CN110382575B - Active energy ray-curable resin composition and coating agent - Google Patents

Active energy ray-curable resin composition and coating agent Download PDF

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CN110382575B
CN110382575B CN201880014095.9A CN201880014095A CN110382575B CN 110382575 B CN110382575 B CN 110382575B CN 201880014095 A CN201880014095 A CN 201880014095A CN 110382575 B CN110382575 B CN 110382575B
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acrylate
mixture
urethane
composition
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CN110382575A (en
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石川祐太
神田幸宗
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Mitsubishi Chemical 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
    • C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings

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  • Polyurethanes Or Polyureas (AREA)
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Abstract

The invention provides an active energy ray-curable resin composition, which contains a urethane (methyl) acrylate composition with small curing shrinkage, difficult curling and capability of forming a cured coating film with excellent hardness and bending property; the active energy ray-curable resin composition contains a urethane (meth) acrylate composition [ I ] which is produced by reacting a hydroxyl group of a (meth) acrylate in a mixture (A) with an isocyanate group of a polyisocyanate (CA), wherein the mixture (A) is a mixture of (meth) acrylates which are a reaction product of pentaerythritol and (meth) acrylic acid, and wherein the hydroxyl value of the mixture (A) is 200mgKOH/g or more.

Description

Active energy ray-curable resin composition and coating agent
Technical Field
The present invention relates to an active energy ray-curable resin composition containing a urethane (meth) acrylate composition and a coating agent, and more particularly, to an active energy ray-curable resin composition which is less likely to curl due to small curing shrinkage when a cured coating film is formed, and which is capable of forming a coating film having further excellent hardness and bendability, and a coating agent using the same.
Background
Conventionally, active energy ray-curable resin compositions have been widely used as coating agents, adhesives, anchor coating agents, and the like for various substrates because they can be cured by irradiation with active energy rays such as extremely short-time radiation and ultraviolet rays, and urethane (meth) acrylate compounds and polyfunctional monomers have been used as curing components thereof. However, when the active energy ray-curable resin composition is used as a coating agent, particularly a coating agent for hard coating, there is a problem that curing shrinkage of a coating film occurs and the cured coating film is liable to curl, and it is desired that curling is not liable to occur.
Further, since the coating agent for hard coating is used as a protective film also in a curved portion of a molded article, a display, or the like, a plastic film having a cured coating film formed thereon is required to have bendability in which cracks and the like are less likely to occur even when the plastic film is curved.
In order to suppress the curing shrinkage in view of the above-mentioned phenomenon of being less likely to curl, it has been proposed that: a curable resin composition containing inorganic fine particles added to a curable resin (see, for example, patent document 1), a curable resin composition containing a urethane (meth) acrylate having a high molecular weight as a curing component (see, for example, patent document 2), and a curable resin composition containing a urethane (meth) acrylate produced by reacting a hydroxyl group in a (meth) acrylic acid adduct of pentaerythritol having a hydroxyl value of 130mgKOH/g or more with an isocyanate group of a polyisocyanate compound (see, for example, patent document 3).
As a method for improving scratch resistance and increasing hardness of a hard coat layer, for example, a technique is known in which a resin composition containing dipentaerythritol hexaacrylate and tripentaerythritol octaacrylate is applied to a triacetylcellulose film having a thickness of 80 μm in a thickness of 12 μm and cured to obtain a film having a pencil hardness of about 5H (see, for example, patent document 4).
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2010-77292
Patent document 2: japanese patent application laid-open No. 2010-180319
Patent document 3: japanese patent laid-open No. 2012-229412
Patent document 4: japanese patent laid-open No. 2009-286924
Disclosure of Invention
Problems to be solved by the invention
However, the technique disclosed in patent document 1 is limited in the use of organic solvents that can be used in consideration of compatibility between inorganic fine particles and curable resins, or in the case where the possibility of abnormality occurring on the surface of a coating film is high, or in general, inorganic fine particles are expensive, so that resins and coatings containing inorganic fine particles are also expensive, and the use application of curable resins is limited to special applications in reality.
In addition, the technique disclosed in patent document 2 has a multistage reaction in the production process for increasing the molecular weight of urethane (meth) acrylate used as a curing component, which makes the operation complicated and reduces the abrasion resistance of the coating film.
On the other hand, in the technique disclosed in patent document 3, a cured coating film with suppressed curling due to reduced curing shrinkage can be obtained, but this technique is insufficient from the viewpoint of hardness.
In addition, the technique disclosed in patent document 4 has high surface hardness of the cured coating film, but the cured coating film has large curl and is hard and brittle, and therefore cracks occur when the coating film is bent.
The present invention provides an active energy ray-curable resin composition containing a urethane (meth) acrylate composition which is less likely to curl due to small curing shrinkage when a cured coating film is formed and which can form a coating film having excellent hardness and bendability, and a coating agent using the same.
Means for solving the problems
The present inventors have made diligent studies in view of the above circumstances, and as a result, have found that: by using the urethane (meth) acrylate composition as a curing component, a cured coating film which is less likely to curl due to a small curing shrinkage and is excellent in hardness and bendability can be obtained; the urethane (meth) acrylate composition is produced by reacting a reaction product of at least one of pentaerythritol and dipentaerythritol and (meth) acrylic acid with a hydroxyl value in a specific range, and reacting the hydroxyl group of the (meth) acrylate in the reaction product with a polyisocyanate.
That is, the invention of claim 1 relates to an active energy ray-curable resin composition containing a urethane (meth) acrylate composition [ I ] obtained by reacting (meth) acrylates (a 1) to (a 3) in a mixture (A) of the following (meth) acrylates (a 1) to (a 4) as a reaction product of pentaerythritol and (meth) acrylic acid with a polyisocyanate (CA),
the mixture (A) has a hydroxyl value of 200mgKOH/g or more;
mixture (A)
(a1) Pentaerythritol mono (meth) acrylate
(a2) Pentaerythritol di (meth) acrylate
(a3) Pentaerythritol tri (meth) acrylate
(a4) Pentaerythritol tetra (meth) acrylate.
The invention also relates to the 2 nd embodiment of the invention to an active energy ray-curable resin composition containing the urethane (meth) acrylate composition [ I ] and the urethane (meth) acrylate composition [ II ],
the urethane (meth) acrylate composition [ II ] is obtained by reacting (meth) acrylates (B1) to (B5) in a mixture (B) of the following (meth) acrylates (B1) to (B6) as a reaction product of dipentaerythritol and (meth) acrylic acid with a polyisocyanate (CB),
the mixture (B) has a hydroxyl value of 40mgKOH/g or more;
mixture (B)
(b1) Dipentaerythritol mono (meth) acrylate
(b2) Dipentaerythritol di (meth) acrylate
(b3) Dipentaerythritol tri (meth) acrylate
(b4) Dipentaerythritol tetra (meth) acrylate
(b5) Dipentaerythritol penta (meth) acrylate
(b6) Dipentaerythritol hexa (meth) acrylate.
The invention also relates to the active energy ray-curable resin composition according to claim 3, which comprises the urethane (meth) acrylate composition [ III ],
the urethane (meth) acrylate composition [ III ] is obtained by reacting (meth) acrylates (a 1) to (a 3) as [ alpha ] below, (meth) acrylates (b 1) to (b 5) as [ beta ] below, and a polyisocyanate (CC);
[ α ] the (meth) acrylic esters (a 1) to (a 3) in a mixture (A) of the following (meth) acrylic esters (a 1) to (a 4) as a reaction product of pentaerythritol and (meth) acrylic acid, and the mixture (A) having a hydroxyl value of 200mgKOH/g or more;
(a1) Pentaerythritol mono (meth) acrylate
(a2) Pentaerythritol di (meth) acrylate
(a3) Pentaerythritol tri (meth) acrylate
(a4) Pentaerythritol tetra (meth) acrylate
[ beta ] the (meth) acrylic esters (B1) to (B5) in a mixture (B) of the following (meth) acrylic esters (B1) to (B6) which is a reaction product of dipentaerythritol and (meth) acrylic acid, and the mixture (B) having a hydroxyl value of 40mgKOH/g or more;
(b1) Dipentaerythritol mono (meth) acrylate
(b2) Dipentaerythritol di (meth) acrylate
(b3) Dipentaerythritol tri (meth) acrylate
(b4) Dipentaerythritol tetra (meth) acrylate
(b5) Dipentaerythritol penta (meth) acrylate
(b6) Dipentaerythritol hexa (meth) acrylate.
The present invention also provides a coating agent containing the active energy ray-curable resin composition.
ADVANTAGEOUS EFFECTS OF INVENTION
The active energy ray-curable resin composition according to the first aspect of the present invention is less likely to curl due to small curing shrinkage, can form a cured coating film having excellent hardness and bendability, can form a non-tacky coating film surface even in a coating film before curing, and is particularly useful in various applications such as a coating agent for hard coating.
The active energy ray-curable resin composition according to claim 2 of the present invention is less likely to curl due to a small cure shrinkage, and can form a cured coating film having excellent hardness and bendability, and is particularly useful for various applications such as a coating agent for hard coating.
Further, the active energy ray-curable resin composition according to claim 3 of the present invention is less likely to curl due to a small cure shrinkage, and can form a cured coating film excellent in hardness, bendability and abrasion resistance, and is particularly useful for various applications such as a coating agent for hard coating.
When the content ratio of the pentaerythritol di (meth) acrylate (a 2) in the mixture (a) of the (meth) acrylic esters (a 1) to (a 4) is 10 to 50% by weight, the composition is excellent in terms of both hardness and bendability.
The content ratio of the pentaerythritol di (meth) acrylate (a 2) to the total amount of the (meth) acrylates (a 1) to (a 3) is preferably 15 to 55% by weight from the viewpoint of achieving both hardness and bendability.
The urethane (meth) acrylate composition [ I ] has a weight average molecular weight of 1000 to 20000, and is excellent in ease of handling of the active energy ray-curable resin composition.
When the content ratio of the dipentaerythritol penta (meth) acrylate (B5) in the mixture (B) of the (meth) acrylic esters (B1) to (B6) is 15 to 60% by weight, the composition is more excellent in terms of satisfying both hardness and bendability.
When the content ratio of dipentaerythritol penta (meth) acrylate (b 5) to the total amount of the (meth) acrylates (b 1) to (b 5) is 45 to 90% by weight, the composition is more excellent in terms of both solid hardness and bendability.
The mixture (B) of the (meth) acrylic esters (B1) to (B6) has a content of dipentaerythritol tetra (meth) acrylate (B4) of 1 to 35% by weight, and thus has excellent bendability.
When the content ratio of dipentaerythritol tetra (meth) acrylate (b 4) to the total amount of the (meth) acrylates (b 1) to (b 5) is 2 to 40% by weight, the flexibility is more excellent.
When the weight average molecular weight of the urethane (meth) acrylate composition [ II ] is 1000 to 20000, the handling ease of the active energy ray-curable resin composition is excellent.
When the weight average molecular weight of the urethane (meth) acrylate composition [ III ] is 1000 to 20000, the handling ease of the active energy ray-curable resin composition is further excellent.
Detailed Description
The present invention is described in detail below.
In the present invention, the (meth) acrylic group means an acrylic group or a methacrylic group, the (meth) acryloyl group means an acryloyl group or a methacryloyl group, and the (meth) acrylate means an acrylate or a methacrylate.
The active energy ray-curable resin composition of the present invention is characterized by containing 3 types of urethane (meth) acrylate compositions selected from the group consisting of the following urethane (meth) acrylate compositions [ I ], the urethane (meth) acrylate compositions [ I ] and [ II ], and the urethane (meth) acrylate composition [ III ].
The urethane (meth) acrylate composition [ I ] is obtained by reacting (meth) acrylates (a 1) to (a 3) in a mixture (a) of the following (meth) acrylates (a 1) to (a 4) as a reaction product of pentaerythritol and (meth) acrylic acid, and the mixture (a) has a hydroxyl value of 200mgKOH/g or more, with a polyisocyanate (CA).
Mixture (A)
(a1) Pentaerythritol mono (meth) acrylate
(a2) Pentaerythritol di (meth) acrylate
(a3) Pentaerythritol tri (meth) acrylate
(a4) Pentaerythritol tetra (meth) acrylate.
The urethane (meth) acrylate composition [ II ] is obtained by reacting (meth) acrylates (B1) to (B5) in a mixture (B) of the following (meth) acrylates (B1) to (B6) which is a reaction product of dipentaerythritol and (meth) acrylic acid, with a polyisocyanate (CB), and the mixture (B) has a hydroxyl value of 40mgKOH/g or more.
Mixture (B)
(b1) Dipentaerythritol mono (meth) acrylate
(b2) Dipentaerythritol di (meth) acrylate
(b3) Dipentaerythritol tri (meth) acrylate
(b4) Dipentaerythritol tetra (meth) acrylate
(b5) Dipentaerythritol penta (meth) acrylate
(b6) Dipentaerythritol hexa (meth) acrylate.
