CN113166363A - Urethane (meth) acrylate resin, curable resin composition, and cured product - Google Patents
Urethane (meth) acrylate resin, curable resin composition, and cured product Download PDFInfo
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- CN113166363A CN113166363A CN201980076312.1A CN201980076312A CN113166363A CN 113166363 A CN113166363 A CN 113166363A CN 201980076312 A CN201980076312 A CN 201980076312A CN 113166363 A CN113166363 A CN 113166363A
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- 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
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- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
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Abstract
Disclosed is a urethane (meth) acrylate resin obtained by reacting a hydroxyl group-containing (meth) acrylate compound with an aromatic group-containing diisocyanate and a polyol-modified aromatic hydrocarbon formaldehyde resin obtained by modifying an aromatic hydrocarbon formaldehyde resin with a polyol.
Description
Technical Field
The present invention relates to a urethane (meth) acrylate resin, a curable resin composition, and a cured product.
Background
In recent years, there has been a demand for curable resin compositions that can form cured films having excellent hardness, flexibility, abrasion resistance, low curling properties, high refractive index, adhesion, and transparency in applications to protective coating materials for preventing scratches on the surfaces of various substrates and contamination, adhesives for various substrates, sealing materials, thin film liquid crystal devices, touch panels, and antireflection films for plastic optical components and the like. Among these required performances, in recent years, it has been particularly required to achieve compatibility between adhesiveness and flexibility and hardness. In order to satisfy such a demand, various compositions have been proposed, but at present, a curable resin composition having characteristics such that a cured film has high hardness and is excellent in adhesion and flexibility has not yet been obtained.
For example, patent document 1 proposes a resin composition for optical materials, which is a reaction product of a (meth) acrylate having 1 hydroxyl group in 1 molecule, an aromatic diisocyanate, and a diol compound as an optional component, and which contains: urethane (meth) acrylate having a bisphenol methane structure in the molecule, a diluent, and methyl benzoylformate as a photopolymerization initiator.
Patent document 2 proposes an active energy ray-curable resin composition containing a specific urethane (meth) acrylate oligomer as an active energy ray-curable resin composition having excellent adhesion to a polycarbonate substrate.
Patent document 3 proposes a cured coating film having excellent hardness and scratch resistance and less occurrence of curl and crack, and a urethane (meth) acrylate compound that provides the cured coating film.
Patent document 4 relates to an active energy ray-curable resin composition containing a urethane (meth) acrylate composition and a coating agent, and proposes an active energy ray-curable resin composition capable of forming a coating film having a small cure shrinkage, being less likely to curl, and having excellent bendability when forming a cured coating film.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 10-324726
Patent document 2: japanese patent laid-open No. 2006-45361
Patent document 3: international publication No. 2010/146801
Patent document 4: japanese patent laid-open publication No. 2017-203068
Disclosure of Invention
Problems to be solved by the invention
As described above, various urethane (meth) acrylate resin compositions have been proposed, but currently, no curable resin composition is obtained which imparts to a cured film excellent in all of hardness, solvent resistance, adhesion, low curling properties, and flexibility.
Patent document 1 mainly aims at rapid curing and adhesion to methacrylic resins, but does not mention properties such as flexibility and low curling properties.
Patent document 2 discloses excellent adhesion to polycarbonate plates, but does not mention properties such as adhesion to other resin substrates, hardness, solvent resistance, low curling properties, and flexibility.
Patent documents 3 and 4 are excellent in hardness, but for the purpose of improving flexibility and low curling properties, there is still room for improvement in flexibility and low curling properties.
The present invention has been made in view of the above circumstances, and an object thereof is to provide: a urethane (meth) acrylate resin which can provide a cured film having excellent adhesion in addition to excellent hardness, solvent resistance, flexibility and low curling properties, a curable resin composition containing the same, and a cured product of the resin composition.
Means for solving the problems
The present inventors have conducted intensive studies and, as a result, have found that: the present inventors have completed the present invention by solving the above problems by reacting a polyol-modified aromatic hydrocarbon formaldehyde resin obtained by modifying an aromatic hydrocarbon formaldehyde resin with a polyol, a urethane (meth) acrylate resin obtained by reacting an aromatic group-containing diisocyanate and a hydroxyl group-containing (meth) acrylate.
Namely, the present invention is as follows.
(1)
A urethane (meth) acrylate resin obtained by reacting a polyol-modified aromatic hydrocarbon formaldehyde resin, which is obtained by modifying an aromatic hydrocarbon formaldehyde resin with a polyol, with an aromatic group-containing diisocyanate, and with a hydroxyl group-containing (meth) acrylate compound.
