(Meth)acrylate compounds, photocurable resin compositions, and their cured products

Abstract

The present invention aims to provide a resin composition that exhibits excellent curing shrinkage, high heat resistance, excellent adhesion to metals even in high-temperature environments, and provides a cured film with excellent weight reduction and flexibility. [Solution] In order to solve the above problems, the present inventors conducted diligent research and found that a (meth)acrylate compound (A) and a resin composition containing the (meth)acrylate compound (A) can solve the above problems, which are obtained by adding a heterogeneous five-membered ring compound (b) containing one or more nitrogen atoms to a polyfunctional acrylate compound (a) having two or more (meth)acrylic groups in one molecule.

Description

Technical Field

[0001] The present invention relates to a (meth)acrylate compound, a photocurable resin composition, and a cured product thereof.

[0002] The (meth)acrylate compound of the present invention is excellent in curing shrinkage, has high heat resistance, and possesses metal adhesion properties and heat-resistant flex properties, so it can be used as a coating material, a photofabrication material, a pressure-sensitive adhesive or adhesive, and a wiring protection or insulating material for electronic materials.

Background Art

[0003] It is known that polyfunctional (meth)acrylate compounds cure under light or heat, and they are widely used in coating materials, three-dimensional photofabrication materials, wiring protection materials, insulating materials and the like. However, due to large curing shrinkage, there is a problem of warpage of the base material and occurrence of cracks in the cured film. Therefore, alkylene oxide-modified polyfunctional (meth)acrylates and caprolactone-modified polyfunctional (meth)acrylates are known. However, the weight loss and the decrease in adhesion in a high-temperature environment are significant. Acrylate compounds of phenolphthalein anilide derivatives that have high heat resistance, transparency, and excellent curing shrinkage properties have also been developed, but higher flexibility has been required. Urethane-modified polyfunctional (meth)acrylates are also known to suppress curing shrinkage, but their heat resistance is low, and satisfactory properties have not been achieved.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

[0005] The present invention aims to provide a resin composition that exhibits excellent curing shrinkage, high heat resistance, excellent adhesion to metals even in high-temperature environments, and provides a cured film with excellent weight reduction and flexibility. [Means for solving the problem]

[0006] In order to solve the aforementioned problems, the present inventors conducted diligent research and found that compounds containing unsaturated groups having a heteropentacyclic structure and compositions thereof can solve the aforementioned problems, thus completing the present invention. More specifically, we found that a (meth)acrylate compound (A) and a resin composition containing the (meth)acrylate compound (A) can solve the aforementioned problems, and thus arrived at the present invention.

[0007] In other words, the present invention relates to the following. [1] A (meth)acrylate compound (A) is obtained by adding a heterogeneous five-membered ring compound (b) containing one or more nitrogen atoms to a polyfunctional (meth)acrylate compound (a) having two or more (meth)acrylic groups in one molecule. [2] The (meth)acrylate compound (A) described in [1], wherein the heterogeneous five-membered ring compound (b) containing one or more nitrogen atoms in one molecule has a benzene ring structure. [3] The (meth)acrylate compound (A) according to [1] or [2], wherein the heterogeneous five-membered ring compound (b) containing one or more nitrogen atoms in one molecule contains two or more nitrogen atoms. [4] The (meth)acrylate compound (A) according to any one of the following [1] to [3], wherein the polyfunctional (meth)acrylate compound (a) having two or more (meth)acrylic groups in one molecule is a polyfunctional (meth)acrylate compound having three or more (meth)acrylic groups in one molecule. [5] A photocurable resin composition comprising a (meth)acrylate compound (A) and a photopolymerization initiator (b) as described in any one of items [1] to [4]. [Effects of the Invention]

[0008] The (meth)acrylate compound (A) of the present invention exhibits excellent transparency, and resin compositions containing it have low curing shrinkage, high heat resistance, and maintain adhesion to metals and flexibility even in high-temperature environments. Therefore, it can be suitably used in materials requiring the above-mentioned physical properties. [Brief explanation of the drawing]

[0009] [Figure 1] 1H-NMR chart of (meth)acrylate compound (A1) obtained in Example 1 [Modes for carrying out the invention]

[0010] The (meth)acrylate compound (A) in the present invention is obtained by reacting a polyfunctional (meth)acrylate compound (a) having one or more (meth)acrylic groups in one molecule with a heterogeneous five-membered ring compound (b) containing one or more nitrogen atoms in one molecule.

[0011] In the present invention, the polyfunctional (meth)acrylate compound (a) is preferably an acrylate compound having two (meth)acrylic groups in one molecule. Examples of polyfunctional acrylate compounds having two (meth)acrylic groups in one molecule include hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, tripropylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, hydroxypivalate neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, dicyclopentenyl(meth)acrylate, dicyclopentenyloxyethyl(meth)acrylate, and dicyclopentanyl di(meth)acrylate.