The urethane (meth) acrylate composition [ III ] is obtained by reacting (meth) acrylates (a 1) to (a 3) as the following [ α ], (meth) acrylates (b 1) to (b 5) as the following [ β ], and a polyisocyanate (CC).
[ alpha ] the (meth) acrylic esters (a 1) to (a 3) in a mixture (A) of the following (meth) acrylic esters (a 1) to (a 4) which are reaction products of pentaerythritol and (meth) acrylic acid, and the mixture (A) has a hydroxyl value of 200mgKOH/g or more.
(a1) Pentaerythritol mono (meth) acrylate
(a2) Pentaerythritol di (meth) acrylate
(a3) Pentaerythritol tri (meth) acrylate
(a4) Pentaerythritol tetra (meth) acrylate.
[ beta ] the (meth) acrylic esters (B1) to (B5) in a mixture (B) of the following (meth) acrylic esters (B1) to (B6) which is a reaction product of dipentaerythritol and (meth) acrylic acid, and the mixture (B) has a hydroxyl value of 40mgKOH/g or more.
(b1) Dipentaerythritol mono (meth) acrylate
(b2) Dipentaerythritol di (meth) acrylate
(b3) Dipentaerythritol tri (meth) acrylate
(b4) Dipentaerythritol tetra (meth) acrylate
(b5) Dipentaerythritol penta (meth) acrylate
(b6) Dipentaerythritol hexa (meth) acrylate.
< urethane (meth) acrylate composition [ I ] >
First, the urethane (meth) acrylate composition [ I ] will be described.
In the present invention, the hydroxyl value of the mixture (A) of the (meth) acrylic esters (a 1) to (a 4) obtained by reacting pentaerythritol and (meth) acrylic acid is preferably 200mgKOH/g or more, more preferably 210 to 380mgKOH/g, and still more preferably 230 to 320mgKOH/g.
When the hydroxyl value of the mixture (a) is too small, the weight average molecular weight of the urethane (meth) acrylate composition [ III ] decreases, and therefore curing shrinkage during curing increases, which tends to make the composition more likely to curl and to reduce bendability. In general, if the hydroxyl value is excessively increased, the viscosity tends to be increased with an increase in molecular weight, and the handling tends to be difficult.
In the present invention, the hydroxyl value can be determined by the method in accordance with JIS K0070 1992.
In the present invention, if the content ratio of the pentaerythritol di (meth) acrylate (a 2) in the mixture (a) of the (meth) acrylic esters (a 1) to (a 4) is 10 to 50% by weight, it is preferable from the viewpoint of satisfying both hardness and bendability, and it is more preferably 15 to 45% by weight, and still more preferably 20 to 40% by weight. If the content ratio is too small, the bendability tends to be low, and if it is too large, the hardness tends to be low or the viscosity tends to be high.
When the content of the pentaerythritol di (meth) acrylate (a 2) relative to the total amount of the (meth) acrylates (a 1) to (a 3) is 15 to 55% by weight, it is preferable from the viewpoint of satisfying both hardness and bendability, and it is more preferably 20 to 50% by weight, and still more preferably 25 to 45% by weight. If the content ratio is too small, bendability tends to decrease, and if it is too large, hardness tends to decrease or viscosity tends to increase.
In the present invention, the (meth) acrylic acid adduct of pentaerythritol is produced by reacting pentaerythritol with (meth) acrylic acid, but the reaction of pentaerythritol with (meth) acrylic acid can be carried out by a known and ordinary method. In this reaction, a mixture (a) of pentaerythritol mono (meth) acrylate (a 1) to which 1 (meth) acrylic acid is added, pentaerythritol di (meth) acrylate (a 2) to which 2 (meth) acrylic acids are added, pentaerythritol tri (meth) acrylate (a 3) to which 3 (meth) acrylic acids are added, and pentaerythritol tetra (meth) acrylate (a 4) to which 4 (meth) acrylic acids are added is obtained, and a mixture (a) having the above-mentioned hydroxyl value is obtained as a whole.
The mixture (a) may contain a side reaction product such as a michael adduct of acrylic acid.
The hydroxyl value can be adjusted by adjusting the content ratio of the (meth) acrylic esters (a 1) to (a 4), for example.
In the present invention, the polyisocyanate (CA) is reacted with the (meth) acrylic esters (a 1) to (a 3), and specific examples thereof include: aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, phenylene diisocyanate and naphthalene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate and lysine triisocyanate; alicyclic polyisocyanates such as hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, and norbornene diisocyanate; and trimer compounds or multimer compounds of these polyisocyanates, urethane (allophanate) polyisocyanates, biuret polyisocyanates, and water-dispersible polyisocyanates (for example, "Aquanate 105", "Aquanate 120", and "Aquanate 210" manufactured by Tosoh corporation). These can be used alone or in combination of 2 or more.
Among these, the alicyclic polyisocyanate and the aromatic polyisocyanate are preferable from the viewpoint of strength, and isophorone diisocyanate, hydrogenated xylylene diisocyanate, and toluene diisocyanate are more preferable.
In the present invention, the urethane (meth) acrylate composition [ I ] is obtained by reacting the hydroxyl groups of the (meth) acrylates (a 1) to (a 3) in the mixture (a) of the (meth) acrylates (a 1) to (a 4) with the isocyanate groups of the polyisocyanate (CA). In this case, the urethane (meth) acrylate composition [ I ] contains a reaction product of the (meth) acrylate (a 1) and the polyisocyanate (CA), a reaction product of the (meth) acrylate (a 2) and the polyisocyanate (CA), and a reaction product of the (meth) acrylate (a 3) and the polyisocyanate (CA), and further contains an unreacted product of the (meth) acrylates (a 1) to (a 3), an unreacted (meth) acrylate (a 4), and the like.
The reaction of the (meth) acrylic esters (a 1) to (a 3) with the polyisocyanate (CA) can be carried out by adjusting the molar ratio of the hydroxyl group to the functional group of the isocyanate group, and if necessary, can be carried out by using a reaction catalyst described later.
The molar ratio of the reaction between the polyisocyanate (CA) and the feed of the mixture (a) of (meth) acrylic esters (a 1) to (a 4) is such that when the polyisocyanate (CA) has 2 isocyanate groups, the polyisocyanate (CA): the (meth) acrylate mixture (a) is preferably 1:1 to 1:5, more preferably 1:1 to 1:3, more preferably 1:1 to 1:2.
when the ratio of the mixture (a) is too large, the amount of the low-molecular-weight monomer increases, and curing shrinkage increases, so that curling tends to increase, and when the ratio of the mixture (a) is too small, unreacted polyisocyanate (CA) remains, and stability and safety of a cured coating film tend to decrease.
The reaction of the (meth) acrylic esters (a 1) to (a 3) in the (meth) acrylic ester mixture (A) with the polyisocyanate (CA) may be carried out by feeding the mixture (A) and the polyisocyanate (CA) to a reactor all at once or separately and reacting them.
Among the above reactions, a catalyst is also preferably used for promoting the reaction, and examples of the catalyst include: organic metal compounds such as dibutyltin dilaurate, dibutyltin diacetate, trimethyltin hydroxide, tetra-n-butyltin, zinc bisacetylacetonate, zirconium tris (acetylacetonate) ethylacetoacetate, and zirconium tetraacetylacetonate; metal salts such as tin octylate, zinc caproate, zinc octylate, zinc stearate, zirconium 2-ethylhexanoate, cobalt naphthenate, stannous chloride (II), tin tetrachloride (IV), potassium acetate, and the like; amine catalysts such as triethylamine, triethylenediamine, benzyldiethylamine, 1, 4-diazabicyclo [2, 2] octane, 1, 8-diazabicyclo [5,4,0] undecene, N, N, N ', N' -tetramethyl-1, 3-butanediamine, N-methylmorpholine and N-ethylmorpholine; bismuth nitrate, bismuth bromide, bismuth iodide, bismuth sulfide and the like, as well as organic bismuth compounds such as dibutyl bismuth dilaurate and dioctyl bismuth dilaurate, bismuth 2-ethylhexanoate, bismuth naphthenate, bismuth isodecanoate, bismuth neodecanoate, bismuth laurate, bismuth maleate, bismuth stearate, bismuth oleate, bismuth linoleate (linoleic acid) salt, bismuth acetate, bismuth neodecanoate, bismuth disalicylate, bismuth digallate and other organic acid bismuth salts, and the like, and among them, dibutyl tin dilaurate and 1, 8-diazabicyclo [5,4,0] undecene are preferable. These can be used alone or in combination of 2 or more.
In the above reaction, it is more preferable to further use a polymerization inhibitor. The polymerization inhibitor may be any of the known and common polymerization inhibitors, and examples thereof include: quinones such as p-benzoquinone, naphthoquinone, toluquinone, 2, 5-diphenyl-p-benzoquinone, hydroquinone, 2, 5-di-t-butylhydroquinone, methylhydroquinone, and mono-t-butylhydroquinone; aromatic compounds such as 4-methoxyphenol and 2, 6-di-t-butylcresol; p-tert-butylcatechol, and the like. Among these, aromatic compounds are preferable, and 4-methoxyphenol and 2, 6-di-tert-butylcresol are more preferable. These may be used alone or in combination of 2 or more.
In addition, in the above reaction, an organic solvent having no functional group reactive to an isocyanate group may be used, for example: esters such as ethyl acetate and butyl acetate; ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic organic solvents such as toluene and xylene. These may be used alone or in combination of 2 or more.
The reaction temperature is usually 30 to 90 ℃, more preferably 40 to 80 ℃, and the reaction time is usually 4 to 72 hours, more preferably 8 to 48 hours.
In this way, the urethane (meth) acrylate-based composition [ I ] used in the present invention can be obtained.
The weight average molecular weight of the urethane (meth) acrylate composition [ I ] is preferably 1000 to 20000, more preferably 2000 to 18000, and still more preferably 3000 to 16000. When the weight average molecular weight is too small, the cured coating film tends to become brittle, and when it is too large, the viscosity tends to increase, making handling difficult.
The weight average molecular weight is measured by using high performance liquid chromatography (available APC system, manufactured by watty) with 1 available APC XT 450, 1 available APC XT 200, 2 available APC XT 45, and a total of 4 columns connected in series as a column, the weight average molecular weight being obtained by converting the weight average molecular weight of standard polystyrene.
The content of the urethane (meth) acrylate in the urethane (meth) acrylate composition [ I ] is more preferably 50% by weight or more, still more preferably 60% by weight or more, still more preferably 70% by weight or more, and particularly preferably 80% by weight or more. The upper limit is usually 95% by weight.
< urethane (meth) acrylate composition [ II ]
Next, the urethane (meth) acrylate composition [ II ] will be described.
In the present invention, the hydroxyl value of the mixture (B) of the (meth) acrylic esters (B1) to (B6) obtained by reacting dipentaerythritol with (meth) acrylic acid is preferably 40mgKOH/g or more, more preferably 43 to 130mgKOH/g, still more preferably 45 to 125mgKOH/g, and yet more preferably 70 to 120mgKOH/g.
If the hydroxyl value of the mixture (B) is too small, the mixture has a low molecular weight and a large number of ethylenically unsaturated groups, and the content of dipentaerythritol hexa (meth) acrylate (B6) that does not react with isocyanate increases, so that curing shrinkage during curing increases, and curling tends to occur easily, and further bendability tends to decrease. In addition, when the hydroxyl value is too large, the viscosity tends to increase with an increase in molecular weight, and handling tends to be difficult.
In the present invention, if the content ratio of the dipentaerythritol penta (meth) acrylate (B5) in the mixture (B) of the (meth) acrylic esters (B1) to (B6) is 15 to 60% by weight, it is preferable from the viewpoint of satisfying both hardness and bendability, and it is more preferably 20 to 55% by weight, and still more preferably 25 to 55% by weight. If the content ratio is too small, bendability tends to decrease, and if it is too large, hardness tends to decrease or viscosity tends to increase.
When the content of the dipentaerythritol penta (meth) acrylate (b 5) is from 45 to 90% by weight based on the total amount of the (meth) acrylates (b 1) to (b 5), it is preferable from the viewpoint of satisfying both hardness and bendability, and it is more preferably from 50 to 90% by weight, and still more preferably from 55 to 90% by weight. If the content ratio is too small, bendability tends to decrease, and if it is too large, hardness tends to decrease or viscosity tends to increase.
The content ratio of the dipentaerythritol tetra (meth) acrylate (B4) in the mixture (B) of the (meth) acrylic esters (B1) to (B6) is preferably 1 to 35% by weight, more preferably 2 to 30% by weight, and still more preferably 3 to 25% by weight, from the viewpoint of flexibility. If the content ratio is too small, the bendability tends to be low, and if it is too large, the hardness tends to be low or the viscosity tends to be high.
When the content of the dipentaerythritol tetra (meth) acrylate (b 4) is 2 to 40% by weight based on the total amount of the (meth) acrylates (b 1) to (b 5), the content is preferably 3 to 35% by weight, more preferably 4 to 30% by weight, from the viewpoint of flexibility. If the content ratio is too small, the bendability tends to be low, and if it is too large, the hardness tends to be low or the viscosity tends to be high.
