JP7192319B2 - (Meth)acrylate resin, curable resin composition, and cured product - Google Patents

Description

The present invention relates to (meth)acrylate resins, curable resin compositions, and cured products.

In recent years, in applications such as protective coating materials for preventing scratches and contamination on various substrate surfaces, adhesives for various substrates, sealing materials, film-type liquid crystal elements, touch panels, and anti-reflection coatings for plastic optical parts, hardness There is a demand for a curable composition capable of forming a cured film having excellent solvent resistance, adhesion and flexibility.

Various compositions have been proposed to meet such demands.
For example, Patent Document 1 proposes a photocurable resin composition using an alkylene oxide-modified (meth)acrylate of benzyl alcohol as a reactive diluent.
Patent Document 2 proposes a polyurethane acrylate blended with an organically modified polysiloxane having dimethylsiloxane structural units.
Patent Document 3 proposes a resinous composition containing a reaction product of an aromatic hydrocarbon formaldehyde resin and methacrylic acid or acrylic acid.
Patent Document 4 proposes a radiation-curable resin obtained by converting the hydroxyl group or methylol group of a phenol-modified xylene resin into an acrylic acid or methacrylic acid ester.

JP-A-6-329738 Japanese Patent No. 2547087 JP-A-56-10513 Japanese Patent Publication No. 5-64165

As described above, various compositions have been proposed so far, but the current situation is that a curable composition that gives a cured film that is excellent in all of hardness, solvent resistance, adhesion, and flexibility has not yet been obtained. is.
The main purpose of Patent Document 1 is rapid curability, and there is a drawback that the cured product obtained from the photocurable resin composition described in Patent Document 1 is inferior in hardness.
Patent Document 2 aims to improve flexibility, scratch resistance, etc., but there is still room for improvement in terms of hardness.
Patent Literature 3 mainly aims at odorlessness or low odor, and does not mention performances such as adhesion and flexibility.
In Patent Document 4, since the esterification reaction is performed using acrylic acid or methacrylic acid, the alcoholic hydroxyl group (methylol group) contained in the phenol-modified xylene resin is actually esterified. The phenolic hydroxyl group of remains without being esterified. This is confirmed by the presence of an absorption band of a phenolic hydroxyl group near 3300 cm ⁻¹ in the infrared absorption spectra in Tables 1 and 3 described in Patent Document 4. Therefore, as described in Patent Document 4, when an esterification reaction is performed using acrylic acid or methacrylic acid, the amount of (meth)acryloyl groups introduced in the resin decreases, and as a result, the resin is not sufficiently cured. , there is a risk that sufficient hardness and solvent resistance cannot be obtained. In addition, if the exposure dose is increased in order to advance the curing of the resin, the production efficiency is deteriorated, and the cured product may become brittle due to the heat generated by the exposure, resulting in a decrease in flexibility.

The present invention has been made in view of the above circumstances, and includes a (meth)acrylate resin capable of giving a cured film excellent in all of hardness, solvent resistance, adhesion, and flexibility, and the resin. An object of the present invention is to provide a curable resin composition and a cured product of the composition.

As a result of intensive studies, the present inventors found that a (meth)acrylate resin obtained by an esterification reaction between a phenol-modified aromatic hydrocarbon formaldehyde resin and a (meth)acrylic acid halide can solve the above problems. , have completed the present invention.

That is, the present invention is as follows.
(1)
A (meth)acrylate resin obtained by an esterification reaction between a phenol-modified aromatic-hydrocarbon-formaldehyde resin obtained by modifying an aromatic-hydrocarbon-formaldehyde resin with a phenol and a (meth)acrylic acid halide.
(2)
The (meth)acrylate resin according to (1), which has a weight average molecular weight (Mw) of 300 to 10,000.
(3)
The (meth)acrylate resin according to (1) or (2), wherein the phenol-modified aromatic hydrocarbon formaldehyde resin has a weight average molecular weight of 200 to 10,000.
(4)
The (meth)acrylate resin according to any one of (1) to (3), which has a hydroxyl value of 100 mgKOH/g or less.
(5)
The (meth)acrylate resin according to any one of (1) to (4), wherein the phenol-modified aromatic hydrocarbon formaldehyde resin has a hydroxyl value of 100 to 550 mgKOH/g.
(6)
The (meth)acrylate resin according to any one of (1) to (5), which has a phenolic hydroxyl value of 100 mgKOH/g or less.
(7)
The (meth)acrylate resin according to any one of (1) to (6), wherein the phenolic modified aromatic hydrocarbon formaldehyde resin has a phenolic hydroxyl value of 100 to 550 mgKOH/g.
(8)
The (meth)acrylate resin according to any one of (1) to (7), wherein the phenol-modified aromatic hydrocarbon formaldehyde resin contains a phenol-modified xylene formaldehyde resin.
(9)
A curable resin composition comprising the (meth)acrylate resin according to any one of (1) to (8).
(10)
A cured product obtained by curing the curable resin composition according to (9).

According to the present invention, a cured film excellent in all of hardness, solvent resistance, adhesion and flexibility can be provided.