[0012] A polyfunctional acrylate compound having 3 or more (meth)acrylic groups in one molecule is more preferred, and examples thereof include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, caprolactone-modified trimethylolpropane tri(meth)acrylate, EO-modified trimethylolpropane tri(meth)acrylate, PO-modified trimethylolpropane tri(meth)acrylate, tris(acryloxyethyl) isocyanurate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, dipentaerythritol hydroxypenta(meth)acrylate, alkyl-modified dipentaerythritol penta(meth)acrylate, dipentaerythritol poly(meth)acrylate, alkyl-modified dipentaerythritol tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol ethoxytetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, ECH (epichlorohydrin)-modified glycerol tri(meth)acrylate, EO (ethylene oxide)-modified glycerol tri(meth)acrylate, PO (propylene oxide)-modified glycerol tri(meth)acrylate, EO-modified tri(meth)acrylate phosphate, and the like are mentioned as preferred examples. These compounds may be used alone singly, or two or more of them may be used in combination.

[0013] Examples of the 5-membered heterocyclic compound (b) containing one or more nitrogen atoms in one molecule in the present invention include oxazole compounds, thiazole compounds, pyrrole compounds and the like

[0014] Among the 5-membered heterocyclic compounds (b) containing one or more nitrogen atoms in one molecule, examples of those containing two or more nitrogen atoms in one molecule include 1,2,3-triazole, 1,2,4-triazole, pyrazole, imidazole, tetrazole, pentazole and the like.

[0015] Among the 5-membered heterocyclic compounds (b) containing one or more nitrogen atoms in one molecule, examples of those having a benzene ring include indole, benzoxazole, benzimidazole, oxindole, benzimidazolinone, benzoxazolinone, benzothiazole, and benzothiazolone.

[0016] The above benzene ring may have a substituent, and examples thereof include an alkyl group, an alkenyl group, an aralkyl group, an aryl group, a carboxy group, and an aldehyde group. Specific examples include 1H-methylbenzotriazole, 1H-ethylbenzotriazole, 1H-methylimidazole, 1H-methylbenzimidazolinone, 1H-benzoxazolinone, and 1H-benzotriazole-carboxylic acid.

[0017] The 5-membered heterocyclic compound (b) containing one or more nitrogen atoms in one molecule is preferably in a range where the amount is such that 1 mole of the amino group of (b) is 0.01 to 0.99 relative to 1 mole of the unsaturated bond of the polyfunctional (meth)acrylate compound (a) having two or more (meth)acrylic groups in one molecule, and more preferably in a range where the amount is 0.02 to 0.9 from the viewpoints of curability and crosslinking density

[0018] In the process of producing (meth)acrylate compound (a), dilution with an organic solvent may be used as needed. Examples of solvents that can be used include: alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol monobutyl ether; methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, and propylene glycol methyl ether. Alkylene glycol monoalkyl ether acetates such as methyl acetate and 3-methoxybutyl-1-acetate; aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone, and 4-hydroxy-4-methyl-2-pentanone; and esters such as ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethyl acetate, butyl acetate, methyl lactate, and ethyl lactate. These solvents may be used individually or in mixtures of two or more.

[0019] Furthermore, catalysts can be used to accelerate the reaction as needed. Examples of catalysts include trimethylamine, triethylamine, tripropylamine, dimethylaniline, isoquinoline, trisdimethylaminophenol, lutidine, triethylenediamine, dimethylbenzylamine, dimethylpiperazine, cyclohexylamine, diisopropylamine, imidazole, diazabicycloundecene, pyridine, morpholine, piperazine, piperidine, triphenylphosphine, tory-p-tolylphosphine, sodium hydroxide, potassium hydroxide, and the like.

[0020] Polymerization inhibitors may also be added during the reaction as needed. Examples of such polymerization inhibitors include hydroquinone, p-methoxyphenol, 2,4-dimethyl-6-t-butylphenol, 3-hydroxythiophenol, p-benzoquinone, 2,5-dihydroxy-p-benzoquinone, and phenothiazine. The amount used is 0.01 to 1% by mass relative to the reaction mixture.

[0021] During the reaction, heating may be added as needed, preferably in the range of 60°C to 160°C, and particularly preferably in the range of 70°C to 150°C, and the reaction time is preferably 1 to 60 hours.

[0022] The (meth)acrylate compound (A) of the present invention is obtained as described above. Preferably, the (meth)acrylate compound (A) has one or more (meth)acrylic groups in one molecule.