In the present invention, the reaction of dipentaerythritol with (meth) acrylic acid to prepare a (meth) acrylic acid adduct of dipentaerythritol by reacting dipentaerythritol with (meth) acrylic acid can be carried out according to a known and ordinary method. In this reaction, a mixture (B) containing dipentaerythritol mono (meth) acrylate (B1) obtained by adding 1 (meth) acrylic acid to dipentaerythritol, dipentaerythritol di (meth) acrylate (B2) obtained by adding 2 (meth) acrylic acids, dipentaerythritol tri (meth) acrylate (B3) obtained by adding 3 (meth) acrylic acids, dipentaerythritol tetra (meth) acrylate (B4) obtained by adding 4 (meth) acrylic acids, dipentaerythritol penta (meth) acrylate (B5) obtained by adding 5 (meth) acrylic acids, and dipentaerythritol hexa (meth) acrylate (B6) obtained by adding 6 (meth) acrylic acids is obtained, and a mixture (B) having the above hydroxyl value as a whole can be obtained.
The mixture (B) may contain a side reaction product such as a Michael addition product of acrylic acid.
When the hydroxyl value is adjusted, for example: the content ratio of the (meth) acrylic esters (b 1) to (b 6) can be adjusted.
In the present invention, the polyisocyanate (CB) is reacted with the (meth) acrylic esters (b 1) to (b 5), and specifically, the same polyisocyanate (CA) as described above can be used. The polyisocyanate (CB) may be the same as or different from the polyisocyanate (CA).
In addition, the polyisocyanate (CB) may be a reaction product of the above polyisocyanate and a polyol. Polyols such as these are, for example: specific examples of the low molecular weight polyol and the high molecular weight polyol include polyether polyols, polyester polyols, polycarbonate polyols, polybutadiene polyols, polyolefin polyols obtained by reacting ethylene, isoprene, butadiene, and the like, and hydrogenated products thereof, other polyolefin polyols, (meth) acrylic polyols, and the like.
Of these polyisocyanates (CB), alicyclic polyisocyanates and aromatic polyisocyanates are preferable from the viewpoint of weather resistance and strength, and isophorone diisocyanate, hydrogenated xylylene diisocyanate, and toluene diisocyanate are more preferable.
In the present invention, the urethane (meth) acrylate composition [ II ] is obtained by reacting the hydroxyl groups of the (meth) acrylates (B1) to (B5) in the mixture (B) of the (meth) acrylates (B1) to (B6) with the isocyanate groups of the polyisocyanate (CB). In this case, the urethane (meth) acrylate composition [ II ] contains a product obtained by reacting the (meth) acrylate (b 1) with the polyisocyanate (CB), a product obtained by reacting the (meth) acrylate (b 2) with the polyisocyanate (CB), a product obtained by reacting the (meth) acrylate (b 3) with the polyisocyanate (CB), a product obtained by reacting the (meth) acrylate (b 4) with the polyisocyanate (CB), and a product obtained by reacting the (meth) acrylate (b 5) with the polyisocyanate (CB), and further contains an unreacted product of the (meth) acrylates (b 1) to (b 5), an unreacted (meth) acrylate (b 6), and the like.
The reaction molar ratio of the polyisocyanate (CB) to the feed of the mixture (B) of (meth) acrylic esters (B1) to (B6), for example: when the isocyanate group of the polyisocyanate (CB) is 2, the polyisocyanate (CB): the (meth) acrylate mixture (B) is preferably 1:1 to 1:5, more preferably 1:1 to 1:4, more preferably 1:1 to 1:3.
when the ratio of the mixture (B) is too large, the amount of the low-molecular-weight monomer increases, and curing shrinkage increases, so that curling tends to increase, and when the ratio of the mixture (B) is too small, unreacted polyisocyanate (CB) remains, and stability and safety of the cured coating film tend to decrease.
The (meth) acrylic esters (B1) to (B5) in the (meth) acrylic ester mixture (B) are reacted with the polyisocyanate (CB), and the mixture (B) and the polyisocyanate (CB) are usually fed all at once or separately to a reactor and reacted.
In the above reaction, a catalyst is preferably used for promoting the reaction, and examples of the catalyst include those described in the above urethane (meth) acrylate composition [ I ].
In the above reaction, the same ones as described in the above urethane (meth) acrylate composition [ I ] can be used in the case of using a polymerization inhibitor or an organic solvent having no functional group reactive with an isocyanate group.
The urethane (meth) acrylate composition [ II ] can be prepared in accordance with the preparation of the urethane (meth) acrylate composition [ I ].
Thus, the urethane (meth) acrylate composition [ II ] used in the present invention was obtained.
The weight average molecular weight of the urethane (meth) acrylate composition [ II ] is preferably 1000 to 20000, more preferably 1500 to 18000, and still more preferably 2000 to 16000. When the weight average molecular weight is too small, the cured coating film tends to become brittle, and when it is too large, the viscosity tends to be high, making handling difficult.
The measurement method of the weight average molecular weight is the same as the above measurement method.
The viscosity of the urethane (meth) acrylate composition [ II ] at 60 ℃ is preferably 1000 to 300000 mPas, more preferably 1500 to 200000 mPas, and still more preferably 2000 to 100000 mPas. When the viscosity is outside the above range, the coatability tends to be lowered.
The measurement of the viscosity at 60 ℃ was carried out by using an E-type viscometer.
The content of the urethane (meth) acrylate in the urethane (meth) acrylate composition [ II ] is more preferably 35% by weight or more, still more preferably 40% by weight or more, still more preferably 45% by weight or more, particularly preferably 50% by weight or more, and still more preferably 60% by weight or more. In addition, the upper limit is usually 95% by weight.
< urethane (meth) acrylate composition [ III ]
Further, the urethane (meth) acrylate composition [ III ] will be described.
< mixture (A) >
First, a mixture (a) containing (meth) acrylates (a 1) to (a 3) as constituent materials of the urethane (meth) acrylate composition [ III ] will be described.
The mixture (A) is a mixture of the (meth) acrylic esters (a 1) to (a 4) obtained by reacting pentaerythritol and (meth) acrylic acid, and the hydroxyl value thereof is preferably 200mgKOH/g or more, more preferably 210 to 380mgKOH/g, and still more preferably 230 to 320mgKOH/g.
The mixture (A) may be the same as described in the urethane (meth) acrylate composition [ I ].
In the mixture (a), the hydroxyl group-containing (meth) acrylates (a 1) to (a 3) react with the polyisocyanate (CC) described later.
< mixture (B) >
Next, the mixture (B) containing the (meth) acrylic esters (B1) to (B5) as the constituent materials of the urethane (meth) acrylate composition [ III ] will be described.
The mixture (B) is a mixture of the (meth) acrylic esters (B1) to (B6) obtained by reacting the dipentaerythritol with (meth) acrylic acid, and the hydroxyl value thereof is desirably 40mgKOH/g or more, more preferably 43 to 130mgKOH/g, still more preferably 45 to 125mgKOH/g, and yet more preferably 70 to 120mgKOH/g.
The mixture (B) may be the same as that described in the urethane (meth) acrylate composition [ II ].
In the above mixture (B), the (meth) acrylates (B1) to (B5) having a hydroxyl group are reacted with the following polyisocyanate (CC).
< polyisocyanate (CC) >
Next, a description will be given of a polyisocyanate (CC) as a constituent material of the urethane (meth) acrylate composition [ III ].
In the present invention, the polyisocyanate (CC) is reacted with a hydroxyl group-containing (meth) acrylate, that is, the (meth) acrylates (a 1) to (a 3) and the (meth) acrylates (b 1) to (b 5), and specifically, the polyisocyanate (CA) described in the urethane (meth) acrylate composition [ I ] and the polyisocyanate (CB) described in the urethane (meth) acrylate composition [ II ] are the same. The polyisocyanate (CC) may be the same as or different from the polyisocyanate (CA) or the polyisocyanate (CB).
The polyisocyanate (CC), together with the polyisocyanate (CA) and the polyisocyanate (CB) may be collectively referred to as "polyisocyanate (C)".
In the present invention, the urethane (meth) acrylate composition [ III ] can be obtained by reacting the hydroxyl groups of the (meth) acrylates (a 1) to (a 3) in the mixture (a) of the (meth) acrylates (a 1) to (a 4), the hydroxyl groups of the (meth) acrylates (B1) to (B5) in the mixture (B) of the (meth) acrylates (B1) to (B6), and the isocyanate groups of the polyisocyanate (CC). In this case, the urethane (meth) acrylate composition [ III ] contains a reaction product of the (meth) acrylate (a 1) and the polyisocyanate (CC), a reaction product of the (meth) acrylate (a 2) and the polyisocyanate (CC), a reaction product of the (meth) acrylate (a 3) and the polyisocyanate (CC), a reaction product of the (meth) acrylate (b 1) and the polyisocyanate (CC), a reaction product of the (meth) acrylate (b 2) and the polyisocyanate (CC), a reaction product of the (meth) acrylate (b 3) and the polyisocyanate (CC), a reaction product of the (meth) acrylate (b 4) and the polyisocyanate (CC), a reaction product of the (meth) acrylate (b 5) and the polyisocyanate (CC), a reaction product of the (a 1) to (a 3) and the (meth) acrylates (b 1) to (b 5) mixed and the polyisocyanate (CC), and the unreacted (b 4) of the (meth) acrylates (a 1) to (a 3) and the (b 1) to (b 5), and the unreacted (b 4) in the system.
In the reaction of the (meth) acrylates (a 1) to (a 3) and the (meth) acrylates (b 1) to (b 5) with the polyisocyanate (CC), the molar ratio of the hydroxyl group to the functional group of the isocyanate group can be adjusted, and the reaction can be carried out using a reaction catalyst described later as required.
The molar ratio of the reaction between the mixture (a) of (meth) acrylic esters (a 1) to (a 4) and the mixture (B) of (meth) acrylic esters (B1) to (B6) and the feed of the polyisocyanate (CC) is such that, when the isocyanate group of the polyisocyanate (CC) is 2, the polyisocyanate (CC): the total of the (meth) acrylate mixture (a) and the (meth) acrylate mixture (B) is preferably 1:1 to 1:5, more preferably 1:1 to 1:3, more preferably 1:1 to 1:2. further, the (meth) acrylate mixture (a): the (methyl) acrylate mixture (B) is 90:10 to 10: more preferably, 90, still more preferably 70: 30-15: 85, more preferably 50: 50-20: 80.
if the ratio of the total amount of the mixture (a) to the mixture (B) to the polyisocyanate (CC) is too large, the amount of the low-molecular-weight monomer increases, and curing shrinkage increases, so curling tends to increase, while if the ratio of the total amount of the mixture (a) to the mixture (B) is too small, the unreacted polyisocyanate (CC) remains, and stability and safety of the cured coating film tend to decrease.
When the ratio of the mixture (B) to the mixture (a) is too large, the low-molecular-weight monomer increases, and curing shrinkage increases, so that curling tends to increase, and when the ratio of the mixture (B) is too small, hardness and scratch properties tend to decrease.
The reaction of the (meth) acrylic esters (a 1) to (a 3) in the (meth) acrylic ester mixture (a) and the (meth) acrylic esters (B1) to (B5) in the (meth) acrylic ester mixture (B) with the polyisocyanate (CC) is usually carried out by feeding the mixture (a), the mixture (B) and the polyisocyanate (CC) to a reactor all at once or separately.
In the above reaction, a catalyst is also preferably used for promoting the reaction, and examples of the catalyst include the same ones as described in the above urethane (meth) acrylate composition [ I ].
In the above reaction, the same polymerization inhibitor and the organic solvent having no functional group reactive with an isocyanate group as described in the above urethane (meth) acrylate composition [ I ] can be used.
The urethane (meth) acrylate composition [ III ] can be prepared in accordance with the preparation of the urethane (meth) acrylate composition [ I ].
In this manner, a urethane (meth) acrylate composition [ III ] obtained by reacting the (meth) acrylates (a 1) to (a 3) as [ α ], the (meth) acrylates (b 1) to (b 5) as [ β ], and a polyisocyanate (CC) is obtained.
In the present invention, a urethane (meth) acrylate composition [ III ] composed of (meth) acrylates (a 1) to (a 3) as [ α ], (meth) acrylates (b 1) to (b 5) as [ β ], a polyisocyanate (CC), and a polyol can be obtained by reacting the polyol with a polyisocyanate (CC).
The above-mentioned polyhydric alcohols are, for example: specific examples of the low molecular weight polyol and the high molecular weight polyol include polyolefin polyols obtained by reacting polyether polyols, polyester polyols, polycarbonate polyols, ethylene/isoprene/butadiene and the like, and hydrogenated products thereof, and other polyolefin polyols and (meth) acrylic polyols.
The weight average molecular weight of the urethane (meth) acrylate composition [ III ] is more preferably 1000 to 20000, more preferably 2000 to 15000, still more preferably 3000 to 12000, and particularly preferably 4000 to 10000. When the weight average molecular weight is too small, the cured coating film tends to become brittle, and when it is too large, the cured coating film tends to have a high viscosity, which makes handling difficult.