(2)
The urethane (meth) acrylate resin according to (1), wherein the weight average molecular weight (Mw) is 500 to 100000.
(3)
The urethane (meth) acrylate resin according to (1) or (2), wherein the weight average molecular weight of the polyol-modified aromatic hydrocarbon formaldehyde resin is 300 to 5000.
(4)
The urethane (meth) acrylate resin according to any one of (1) to (3), wherein the hydroxyl value of the polyol-modified aromatic hydrocarbon formaldehyde resin is 100 to 400 mgKOH/g.
(5)
The urethane (meth) acrylate resin according to any one of (1) to (4), wherein the molar ratio (OH/NCO) of the hydroxyl group of the polyol-modified aromatic hydrocarbon formaldehyde resin to the isocyanate group of the aromatic group-containing diisocyanate is 0.50 to 0.95, the molar ratio (OH/NCO) of the hydroxyl group of the polyol-modified aromatic hydrocarbon formaldehyde resin to the total hydroxyl group of the hydroxyl group-containing (meth) acrylate compound to the isocyanate group of the aromatic group-containing diisocyanate is 0.50 to 0.95, and the molar ratio (OH/NCO) of the hydroxyl group of the polyol-modified aromatic hydrocarbon formaldehyde resin to the total hydroxyl group of the hydroxyl group-containing (meth) acrylate compound to the isocyanate group of the aromatic group-containing diisocyanate is 0.4T/NCO) is 1.0-1.2.
(6)
The urethane (meth) acrylate resin according to any one of (1) to (5), wherein the polyol-modified aromatic hydrocarbon formaldehyde resin contains an ethylene glycol-modified xylene formaldehyde resin.
(7)
The urethane (meth) acrylate resin according to any one of (1) to (6), wherein the aromatic group-containing diisocyanate is at least 1 aromatic diisocyanate selected from the group consisting of diphenylmethane diisocyanate and tolylene diisocyanate.
(8)
A curable resin composition comprising the urethane (meth) acrylate resin according to any one of (1) to (7).
(9)
A cured product obtained by curing the curable resin composition of (8).
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a cured film having hardness, solvent resistance, flexibility, low curling properties, and excellent adhesion can be provided.
Detailed Description
Hereinafter, a mode for carrying out the present invention (hereinafter, simply referred to as "the present embodiment") will be described in detail. The following embodiments are examples for illustrating the present invention, and the present invention is not intended to be limited to the following. The present invention can be suitably modified and implemented within the scope of the gist thereof. In the present specification, the expression "XX to YY" means "XX or more and YY or less".
The "(meth) acrylate" in the present specification means both "acrylate" and "methacrylate". The same applies to other similar terms ("(meth) acrylic acid", "(meth) acryl", etc.).
[ urethane (meth) acrylate resin ]
The urethane (meth) acrylate resin of the present embodiment is obtained by reacting a polyol-modified aromatic hydrocarbon formaldehyde resin, an aromatic group-containing diisocyanate, and a hydroxyl group-containing (meth) acrylate compound.
The urethane (meth) acrylate resin of the present embodiment contains a (meth) acryloyl group, and thus can be easily cured by irradiation with UV or the like or heating. The resulting cured product has high hardness and high solvent resistance, and further has excellent adhesion and flexibility. This is considered to be due to the characteristics inherent in the aromatic hydrocarbon formaldehyde resin, i.e., excellent adhesion and flexibility.
Since the urethane (meth) acrylate resin of the present embodiment is obtained from a polyol-modified aromatic hydrocarbon formaldehyde resin having a structure that is difficult to specify by analysis, it is also difficult to analyze and specify the structure of the urethane (meth) acrylate resin.
From the viewpoint of improving the adhesion, the weight average molecular weight (Mw) of the urethane (meth) acrylate resin of the present embodiment is preferably 500 to 100000, more preferably 500 to 70000, and further preferably 700 to 50000 in terms of polystyrene. The weight average molecular weight (Mw) can be determined by Gel Permeation Chromatography (GPC).
The urethane (meth) acrylate resin of the present embodiment is obtained by reacting a polyol-modified aromatic hydrocarbon formaldehyde resin, an aromatic group-containing diisocyanate, and a hydroxyl group-containing (meth) acrylate compound as described above, and specifically, preferably, the molar ratio (OH/NCO) of the hydroxyl group of the polyol-modified aromatic hydrocarbon formaldehyde resin to the isocyanate group of the aromatic group-containing diisocyanate is 0.50 to 0.95, and the molar ratio (OH/NCO) of the total hydroxyl group of the polyol-modified aromatic hydrocarbon formaldehyde resin and the hydroxyl group of the hydroxyl group-containing (meth) acrylate compound to the isocyanate group of the aromatic group-containing diisocyanate is 0.50 to 0.95T/NCO) is 1.0-1.2.