[0023] The photopolymerization initiator used in the photocurable resin composition of the present invention can be used without particular limitations, but specifically, for example, benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenones such as acetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxychlorohexylphenyl ketone, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (for example, Omnirad-907 described in the examples below); 2-ethylanthraquinone, 2 Examples include anthraquinones such as tert-butylanthraquinone, 2-chloroanthraquinone, and 2-amylanthraquinone; thioxanthones such as 2,4-diethylthioxanthone (e.g., DETX-S described in the examples below), 2-isopropylthioxanthone, and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, and 4,4'-bismethylaminobenzophenone; and phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide. The photopolymerization initiator (C) may be used alone or in combination of two or more types. The content ratio in these photocurable resin compositions is typically 0.1 to 20% by mass, preferably 0.2 to 10% by mass, when the solid content of the photocurable resin composition is taken as 100% by mass.

[0024] These photopolymerization initiators (C) can be used alone or as a mixture of two or more, and can also be used in combination with accelerators such as tertiary amines like triethanolamine and methyldiethanolamine, and benzoic acid derivatives such as ethyl N,N-dimethylaminobenzoate and isoamyl N,N-dimethylaminobenzoate. The amount of these accelerators added is preferably 100% by mass or less relative to the photopolymerization initiator (C).

[0025] The resin composition of the present invention can be diluted with an organic solvent as needed, and examples of usable solvents include the organic solvents described above.

[0026] Furthermore, the resin composition of the present invention may optionally contain inorganic fillers, organic fillers, adhesive aids, surfactants, antioxidants, tackifiers, defoamers, plasticizers, ultraviolet absorbers, flame retardants, dyes, and the like.

[0027] Examples of inorganic fillers include silicon dioxide, silicon oxide, calcium carbonate, calcium silicate, magnesium carbonate, magnesium oxide, titanium dioxide, zirconium oxide, talc, kaolin clay, calcined clay, zinc oxide, zinc sulfate, aluminum hydroxyl, aluminum oxide, glass, mica, barium sulfate, alumina white, zeolite, silica balloons, glass balloons, etc. These inorganic fillers can also be given functional groups such as halogen groups, epoxy groups, hydroxyl groups, and thiol groups by adding and reacting silane coupling agents, titanate-based coupling agents, aluminum-based coupling agents, zirconate-based coupling agents, etc.

[0028] Examples of organic fillers include benzoguanamine resin, silicone resin, low-density polyethylene, high-density polyethylene, polyolefin resin, ethylene-acrylic acid copolymer, polystyrene, acrylic copolymer, polymethyl methacrylate resin, fluororesin, nylon 12, nylon 6 / 66, phenolic resin, epoxy resin, urethane resin, polyimide resin, organic pigments, and organic dyes.

[0029] Examples of adhesive aids include silane coupling agents and metal chelates. These include silane coupling agents such as γ-glycidoxypropyltrimethoxysilane or γ-chloropropyltrimethoxysilane; titanate coupling agents such as tetra(2,2-diallyloxymethyl-1-butyl)bis(ditridecyl)phosphite titanate and bis(dioctylpyrophosphate)ethylene titanate; aluminum coupling agents such as acetalkoxyaluminum diisopropylate; and zirconium coupling agents such as acetylacetone zirconium complexes.

[0030] Surfactants can be used to improve the applicability (wetting spread and reduction of uneven application) of the composition of the present invention. Examples of surfactants include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.

[0031] Examples of antioxidants include hindered phenol antioxidants, phosphite ester antioxidants, and thioether antioxidants.

[0032] Any tackifier, defoamer, plasticizer, ultraviolet absorber, flame retardant, and dye that can be used in the active energy ray curable resin composition of the present invention can be used without particular limitation, provided that they are known and commonly used, as long as they do not impair the curability and resin properties.

[0033] To obtain the active energy ray curable resin composition of the present invention, the above-mentioned components can be mixed, and the order and method of mixing are not particularly limited. [Examples]

[0034] Next, the present invention will be described in more detail with reference to examples. However, the present invention is not limited in any way by the following examples.

[0035] Example 1 In a 300 mL flask equipped with a stirrer and reflux tubing, 76 g of KAYARAD DPHA (dipentaerythritol penta / hexaacrylate mixture, Nippon Kayaku Co., Ltd.), 34 g of benzotriazole, 0.3 g of triethylamine, and 0.05 g of dibutyl tertiary cresol were added. The mixture was stirred at 60°C for 1 hour and then reacted at 110°C for 8 hours. After cooling to room temperature, acrylate compound (A1) was obtained. 1 Identification using 1H-NMR confirmed that the reaction was proceeding.

[0036] Example 2 In a 300 mL flask equipped with a stirrer and reflux tubing, 88 g of KAYARAD T-1420 (ditrimethylolpropanetetraacrylate, Nippon Kayaku Co., Ltd.), 34 g of benzotriazole, 0.5 g of diisopropylethylamine, and 0.05 g of dibutyl tert-cresol were added. The mixture was stirred at 60°C for 1 hour and then reacted at 110°C for 8 hours. After cooling to room temperature, acrylate compound (A2) was obtained.