The weight average molecular weight is determined by using a weight average molecular weight obtained by conversion of a standard polystyrene molecular weight, and using 1 ACQUITY APC XT 450, 1 ACQUITY APC XT 200, 2 ACQUITY APC XT 45, and a total of 4 pieces in series as a column by high performance liquid chromatography ("ACQUITY APC system", volter corporation).
The content of the urethane (meth) acrylate in the urethane (meth) acrylate composition [ III ] is more preferably 50% by weight or more, still more preferably 60% by weight or more, still more preferably 70% by weight or more, and particularly preferably 80% by weight or more. In addition, the upper limit is usually 95% by weight.
< active energy ray-curable resin composition >
The active energy ray-curable resin composition of the present invention includes: embodiment 1 of the present invention is directed to a composition comprising the urethane (meth) acrylate composition [ I ] < the invention of claim 1; the 2 nd embodiment containing the urethane (meth) acrylate composition [ I ] and the urethane (meth) acrylate composition [ II ] (the 2 nd embodiment); and embodiment 3 (invention of claim 3) which contains the urethane (meth) acrylate composition [ III ].
The active energy ray-curable resin composition according to the 2 nd embodiment contains the urethane (meth) acrylate composition [ I ] and the urethane (meth) acrylate composition [ II ] as described above. The content ratio ([ I ]/[ II ]) of the urethane (meth) acrylate composition [ I ] to the urethane (meth) acrylate composition [ II ] is preferably 90/10 to 10/90, more preferably 87/13 to 20/80, still more preferably 85/15 to 30/70, particularly preferably 80/20 to 55/45, and still more preferably 80/20 to 65/35 by weight ratio. If the content ratio is too small, bendability tends to decrease, and if it is too large, hardness tends to be insufficient.
The active energy ray-curable resin composition of the present invention according to the above-described embodiments 1 to 3 (hereinafter, may be simply referred to as "resin composition") preferably further contains a photopolymerization initiator (D). In addition, other urethane (meth) acrylate, an ethylenically unsaturated monomer other than urethane (meth) acrylate, an acrylic resin, a surface conditioner, a leveling agent, a polymerization inhibitor, and the like may be added as long as the effects of the present invention are not impaired, and a filler, a dye, a pigment, oil, a plasticizer, waxes, a drying agent, a dispersing agent, a wetting agent, a gelling agent, a stabilizer, an antifoaming agent, a surfactant, a leveling agent, a thixotropy imparting agent, an antioxidant, a flame retardant, an antistatic agent, a filler, a reinforcing agent, a matting agent, a crosslinking agent, silica dispersed or dispersed in water, a zirconium compound, a preservative, and the like may be further added.
Examples of the photopolymerization initiator (D) include: acetophenones such as diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzildimethylketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenone, 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl ] -phenyl } -2-methyl-propane, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] propanone oligomer; benzine such as benzine, benzine methyl ether, benzine ethyl ether, benzine isopropyl ether, and benzine isobutyl ether; benzophenones such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4- (4-methoxyphenyl) -2-butanone, 3', 4' -tetrakis (t-butylperoxycarbonyl) benzophenone, 2,4, 6-trimethylbenzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl ] bromobenzylamine, and (4-benzoylbenzyl) trimethylammonium chloride; thioxanthones such as 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-dichlorothioxanthone, 1-chloro-4-propoxytiranone, 2- (3-dimethylamino-2-hydroxy) -3, 4-dimethyl-9H-thioxanthone-9-one meso (meso) chloride; acylphosphine oxides such as 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, bis (2, 6-dimethoxybenzoyl) -2, 4-trimethyl-pentylphosphine oxide, bis (2, 4, 6-trimethylbenzoyl) -phenylphosphine oxide and the like; oxime esters such as 2-octanedione and 1- [4- (phenylthio) -,2- (o-benzoyloxime) ], and the like. These photopolymerization initiators (D) may be used alone in 1 kind, or 2 or more kinds may be used in combination.
Of these, benzildimethyl ketal, 1-hydroxycyclohexylphenone, benzidine isopropyl ether, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, and 2-hydroxy-2-methyl-1-phenylpropan-1-one are more preferably used.
In addition, as auxiliaries therefor, for example: triethanolamine, triisopropanolamine, 4' -bis (dimethylamino) benzophenone (Michler's ketone), 4' -diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid (n-butoxy) ethyl ester, 4-dimethylaminobenzoic acid isoamyl ester, 4-dimethylaminobenzoic acid 2-ethylhexyl ester, 2, 4-diethylthioxanthone, 2, 4-diisopropylthioxanthone, and the like. These may be used alone or in combination of 2 or more.
The content of the photopolymerization initiator (D) is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, and still more preferably 1 to 10 parts by weight, based on 100 parts by weight of the curing component contained in the resin composition. If the content of the photopolymerization initiator (D) is too small, curing failure tends to occur, and a film is not easily formed, while if too large, yellowing of the cured coating film tends to occur, and a problem of coloring tends to occur.
Examples of the ethylenically unsaturated monomer other than the urethane (meth) acrylate include: a monofunctional monomer, a bifunctional monomer, and a polyfunctional monomer having three or more functions. These can be used alone or in combination of 2 or more.
Examples of the monofunctional monomer include: styrene monomers such as styrene, vinyl toluene, chlorostyrene, and α -methylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate, acrylonitrile, 2-methoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, monoglyceride (meth) acrylate, glycidyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 2-methyl-2-ethyl-1, 3-dioxolan-4-yl) - (meth) acrylate, cyclohexanspiro-2- (1, 3-dioxolan-4-yl) - (meth) acrylate, 3-ethyl-3-oxetanyl methyl (meth) acrylate, gamma-butyrolactone (meth) acrylate, (meth) acrylate monomers such as n-butyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, n-stearyl (meth) acrylate, benzyl (meth) acrylate, phenol ethylene oxide-modified (n = 2) (meth) acrylate, nonylphenol propylene oxide-modified (n = 2.5) (meth) acrylate, 2- (meth) acryloyloxyethyl acid phosphate, hemi (meth) acrylates of phthalic acid derivatives such as 2- (meth) acryloyloxy-2-hydroxypropylphthalic acid, furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, carbitol (meth) acrylate, benzyl (meth) acrylate, butoxyethyl (meth) acrylate, allyl (meth) acrylate, (meth) acryloylmorpholine, polyoxyethylene secondary alkyl ether acrylate, and the like; 2-hydroxyethyl acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylpyrrolidone, 2-vinylpyridine, vinyl acetate, and the like.
Examples of the bifunctional monomer include: ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide-modified bisphenol a type di (meth) acrylate, propylene oxide-modified bisphenol a type di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, ethoxylated cyclohexanedimethanol di (meth) acrylate, dimethyloldicyclopentane di (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, trimethyleneacetate-modified diethylene glycol di (meth) acrylate, ethylene oxide di (meth) acrylate, and isocyanuric acid.
Examples of the trifunctional or higher monomer include: trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tris (meth) acryloyloxyethoxytrimethylolpropane, glycerol polyglycidyl ether poly (meth) acrylate, ethylene oxide-modified triacrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, ethylene oxide-modified dipentaerythritol penta (meth) acrylate, ethylene oxide-modified dipentaerythritol hexa (meth) acrylate, ethylene oxide-modified pentaerythritol tri (meth) acrylate, ethylene oxide-modified pentaerythritol tetra (meth) acrylate, ethoxylated 15 glycerol triacrylate, and the like.
Further, a Michael addition product of acrylic acid such as a (meth) acrylic acid dimer, a (meth) acrylic acid trimer, or a (meth) acrylic acid tetramer, or a 2-acryloyloxyethyldicarboxylic acid monoester may be used in combination. The above-mentioned 2-acryloyloxyethyl dicarboxylic acid monoester is a carboxylic acid having a specific substituent, for example: 2-acryloyloxyethyl succinic acid monoester, 2-methacryloyloxyethyl succinic acid monoester, 2-acryloyloxyethyl phthalic acid monoester, 2-methacryloyloxyethyl phthalic acid monoester, 2-acryloyloxyethyl hexahydrophthalic acid monoester, 2-methacryloyloxyethyl hexahydrophthalic acid monoester, and the like. Other oligoester acrylates and the like can also be mentioned.
The content of the ethylenically unsaturated monomer other than the urethane (meth) acrylate in the invention of claim 1 and the invention of claim 2 is preferably 60% by weight or less, more preferably 55% by weight or less, and even more preferably 50% by weight or less of the total curing components contained in the active energy ray-curable resin composition. The lower limit is usually 5% by weight.
On the other hand, in the invention according to claim 3 of the present invention, the content of the ethylenically unsaturated monomer other than the urethane (meth) acrylate is preferably 50% by weight or less, more preferably 40% by weight or less, even more preferably 30% by weight or less, and particularly preferably 20% by weight or less of the total curing components contained in the active energy ray-curable resin composition. The lower limit is usually 5% by weight.
Examples of the surface conditioner include: cellulose resins, alkyd resins, and the like. The cellulose resin has an effect of improving the surface smoothness of a coating film, and the alkyd resin has an effect of imparting film-forming properties upon coating. These can be used alone or in combination of 2 or more.
The leveling agent may be any agent having an action of imparting moisture permeability to the base material or an action of lowering surface tension, and known ordinary leveling agents such as: silicone-modified resins, fluorine-modified resins, alkyl-modified resins, and the like. These may be used alone or in combination of 2 or more.
The polymerization inhibitor may be the same as that used in the reaction, and examples thereof include: quinones such as p-benzoquinone, naphthoquinone, toluquinone, 2, 5-diphenyl-p-benzoquinone, hydroquinone, 2, 5-di-tert-butylhydroquinone, methylhydroquinone, hydroquinone monomethyl ether, and mono-tert-butylhydroquinone; aromatic compounds such as 4-methoxyphenol and 2, 6-di-t-butylcresol; p-tert-butylcatechol, and the like. These can be used alone or in combination of 2 or more.
In the active energy ray-curable resin composition of the present invention, an organic solvent for dilution is also preferably used in order to make the viscosity suitable for application, if necessary. Examples of the organic solvent include: alcohols such as methanol, ethanol, propanol, n-butanol, and isobutanol; ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone, and cyclohexanone; celluloid thres such as ethyl celluloid threo; aromatic compounds such as toluene and xylene; glycol ethers such as propylene glycol monomethyl ether; acetates such as methyl acetate, ethyl acetate, and butyl acetate; diacetone alcohol, and the like. These organic solvents may be used alone or in combination of 2 or more.
When 2 or more kinds are used in combination, 2 or more kinds are selected from the group consisting of a combination of a glycol ether such as propylene glycol monomethyl ether and a ketone such as methyl ethyl ketone, an alcohol such as methanol, a combination of a ketone such as methyl ethyl ketone and an alcohol such as methanol, and it is preferable from the viewpoint of appearance of the coating film.
The active energy ray-curable resin composition of the present invention is useful as a curable composition for forming a coating film, such as a topcoat agent or an anchor coating agent for various substrates. The active energy ray-curable resin composition can be cured by applying the active energy ray-curable resin composition to a substrate (after further drying when the resin composition diluted with an organic solvent is applied).
Examples of the substrate to be coated with the active energy ray-curable resin composition of the present invention include: polyolefin-based resins, polyester-based resins, polycarbonate-based resins, acrylonitrile butadiene styrene copolymers (ABS), polystyrene-based resins, and the like, plastic substrates such as molded articles thereof (films, sheets, cups, and the like), optical films such as polyethylene terephthalate films, triacetyl cellulose films, cycloolefin films, composite substrates thereof, and the like in which glass fibers and inorganic substances are mixed, metals (aluminum, copper, iron, SUS, zinc, magnesium, alloys thereof, and the like), glass, substrates in which an undercoat layer is provided on these substrates, and the like.
Examples of the method for applying the active energy ray-curable resin composition of the present invention include: wet coating methods such as spraying, shower, gravure coating, dipping, roll coating, spin coating, screen printing, and the like, are usually applied to a substrate at normal temperature.
The active energy ray-curable resin composition of the present invention may be applied as it is or may be diluted with an organic solvent and applied. In the case of dilution, the organic solvent is used to dilute the solution so that the solid content concentration is usually 3 to 70% by weight, more preferably 5 to 60% by weight.
The drying conditions for the dilution with the organic solvent are usually 40 to 120 ℃ and more preferably 50 to 100 ℃ and the drying time is usually 1 to 20 minutes and more preferably 2 to 10 minutes.
When the active energy ray-curable resin composition of the present invention is applied, the viscosity of the resin composition at 20 ℃ is preferably 5 to 50000 mPas, more preferably 10 to 10000 mPas, and still more preferably 50 to 5000 mPas. If the viscosity is outside the above range, the coatability tends to be lowered.
The measurement of the viscosity at 20 ℃ was carried out by means of a B-type viscometer. However, since the viscosity is high in a state of not being diluted with a solvent, when the measurement cannot be performed with the B-type viscometer at 20 ℃, the measurement is performed with the E-type viscometer at 60 ℃.