The molar ratio of the hydroxyl group of the polyol-modified aromatic hydrocarbon formaldehyde resin to the isocyanate group of the aromatic group-containing diisocyanate to the hydroxyl group of the hydroxyl group-containing (meth) acrylate is in the above range, and thus a urethane (meth) acrylate resin having excellent adhesion and flexibility, high hardness, and high solvent resistance can be obtained.
The molar ratio (OH/NCO) of the hydroxyl group of the polyol-modified aromatic hydrocarbon formaldehyde resin to the isocyanate group of the aromatic group-containing diisocyanate is more preferably 0.50 to 0.90, and still more preferably 0.50 to 0.80.
A total of hydroxyl groups (OH) of the hydroxyl groups of the polyol-modified aromatic hydrocarbon formaldehyde resin and the hydroxyl groups of the hydroxyl group-containing (meth) acrylate compoundT) The molar ratio (OH) to the isocyanate group of the aromatic group-containing diisocyanateTNCO) is more preferably 1.0 to 1.1, still more preferably 1.0 to 1.05.
The hydroxyl value of the urethane (meth) acrylate resin of the present embodiment is preferably 40mgKOH/g or less, and more preferably 20mgKOH/g or less, from the viewpoint of UV curability. The lower limit is not particularly limited, but is, for example, 5mgKOH/g or more. The hydroxyl value can be measured by a method according to the acetic anhydride-pyridine method (JIS K1557-1: 2007).
The urethane (meth) acrylate in the present embodiment can sufficiently carbamate the hydroxyl groups (alcoholic hydroxyl groups) contained in the polyol-modified aromatic hydrocarbon formaldehyde resin. Therefore, the hydroxyl value of the urethane (meth) acrylate resin can be suppressed to be low.
[ polyhydric alcohol-modified aromatic Hydrocarbon Formaldehyde resin ]
In the present embodiment, the polyol-modified aromatic hydrocarbon formaldehyde resin refers to an aromatic hydrocarbon formaldehyde resin modified with a polyol.
(aromatic Hydrocarbon Formaldehyde resin)
The aromatic hydrocarbon formaldehyde resin is obtained by reacting an aromatic hydrocarbon with formaldehyde. Examples of the aromatic hydrocarbon include at least 1 selected from the group consisting of benzene, toluene, xylene, mesitylene, ethylbenzene, propylbenzene, decylbenzene, cyclohexylbenzene, biphenyl, methylbiphenyl, naphthalene, methylnaphthalene, dimethylnaphthalene, ethylnaphthalene, anthracene, methylanthracene, dimethylanthracene, ethylanthracene, and binaphthyl. From the viewpoint of more excellent adhesiveness, at least 1 selected from the group consisting of xylene, toluene, and mesitylene is preferable, and xylene is more preferable. From the same viewpoint as described above, the aromatic hydrocarbon formaldehyde resin of the present embodiment preferably contains at least 1 selected from a xylene formaldehyde resin obtained by reacting xylene with formaldehyde, a toluene formaldehyde resin obtained by reacting toluene with formaldehyde, and a mesitylene formaldehyde resin obtained by reacting mesitylene with formaldehyde, and more preferably contains a xylene formaldehyde resin.
The aromatic hydrocarbon formaldehyde resin may be a commercially available one or may be prepared by a known method. Examples of commercially available products include "NIKANOL LL" manufactured by Fudow co. Known methods include, for example: a method of condensation reacting an aromatic hydrocarbon with formaldehyde in the presence of a catalyst by the method described in Japanese patent publication No. 37-5747 and the like.
(polyols)
As the polyol, an aliphatic polyol is preferable. The aliphatic polyhydric alcohol is not particularly limited, and examples thereof include trimethylolpropane, neopentyl glycol, esterdiol, spiroglycol, pentaerythritol, ethylene glycol, diethylene glycol, dipropylene glycol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 2, 5-hexanediol, 1, 2-hexanediol, trimethylolethane, 1, 2-octanediol, 1, 10-decanediol, 3-hexyne-2, 5-diol, 2, 5-dimethyl-3-hexyne-2, 5-diol, 2, 4-trimethyl-1, 3-pentanediol, polyethylene glycol, and polyoxypropylene glycol. Among them, trimethylolpropane and ethylene glycol are more preferable. These polyols may be used alone in 1 kind, or in combination of 2 or more kinds.