EMBODIMENT OF THE INVENTION Hereinafter, the form (only henceforth "this embodiment") for implementing this invention is demonstrated in detail. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be appropriately modified and implemented within the scope of the gist thereof.

In this specification, "(meth)acrylate" means both "acrylate" and "methacrylate", and other similar terms ("(meth)acrylic acid", "(meth)acryloyl group", etc.) It is the same.

[(Meth)acrylate resin]
The (meth)acrylate resin of the present embodiment is obtained by subjecting a phenol-modified aromatic hydrocarbon-formaldehyde resin and a (meth)acrylic acid halide to an esterification reaction.
Since the (meth)acrylate resin of the present embodiment contains a (meth)acryloyl group, it can be easily cured by irradiation with UV or the like or by heating, and the cured product thus obtained has high hardness and high solvent resistance. have sex. Furthermore, the cured product has high hardness and high solvent resistance, and is also excellent in adhesion and flexibility. It is believed that this is due to the excellent adhesiveness and flexibility, which are inherent characteristics of the aromatic hydrocarbon formaldehyde resin.

Since the (meth)acrylate resin of the present embodiment is obtained as a raw material from a phenol-modified aromatic hydrocarbon formaldehyde resin having a structure that is difficult to analyze and identify, the (meth)acrylate resin also has the structure are difficult to analyze and identify.

The weight average molecular weight (Mw) of the (meth)acrylate resin of the present embodiment is preferably 300 to 10,000, more preferably 300 to 8,000 in terms of polystyrene, from the viewpoint of improving adhesion, More preferably 500 to 7,000. Weight average molecular weight (Mw) can be measured by gel permeation chromatography (GPC).

The hydroxyl value of the (meth)acrylate resin of the present embodiment is preferably 100 mgKOH/g or less, more preferably 90 mgKOH/g or less, still more preferably 5 to 90 mgKOH/g, from the viewpoint of UV curability. . The hydroxyl value can be measured by a method based on the acetic anhydride-pyridine method (JIS-K1557-1:2007).
In the esterification reaction in the present embodiment, (meth)acrylic acid halide is used, so if the hydroxyl group contained in the phenol-modified aromatic hydrocarbon formaldehyde resin (phenolic hydroxyl group and alcoholic hydroxyl group are present, the alcohol functional hydroxyl groups) can be sufficiently esterified. Therefore, it is possible to keep the hydroxyl value of the (meth)acrylate resin low.

The phenolic hydroxyl value of the (meth)acrylate resin of the present embodiment is preferably 100 mgKOH/g or less, more preferably 90 mgKOH/g or less, still more preferably 5 to 90 mgKOH/g, from the viewpoint of UV curability. is. The phenolic hydroxyl value can be measured by the method described in Examples.
Since (meth)acrylic acid halide is used in the esterification reaction in the present embodiment, it is possible to sufficiently esterify the phenolic hydroxyl groups contained in the phenol-modified aromatic hydrocarbon-formaldehyde resin. Therefore, it is possible to keep the phenolic hydroxyl value of the (meth)acrylate resin low.

[Method for producing (meth)acrylate resin]
The method for producing a (meth)acrylate resin of the present embodiment includes a step of subjecting a phenol-modified aromatic hydrocarbon-formaldehyde resin and a (meth)acrylic acid halide to an esterification reaction.
The esterification reaction in the present embodiment is an acylation reaction of a phenol-modified aromatic hydrocarbon-formaldehyde resin accompanied by desorption of hydrogen halide by using a (meth)acrylic acid halide. (Meth)acrylic acid halide is highly reactive not only with alcoholic hydroxyl groups but also with phenolic hydroxyl groups, and the reaction is irreversible. Therefore, the method for producing the (meth)acrylate resin of the present embodiment differs from the case of using the dehydration esterification method using (meth)acrylic acid or the transesterification method using (meth)acrylic acid ester, and the phenol-modified aromatic It is possible to sufficiently esterify the hydroxyl groups (phenolic hydroxyl groups, and alcoholic hydroxyl groups when alcoholic hydroxyl groups are present) contained in group hydrocarbon formaldehyde resins.
(Meth)acrylic acid halides include, for example, (meth)acrylic acid chloride, (meth)acrylic acid bromide, (meth)acrylic acid iodide, and the like. Among these, (meth)acrylic acid chloride is preferred.

In the method for producing a (meth)acrylate resin of the present embodiment, esterification may be performed in the presence of a polymerization inhibitor together with a Lewis acid catalyst.

The Lewis acid catalyst is not particularly limited, and known Lewis acid catalysts can be used. For example, zinc compounds such as zinc chloride, zinc bromide and zinc acetate, aluminum compounds such as aluminum chloride and diethylaluminum chloride, boron compounds such as boron trifluoride and boron trichloride, and titanium compounds such as titanium tetrachloride are preferred. These Lewis acid catalysts may be used singly or in admixture of two or more. The ratio of the Lewis acid catalyst is usually preferably 0.01 to 10 mol % with respect to 1 mol of hydroxyl groups in the phenol-modified aromatic hydrocarbon formaldehyde resin.