As the active energy ray used for curing the active energy ray-curable resin composition applied to the substrate, for example: in addition to light such as far ultraviolet rays, near ultraviolet rays, and infrared rays, and electromagnetic waves such as X-rays and γ -rays, electron beams, proton beams, and neutron beams can be used, but curing by ultraviolet irradiation is advantageous in view of curing speed, availability of an irradiation apparatus, cost, and the like. In addition, when electron beam irradiation is performed, curing can be performed without using the photopolymerization initiator (D).
When curing by ultraviolet irradiation, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an electrodeless discharge lamp, an LED lamp or the like which emits light in a wavelength range of 150 to 450nm can be used, and usually 30 to 3000mJ/cm can be irradiated 2 More preferably 100 to 1500mJ/cm 2 Ultraviolet rays of (4).
After the ultraviolet irradiation, the resin composition may be heated as necessary to be completely cured.
The coating thickness (the thickness after curing) is preferably 1 to 1000. Mu.m, more preferably 2 to 500. Mu.m, and still more preferably 3 to 200. Mu.m, in view of uniform reaction of the photopolymerization initiator (D) as an active energy ray-curable coating film.
The active energy ray-curable resin composition of the present invention is preferably used in the form of a coating agent, and particularly preferably used in the form of a coating agent for hard coating or a coating agent for optical films.
In the present invention, an active energy ray-curable resin composition was applied to a polyethylene terephthalate (PET) film having a size of 15cm × 15cm and a thickness of 100 μm, the thickness of the cured coating film was 10 μm, the cured coating film was dried at 60 ℃ for 3 minutes, and then an 80W high-pressure mercury lamp was prepared at a position 18cm from the PET film surface, and the irradiation was performed at a rate of 5.1 m/min with ultraviolet rays so that the cumulative dose became 500mJ/cm 2 To obtain a cured coating film. The coating agent is preferably a coating film which is cured as follows: the cured coating film was cut into a size of 10cm × 10cm, and the average value of the jump height at the four corners of the cut cured coating film was 40mm or less, particularly 30mm or less, and further 25mm or less.
Further, in the present invention, an active energy ray-curable resin composition was applied to an easily bondable PET film having a size of 15 cm. Times.15 cm and a thickness of 125 μm, the cured coating film had a thickness of 10 μm, dried at 60 ℃ for 3 minutes, prepared in a high-pressure mercury lamp of 80W at a position 18cm from the easily bondable PET film surface, and irradiated with ultraviolet rays at a rate of 5.1 m/min so that the cumulative dose of irradiation became 500mJ/cm 2 Thereby obtaining a cured coating film. The following coating agents are preferably prepared: the cured coating film is subjected to bending evaluation in accordance with JIS K5600-5-1 using a cylindrical mandrel bending tester, and the maximum diameter (integer value, mm) of the cured coating film which is cracked or peeled off when wound on a test bar is 20mm or less, particularly preferably 15mm or less, more preferably 10mm or less, and particularly preferably 8mm or less.
In the present invention, an active energy ray-curable resin composition was applied to an easily bondable PET film having a size of 15 cm. Times.15 cm and a thickness of 125 μm so that the thickness of the cured coating film became 10 μm, the cured coating film was dried at 60 ℃ for 3 minutes, an 80W high-pressure mercury lamp was prepared at a position 18cm from the easily bondable PET film surface, and ultraviolet light was irradiated at a speed of 5.1 m/min,the cumulative exposure dose was set to 500mJ/cm 2 To obtain a cured coating film. For the cured coating film, steel wool (BON STAR #0000 manufactured by japan steel wool corporation) was used, and the surface of the cured coating film was subjected to reciprocating movement 10 times in a state where a load of 500g was applied, and then the degree of surface damage was visually observed.
The invention pertaining to the 1 st aspect of the present invention is an active energy ray-curable resin composition containing a urethane (meth) acrylate composition [ I ] produced by reacting (meth) acrylates (a 1) to (a 3) in a mixture (a) of the above (meth) acrylates (a 1) to (a 4) as a reaction product of pentaerythritol and (meth) acrylic acid with a polyisocyanate (CA), the mixture (a) having a hydroxyl value of 200mgKOH/g or more. The active energy ray-curable resin composition has an effect that a cured coating film having excellent hardness and bendability can be formed because of reduced cure shrinkage and less curling, and further, even in an uncured coating film before curing, the surface of the coating film does not stick and a tack-free coating film surface can be formed.
The invention 2 is an active energy ray-curable resin composition containing a urethane (meth) acrylate composition [ I ] obtained by reacting (meth) acrylates (a 1) to (a 3) in a mixture (a) of the above (meth) acrylates (a 1) to (a 4) which is a reaction product of pentaerythritol and (meth) acrylic acid with a polyisocyanate (CA), and a urethane (meth) acrylate composition [ II ]; the urethane (meth) acrylate composition [ II ] is obtained by reacting (meth) acrylates (B1) to (B5) in a mixture (B) of the following (meth) acrylates (B1) to (B6) which are a reaction product of dipentaerythritol and (meth) acrylic acid with a polyisocyanate (CB); the mixture (A) has a hydroxyl value of 200mgKOH/g or more, and the mixture (B) has a hydroxyl value of 40mgKOH/g or more. The active energy ray-curable resin composition is less likely to curl due to a small cure shrinkage, has an effect of forming a cured coating film excellent in hardness and bendability, and is useful particularly as a coating agent (further, a coating agent for hard coating, a coating agent for optical films), and further, is useful as a coating material, an ink, or the like.
The invention 3 is an active energy ray-curable resin composition containing a urethane (meth) acrylate composition [ III ] produced by reacting (meth) acrylates (a 1) to (a 3) as the above [ α ], (meth) acrylates (b 1) to (b 5) as the above [ β ], and a polyisocyanate (CC). The active energy ray-curable resin composition is less likely to curl due to a small cure shrinkage, and has an effect of forming a cured coating film excellent in hardness, bendability and scratch resistance, and is particularly useful as a coating agent (further, a coating agent for hard coating, a coating agent for optical films). Further, the composition is also useful as a paint, an ink, or the like.
Examples
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples as long as the invention does not exceed the gist thereof. In the examples, "part" and "%" are based on weight.
< example using urethane (meth) acrylate composition [ I ]
As described below, urethane acrylate compositions [ I ] ([ I-1] to [ I-4 ]) were prepared, and comparative urethane acrylate compositions [ I ' ] ([ I ' -1] to [ I ' -4 ]) were prepared.
[ production of urethane acrylate composition [ I-1]
A4-neck flask equipped with a thermometer, stirrer, water-cooled condenser and nitrogen inlet was charged with 36g of isophorone diisocyanate (C-1), 64g of an acrylate mixture (A-1) (acrylic acid adduct of pentaerythritol) having a hydroxyl value of 288mgKOH/g, 100g of ethyl acetate as a solvent, 0.08g of 4-methoxyphenol as a polymerization inhibitor and 0.05g of dibutyltin dilaurate as a reaction catalyst, and the reaction was terminated when the remaining isocyanate group became 0.1%, whereby a urethane acrylate composition [ I-1] (resin component concentration: 50%) was obtained.
The weight average molecular weight of the resulting urethane acrylate-based composition [ I-1] was 4700, and the viscosity at 20 ℃ was 80 mPas. The measurement of the viscosity at 20 ℃ was carried out using a B-type viscometer. The viscosity measurement at 20 ℃ is the same as follows.
In the acrylate mixture (a-1), the content ratio of each component to the total amount of the following components (a 1) to (a 4) is as follows.
Figure BDA0002179844210000281
The content ratio of each component in the mixture was measured by liquid chromatography (made by Agilent, "Technology HP 1100") using a column (made by Imtakt, cadenza CD-C18X 3mm 3 μm).
[ production of urethane acrylate composition [ I-2]
33g of hydrogenated xylylene diisocyanate (C-2), 67g of an acrylate mixture (A-1) (acrylic adduct of pentaerythritol) having a hydroxyl value of 288mgKOH/g, 100g of ethyl acetate as a solvent, 0.08g of 4-methoxyphenol as a polymerization inhibitor, and 0.05g of dibutyltin dilaurate as a reaction catalyst were charged into a 4-neck flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen inlet, and the reaction was terminated when the remaining isocyanate group became 0.1%, whereby a urethane acrylate composition [ I-2] (resin component concentration: 50%) was obtained.
The weight average molecular weight of the resulting urethane acrylate-based composition [ I-2] was 6200, and the viscosity at 20 ℃ was 65 mPas.
[ production of urethane acrylate composition [ I-3]
A4-neck flask equipped with a thermometer, a stirrer, a water-cooled condenser and a nitrogen inlet was charged with 43g of tolylene diisocyanate (C-3), 97g of an acrylate mixture (A-1) (an acrylic acid adduct of pentaerythritol) having a hydroxyl value of 288mgKOH/g, 60g of ethyl acetate as a solvent, 0.08g of 4-methoxyphenol as a polymerization inhibitor and 0.05g of dibutyltin dilaurate as a reaction catalyst, and the reaction was terminated when the remaining isocyanate group became 0.1%, whereby a urethane acrylate composition [ I-3] (resin component concentration: 70%) was obtained.
The weight-average molecular weight of the obtained urethane acrylate composition [ I-3] was 7300, and the viscosity at 20 ℃ was 161000 mPas.
[ production of urethane acrylate composition [ I-4]
48g of xylylene diisocyanate (C-4), 90g of an acrylate mixture (A-1) (an acrylic acid adduct of pentaerythritol) having a hydroxyl value of 288mgKOH/g, 60g of ethyl acetate as a solvent, 0.08g of 4-methoxyphenol as a polymerization inhibitor, and 0.05g of dibutyltin dilaurate as a reaction catalyst were put into a 4-neck flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen inlet, and the reaction was terminated when the remaining isocyanate group became 0.1%, whereby a urethane acrylate composition [ I-4] (resin component concentration 70%) was obtained.
The weight-average molecular weight of the obtained urethane acrylate composition [ I-4] was 12000, and the viscosity at 20 ℃ was high and was not measured.
[ production of urethane acrylate composition [ I' -1]
A flask equipped with a thermometer, a stirrer, a water-cooled condenser and a nitrogen inlet was charged with 38.4g of isophorone diisocyanate (C-1), 161.6g of an acrylate mixture (A '-1) (acrylic acid adduct of pentaerythritol) having a hydroxyl value of 120mgKOH/g, 0.01g of hydroquinone methyl ether as a polymerization inhibitor and 0.01g of dibutyltin dilaurate as a reaction catalyst were added thereto, and the reaction was allowed to proceed at 60 ℃ for 8 hours, whereupon the reaction was terminated when the remaining isocyanate group became 0.3% or less, whereby a urethane acrylate composition [ I' -1] (resin component concentration 100%) was obtained.
The weight average molecular weight of the obtained urethane acrylate composition [ I' -1] was 1400, and the viscosity at 60 ℃ was 3000 mPas. However, since the viscosity was high, the measurement was carried out using an E-type viscometer.
In the acrylate mixture (a' -1), the content ratio of each component to the total amount of the following components (a 1) to (a 4) is as follows.
(a2) Pentaerythritol diacrylate 5%
(a3) 50 percent of pentaerythritol triacrylate
(a4) Pentaerythritol tetraacrylate 45%
However, the content of the (a 1) pentaerythritol monoacrylate is not more than the measurement limit, and therefore the content ratios of the components (a 2) to (a 4) are shown.
[ production of urethane acrylate composition [ I' -2]
37g of isophorone diisocyanate (C-1), 14g of an acrylate mixture (A-1) (acrylic acid adduct of pentaerythritol) having a hydroxyl value of 288mgKOH/g, 114g of a polyester polyol (manufactured by DIC corporation, "ODX-2044", number average molecular weight: about 2000), 0.08g of 4-methoxyphenol as a polymerization inhibitor, and 0.05g of dibutyltin dilaurate as a reaction catalyst were charged into a 4-neck flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas blowing port, reacted at 60 ℃, and 35g of the acrylate mixture (A-1) (acrylic acid adduct of pentaerythritol) having a hydroxyl value of 288mgKOH/g was added when the remaining isocyanate group became 3.9%, and further reacted at 60 ℃. The reaction was terminated when the residual isocyanate group became 0.1%, whereby a urethane acrylate composition [ I' -2] (resin component concentration 100%) was obtained.
In addition, according to the above procedure, the urethane acrylate composition [ I' -2] obtained did not contain a reaction product of only (A-1) and (C-1).
The weight average molecular weight of the obtained urethane acrylate-based composition [ I' -2] was 18000, and the viscosity at 60 ℃ was 700000 mPas. However, since the viscosity was high, the measurement was carried out using an E-type viscometer.