The polyol-modified aromatic hydrocarbon formaldehyde resin preferably contains at least 1 selected from the group consisting of a polyol-modified xylene formaldehyde resin, a polyol-modified toluene formaldehyde resin, and a polyol-modified mesitylene formaldehyde resin, and more preferably contains a polyol-modified xylene formaldehyde resin, from the viewpoint of flexibility. Among them, ethylene glycol-modified xylene formaldehyde resins are preferably contained.
The polyol-modified aromatic hydrocarbon formaldehyde resin of the present embodiment may be a commercially available product or may be produced by a known method. Examples of commercially available products include "K-100", "K-140", "K-100E" and "K-140E" manufactured by Fudow Co., Ltd. A known method can be produced by subjecting an aromatic hydrocarbon formaldehyde resin and a polyhydric alcohol to a condensation reaction in the presence of an acidic catalyst, as described in japanese patent application laid-open No. 04-224815, for example.
[ Properties of polyol-modified aromatic Hydrocarbon Formaldehyde resin ]
The hydroxyl value (OH value) of the polyol-modified aromatic hydrocarbon formaldehyde resin is preferably 100 to 400mgKOH/g, more preferably 130 to 300mgKOH/g, and still more preferably 140 to 190 mgKOH/g. When the hydroxyl value is in the above range, the properties (hardness, solvent resistance, etc.) of the obtained urethane (meth) acrylate and the properties (adhesion, flexibility, etc.) of the polyol-modified aromatic hydrocarbon formaldehyde resin can be well balanced. The hydroxyl value can be measured by a method according to the acetic anhydride-pyridine method (JIS K1557-1: 2007).
The polyol-modified aromatic hydrocarbon formaldehyde resin of the present embodiment preferably has a weight average molecular weight in GPC of 300 to 5000, more preferably 400 to 1000, further preferably 500 to 800, and further preferably 550 to 700 in terms of polystyrene. By setting the weight average molecular weight in the above range, a urethane (meth) acrylate resin having excellent hardness, solvent resistance, flexibility, etc. and excellent adhesion can be obtained to be provided to a cured film.
[ aromatic group-containing diisocyanate ]
The aromatic group-containing diisocyanate in the present embodiment is an isocyanate compound having 2 isocyanate groups and an aromatic ring present in the molecule, and is not particularly limited as long as the characteristic is satisfied. Specific examples of the aromatic group-containing diisocyanate include at least 1 selected from the group consisting of 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, diphenylmethane diisocyanate, cycloalkylene diisocyanate, tolylene diisocyanate, dimethylbiphenyl diisocyanate, diphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, dibenzyl diisocyanate, phenylene diisocyanate, xylene diisocyanate, and the like.
Among them, as the aromatic group-containing diisocyanate, at least 1 aromatic diisocyanate selected from the group consisting of diphenylmethane diisocyanate and tolylene diisocyanate is more preferably used. "aromatic diisocyanate" refers to an isocyanate compound in which 2 isocyanate groups present in the molecule are directly bonded to an aromatic ring.
[ hydroxyl group-containing (meth) acrylate Compound ]
The hydroxyl group-containing (meth) acrylate compound in the present embodiment is not particularly limited as long as it is a compound having at least a hydroxyl group and a (meth) acryloyl group in 1 molecule. Specific examples of the hydroxyl group-containing (meth) acrylate compound include: hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, 5-hydroxycyclooctyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, and the like; polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate; hydroxyl group-containing (meth) acrylamides such as N-methylol (meth) acrylamide; and (c) a reaction product obtained by reacting (meth) acrylic acid with vinyl alcohol, vinylphenol, and a diglycidyl ester of bisphenol a. Among them, hydroxyalkyl (meth) acrylates are preferable, and 2-hydroxyethyl (meth) acrylate is more preferable.
[ Process for producing urethane (meth) acrylate resin ]
The urethane (meth) acrylate resin in the present embodiment can be produced by adding the above-mentioned polyol-modified aromatic hydrocarbon formaldehyde resin, aromatic group-containing diisocyanate compound, and hydroxyl group-containing (meth) acrylate to an organic solvent and reacting them.
Alternatively, the polyol-modified aromatic hydrocarbon formaldehyde resin may be obtained by reacting the above-mentioned polyol-modified aromatic hydrocarbon formaldehyde resin with an aromatic group-containing diisocyanate compound to obtain a terminal isocyanate urethane prepolymer, and reacting the obtained terminal isocyanate urethane prepolymer with a hydroxyl group-containing (meth) acrylate.
The above reaction is a reaction between a hydroxyl group and an isocyanate group, and can be carried out by using a general urethanization catalyst such as dibutyltin dilaurate or dibutyltin diethylhexanoate in the presence of an organic solvent which is inactive to an isocyanate group, that is, a hydrocarbon-based or ester-based organic solvent, and continuing the reaction at a temperature of usually 10 to 100 ℃, preferably 30 to 90 ℃ for about 1 to 20 hours.
