KR20220108046A - (meth)acrylate, curable resin composition and cured product - Google Patents

Abstract

The present invention provides a novel (meth)acrylate, which is a material for forming a cured product capable of maintaining high insulation for a long time under high temperature and high humidity, a curable resin composition containing this (meth)acrylate, and a cured product obtained by curing the curable resin composition aim to do The novel (meth)acrylate according to the present invention is represented by the following general formula (1) or (2). (in formula (1), R ¹ to R ⁴ are each independently H or a methyl group; R ⁵ to R ⁷ are each independently a halogen group, an alkyl group, an alkoxy group, or an aromatic group, AO is an ethyleneoxy group, or a propyleneoxy group, m and n are each independently an integer of 0 to 5, and p is It is an integer of 0 to 2, and r and s are each independently an integer of 0 to 15.) (In Formula (2), R ¹ to R ⁴ are each independently H or a methyl group, and R ⁵ to R ⁷ are each independently a halogen group, an alkyl group, an alkoxy group, or an aromatic group, AO is an ethyleneoxy group, or a propyleneoxy group, m and n are each independently an integer from 0 to 5, p is an integer from 0 to 2, , r and s are each independently an integer from 0 to 15.)

Description

(meth)acrylate, curable resin composition and cured product

The present invention relates to a novel (meth)acrylate, a curable resin composition containing this (meth)acrylate, and a cured product obtained by curing the curable resin composition.

With the recent miniaturization of electronic components, the distance between wirings of a circuit board is getting narrower, and in order to miniaturize electronic components, insulation of an insulating film used between wirings is becoming increasingly important. In particular, electronic components such as circuit boards are sometimes used in harsh environments such as high temperature and high humidity, and an insulating film used for electronic components is required to maintain high insulating properties even under such harsh environments.

Conventionally, photosensitive polyimide has been used as the insulating film used for the above purpose. However, since the film forming process includes a process of applying heat of 300 to 400 ° C., the performance of electronic components is deteriorated due to heat. There is a risk of deterioration.

Moreover, when the photosensitive materials of acryl-type and epoxy-type other than a polyimide are used in harsh environments, such as high temperature and high humidity, there exists a problem that insulation deterioration is easy to raise|generate.

Patent Document 1 discloses a thermally conductive sheet capable of realizing a semiconductor device with high insulation reliability, including a thermosetting resin and an inorganic filler dispersed in the thermosetting resin, and according to JIS K6911, a voltage at an applied voltage of 1000 V A thermally conductive sheet is disclosed wherein the volume resistivity of the cured product of the thermally conductive sheet at 175°C measured 1 minute after application is 1.0×10 ⁸ Ω·m or more.

Moreover, in patent document 2, as a high-resistance photosensitive resin composition excellent in light-shielding property and insulation, (a) alkali-soluble resin, (b) photopolymerizable monomer, (c) photoinitiator of a specific structure and (d) a photosensitive resin composition containing high-resistance carbon black as a color material.

1. Japanese Patent Laid-Open No. 2015-146387 2. International Publication No. 2019/065789

However, the cured film obtained from the thermal conductive sheet of patent document 1 and the photosensitive resin composition of patent document 2 cannot maintain high insulation under high temperature, high humidity for a long time.

The present invention relates to a novel (meth)acrylate, which is a material for forming a cured product capable of maintaining high insulation under high temperature and high humidity for a long time, a curable resin composition containing this (meth)acrylate, and a cured product obtained by curing the curable resin composition intended to provide

MEANS TO SOLVE THE PROBLEM The present inventors discovered that the said objective can be achieved with the novel (meth)acrylate, curable resin composition, and hardened|cured material shown below, as a result of repeating close examination in order to solve the said subject, and this invention came to completion.

This invention relates to the (meth)acrylate represented by the following general formula (1) or (2).

<Formula 1>

(Wherein, R ¹ to R ⁴ are each independently H or a methyl group, R ⁵ to R ⁷ are each independently a halogen group, an alkyl group, an alkoxy group or an aromatic group, and AO is an ethyleneoxy group, or a propyleneoxy group and m and n are each independently an integer of 0-5, p is an integer of 0-2, and r and s are each independently an integer of 0-15.)