[ production of urethane acrylate composition [ I' -3]
A4-neck flask equipped with a thermometer, stirrer, water-cooled condenser and nitrogen inlet was charged with 25.8g of isophorone diisocyanate (C-1), 74.2g of an acrylate mixture (A '-2) (acrylic adduct of pentaerythritol) having a hydroxyl value of 184.2mgKOH/g, 100g of ethyl acetate as a solvent, 0.08g of 4-methoxyphenol as a polymerization inhibitor and 0.05g of dibutyltin dilaurate as a reaction catalyst, and the reaction was terminated when the residual isocyanate group became 0.1%, to obtain a urethane acrylate composition [ I' -3] (resin component concentration 50%).
The weight-average molecular weight of the obtained urethane acrylate composition [ I' -3] was 2100, and the viscosity at 20 ℃ was 73 mPas.
In the acrylate mixture (a' -2), the content ratio of each component to the total amount of the following components (a 1) to (a 4) is as follows.
Figure BDA0002179844210000301
Figure BDA0002179844210000311
[ production of urethane acrylate composition [ I' -4]
A4-neck flask equipped with a thermometer, a stirrer, a water-cooled condenser and a nitrogen inlet was charged with 23.3g of hydrogenated xylylene diisocyanate (C-2), 76.7g of an acrylate mixture (A '-2) (acrylic acid adduct of pentaerythritol) having a hydroxyl value of 184.2mgKOH/g, 100g of ethyl acetate as a solvent, 0.08g of 4-methoxyphenol as a polymerization inhibitor and 0.05g of dibutyltin dilaurate as a reaction catalyst, and the reaction was allowed to proceed at 60 ℃ to complete the reaction when the remaining isocyanate group became 0.1%, thereby obtaining a urethane acrylate composition [ I' -4] (resin component concentration: 50%).
The weight average molecular weight of the obtained urethane acrylate-based composition [ I' -4] was 2200, and the viscosity at 20 ℃ was 85 mPas.
< examples 1 to 4 and comparative examples 1 to 4>
[ production of an active energy ray-curable resin composition ]
In the urethane acrylate compositions ([ I ] and [ I' ]) obtained above, 4 parts of 1-hydroxycyclohexyl phenyl ketone (IGM 184 "), which is a photopolymerization initiator (D), was added to 100 parts of the curing component to obtain an active energy ray-curable resin composition.
An active energy ray-curable resin composition was obtained in the same manner as described above except that the urethane acrylate compositions ([ I ] and [ I' ]) obtained in examples 3,4 and comparative examples 1,2 were diluted with ethyl acetate so that the resin components became 50%.
With respect to the obtained active energy ray-curable resin composition, a coating film before curing (dried coating film) was formed and the viscosity of the coating film was evaluated as follows. A cured coating film was formed as follows, and the hardness and bendability of the cured coating film were evaluated. The evaluation results are shown in Table 1 below.
[ tackiness of dried coating film ]
The active energy ray-curable resin composition obtained above was coated on an easy-to-bond PET film (manufactured by Toyo Kabushiki Kaisha, "A4300", 15 cm. Times.15 cm in size, 125 μm in thickness) substrate using a coating rod so that the thickness of the coating film after curing became 10 μm, and the coating film was dried at 60 ℃ for 3 minutes. The obtained coating film before curing was subjected to a probe tack test using a tack tester ("TAC-II") under conditions of a push-in speed of 120 mm/min, a pull-up speed of 600 mm/min, a pressure of 20.4gf, and a pressing time of 1.0 second.
[ hardness of cured coating film ]
The active energy ray-curable resin composition obtained above was coated on an easy-adhesion PET film (manufactured by Toyo Co., ltd., "A4300", 15 cm. Times.15 cm in size, 125 μm in thickness) substrate using a coating bar so that the thickness of the coating film after curing became 10 μmAfter drying at 60 ℃ for 3 minutes, 2 passes of ultraviolet irradiation (cumulative dose 500 mJ/cm) was carried out at a conveyor speed of 5.1 m/min from a height of 18cm using a high-pressure mercury lamp 80W or 1 lamp 2 ) To form a cured coating film.
The cured coating film coated on the easy-adhesion PET film was tested in accordance with JIS K-5600 to measure the pencil hardness.
[ bendability of cured coating film ]
A cured coating film was formed in the same manner as in the above hardness evaluation, and the cured coating film coated on the easy-adhesion PET film was subjected to the bending property evaluation in accordance with JIS K5600-5-1 using a cylindrical mandrel bending tester. The maximum diameter (integral value, mm) of the cured coating film for evaluation that cracked or peeled when the film was wound around a test bar with the film surface on the outside was measured. This means that the smaller the value, the higher the flexibility of the coating film.
[ Table 1]
Figure BDA0002179844210000331
From the above evaluation results, it was found that: the cured coating films obtained from the active energy ray-curable resin compositions containing the urethane acrylate-based compositions [ I ] of examples 1 to 4 were excellent in hardness and bendability, and did not have tackiness even in the uncured state before curing.
On the other hand, in each comparative example using a urethane acrylate composition other than the specific urethane acrylate composition [ I ], the cured coating film of comparative example 1 was poor in bendability and sticky before curing. In comparative example 2, the cured coating film had poor hardness and was sticky before curing. In comparative examples 3 and 4, the cured coating film had poor bendability.
Thus, it can be seen that: the active energy ray-curable resin compositions of examples 1 to 4 were free from tackiness, had good hardness and bendability, and were useful for applications such as coating agents, particularly coating agents for hard coating and coating agents for optical films.
< examples using urethane (meth) acrylate compositions [ I ] and [ II >)
Urethane acrylate compositions [ I ] ([ I-5] to [ I-7 ]), and [ II ] ([ II-1] to [ II-2 ]) were prepared as follows, and urethane acrylate compositions [ I ' ] ([ I ' -5] to [ I ' -7 ]) for comparison were prepared.
[ urethane acrylate-based composition [ I-5] ]
A4-neck flask equipped with a thermometer, stirrer, water-cooled condenser and nitrogen inlet was charged with 36g of isophorone diisocyanate (C-1), 64g of an acrylate mixture (A-1) (acrylic acid adduct of pentaerythritol) having a hydroxyl value of 288mgKOH/g, 100g of ethyl acetate as a solvent, 0.08g of 4-methoxyphenol as a polymerization inhibitor and 0.05g of dibutyltin dilaurate as a reaction catalyst, and the reaction was terminated when the remaining isocyanate group became 0.1%, whereby a urethane acrylate composition [ I-5] (resin component concentration: 50%) was obtained.
The weight-average molecular weight of the obtained urethane acrylate composition [ I-5] was 4700, and the viscosity at 20 ℃ was 80 mPas. The measurement of the viscosity at 20 ℃ was carried out using a type B viscometer. The viscosity at 20 ℃ was measured in the same manner as described below.
In the acrylate mixture (a-1), the content ratio of each component to the total amount of the following components (a 1) to (a 4) is as follows.
Figure BDA0002179844210000341
[ production of urethane acrylate composition [ I-6]
A4-neck flask equipped with a thermometer, a stirrer, a water-cooled condenser and a nitrogen inlet was charged with 33g of hydrogenated xylylene diisocyanate (C-2), 67g of an acrylate mixture (A-1) (an acrylic acid adduct of pentaerythritol) having a hydroxyl value of 288mgKOH/g, 100g of ethyl acetate as a solvent, 0.08g of 4-methoxyphenol as a polymerization inhibitor and 0.05g of dibutyltin dilaurate as a reaction catalyst, and the reaction was terminated when the remaining isocyanate group became 0.1%, whereby a urethane acrylate composition [ I-6] (resin component concentration: 50%) was obtained.
The weight-average molecular weight of the obtained urethane acrylate composition [ I-6] was 6200, and the viscosity at 20 ℃ was 65 mPas.
[ production of urethane acrylate composition [ I-7]
A4-neck flask equipped with a thermometer, a stirrer, a water-cooled condenser and a nitrogen inlet was charged with 32g of xylylene diisocyanate (C-4), 68g of an acrylate mixture (A-1) (acrylic acid adduct of pentaerythritol) having a hydroxyl value of 288mgKOH/g, 100g of ethyl acetate as a solvent, 0.08g of 4-methoxyphenol as a polymerization inhibitor and 0.05g of dibutyltin dilaurate as a reaction catalyst, and the reaction was terminated when the remaining isocyanate group became 0.1% to obtain a urethane acrylate composition [ I-7] (resin component concentration: 50%).
The weight-average molecular weight of the obtained urethane acrylate composition [ I-7] was 5900, and the viscosity at 20 ℃ was 50 mPas.
[ production of urethane acrylate composition [ II-1]
A4-neck flask equipped with a thermometer, stirrer, water-cooled condenser and nitrogen inlet was charged with 27.9g of hydrogenated xylylene diisocyanate (C-2), 172.1g of an acrylate mixture (B-1) (acrylic acid adduct of dipentaerythritol) having a hydroxyl value of 96mgKOH/g, 0.08g of 4-methoxyphenol as a polymerization inhibitor and 0.1g of dibutyltin dilaurate as a reaction catalyst, and the reaction was terminated at 60 ℃ when the remaining isocyanate group became 0.1%, whereby a urethane acrylate composition [ II-1] (resin component concentration 100%) was obtained.
The weight-average molecular weight of the obtained urethane acrylate-based composition [ II-1] was 5500, and the viscosity at 60 ℃ was 39400 mPas. The measurement of the viscosity at 60 ℃ was carried out using an E-type viscometer. The viscosity measurement at 60 ℃ is the same as follows.
In the acrylate mixture (B-1), the content ratio of each component to the total amount of the following components (B1) to (B6) is as follows.
(b4) Dipentaerythritol tetraacrylate 18%
(b5) 51 percent of dipentaerythritol pentaacrylate
(b6) Dipentaerythritol hexaacrylate 31%
However, the content ratios of the components (b 4) to (b 6) are shown because the content of (b 1) dipentaerythritol monoacrylate, (b 2) dipentaerythritol diacrylate, and (b 3) dipentaerythritol triacrylate is not more than the measurement limit value.
[ production of urethane acrylate composition [ II-2]
A4-neck flask equipped with a thermometer, stirrer, water-cooled condenser and nitrogen inlet was charged with 31.3g of isophorone diisocyanate (C-1), 168.7g of an acrylate mixture (B-1) (acrylic adduct of dipentaerythritol) having a hydroxyl value of 96mgKOH/g, 0.08g of 4-methoxyphenol as a polymerization inhibitor and 0.1g of dibutyltin dilaurate as a reaction catalyst, and the reaction was allowed to proceed at 60 ℃ to terminate when the remaining isocyanate group became 0.1%, thereby obtaining a urethane acrylate composition [ II-2] (resin component concentration 100%).
The weight average molecular weight of the resulting urethane acrylate-based composition [ II-2] was 67000, and the viscosity at 60 ℃ was 65000 mPas.
[ production of urethane acrylate composition [ II-3]
13.2g of isophorone diisocyanate (C-1), 186.8g of an acrylate mixture (B-2) (an acrylic acid adduct of dipentaerythritol) having a hydroxyl value of 50mgKOH/g, 0.08g of 4-methoxyphenol as a polymerization inhibitor, and 0.1g of dibutyltin dilaurate as a reaction catalyst were charged in a 4-neck flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen inlet, and the reaction was terminated when the remaining isocyanate group became 0.1% by reacting at 60 ℃ to obtain a urethane acrylate composition [ II-3] (resin component concentration 100%).
The weight-average molecular weight of the obtained urethane acrylate composition [ II-3] was 2000, and the viscosity at 60 ℃ was 1700 mPas.
In the acrylate mixture (B-2), the content ratio of each component to the total amount of the following components (B1) to (B6) is as follows.
(b4) Dipentaerythritol tetraacrylate 6%
(b5) 54 percent of dipentaerythritol pentaacrylate
(b6) Dipentaerythritol hexaacrylate 40%
However, the content of the components (b 4) to (b 6) is shown because the content of (b 1) dipentaerythritol monoacrylate, (b 2) dipentaerythritol diacrylate and (b 3) dipentaerythritol triacrylate is not more than the measurement limit value.
[ production of urethane acrylate composition [ I' -5]
A flask equipped with a thermometer, a stirrer, a water-cooled condenser and a nitrogen inlet was charged with 38.4g of isophorone diisocyanate (C-1), 161.6g of an acrylate mixture (A '-1) (acrylic acid adduct of pentaerythritol) having a hydroxyl value of 118mgKOH/g, 0.01g of hydroquinone methyl ether as a polymerization inhibitor and 0.01g of dibutyltin dilaurate as a reaction catalyst, and the reaction was allowed to proceed at 60 ℃ for 8 hours, whereupon the reaction was terminated when the remaining isocyanate group became 0.3% or less, and a urethane acrylate composition [ I' -5] (resin component concentration 100%) was obtained.
The weight average molecular weight of the obtained urethane acrylate composition [ I' -5] was 1400, and the viscosity at 60 ℃ was 3000 mPas.
In the acrylate mixture (a' -1), the content ratio of each component to the total amount of the following components (a 1) to (a 4) is as follows.