Although the polymerization inhibitor is not particularly limited, copper (II) chloride, phenothiazine, hydroquinone, hydroquinone monomethyl ether, and the like are preferable. These can be used singly or in an appropriate mixture of two or more.
Among these, copper (II) chloride is preferable because it has a strong polymerization inhibitory action and is inexpensive.
The addition ratio of the polymerization inhibitor is usually preferably 5 to 20,000 mass ppm, more preferably 25 to 3,000 mass ppm, and still more preferably 25 to 1,000 mass ppm with respect to the reaction solution. . If the addition ratio is 5 ppm by mass or more, the effect of inhibiting polymerization is sufficient, and if it is 20,000 ppm by mass or less, it is economical, and the resulting (meth)acrylate resin is not colored.

The esterification reaction of the phenol-modified aromatic hydrocarbon-formaldehyde resin and (meth)acrylic acid halide may be carried out according to a standard method. A method of esterifying a phenol-modified aromatic hydrocarbon formaldehyde resin and a (meth)acrylic acid halide by heating and stirring in the presence of a Lewis acid catalyst and a polymerization inhibitor.

As the esterification reaction progresses, hydrogen halide is generated in an amount equal to that of the aromatic ester produced. Such hydrogen halide is preferably not retained in the reaction solution, and in order to expel the hydrogen halide from the reaction solution, the reaction is preferably carried out while nitrogen gas or a mixture of nitrogen gas and oxygen gas is passed through the reaction system.

The esterification reaction can be carried out with or without a solvent. Examples of the solvent include, but are not limited to, aromatic hydrocarbons such as toluene, benzene and xylene; aliphatic hydrocarbons such as hexane, cyclohexane and heptane; organic chlorine compounds such as trichloroethane and tetrachloroethylene. These solvents can be used singly or in an appropriate mixture of two or more. The amount of these solvents used is not particularly limited, but is preferably 0.1 to 10 times, more preferably 1 to 5 times the weight of the reaction raw materials.

Although the reaction temperature is not particularly limited, it is preferably 0 to 90°C, more preferably 15 to 70°C, from the viewpoint of shortening the reaction time and preventing polymerization. If the temperature is 0° C. or higher, the reaction rate is sufficient and the yield is good. Moreover, if the temperature is 90° C. or lower, there is no risk of thermal polymerization of the (meth)acrylate resin.

The product obtained by the esterification reaction may be purified according to a standard method.
Specifically, a method of neutralizing and washing the reaction solution with water, separating the aqueous layer, and distilling off a certain amount of the reaction solvent under reduced pressure can be used.

[Phenol modified aromatic hydrocarbon formaldehyde resin]
The phenol-modified aromatic-hydrocarbon-formaldehyde resin, which is the raw material of the (meth)acrylate resin of the present embodiment, refers to an aromatic-hydrocarbon-formaldehyde resin modified with phenols.

(Aromatic hydrocarbon formaldehyde resin)
The aromatic hydrocarbon formaldehyde resin in this embodiment is obtained by reacting an aromatic hydrocarbon and formaldehyde. Aromatic hydrocarbons include benzene, toluene, xylene, mesitylene, ethylbenzene, propylbenzene, decylbenzene, cyclohexylbenzene, biphenyl, methylbiphenyl, naphthalene, methylnaphthalene, dimethylnaphthalene, ethylnaphthalene, anthracene, methylanthracene, dimethylanthracene, At least one selected from the group consisting of ethylanthracene and binaphthyl, preferably at least one selected from the group consisting of xylene, toluene, and mesitylene from the viewpoint of even better adhesion and flexibility, Xylene is more preferred. That is, from the same viewpoint as above, the aromatic hydrocarbon formaldehyde resin in the present embodiment is a xylene formaldehyde resin obtained by reacting xylene and formaldehyde, and a toluene formaldehyde resin obtained by reacting toluene and formaldehyde. , and a mesitylene-formaldehyde resin obtained by reacting mesitylene with formaldehyde, and more preferably a xylene-formaldehyde resin.

The aromatic hydrocarbon formaldehyde resin in this embodiment may be a commercially available product or may be prepared by a known method. Commercially available products include, for example, “Nikanol Y-100” manufactured by Fudo Co., Ltd. Known methods include, for example, a method described in Japanese Patent Publication No. 37-5747, etc., in which an aromatic hydrocarbon and formaldehyde are subjected to a condensation reaction in the presence of a catalyst.

(Phenols)
Examples of phenols include, but are not limited to, phenol, cresol (eg, ortho-cresol, meta-cresol, and para-cresol), xylenol (eg, 2,6-xylenol, 3,5-xylenol, 2,3-xylenol, 2 ,5-xylenol, 2,4-xylenol, and 3,4-xylenol), butylphenol (e.g., p-tert-butylphenol), octylphenol, nonylphenol, cardanol, and at least one selected from the group consisting of terpenephenol is preferred.

The phenol-modified aromatic hydrocarbon formaldehyde resin in the present embodiment is at least one selected from phenol-modified xylene formaldehyde resin, phenol-modified toluene formaldehyde resin, and phenol-modified mesitylene formaldehyde resin from the viewpoint of adhesion and flexibility. It preferably contains seeds, and more preferably contains phenol-modified xylene formaldehyde resin.