As described above, the molar ratio (OH/NCO) of the hydroxyl group of the polyol-modified aromatic hydrocarbon formaldehyde resin to the isocyanate group of the aromatic group-containing diisocyanate is 0.50 to 0.95, the total hydroxyl group of the polyol-modified aromatic hydrocarbon formaldehyde resin and the hydroxyl group of the hydroxyl group-containing (meth) acrylate compound, and the molar ratio (OH) to the isocyanate group of the aromatic group-containing diisocyanateT/NCO) is preferably 1.0 to 1.2, so that a urethane (meth) acrylate resin having excellent adhesiveness and flexibility, high hardness, and high solvent resistance can be produced. More preferred molar ratios are as described above.
Known urethanization catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, bismuth tris (2-ethylhexanoate), zirconium tetraacetylacetonate, etc. can be used. The urethanization catalyst may be used in an amount of usually 50 to 1000 mass ppm, preferably 50 to 500 mass ppm, based on the total mass of the raw materials to be reacted. However, in order to maintain the properties of the obtained urethane (meth) acrylate well, it is preferable to use a smaller amount of the urethane-forming catalyst.
In the reaction in the presence of the (meth) acrylate, it is preferable to carry out in the presence of air or oxygen for the purpose of preventing polymerization of the (meth) acryloyl group. The reaction can be carried out by adding a commonly used polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, or 2, 6-di-t-butyl-4-methylphenol (BHT).
[ curable resin composition containing urethane (meth) acrylate resin ]
The curable resin composition of the present embodiment contains the urethane (meth) acrylate resin.
The curable resin composition may contain, within a range not to impair the characteristics of the present embodiment: resins other than the urethane (meth) acrylate resin, such as epoxy resins, cyanate ester compounds, phenol resins, oxetane resins, and benzoxazine compounds, various high molecular compounds such as oligomers and elastomers, monomers having a polymerizable functional group such as a compound having an ethylenically unsaturated group, maleimide compounds, fillers, flame retardants, silane coupling agents, moisture dispersants, photopolymerization initiators, photocuring initiators, thermosetting accelerators, and various additives. The components contained in the curable resin composition of the present embodiment are not particularly limited as long as they are generally used.
Examples of the various additives include ultraviolet absorbers, antioxidants, fluorescent brighteners, photosensitizers, dyes, pigments, thickeners, lubricants, defoamers, leveling agents, surface conditioners, gloss agents, and polymerization inhibitors.
The above components other than the urethane (meth) acrylate resin may be used alone in 1 kind, or may be suitably mixed in 2 or more kinds. The amount of each component may be adjusted in various ways depending on the application.
In the curable resin composition of the present embodiment, in order to obtain the characteristics of the present embodiment, the urethane (meth) acrylate resin is preferably 40% by mass or more. The urethane (meth) acrylate resin in the curable resin composition is more preferably 60% by mass or more, and still more preferably 70% by mass or more.
The method for producing the curable resin composition of the present embodiment is not particularly limited. For example, the following methods may be mentioned: the above components are mixed in a solvent in this order and sufficiently stirred.
In the production of the cured resin composition, a known treatment (stirring, mixing, kneading, etc.) for uniformly dissolving or dispersing each component may be performed as necessary. The stirring, mixing and kneading treatment can be suitably carried out by using a known apparatus such as a stirring apparatus for dispersion purpose, e.g., an ultrasonic homogenizer, an apparatus for mixing purpose, e.g., a three-roll mill, a ball mill, a bead mill or a sand mill, or a revolution or rotation type mixing apparatus.
In the preparation of the composition of the present embodiment, an organic solvent may be used as necessary. The type of the organic solvent is not particularly limited as long as the resin in the composition can be dissolved.
The organic solvent is not particularly limited, and examples thereof include ketones such as acetone, methyl ethyl ketone, and methyl cellosolve; aromatic hydrocarbons such as toluene and xylene; amides such as dimethylformamide; propylene glycol monomethyl ether and its acetate. These organic solvents may be used alone in 1 kind, or may be suitably mixed in 2 or more kinds.
[ cured product ]
The cured product of the present embodiment is obtained by curing the above-described curable resin composition. The cured product can be obtained by various known methods. Examples of the curing method include irradiation with UV, EUV, or the like, heating, or the like, and these may be used in combination.