(a2) 5 percent of pentaerythritol diacrylate
(a3) 50 percent of pentaerythritol triacrylate
(a4) Pentaerythritol tetraacrylate 45%
However, the content of the (a 2) to (a 4) components is shown because the content of the (a 1) pentaerythritol monoacrylate is not more than the measurement limit value.
[ production of urethane acrylate composition [ I' -6]
A4-neck flask equipped with a thermometer, a stirrer, a water-cooled condenser and a nitrogen inlet was charged with 23.3g of hydrogenated xylylene diisocyanate (C-2), 76.7g of an acrylate mixture (A '-2) (acrylic acid adduct of pentaerythritol) having a hydroxyl value of 184.2mgKOH/g, 100g of ethyl acetate as a solvent, 0.08g of 4-methoxyphenol as a polymerization inhibitor and 0.05g of dibutyltin dilaurate as a reaction catalyst, and the reaction was terminated when the remaining isocyanate group became 0.1%, whereby a urethane acrylate composition [ I' -6] (resin component concentration: 50%) was obtained.
The weight average molecular weight of the obtained urethane acrylate composition [ I' -6] was 2200, and the viscosity at 20 ℃ was 85 mPas.
In the acrylate mixture (a' -2), the content ratio of each component to the total amount of the following components (a 1) to (a 4) is as follows.
Figure BDA0002179844210000371
[ production of urethane acrylate composition [ I' -7]
A4-neck flask equipped with a thermometer, stirrer, water-cooled condenser and nitrogen inlet was charged with 25.8g of isophorone diisocyanate (C-1), 74.2g of an acrylate mixture (A '-2) (acrylic adduct of pentaerythritol) having a hydroxyl value of 184.2mgKOH/g, 100g of ethyl acetate as a solvent, 0.08g of 4-methoxyphenol as a polymerization inhibitor and 0.05g of dibutyltin dilaurate as a reaction catalyst, and the reaction was terminated when the residual isocyanate group became 0.1%, to obtain a urethane acrylate composition [ I' -7] (resin component concentration 50%).
The weight-average molecular weight of the obtained urethane acrylate composition [ I' -7] was 2100, and the viscosity at 20 ℃ was 73 mPas.
< examples 5 to 12 and comparative examples 5 to 9>
[ production of an active energy ray-curable resin composition ]
The urethane acrylate-based composition obtained above ([ I ], [ II ], [ I' ]) was prepared to have a compounding composition shown in table 2 below, and 4 parts of 1-hydroxycyclohexyl phenyl ketone (ommirad 184, product of IGM) as a photopolymerization initiator (D) were added to 100 parts of the cured component to obtain an active energy ray-curable resin composition.
With respect to the obtained active energy ray-curable resin composition, a cured coating film was formed as follows, and the hardness and bendability of the cured coating film were evaluated. The evaluation results are shown in Table 2 below.
[ hardness of cured coating film ]
The active energy ray-curable resin composition obtained above was coated on an easy-adhesion PET film (manufactured by Toyo Co., ltd. "A4300", 15 cm. Times.15 cm in size, 125 μm in thickness) substrate using a coating bar, the cured coating film was 10 μm in thickness, dried at 60 ℃ for 3 minutes, and subjected to 2 passes of ultraviolet irradiation (cumulative irradiation amount 500 mJ/cm) from 18cm height at a conveyor speed of 5.1 m/min using high-pressure mercury lamps 80W and 1 lamp 2 ) To form a cured coating film.
The cured coating film coated on the easy-adhesion PET film was tested in accordance with JIS K-5600 to measure the pencil hardness.
[ bendability of cured coating film ]
A cured coating film was formed in the same manner as in the above hardness evaluation, and the cured coating film coated on the easy-to-bond PET film was subjected to bending evaluation in accordance with JIS K5600-5-1 using a cylindrical mandrel bending tester. The maximum diameter (integral value, mm) of the cured coating film for evaluation that cracked or peeled when the film was wound around a test bar with the film surface on the outside was measured. The smaller the value, the higher the flexibility of the coating film.
[ Table 2]
Figure BDA0002179844210000401
From the above evaluation results, it was found that: cured coatings obtained from active energy ray-curable resin compositions containing the urethane acrylate compositions [ I ] and [ II ] of examples 5 to 12 were excellent in hardness and bendability.
On the other hand, comparative example 5, which did not contain the urethane acrylate composition [ I ] but used only the urethane acrylate composition [ II ], exhibited poor bendability of the cured coating film. In addition, in comparative examples 6 and 7, which contained urethane acrylate compositions prepared using an acrylate mixture having a low hydroxyl value, the cured coating film had poor flexibility.
In addition, in comparative examples 8 and 9, which contained urethane acrylate compositions prepared using an acrylate mixture having a slightly higher hydroxyl value, the cured coating film was also poor in flexibility.
Thus, it can be seen that: the active energy ray-curable resin compositions of examples 5 to 12 were excellent in hardness and bendability, and useful for applications such as coating agents, particularly coating agents for hard coating and coating agents for optical films.
< example Using urethane (meth) acrylate composition [ III ]
Prior to the production of the urethane (meth) acrylate composition, the mixture (a), the mixture (a') for comparative example, the mixture (B), the polyisocyanate (C), and the photopolymerization initiator (D) were prepared as follows.
[ mixture (A) ]
A-1: the content ratio of each component to the total amount of the following components (a 1) to (a 4) is as follows.
Figure BDA0002179844210000411
[ mixture (A') (for comparative example) ]
A' -1: the content ratio of each component to the total amount of the following components (a 1) to (a 4) is as follows, and the content ratio is 118mgKOH/g of an acrylic acid adduct of pentaerythritol.
(a2) 5 percent of pentaerythritol diacrylate
(a3) 50 percent of pentaerythritol triacrylate
(a4) Pentaerythritol tetraacrylate 45%
However, the content of the (a 2) to (a 4) components is shown because the content of the (a 1) pentaerythritol monoacrylate is not more than the measurement limit value.
A' -2: the content ratio of each component to the total amount of the following components (a 1) to (a 4) in an acrylic acid adduct of pentaerythritol having a hydroxyl value of 184.2mgKOH/g is as follows.
Figure BDA0002179844210000412
Figure BDA0002179844210000421
[ mixture (B) ]
B-1: the content ratio of each component to the total amount of the following components (b 1) to (b 6) is as follows.
(b4) Dipentaerythritol tetraacrylate 18%
(b5) Dipentaerythritol pentaacrylate 51%
(b6) Dipentaerythritol hexaacrylate 31%
However, the content of the components (b 4) to (b 6) is shown because the content of (b 1) dipentaerythritol monoacrylate, (b 2) dipentaerythritol diacrylate, and (b 3) dipentaerythritol triacrylate is not more than the measurement limit value.
B-2: the content ratio of each component to the total amount of the following components (b 1) to (b 6) is as follows, and the acrylic acid adduct of dipentaerythritol having a hydroxyl value of 54mgKOH/g is obtained.
(b4) Dipentaerythritol tetraacrylate 6%
(b5) 54 percent of dipentaerythritol pentaacrylate
(b6) Dipentaerythritol hexaacrylate 40%
However, the content of the components (b 4) to (b 6) is shown because the content of (b 1) dipentaerythritol monoacrylate, (b 2) dipentaerythritol diacrylate, and (b 3) dipentaerythritol triacrylate is not more than the measurement limit value.
[ polyisocyanate (C) ]
C-1: isophorone diisocyanate
C-2: hydrogenated xylylene diisocyanate
C-4: xylylene diisocyanate
[ photopolymerization initiator (D) ]
D-1: 1-Hydroxycyclohexylphenone (manufactured by IGM, "Omnirad 184")
[ Synthesis example 1: urethane acrylate composition (III-1) ]
A4-neck flask equipped with a thermometer, a stirrer, a water-cooled condenser and a nitrogen inlet was charged with 24g of hydrogenated xylylene diisocyanate (C-2), 33g of an acrylate mixture (A-1) (an acrylic adduct of pentaerythritol) having a hydroxyl value of 288mgKOH/g, 43g of an acrylate mixture (B-1) (an acrylic adduct of dipentaerythritol) having a hydroxyl value of 96mgKOH/g, 100g of ethyl acetate as a solvent, 0.08g of 4-methoxyphenol as a polymerization inhibitor and 0.05g of dibutyltin dilaurate as a reaction catalyst, and the reaction was terminated at 60 ℃ when the remaining isocyanate group became 0.1%, whereby a urethane acrylate composition (III-1) (resin component concentration: 50%) was obtained.
The weight-average molecular weight of the obtained urethane acrylate composition (III-1) was 4900, and the viscosity at 20 ℃ was 40 mPas. The viscosity at 20 ℃ was measured using a B-type viscometer. The viscosity at 20 ℃ was measured, and the same applies hereinafter.
[ Synthesis example 2: urethane acrylate composition (III-2) ]
23g of xylylene diisocyanate (C-4), 33g of an acrylate mixture (A-1) (an acrylic acid adduct of pentaerythritol) having a hydroxyl value of 288mgKOH/g, 44g of an acrylate mixture (B-1) (an acrylic acid adduct of dipentaerythritol) having a hydroxyl value of 96mgKOH/g, 100g of ethyl acetate as a solvent, 0.08g of 4-methoxyphenol as a polymerization inhibitor, and 0.05g of dibutyltin dilaurate as a reaction catalyst were charged into a 4-neck flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas blowing port, and the reaction was terminated at 60 ℃ when the remaining isocyanate group became 0.1%, thereby obtaining a urethane acrylate composition (III-2) (resin component concentration: 50%).
The weight-average molecular weight of the obtained urethane acrylate composition (III-2) was 4600, and the viscosity at 20 ℃ was 30 mPas.
[ Synthesis example 3: urethane acrylate composition (III-3) ]
A4-neck flask equipped with a thermometer, a stirrer, a water-cooled condenser and a nitrogen inlet was charged with 24g of hydrogenated xylylene diisocyanate (C-2), 35g of an acrylate mixture (A-1) (an acrylic adduct of pentaerythritol) having a hydroxyl value of 288mgKOH/g, 81g of an acrylate mixture (B-2) (an acrylic adduct of dipentaerythritol) having a hydroxyl value of 54mgKOH/g, 60g of ethyl acetate as a solvent, 0.08g of 4-methoxyphenol as a polymerization inhibitor and 0.05g of dibutyltin dilaurate as a reaction catalyst, and the reaction was terminated at 60 ℃ when the remaining isocyanate group became 0.1%, thereby obtaining a urethane acrylate composition (III-3) (resin component concentration: 70%).
The weight-average molecular weight of the resulting urethane acrylate composition (III-3) was 3300, and the viscosity at 20 ℃ was 460 mPas.
[ Synthesis example 4: urethane acrylate composition (III-4) ]
39g of isophorone diisocyanate (C-1), 49g of an acrylate mixture (A-1) (an acrylic acid adduct of pentaerythritol) having a hydroxyl value of 288mgKOH/g, 112g of an acrylate mixture (B-2) (an acrylic acid adduct of dipentaerythritol) having a hydroxyl value of 54mgKOH/g, 0.08g of 4-methoxyphenol as a polymerization inhibitor, and 0.05g of dibutyltin dilaurate as a reaction catalyst were charged into a 4-neck flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen-blowing port, and the reaction was terminated when the remaining isocyanate group became 0.1%, to obtain a urethane acrylate composition (III-3) (resin component concentration 100%).
The weight average molecular weight of the obtained urethane acrylate-based composition (III-4) was 3800. Since the viscosity was very high, the viscosity could not be measured.
[ Synthesis example 5: urethane acrylate composition (III' -1) ]
A4-neck flask equipped with a thermometer, a stirrer, a water-cooled condenser and a nitrogen inlet was charged with 22g of hydrogenated xylylene diisocyanate (C-2), 78g of an acrylate mixture (A '-1) (an acrylic adduct of pentaerythritol) having a hydroxyl value of 118mgKOH/g, 40g of an acrylate mixture (B-1) (an acrylic adduct of dipentaerythritol) having a hydroxyl value of 96mgKOH/g, 60g of ethyl acetate as a solvent, 0.08g of 4-methoxyphenol as a polymerization inhibitor and 0.05g of dibutyltin dilaurate as a reaction catalyst, and the reaction was terminated at 60 ℃ when the remaining isocyanate group became 0.1%, thereby obtaining a urethane acrylate composition (III' -1) (resin component concentration: 70%).
The weight average molecular weight of the resulting urethane acrylate-based composition (III' -1) was 1700, and the viscosity at 20 ℃ was 140 mPas.
[ Synthesis example 6: urethane acrylate composition (III' -2) ]
A4-neck flask equipped with a thermometer, a stirrer, a water-cooled condenser and a nitrogen inlet was charged with 21.3g of hydrogenated xylylene diisocyanate (C-2), 61.0g of an acrylate mixture (A '-2) (an acrylic adduct of pentaerythritol) having a hydroxyl value of 184.2mgKOH/g, 17.6g of an acrylate mixture (B-1) (an acrylic adduct of dipentaerythritol) having a hydroxyl value of 96mgKOH/g, 100g of ethyl acetate as a solvent, 0.08g of 4-methoxyphenol as a polymerization inhibitor and 0.05g of dibutyltin dilaurate as a reaction catalyst, and the reaction was terminated at 60 ℃ until the remaining isocyanate group became 0.1%, whereby a urethane acrylate composition (III' -2) (resin component concentration: 50%) was obtained.