[0037] Example 3 In a 500 mL flask equipped with a stirrer and reflux tubing, 120 g of trimethylolpropane triacrylate, 34 g of benzotriazole, 0.3 g of dimethylbenzylamine, and 0.05 g of dibutyl tert-cresol were added. The mixture was stirred at 60°C for 1 hour and then reacted at 110°C for 8 hours. After cooling to room temperature, acrylate compound (A3) was obtained.

[0038] Example 4 The synthesis was carried out in the same manner as in Synthesis Example 1, except that benzotriazole was replaced with methyl-1H-benzotriazole, to obtain acrylate compound (A4). 1 Identification using 1H NMR confirmed the presence of acrylic and benzotriazole groups.

[0039] Example 5 The synthesis was carried out in the same manner as in Synthesis Example 1, except that benzotriazole was replaced with benzimidazole, to obtain the acrylate compound (A5).

[0040] The photocurable resin compositions for Examples 6-10 and Comparative Examples 1-4 were prepared by blending the materials in the amounts (parts by mass) shown in Table 1.

[0041] <Characteristic Evaluation> The following properties were measured for the prepared curable resin composition and cured film. The results are shown in Table 1. TIFF2026165910000002.tif62170

[0042] <Photopolymerization initiator> Irgacure907: 2-methyl-1-[(4-methylthio)phenyl]-2-morpholinopropan-1-one <Solvent> MEK: Methyl ethyl ketone

[0043] <Characteristic Evaluation> The following properties were measured for the prepared curable resin composition and cured film. The results are shown in Table 1.

[0044] The photocurable resin compositions obtained in each example and comparative example were applied to 18 μm thick rolled copper foil (BHY-82F-HA-V2 (product name), manufactured by JX Metals Corporation) using an applicator, and then dried at 80°C for 30 minutes to form a film-like photocurable resin composition on the copper foil. The coating thickness of the photocurable resin composition was adjusted so that the film thickness after drying was 10 μm. This film-like photocurable resin composition was irradiated with an active energy ray including a wavelength of 405 nm (h-line) using a light source (USHIO Corporation's ultra-high pressure mercury lamp 500W Multi-Light (product name)) at a rate of 100 mJ / cm². 2 Exposure was performed using [this method]. [hardening shrinkage] The obtained resin-coated copper foil was cut into 5cm x 5cm squares, and the lift at the edges was measured. A lift of 0.5cm or more was marked with an "X," and a lift of less than 0.5cm was marked with an "O." [Heat-resistant weight reduction] The obtained resin-coated copper foil was heated in a 230°C oven for 1 hour, and the weight loss rate before and after heating was calculated. A weight loss of less than 3% was marked with ○, and a weight loss of 3% or more was marked with ×. *Weight reduction rate (%) = 1-weight after heating / initial weight [Heat-resistant adhesion] The resin-coated copper foil obtained as described above was heated in a 230°C oven for 1 hour, then cut into a 100x100 grid pattern, and checked for any peeling or cracking. [Heat resistance and flexibility] Similarly to the above, the film was heated in a 230°C oven for 1 hour, then folded 90° from the center and checked for any defects such as cracks or damage. Films without cracks or damage were marked with ○, and those with cracks or damage were marked with ×. [Industrial applicability]

[0045] The (meth)acrylate compound (A) of the present invention exhibits excellent curing shrinkage and heat resistance, and it is evident that molded articles and cured films can be obtained. Therefore, resin compositions containing the (meth)acrylate compound (A) of the present invention can be suitably used in coating compositions, resin compositions for stereolithography, electronic materials for wiring protection materials and insulating film materials, and the like.

Claims

1. A (meth)acrylate compound (A) is obtained by adding a heterogeneous five-membered ring compound (b) containing one or more nitrogen atoms to a polyfunctional (meth)acrylate compound (a) having two or more (meth)acrylic groups in one molecule.

2. The (meth)acrylate compound (A) according to claim 1, wherein the heterogeneous five-membered ring compound (b) containing one or more nitrogen atoms in one molecule has a benzene ring structure.

3. The (meth)acrylate compound (A) according to claim 1, wherein the heterogeneous five-membered ring compound (b) containing one or more nitrogen atoms in one molecule contains two or more nitrogen atoms.

4. The (meth)acrylate compound (A) according to claim 1, wherein the polyfunctional (meth)acrylate compound (a) having two or more (meth)acrylic groups in one molecule is a polyfunctional (meth)acrylate compound having three or more (meth)acrylic groups in one molecule.

5. A photocurable resin composition comprising the (meth)acrylate compound (A) and a photopolymerization initiator (b) as described in claim 1.

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