The phenol-modified aromatic-hydrocarbon-formaldehyde resin in the present embodiment is a novolac-type phenol-modified aromatic-hydrocarbon-formaldehyde resin obtained by modifying an aromatic-hydrocarbon-formaldehyde resin with phenols in the presence of an acidic catalyst. Alternatively, it may be a resol-type phenol-modified aromatic-hydrocarbon-formaldehyde resin obtained by modifying an aromatic-hydrocarbon-formaldehyde resin with phenols in the presence of a basic catalyst. The resol-type phenol-modified aromatic hydrocarbon-formaldehyde resin contains not only phenolic hydroxyl groups but also methylol groups, which are alcoholic hydroxyl groups.
As the phenol-modified aromatic-hydrocarbon-formaldehyde resin in the present embodiment, a novolac-type phenol-modified aromatic-hydrocarbon-formaldehyde resin is preferable from the viewpoint of handleability.

The phenol-modified aromatic hydrocarbon formaldehyde resin in the present embodiment may be a commercially available product or may be prepared by a known method. Commercially available products include, for example, “Zistar GP-100” and “Zistar P-100” manufactured by Fudo Co., Ltd. As known methods, for example, as described in JP-A-2003-119234, JP-A-2007-297610, and International Publication No. 2013/191012, an aromatic hydrocarbon formaldehyde resin and a phenol under a catalyst. It can be produced by condensation reaction with.

[Physical properties of phenol-modified aromatic hydrocarbon formaldehyde resin]
The weight-average molecular weight (Mw) of the phenol-modified aromatic hydrocarbon-formaldehyde resin in the present embodiment is preferably 200 to 10,000, more preferably 300 to 8, in terms of polystyrene, from the viewpoint of improving adhesion. 000, more preferably 500 to 7,000. Weight average molecular weight (Mw) can be measured by gel permeation chromatography (GPC).

The hydroxyl value of the phenol-modified aromatic hydrocarbon formaldehyde resin in the present embodiment is preferably 100 to 550 mgKOH/g, more preferably 100 to 500 mgKOH/g, from the viewpoint of curability after esterification. Preferably it is 150-450 mgKOH/g. The hydroxyl value can be measured by a method based on the acetic anhydride-pyridine method (JIS-K1557-1:2007).

The phenolic hydroxyl value of the phenol-modified aromatic hydrocarbon formaldehyde resin in the present embodiment is preferably 100 to 550 mgKOH/g, more preferably 100 to 500 mgKOH/g, from the viewpoint of curability after esterification. , and more preferably 150 to 450 mgKOH/g. The phenolic hydroxyl value can be measured by the method described in Examples.

[Composition containing (meth)acrylate resin]
The composition of this embodiment comprises the (meth)acrylate resin of this embodiment.
The composition of the present embodiment contains (meth)acrylate resins other than the (meth)acrylate resin of the present embodiment, epoxy resins, cyanate ester compounds, phenolic resins, and oxetane as long as the properties of the present embodiment are not impaired. Resins, resins such as benzoxazine compounds, various polymer compounds such as oligomers and elastomers, monomers having polymerizable functional groups such as compounds having ethylenically unsaturated groups, maleimide compounds, fillers, flame retardants, silane cups A ring agent, a wetting and dispersing agent, a photopolymerization initiator, a photocuring initiator, a thermosetting accelerator, various additives, and the like can be included. The components contained in the composition of the present embodiment are not particularly limited as long as they are commonly used.

In addition, various additives include ultraviolet absorbers, antioxidants, fluorescent brighteners, photosensitizers, dyes, pigments, thickeners, lubricants, antifoaming agents, leveling agents, surface conditioners, brighteners, Polymerization inhibitors and the like are included.

The above components may be used singly or in admixture of two or more.
Also, the blending amount of each component can be variously adjusted according to the application.

[Method for producing composition]
The composition of the present embodiment is prepared by appropriately mixing the (meth)acrylate resin of the present embodiment and, if necessary, each component described above.

The method for producing the composition is not particularly limited, and an example thereof includes a method in which the components are sequentially added to a solvent and thoroughly stirred.

During the production of the composition, known treatments (stirring, mixing, kneading treatment, etc.) for uniformly dissolving or dispersing each component can be performed as necessary. Stirring, mixing, and kneading can be performed by using, for example, a stirring device for dispersion such as an ultrasonic homogenizer, a device for mixing such as a three-roll mill, ball mill, bead mill, or sand mill, or a revolving or rotating type mixing device. It can be appropriately carried out using a known device such as.

An organic solvent can be used as necessary during the preparation of the composition of the present embodiment. The type of organic solvent is not particularly limited as long as it can dissolve the resin in the composition.

Examples of organic solvents include, but are not limited to, ketones such as acetone, methyl ethyl ketone and methyl cellosolve; aromatic hydrocarbons such as toluene and xylene; amides such as dimethylformamide; mentioned. These organic solvents can be used singly or in admixture of two or more.

[Cured product]
The cured product of the present embodiment is obtained by curing a composition containing the (meth)acrylate resin of the present embodiment.

A cured product can be obtained by various known methods. Curing methods include, for example, irradiation with UV or EUV, heating, and the like, and these methods can be used in combination.