The weight average molecular weight of the obtained urethane acrylate composition (III' -2) was 2300, and the viscosity at 20 ℃ was 65 mPas.
[ Synthesis example 7: urethane acrylate composition (III' -3) ]
Into a 4-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser and a nitrogen inlet were charged 32g of xylylene diisocyanate (C-4), 68g of an acrylate mixture (A-1) (an acrylic acid adduct of pentaerythritol) having a hydroxyl value of 288mgKOH/g, 100g of ethyl acetate as a solvent, 0.08g of 4-methoxyphenol as a polymerization inhibitor and 0.05g of dibutyltin dilaurate as a reaction catalyst, and the reaction was terminated when the residual isocyanate group became 0.1% to obtain a urethane acrylate composition (III' -3) (resin component concentration: 50%).
The weight average molecular weight of the resulting urethane acrylate composition (III' -3) was 5900, and the viscosity at 20 ℃ was 50 mPas.
[ Synthesis example 8: production of urethane acrylate composition (III' -4)
28g of hydrogenated xylylene diisocyanate (C-2), 172g of an acrylate mixture (B-1) (acrylic adduct of dipentaerythritol) having a hydroxyl value of 96mgKOH/g, 0.08g of 4-methoxyphenol as a polymerization inhibitor, and 0.1g of dibutyltin dilaurate as a reaction catalyst were charged in a 4-neck flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen inlet, and the reaction was terminated when the remaining isocyanate group became 0.1%, whereby a urethane acrylate composition (III' -4) (resin component concentration 100%) was obtained.
The weight average molecular weight of the obtained urethane acrylate-based composition (III' -4) was 5500, and the viscosity at 60 ℃ was 39400 mPas. The viscosity at 60 ℃ was measured using an E-type viscometer.
< examples 13 to 16 and comparative examples 10 to 13>
[ active energy ray-curable resin composition ]
The urethane acrylate compositions (III-1 to 4, III' -1 to 4) obtained above were mixed with 4 parts of 1-hydroxycyclohexyl phenyl ketone (Omnirad 184, manufactured by IGM) as a photopolymerization initiator (D) per 100 parts of the curing component to obtain active energy ray-curable resin compositions.
The obtained active energy ray-curable resin composition was subjected to the following processes to form a cured coating film, and the cured coating film was evaluated for hardness, bendability, and scratch resistance. The evaluation results are shown in Table 3 below.
[ hardness of cured coating film ]
The active energy ray-curable resin composition obtained above was coated on an easy-adhesion PET film (manufactured by Toyo Co., ltd. "A4300", 15 cm. Times.15 cm in size, 125 μm in thickness) substrate using a coating bar, the cured coating film was 10 μm in thickness, dried at 60 ℃ for 3 minutes, and subjected to 2 passes of ultraviolet irradiation (cumulative irradiation amount 500 mJ/cm) from 18cm height at a conveyor speed of 5.1 m/min using high-pressure mercury lamps 80W and 1 lamp 2 ) To form a cured coating film.
The cured coating film coated on the easy-adhesion PET film was subjected to a test in accordance with JIS K-5600, and the pencil hardness was measured.
[ bendability of cured coating film ]
A cured coating film was formed in the same manner as in the above hardness evaluation, and the cured coating film coated on the easy-to-bond PET film was subjected to the bending evaluation in accordance with JIS K5600-5-1 using a cylindrical mandrel bending tester. The maximum diameter (integer value, mm) of the cured coating film for evaluation that cracks or peels when the film was wound around a test bar with the coated surface facing outward was measured. The smaller the value, the higher the flexibility of the coating film.
[ scratch resistance of cured coating film ]
A cured coating film was formed in the same manner as in the above hardness evaluation, and steel wool (BON STAR #0000, manufactured by japan steel wool corporation) was used for the cured coating film coated on the easy-to-adhere PET film, and the surface of the cured coating film was subjected to a load of 500g 10 times and then visually observed for the degree of surface damage.
(evaluation)
O. failure to confirm injury
X. confirmation of injury
[ Table 3]
Figure BDA0002179844210000471
From the above evaluation results, it was found that: the cured coating films obtained from the active energy ray-curable resin compositions containing the urethane acrylate composition [ III ] of examples 13 to 16 were excellent in hardness and bendability, and also in abrasion resistance.
On the other hand, in the case of comparative example 10 using an acrylic acid adduct of pentaerythritol having a low hydroxyl value (A' -1) of less than 200mgKOH/g, in the case of comparative example 13 using only an acrylic acid adduct of dipentaerythritol (B-1) in the mixtures (A) and (B), the cured coating film had poor bendability. In addition, in comparative example 11 using an acrylic acid adduct of pentaerythritol (A' -2) having a slightly lower hydroxyl value, hardness was slightly inferior and scratch resistance was poor. In addition, in the case of comparative example 12 in which only the acrylic acid adduct of pentaerythritol (A-1) having a high hydroxyl value was used in the mixtures (A) and (B), the scratch resistance of the cured coating film was not good.
Thus, it can be seen that: the active energy ray-curable resin compositions of examples 13 to 16 were excellent not only in hardness and bendability but also in abrasion resistance, and were useful for applications such as coating agents, particularly coating agents for hard coating and coating agents for optical films.
The above embodiments are disclosed as specific aspects of the present invention, but the above embodiments are merely illustrative and are not to be construed as limiting. Various modifications known to those skilled in the art are considered to be within the scope of the present invention.
Industrial applicability
The active energy ray-curable resin composition of the present invention is less likely to curl due to a small curing shrinkage when forming a cured coating film, and can form a coating film having excellent hardness and bendability, and is useful as a coating agent, particularly a coating agent for hard coating and a coating agent for an optical film. Further, the composition is also useful as a paint, ink, or the like. Further, the resin composition side of the uncured laminated film in which the active energy ray-curable resin composition layer is formed on the film is attached to a molded article, and then active energy ray curing is performed, whereby the cured film can be easily formed into various molded articles.

Claims (6)

1. An active energy ray-curable resin composition characterized by containing a urethane (meth) acrylate composition [ I ],
the urethane (meth) acrylate composition [ I ] is obtained by reacting (meth) acrylates (a 1) to (a 3) in a mixture (A) with a polyisocyanate (CA), wherein the mixture (A) is a mixture composed of the following (meth) acrylates (a 1) to (a 4) which are reaction products of pentaerythritol and (meth) acrylic acid, the content ratio of pentaerythritol di (meth) acrylate (a 2) in the mixture (A) of the (meth) acrylates (a 1) to (a 4) is 10 to 50% by weight,
the content ratio of pentaerythritol di (meth) acrylate (a 2) to the total amount of the (meth) acrylic acid esters (a 1) to (a 3) is 15 to 55% by weight,
the hydroxyl value of the mixture (A) is 230-380 mgKOH/g;
the urethane (meth) acrylate composition [ I ] has a weight-average molecular weight of 1000 to 20000,
(a1) Pentaerythritol mono (meth) acrylate
(a2) Pentaerythritol di (meth) acrylate
(a3) Pentaerythritol tri (meth) acrylate
(a4) Pentaerythritol tetra (meth) acrylate.
2. An active energy ray-curable resin composition comprising a urethane (meth) acrylate composition [ I ] and a urethane (meth) acrylate composition [ II ],
the urethane (meth) acrylate composition [ I ] is obtained by reacting (meth) acrylates (a 1) to (a 3) in a mixture (A) composed of the following (meth) acrylates (a 1) to (a 4) which are a reaction product of pentaerythritol and (meth) acrylic acid with a polyisocyanate (CA),
the urethane (meth) acrylate composition [ II ] is obtained by reacting (meth) acrylates (B1) to (B5) in a mixture (B) composed of the following (meth) acrylates (B1) to (B6) which are a reaction product of dipentaerythritol and (meth) acrylic acid with a polyisocyanate (CB),
in the urethane (meth) acrylate composition [ I ],
the content ratio of pentaerythritol di (meth) acrylate (a 2) in the mixture (A) of the (meth) acrylic esters (a 1) to (a 4) is 10 to 50% by weight,
the content ratio of pentaerythritol di (meth) acrylate (a 2) to the total amount of the (meth) acrylic acid esters (a 1) to (a 3) is 15 to 55% by weight,
the mixture (A) has a hydroxyl value of 230 to 380mgKOH/g,
in the urethane (meth) acrylate-based composition [ II ],
the content ratio of dipentaerythritol penta (meth) acrylate (B5) in the mixture (B) of the (meth) acrylic esters (B1) to (B6) is 15 to 60% by weight,
the content ratio of dipentaerythritol penta (meth) acrylate (b 5) to the total amount of the (meth) acrylic acid esters (b 1) to (b 5) is 45 to 90% by weight,
the content ratio of dipentaerythritol tetra (meth) acrylate (B4) in the mixture (B) of the (meth) acrylic esters (B1) to (B6) is 1 to 35% by weight,
the content ratio of the dipentaerythritol tetra (meth) acrylate (b 4) to the total amount of the (meth) acrylates (b 1) to (b 5) is 2 to 40% by weight,
the mixture (B) has a hydroxyl value of 40 to 130mgKOH/g;
the urethane (meth) acrylate composition [ I ] has a weight-average molecular weight of 1000 to 20000, and the urethane (meth) acrylate composition [ II ] has a weight-average molecular weight of 1000 to 20000;
mixture (A)
(a1) Pentaerythritol mono (meth) acrylate
(a2) Pentaerythritol di (meth) acrylate
(a3) Pentaerythritol tri (meth) acrylate
(a4) Pentaerythritol tetra (meth) acrylate
Mixture (B)
(b1) Dipentaerythritol mono (meth) acrylate
(b2) Dipentaerythritol di (meth) acrylate
(b3) Dipentaerythritol tri (meth) acrylate
(b4) Dipentaerythritol tetra (meth) acrylate
(b5) Dipentaerythritol penta (meth) acrylate
(b6) Dipentaerythritol hexa (meth) acrylate.
3. An active energy ray-curable resin composition characterized by containing a urethane (meth) acrylate composition [ III ],
the urethane (meth) acrylate-based composition [ III ] is obtained by reacting (meth) acrylates (a 1) to (a 3) in a mixture (a) composed of the following (meth) acrylates (a 1) to (a 4) as a reaction product of pentaerythritol and (meth) acrylic acid, and (meth) acrylates (B1) to (B6) as a reaction product of dipentaerythritol and (meth) acrylic acid, with a polyisocyanate (CC);
the content ratio of pentaerythritol di (meth) acrylate (a 2) in the mixture (A) of the (meth) acrylic esters (a 1) to (a 4) is 10 to 50% by weight,
the content ratio of pentaerythritol di (meth) acrylate (a 2) to the total amount of the (meth) acrylic acid esters (a 1) to (a 3) is 15 to 55% by weight,
the content ratio of dipentaerythritol penta (meth) acrylate (B5) in the mixture (B) of the (meth) acrylic esters (B1) to (B6) is 15 to 60% by weight,
the content ratio of dipentaerythritol penta (meth) acrylate (b 5) to the total amount of the (meth) acrylic acid esters (b 1) to (b 5) is 45 to 90% by weight,
the content ratio of dipentaerythritol tetra (meth) acrylate (B4) in the mixture (B) of the (meth) acrylic esters (B1) to (B6) is 1 to 35% by weight,
the content ratio of the dipentaerythritol tetra (meth) acrylate (b 4) to the total amount of the (meth) acrylates (b 1) to (b 5) is 2 to 40% by weight,
the mixture (A) has a hydroxyl value of 230 to 380mgKOH/g, and the mixture (B) has a hydroxyl value of 40 to 130mgKOH/g,
the urethane (meth) acrylate composition [ III ] has a weight-average molecular weight of 1000 to 20000,
mixture (A)
(a1) Pentaerythritol mono (meth) acrylate
(a2) Pentaerythritol di (meth) acrylate
(a3) Pentaerythritol tri (meth) acrylate
(a4) Pentaerythritol tetra (meth) acrylate
Mixture (B)
(b1) Dipentaerythritol mono (meth) acrylate
(b2) Dipentaerythritol di (meth) acrylate
(b3) Dipentaerythritol tri (meth) acrylate
(b4) Dipentaerythritol tetra (meth) acrylate
(b5) Penta (meth) acrylic acid dipentaerythritol ester
(b6) Dipentaerythritol hexa (meth) acrylate.
4. A coating agent comprising the active energy ray-curable resin composition according to any one of claims 1 to 3.
5. The coating agent according to claim 4, wherein the coating agent is used as a coating agent for hard coating.
6. The coating agent according to claim 4, which is used as a coating agent for an optical film.
CN201880014095.9A 2017-03-31 2018-03-30 Active energy ray-curable resin composition and coating agent Active CN110382575B (en)

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