The urethane (meth) acrylate resin of the present embodiment has high reactivity, and is therefore suitable for a process with high productivity in which instantaneous curing is performed under UV, EUV, or the like. Further, since the cured product has high reactivity, a high-quality cured product can be stably supplied. The urethane (meth) acrylate resin and the cured product of the present embodiment can be suitably used for protective coating materials, adhesives for various substrates, sealing materials, antireflection films for film-type liquid crystal devices, touch panels, plastic optical components, and the like.
When the ultraviolet ray is irradiated, the dose of the ultraviolet ray can be adjusted as required, and the dose can be set to 0.05J/cm, for example2～10J/cm2The irradiation is performed with right and left irradiation amounts.
The heating conditions may be appropriately selected depending on the urethane (meth) acrylate resin, the components in the composition containing the resin, the contents of the resin and the components, and the like, and are preferably selected in the range of from 20 minutes to 180 minutes at 150 to 220 ℃, and more preferably in the range of from 30 minutes to 150 minutes at 160 to 200 ℃.
[ use ]
The urethane (meth) acrylate resin, the curable resin composition, and the cured product of the present embodiment can be used for various applications.
Examples thereof include adhesives, and optical materials and medical materials such as touch panels, various lens materials, and dental materials, automotive and construction materials such as paints, coating agents, and primers, artificial leathers and synthetic leathers such as shoes, bags, and bags, polymerization materials, molding materials, gas separation membranes, fuel cell membranes, optical waveguides, and holograms.
Can be particularly suitably used for various UV-curable coating materials/coating materials for self-repairable coatings/coatings for automobiles, mobile terminals/weak electric products, optical disks, optical fibers, cosmetic containers, building materials/floors; UV-curable inkjet inks, UV-curable resins for nanoimprinting, UV-curable resins for 3D printers, UV inks such as photosensitive conductive pastes, UV-curable adhesives, OCAs for touch panels, OCR for touch panels, UV adhesives such as sealing materials for organic EL, and the like; a sealing material; a material for a cushion coating film; lenses (optical readheads, microlenses, spectacle lenses); polarizing films (for liquid crystal displays, etc.); antireflection films (antireflection films for display devices, etc.); a film for a touch panel; a film for a flexible substrate; an optical material for a thin film (such as a filter, a protective film, and an antireflection film) for displays (particularly thin displays) such as PDPs (plasma displays), LCDs (liquid crystal displays), VFDs (vacuum fluorescent displays), SED (surface conduction electron-emitting device displays), FED (field emission displays), NED (nano-emission displays), picture tubes, and electronic papers.
Examples
The present invention will be described in further detail below with reference to examples and comparative examples, but the present invention is not limited to these examples at all.
The evaluation methods used in the present examples and comparative examples are as follows.
(1) Weight average molecular weight (Mw)
The weight average molecular weight (Mw) was determined in terms of polystyrene by GPC analysis. The apparatus and analysis conditions used for the analysis are as follows.
The device comprises the following steps: shodex GPC-101 type (product of Shorey electric corporation)
Column: shodex LF-804X 3 (product of Showa Denko K.K.)
Eluent: tetrahydrofuran (THF)
Flow rate: 1.0 mL/min
Column temperature: 40 deg.C
A detector: RI (differential refraction detector)
(2) Hydroxyl number (OH number, mgKOH/g)
Measured according to the acetic anhydride-pyridine method (JIS K1557-1: 2007).
(3) Brushing test
For the resulting cured coating film, the coating was rubbed with a cotton swab impregnated with acetone. The surface was evaluated as "good" when it was not dissolved and as "good" when it was dissolved.
(4) Hardness of pencil
For the obtained cured coating film, the film thickness was measured in accordance with JIS K5600-5-4: 1999.
(5) Flexibility
For the obtained cured coating film, the film thickness was measured in accordance with JIS K5600-5-1: 1999, evaluation was made based on the following criteria.
O: the cured film was not cracked or peeled off with a mandrel having a diameter of 2 mm.
X: the cured film was cracked and peeled off with a mandrel having a diameter of 2 mm.
(6) Crimpability (four corners bounce height)
The coating was applied to an easy-adhesion PET film (COSMOSHINE A4100, manufactured by Toyo Boseki K.K.), the cured coating film was cut out so as to be 10 cm. times.10 cm, and the curl value was determined as the average value (mm) of the heights of four corners which bounce. Evaluation criteria are shown below.
O: the mean value of the bounce heights of the four corners is less than 5 mm.
X: the average value of the bounce heights of the four corners is more than 5 mm.
(7) Adhesion Property
For the obtained cured coating film, the film thickness was measured in accordance with JIS K5600-5-6: 1999, 100 grid-like cuts were introduced at intervals of 1mm, and adhesion was evaluated. Evaluation criteria are shown below.