Since the (meth)acrylate resin of the present embodiment has high reactivity, it is suitable for a high-productivity process that instantaneously cures with UV, EUV, or the like. Moreover, since it has high reactivity, it can stably supply a high-quality cured product. The (meth)acrylate resin and cured product of the present embodiment can be suitably used in the fields of inks, paints, and optical materials.

In the case of irradiating with ultraviolet rays, the irradiation amount can be adjusted as necessary, for example, irradiation can be performed at an irradiation amount of about 0.05 J/cm ² to 10 J/cm ² .

The heating conditions may be appropriately selected according to the (meth)acrylate resin, each component in the composition containing the resin, the content of the resin and each component, etc., preferably 150 ° C. to 220 ° C. 20 to 180 minutes at 160° C. to 200° C., preferably 30 to 150 minutes at 160° C. to 200° C.

[Use]
The (meth)acrylate resin, composition and cured product of the present embodiment can be used for various purposes.

For example, adhesives, adhesives, home appliances such as touch panels, various lens materials, dental materials and other optical materials and medical materials, paints, coatings, primers and other automotive and building material applications, shoes, bags, school bags and other artificial materials. Examples include leather and synthetic leather applications, knit products, synthetic fiber applications such as spandex, polymerization raw materials, molding materials, gas separation membranes, fuel cell membranes, optical waveguides, holograms, and the like.

In particular, various UV curable paints and coating materials for automobiles, mobile terminals, light electrical appliances, optical discs, optical fibers, cosmetic containers, building materials and floors, self-healing paints and coatings, and UV curable inkjet inks. , UV curable resin for nanoimprint, UV curable resin for 3D printer, UV ink such as photosensitive conductive paste, UV curable adhesive, OCA for touch panel, OCR for touch panel, UV adhesive such as sealing material for organic EL, Materials for buffer coat films, lenses (pickup lenses, microlenses, eyeglass lenses), polarizing films (for liquid crystal displays, etc.), anti-reflection films (anti-reflection films for display devices, etc.), films for touch panels, films for flexible substrates, displays Film for [PDP (Plasma Display), LCD (Liquid Crystal Display), VFD (Vacuum Fluorescent Display), SED (Surface Conduction Electron Emission Device Display), FED (Field Emission Display), NED (Nano Emissive Display), CRT , films (filters, protective films, etc.) for displays such as electronic paper (particularly thin displays), etc.].

[Raw materials and modifiers such as urethane resins, acrylic resins, vinyl ester resins, alkyd resins, epoxy resins, and unsaturated polyester resins]
When the (meth)acrylate resin of the present embodiment is used as raw materials such as urethane resins, acrylic resins, vinyl ester resins, alkyd resins, epoxy resins, and unsaturated polyester resins, and as additives and modifiers for resins, The water resistance, chemical resistance, and heat resistance of these resins can be improved.

A urethane resin is a polymer compound having a urethane bond, and is a resin obtained, for example, by polymerization addition of an aliphatic diamine or glycols and diisocyanates.

Acrylic resins are obtained by copolymerizing several types of (meth)acrylic monomers such as acrylic acid, methacrylic acid, and their derivatives. (Meth)acrylic monomers include (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and hydroxyethyl (meth)acrylate.

Vinyl ester resin is, for example, in the presence of an addition catalyst to polyepoxide, the reaction product obtained by adding an epoxy group and approximately equivalent moles of α, β-unsaturated monobasic acid with a polymerizable monomer such as styrene. It is a resin obtained by mixing and adding a polymerization inhibitor or the like as necessary.

An alkyd resin is a resin obtained by condensing a polyhydric alcohol and a polybasic acid. Polyhydric alcohols include, for example, glycerin, pentaerythritol, neopentyl glycol, ethylene glycol, diethylene glycol and the like. Examples of polybasic acids include phthalic anhydride and maleic anhydride.

Epoxy resins are resins having epoxy groups that are cured by amines, acid anhydrides, and the like. The resin etc. which are obtained are mentioned. Specifically, epoxy resins having amines as precursors include various isomers of tetraglycidyldiaminodiphenylmethane, triglycidyl-p-aminophenol, triglycidyl-m-aminophenol, and triglycidylaminocresol. Examples of epoxy resins having phenols as precursors include bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, bisphenol S-type epoxy resins, phenol novolac-type epoxy resins, cresol novolak-type epoxy resins, and resorcinol-type epoxy resins. Alicyclic epoxy resins are examples of epoxy resins whose precursor is a compound having a carbon-carbon double bond.

Unsaturated polyester resin is produced by, for example, mixing an unsaturated polyester obtained by reacting an acid such as an unsaturated dibasic acid and an alcohol with a polymerizable monomer such as styrene, and adding a polymerization inhibitor or the like as necessary. It is a resin obtained by Acids include, for example, unsaturated dibasic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, and anhydrides of these acids. Phthalic acid, isophthalic acid, terephthalic acid, 3,6-endomethylenetetrahydrophthalic anhydride, adipic acid, sebacic acid, etc., or anhydrides of these acids may be used as part of these unsaturated dibasic acids. Examples of alcohol include ethylene glycol, propylene glycol, 1,3-methylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, hexylene glycol and the like. Monohydric alcohols such as cyclohexyl alcohol and benzyl alcohol, or polyhydric alcohols such as glycerin and trimethylolpropane may be used as part of these.

