl resistance.
Evaluation of adhesion
The following tests were carried out: the laminated film was stored at room temperature of 85 ℃ and humidity of 85% RH for 250 hours. Then, cuts were made at intervals of 1mm on the coating film surface side of the laminated film in a 10 × 10 mesh pattern by a cutter knife to prepare 100 meshes. Then, after the cellophane tape was adhered to the mesh, the tape was peeled off at a high speed, and the number of the non-peeled ones in 100 meshes was evaluated.
A: more than 95
B: more than 80
C: more than 60
D: less than 60
[ Table 1]
Figure BDA0002314914680000321
[ Table 2]
Figure BDA0002314914680000331

Claims (5)

1. A curable composition characterized by containing: an acrylic resin (A) containing a (meth) acryloyl group and a (meth) acrylate (B) of dipentaerythritol,
the hydroxyl value of the (meth) acrylic acid esterified product (B) of dipentaerythritol is in the range of 40 to 140mgKOH/g,
80% by mass or more of the reaction raw materials of the (meth) acryloyl group-containing acrylic resin (A) is a (meth) acrylate monomer containing no aromatic ring,
the total content of the (meth) acryloyl group-containing acrylic resin (a) and the (meth) acrylate (B) of dipentaerythritol is 70 mass% or more of the total of the (meth) acryloyl group-containing compound components contained in the curable composition.
2. The curable composition according to claim 1, wherein the (meth) acryloyl group content in the total of the (meth) acryloyl group-containing compound components is in the range of 3.8 to 8.5 mmol/g.
3. The curable composition according to claim 1, wherein the mass ratio [ (A)/(B) ] of the (meth) acryloyl group-containing acrylic resin (A) to the (meth) acrylate (B) of dipentaerythritol is in the range of 30/70 to 99/1.
4. A coating film formed from the curable composition according to any one of claims 1 to 3.
5. A laminated film having a layer comprising the coating film of claim 4.
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