O: the number of the non-peeled grids in 100 grids is 90 or more.
X: the number of non-peeled grids of the 100 grids was less than 90.
< example 1 >
A2L three-necked flask was charged with 240 parts by mass of toluene, 205 parts by mass of diphenylmethane diisocyanate, 260 parts by mass of K-140E (Fudow Co., Ltd., manufactured by Ltd., glycol-modified xylene resin, hydroxyl value: 177mgKOH/g, weight average molecular weight: 580), 95 parts by mass of 2-hydroxyethyl acrylate, 0.2 part by mass of dibutyltin dilaurate, and 0.4 part by mass of 2, 6-tert-butyl-4-methylphenol (BHT), and uniformly mixed (the molar ratio (OH/NCO) of the hydroxyl group of the glycol-modified xylene resin to the isocyanate group of diphenylmethane diisocyanate was 0.50, and the molar ratio (OH/NCO) of the total of the hydroxyl group (glycol-modified xylene resin + 2-hydroxyethyl acrylate) and the isocyanate group of diphenylmethane diisocyanate was 0.50TNCO) 1.0). After uniformly mixing, the temperature was raised to 70 ℃ and the solution was stirred for 15 hours while controlling the temperature of the solution to 70 ℃ to complete the reaction, thereby obtaining a target urethane (meth) acrylate resin solution A (weight average molecular weight: 3517). The resin concentration in the obtained urethane (meth) acrylate resin solution a was 70 mass%.
< example 2 >
Urethane (meth) acrylate resin solution B (weight-average molecular weight: 2038) (hydroxyl group of ethylene glycol-modified xylene resin and toluene diisocynate) was obtained in the same manner as in example 1 except that 161 parts by mass of toluene diisocyanate was used instead of diphenylmethane diisocyanate, and 292 parts by mass of K-140E (Fudow Co., Ltd., manufactured by Ltd., ethylene glycol-modified xylene resin, hydroxyl value: 177mgKOH/g, weight-average molecular weight: 580) and 107 parts by mass of 2-hydroxyethyl acrylate were usedThe molar ratio of the isocyanate group of the acid ester (OH/NCO) was 0.50, and the molar ratio of the total of the hydroxyl groups (ethylene glycol-modified xylene resin + 2-hydroxyethyl acrylate) to the isocyanate group of toluene diisocyanate (OH)TNCO) 1.0). The resin concentration in the obtained urethane (meth) acrylate resin solution B was 70 mass%.
< example 3 >
Urethane (meth) acrylate resin solution C (weight-average molecular weight: 2727) (molar ratio of hydroxyl groups of ethylene glycol-modified xylene resin to isocyanate groups of m-xylene diisocyanate (OH/NCO) was 0.50, and molar ratio of total hydroxyl groups (ethylene glycol-modified xylene resin + 2-hydroxyethyl acrylate) to isocyanate groups of m-xylene diisocyanate (OH/NCO) was 0.50, except that 170 parts by mass of m-xylene diisocyanate was used instead of diphenylmethane diisocyanate, and K-140E (Fudow co., ltd. system, ethylene glycol-modified xylene resin, hydroxyl value: 177mgKOH/g, weight-average molecular weight: 580) and 105 parts by mass of 2-hydroxyethyl acrylate were used in place of diphenylmethane diisocyanateTNCO) 1.0). The resin concentration in the obtained urethane (meth) acrylate resin solution C was 70 mass%.
< comparative example 1 >
Urethane (meth) acrylate resin solution D (weight-average molecular weight: 3621) was obtained in the same manner as in example 1, except that dicyclohexylmethane-4, 4' -diisocyanate 211 parts by mass was used in place of diphenylmethane diisocyanate, and that 255 parts by mass of K-140E (Fudow co., ltd., ethylene glycol-modified xylene resin, hydroxyl value: 177mgKOH/g, weight-average molecular weight: 580) and 94 parts by mass of 2-hydroxyethyl acrylate were used. The resin concentration in the obtained urethane (meth) acrylate resin solution D was 70%.
< comparative example 2 >
A urethane (meth) acrylate resin solution E (weight-average molecular weight: 3039) was obtained in the same manner as in example 1, except that 157 parts by mass of hexamethylene diisocyanate was used instead of the diphenylmethane diisocyanate, and 295 parts by mass of K-140E (Fudow Co., Ltd., ethylene glycol-modified xylene resin, hydroxyl value: 177mgKOH/g, weight-average molecular weight: 580) and 108 parts by mass of 2-hydroxyethyl acrylate were used. The resin concentration in the obtained urethane (meth) acrylate resin solution E was 70%.