The present invention will be described in more detail with reference to the following examples and comparative examples, but the present invention is in no way limited by the following examples. The evaluation methods employed in the examples and comparative examples are as follows.

(1) weight average molecular weight (Mw)
A polystyrene equivalent weight average molecular weight (Mw) was determined by GPC analysis. The apparatus and analysis conditions used for analysis were as follows.
Apparatus: Shodex GPC-101 type (manufactured by Showa Denko K.K.)
Column: Shodex KF-801×2, KF-802.5, KF-803L
Eluent: Tetrahydrofuran Flow rate: 1.0 ml/min.
Column temperature: 40°C
Detector: RI (differential refraction detector)

(2) hydroxyl value (OH value, mgKOH/g)
Measured according to the acetic anhydride-pyridine method (JIS-K1557-1:2007).

(3) Phenolic hydroxyl value (phenolic OH value, mgKOH/g)
25 mL of anhydrous ethylenediamine is weighed into an Erlenmeyer flask with a whole pipette, 2 drops of o-nitroaniline indicator is added, and the mixture is titrated with 0.1N sodium methylate solution until it becomes red. The sample was added to this and titrated again, and the phenolic hydroxyl value in the sample was calculated by the following formula.
Phenolic hydroxyl value (mgKOH/g) = A x 94.11 x F/W
In the above formula, A: amount (mL) of 0.1N sodium methylate solution required for sample titration, F: normality of sodium methylate solution, W: sample amount (g).

(4) Pencil hardness The obtained cured coating film was measured according to JIS K5600-5-4:1999.

(5) Rubbing test (solvent resistance)
For the resulting cured coating film, the coating layer was rubbed with a cotton swab impregnated with acetone. When the surface was not dissolved, it was evaluated as ◯, and when it was dissolved, it was evaluated as ×.

(6) Adhesion Adhesion was evaluated by making 100 grid-like incisions at intervals of 2 mm on the resulting cured coating film according to JIS K5600-5-6:1999. Evaluation criteria are shown below.
⊚: 90 or more squares were not peeled out of 100 squares.
Good: 60 or more and less than 90 of the 100 squares were not peeled off.
Δ: The number of unpeeled squares was 30 or more and less than 60 out of 100 squares.
x: Less than 30 of the 100 squares were not peeled off.

(7) Flexibility The resulting cured coating film was evaluated based on the following criteria after winding the substrate on which the cured film was formed around a core rod in accordance with JIS K5600-5-1:1999.
○: No cracking or peeling of the cured film with a core rod of 2 mm in diameter ×: Cracking or peeling of the cured film with a core rod of 32 mm in diameter

<Example 1>
In a four-necked flask with an internal volume of 200 mL equipped with a stirrer, a thermometer, and a gas inlet tube, a novolak-type phenol-modified xylene resin manufactured by Fudo Co., Ltd. as a phenol-modified aromatic hydrocarbon formaldehyde resin "Zestar GP-100""(Hydroxyl value: 289 mg KOH / g, phenolic hydroxyl value: 284 mg KOH / g, weight average molecular weight: 1100) 15 g, toluene 37.5 g, copper (II) chloride 0.01 g, acrylic acid chloride 7.8 g After charging and dissolving, 0.1 g of zinc chloride was added and the temperature was raised to 40°C. The mixture was maintained for 1 hour while blowing air to complete the reaction, and water was added to the reaction mixture and stirred to separate the mixture. The organic layer was washed successively with a 5% aqueous sodium hydroxide solution and saturated brine, and then dried over anhydrous magnesium sulfate. After adding 0.01 g of a polymerization inhibitor, hydroquinone monomethyl ether, the mixture was filtered, and the filtrate was concentrated under reduced pressure to obtain a 36% toluene solution of curable resin A. The resulting curable resin A had a weight average molecular weight of 1234, a hydroxyl value of 41 mgKOH/g, and a phenolic hydroxyl value of 34 mgKOH/g.

<Example 2>
As a phenol-modified aromatic hydrocarbon formaldehyde resin, instead of "Zeister GP-100" manufactured by Fudo Co., Ltd., a novolac-type phenol-modified xylene resin "Zestar P-100" manufactured by Fudo Co., Ltd. (Hydroxyl value: 305 mg KOH / g, phenolic hydroxyl value: 265 mg KOH / g, weight average molecular weight: 3600), and the amount of acrylic acid chloride charged was changed from 7.8 g to 8.1 g. A 54% toluene solution of curable resin B was obtained. The resulting curable resin B had a weight average molecular weight of 4671, a hydroxyl value of 87 mgKOH/g, and a phenolic hydroxyl value of 72 mgKOH/g.

<Comparative Example 1>
Instead of phenol-modified aromatic hydrocarbon formaldehyde resin (“Zystar GP-100” manufactured by Fudo Co., Ltd.), phenol novolac resin (“Resitop PSK-2320” manufactured by Gun Ei Chemical Industry Co., Ltd. (Hydroxyl value: 529 mg KOH / g, phenolic hydroxyl value: 436 mgKOH/g, weight average molecular weight: 4069)), changing the charged amount of acrylic acid chloride to 14.1 g, and changing the charged amount of zinc chloride to 0.2 g A 55% toluene solution of curable resin C was obtained in the same manner as in Example 1 except for the above. The resulting curable resin C had a weight average molecular weight of 6479, a hydroxyl value of 35 mgKOH/g, and a phenolic hydroxyl value of 6 mgKOH/g.

<Comparative Example 2>
Instead of phenol-modified aromatic hydrocarbon formaldehyde resin (“Zystar GP-100” manufactured by Fudo Co., Ltd.), phenol novolak resin (“Resitop PSM-2222” manufactured by Gun Ei Chemical Industry Co., Ltd. (Hydroxyl value: 531 mg KOH / g, phenolic hydroxyl value: 467 mgKOH/g, weight average molecular weight: 1979)), changing the charged amount of acrylic acid chloride to 14.1 g, and changing the charged amount of zinc chloride to 0.2 g A 33% toluene solution of curable resin D was obtained in the same manner as in Example 1 except for the above. The resulting curable resin D had a weight average molecular weight of 2510, a hydroxyl value of 62 mgKOH/g, and a phenolic hydroxyl value of 49 mgKOH/g.

<Examples 3-4 and Comparative Examples 3-4>
The toluene solutions of the curable resins A to D obtained in Examples 1 and 2 and Comparative Examples 1 and 2 were mixed with a photopolymerization initiator (manufactured by BASF, Irgacure (registered trademark) 184), and the blended composition was prepared. Obtained.
Subsequently, this compounded composition was applied to various substrates using a bar coater, dried by heating at 100° C. for 2 minutes, and then subjected to an ultraviolet irradiation device (high-pressure mercury lamp, manufactured by Eye Graphics Co., Ltd. ECS-1511U”) was used to irradiate UV at 500 mJ/cm ² to obtain a cured coating film. Each of the above evaluation tests was carried out on the obtained cured coating film. Table 1 shows the results.
In addition, the used base material is as follows.
・ PET (“A4100” manufactured by Toyobo Co., Ltd., thickness: 100 μm)
・ Steel plate (“PB-N144” manufactured by Paltec Co., Ltd., thickness: 200 μm)
・PC (general-purpose product, thickness: 2 mm)
・PMMA (general-purpose product, thickness: 2mm)

Compared with Examples 3 and 4, Comparative Example 3 had lower adhesion to PMMA and lower flexibility in the steel plate, and Comparative Example 4 had lower adhesion to the steel plate and lower flexibility in the steel plate. This is presumed to be due to the fact that the phenol novolak resins used in Comparative Examples 3 and 4 do not have an aromatic ring nucleus (xylene nucleus) derived from a phenol-modified aromatic hydrocarbon formaldehyde resin. The present invention is in no way limited by this speculation.

<Example 5>
In a four-necked flask with an internal volume of 200 mL equipped with a stirrer, a thermometer, and a gas inlet tube, "PR-1440M" manufactured by Fudo Co., Ltd. (phenol-modified resol-type phenol-modified as a formaldehyde resin 30 g of xylene resin (a varnish containing 45 mass % of xylene resin (hydroxyl value: 416 mg KOH/g, phenolic hydroxyl value: 296 mg KOH/g, weight average molecular weight: 5374) in methanol) and 30 g of isophorone were charged, and the methanol contained in the varnish was decompressed. Removed. 0.01 g of copper (II) chloride and 14.8 g of acrylic acid chloride were added to the varnish from which methanol was removed and dissolved therein, then 0.1 g of zinc chloride was added and the temperature was raised to 40°C. The mixture was maintained for 1 hour while blowing air to complete the reaction, and water was added to the reaction mixture and stirred to separate the mixture. The organic layer was washed successively with a 5% aqueous sodium hydroxide solution and saturated brine, and then dried over anhydrous magnesium sulfate. After adding 0.01 g of a polymerization inhibitor, hydroquinone monomethyl ether, the mixture was filtered, and the filtrate was concentrated under reduced pressure to obtain a 76% solution of curable resin E in isophorone. The resulting curable resin E had a weight average molecular weight of 3114, a hydroxyl value of 45 mgKOH/g, and a phenolic hydroxyl value of 45 mgKOH/g.