< comparative example 3 >
A urethane (meth) acrylate resin solution F (weight-average molecular weight: 2803) was obtained in the same manner as in example 1, except that 170 parts by mass of 1, 3-bis (isocyanatomethyl) cyclohexane was used in place of diphenylmethane diisocyanate, and 286 parts by mass of K-140E (Fudow Co., Ltd., ethylene glycol-modified xylene resin, hydroxyl value: 177mgKOH/g, weight-average molecular weight: 580) and 105 parts by mass of 2-hydroxyethyl acrylate were used. The resin concentration in the obtained urethane (meth) acrylate resin solution F was 70%.
< examples 4 to 6 and comparative examples 4 to 6 >
The urethane (meth) acrylate resin solutions a to F obtained in examples 1 to 3 and comparative examples 1 to 3 were mixed with a photopolymerization initiator (Irgacure ((registered trademark) 184, manufactured by BASF) to obtain curable resin compositions.
Next, the curable resin composition was applied to various substrates by a bar coater, dried at 100 ℃ for 2 minutes, and then irradiated with ultraviolet light (high pressure mercury lamp, ECS-1511U manufactured by EYEGRAPHICS K.) to a concentration of 500mJ/cm2The cured coating film was obtained by UV irradiation. The cured coating film obtained was subjected to the above-described evaluation tests. The results are shown in Table 1.
The substrates used are as follows.
PET (Toyo Boseki Kabushiki Kaisha "A4100", thickness: 100 μm)
Steel plate ("PB-N144" manufactured by Paltek Corporation, thickness: 200 μm)
Polycarbonate plate (general purpose article, thickness: 2mm)
Acrylic plate (general purpose article, thickness: 2mm)
ABS (acrylonitrile-butadiene-styrene copolymer resin) plate (general purpose article, thickness: 2mm)
[ Table 1]
TABLE 1
The adhesion of comparative examples 4 to 6 to the plastic substrate was reduced as compared with examples 4 to 6. This is presumed to be derived from the fact that the urethane (meth) acrylate resins used in comparative examples 4 to 6 do not have an aromatic ring in the diisocyanate moiety, but the present invention is not limited to this presumption at all.
Claims (9)
1. A urethane (meth) acrylate resin obtained by reacting a polyol-modified aromatic hydrocarbon formaldehyde resin, which is obtained by modifying an aromatic hydrocarbon formaldehyde resin with a polyol, with an aromatic group-containing diisocyanate, and with a hydroxyl group-containing (meth) acrylate compound.
2. The urethane (meth) acrylate resin according to claim 1, which has a weight average molecular weight (Mw) of 500 to 100000.
3. The urethane (meth) acrylate resin according to claim 1 or 2, wherein the polyol-modified aromatic hydrocarbon formaldehyde resin has a weight average molecular weight of 300 to 5000.
4. The urethane (meth) acrylate resin according to any one of claims 1 to 3, wherein the hydroxyl value of the polyol-modified aromatic hydrocarbon formaldehyde resin is 100 to 400 mgKOH/g.
5. The urethane (meth) acrylate resin according to any one of claims 1 to 4, wherein the molar ratio (OH/NCO) of the hydroxyl group of the polyol-modified aromatic hydrocarbon formaldehyde resin to the isocyanate group of the aromatic group-containing diisocyanate is 0.50 to 0.95, and the hydroxyl group of the polyol-modified aromatic hydrocarbon formaldehyde resin and the hydroxyl group of the hydroxyl group-containing (meth) acrylate compound are used as the hydroxyl groupThe molar ratio (OH) of the total hydroxyl groups of the groups to the isocyanate groups of the aromatic group-containing diisocyanateT/NCO) is 1.0-1.2.
6. The urethane (meth) acrylate resin according to any one of claims 1 to 5, wherein the polyol-modified aromatic hydrocarbon formaldehyde resin contains a glycol-modified xylene formaldehyde resin.
7. The urethane (meth) acrylate resin according to any one of claims 1 to 6, wherein the aromatic group-containing diisocyanate is at least 1 aromatic diisocyanate selected from the group consisting of diphenylmethane diisocyanate and toluene diisocyanate.
8. A curable resin composition comprising the urethane (meth) acrylate resin according to any one of claims 1 to 7.
9. A cured product obtained by curing the curable resin composition according to claim 8.
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| JP2018223769 | 2018-11-29 | ||
| JP2018-223769 | 2018-11-29 | ||
| PCT/JP2019/045947 WO2020110990A1 (en) | 2018-11-29 | 2019-11-25 | Urethane (meth)acrylate resin, curable resin composition, and cured product |
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| CN113166363B (en) | 2023-10-20 |
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| WO2020110990A1 (en) | 2020-06-04 |
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