<Comparative Example 5>
In a four-necked flask with an internal volume of 200 mL equipped with a stirrer, a thermometer, and a gas inlet tube, "PR-1440M" manufactured by Fudo Co., Ltd. (phenol-modified resol-type phenol-modified as a formaldehyde resin 30 g of xylene resin (a varnish containing 45 mass % of xylene resin (hydroxyl value: 416 mg KOH/g, phenolic hydroxyl value: 296 mg KOH/g, weight average molecular weight: 5375) in methanol) and 30 g of isophorone were charged, and the methanol contained in the varnish was decompressed. Removed. 0.03 g of copper (II) chloride and 30.6 g of acrylic acid were charged and dissolved in the varnish from which methanol was removed, and then 0.26 g of p-toluenesulfonic acid was added, and the pressure was reduced to 13 kPa while blowing air. . After the temperature was raised to 60° C. and maintained for 5 hours to complete the reaction, unreacted acrylic acid was removed under reduced pressure to obtain a 50% solution of curable resin F in isophorone. The resulting curable resin F had a weight average molecular weight of 4175, a hydroxyl value of 198 mgKOH/g, and a phenolic hydroxyl value of 148 mgKOH/g.
The reason why the weight average molecular weight of the obtained curable resin F was lower than that of the raw material "PR-1440M" is presumed as follows. That is, since the resole-type phenol-modified aromatic hydrocarbon formaldehyde resin contains a methylol group, there is a possibility that an ether bond is contained in the molecule due to self-condensation, but by acrylated under acidic conditions, It is presumed that molecular chain scission occurred during the reaction, leading to a decrease in the weight average molecular weight.

In Example 5 and Comparative Example 5, the same phenol-modified aromatic hydrocarbon formaldehyde resin ("PR-1440M" manufactured by Fudo Co., Ltd.) was used as the raw material resin, but the esterification method was different. As shown, the curable resin F obtained in Comparative Example 5 had a higher hydroxyl value and a higher phenolic hydroxyl value than the curable resin E obtained in Example 5. That is, the curable resin F is considered to have a smaller amount of acryloyl groups introduced than the curable resin E.

<Example 6 and Comparative Example 6>
The isophorone solutions of the curable resins E and F obtained in Example 5 and Comparative Example 5 were mixed with a photopolymerization initiator (Irgacure (registered trademark) 184, manufactured by BASF) to obtain compounded compositions.
Subsequently, this compounded composition was applied to various substrates using a bar coater, heated at 60° C. for 30 minutes, further heated at 100° C. for 60 minutes and dried, followed by an ultraviolet irradiation device (high-pressure mercury lamp). , "ECS-1511U" manufactured by Eye Graphics Co., Ltd.) was used to perform UV irradiation at 500 mJ/cm ² to obtain a cured coating film. Each of the above evaluation tests was carried out on the obtained cured coating film. Table 3 shows the results.

<Comparative Example 7>
The isophorone solution of curable resin F obtained in Comparative Example 5 was mixed with a photopolymerization initiator (Irgacure (registered trademark) 184, manufactured by BASF) to obtain a compounded composition.
Subsequently, this compounded composition was applied to various substrates using a bar coater, heated at 60° C. for 30 minutes, further heated at 100° C. for 60 minutes and dried, followed by an ultraviolet irradiation device (high-pressure mercury lamp). , "ECS-1511U" manufactured by Eye Graphics Co., Ltd.) was used to perform UV irradiation at 4500 mJ/cm ² to obtain a cured coating film. Each of the above evaluation tests was carried out on the obtained cured coating film. Table 3 shows the results.

Compared with Example 6, Comparative Example 6 had lower hardness and solvent resistance. It is presumed that this is due to the fact that the resin was not sufficiently cured because the amount of acryloyl groups introduced into the curable resin F was smaller than that of the curable resin E. The present invention is based on this presumption. It is not limited at all.
Also, in Comparative Example 7, which used curable resin F as in Comparative Example 6, the hardness and solvent resistance comparable to those of Example 6 were obtained by increasing the amount of exposure. However, on the other hand, the flexibility in PET decreased. It is presumed that this is due to the fact that the heat generated by the UV irradiation made the cured product brittle due to the increase in the amount of UV exposure, but the present invention is not limited by this presumption.

Claims (10)

A (meth)acrylate resin obtained by an esterification reaction between a phenol-modified aromatic-hydrocarbon-formaldehyde resin obtained by modifying an aromatic-hydrocarbon-formaldehyde resin with a phenol and a (meth)acrylic acid halide,
A (meth)acrylate resin in which the phenol-modified aromatic hydrocarbon formaldehyde resin contains a phenol-modified xylene formaldehyde resin. The (meth)acrylate resin according to claim 1, having a weight average molecular weight (Mw) of 300 to 10,000. 3. The (meth)acrylate resin according to claim 1, wherein the phenol-modified aromatic hydrocarbon formaldehyde resin has a weight average molecular weight of 200 to 10,000. The (meth)acrylate resin according to any one of claims 1 to 3, which has a hydroxyl value of 100 mgKOH/g or less. The (meth)acrylate resin according to any one of claims 1 to 4, wherein the phenol-modified aromatic hydrocarbon formaldehyde resin has a hydroxyl value of 100 to 550 mgKOH/g. The (meth)acrylate resin according to any one of claims 1 to 5, which has a phenolic hydroxyl value of 100 mgKOH/g or less. The (meth)acrylate resin according to any one of claims 1 to 6, wherein the phenolic modified aromatic hydrocarbon formaldehyde resin has a phenolic hydroxyl value of 100 to 550 mgKOH/g. The (meth)acrylate resin according to any one of claims 1 to 7, wherein the phenol-modified aromatic hydrocarbon formaldehyde resin is a phenol-modified xylene formaldehyde resin. A curable resin composition comprising the (meth)acrylate resin according to any one of claims 1 to 8. A cured product obtained by curing the curable resin composition according to claim 9 .