<Formula 2>

(Wherein, R ¹ to R ⁴ are each independently H or a methyl group, R ⁵ to R ⁷ are each independently a halogen group, an alkyl group, an alkoxy group or an aromatic group, and AO is an ethyleneoxy group, or a propyleneoxy group and m and n are each independently an integer of 0-5, p is an integer of 0-2, and r and s are each independently an integer of 0-15.)

Curable resin composition of this invention contains at least 1 sort(s) of said (meth)acrylate, a base polymer, a polymerization initiator, and a solvent.

It is preferable that content of the said (meth)acrylate in the said curable resin composition is 20-100 mass parts with respect to 100 mass parts of said base polymers.

It is preferable that the said curable resin composition contains a polyfunctional monomer and/or an epoxy resin further.

The cured product of the present invention is obtained by curing the curable resin composition.

It is preferable that the water absorption of the said hardened|cured material is 1 % or less.

Since the (meth)acrylate represented by the said General formula (1) and/or (2) is used for the hardened|cured material obtained by hardening the curable resin composition of this invention, the water absorption is very low, and it is high under high temperature and high humidity. Insulation can be maintained for a long time.

<(meth)acrylate represented by general formula (1) or (2)>

The novel (meth)acrylate according to the present invention is represented by the following general formula (1) or (2) (hereinafter also collectively referred to as (meth)acrylate X). In addition, in this invention, (meth)acrylate means an acrylate, a methacrylate, or a mixture thereof. The same is true for other compounds described similarly.

<Formula 3>

(Wherein, R ¹ to R ⁴ are each independently H or a methyl group, R ⁵ to R ⁷ are each independently a halogen group, an alkyl group, an alkoxy group or an aromatic group, and AO is an ethyleneoxy group, or a propyleneoxy group and m and n are each independently an integer of 0-5, p is an integer of 0-2, and r and s are each independently an integer of 0-15.)

<Formula 4>

(Wherein, R ¹ to R ⁴ are each independently H or a methyl group, R ⁵ to R ⁷ are each independently a halogen group, an alkyl group, an alkoxy group or an aromatic group, and AO is an ethyleneoxy group, or a propyleneoxy group and m and n are each independently an integer of 0-5, p is an integer of 0-2, and r and s are each independently an integer of 0-15.)

In the above formula, the halogen group is not particularly limited, and examples thereof include fluorine, chlorine, bromine and iodine.

In the above formula, the alkyl group is not particularly limited, and may be linear, branched, cyclic, or a combination thereof. The number of carbon atoms in the alkyl group is not particularly limited, and is usually 1 to 10, preferably 1 to 5, and more preferably 1 to 3.

In the above formula, the alkoxy group is not particularly limited, and may be linear, branched, cyclic, or a combination thereof. The number of carbon atoms in the alkoxy group is not particularly limited, and is usually 1 to 10, preferably 1 to 5, and more preferably 1 to 3.

In the above formula, the aromatic group is not particularly limited, and may be an aromatic hydrocarbon group or an aromatic heterocyclic group. Moreover, the aromatic group may have a substituent.

In the above formula, AO is an ethyleneoxy group or a propyleneoxy group, and when m and n are integers of 2 or more, AO may be only an ethyleneoxy group or only a propyleneoxy group, and may be an ethyleneoxy group and a propyleneoxy group.

In said formula, m and n are each independently an integer of 0-5, Preferably it is an integer of 0-3, More preferably, it is 0 or 1, More preferably, it is 0.

In said formula, p is an integer of 0-2, Preferably it is 0 or 1, More preferably, it is 0.

In said formula, r and s are each independently an integer of 0-15, Preferably it is an integer of 0-10, More preferably, it is an integer of 0-5, More preferably, it is 0.

As (meth)acrylate represented by the said General formula (1), the (meth)acrylate represented by following formula (3) is mentioned, for example.

<Formula 5>

The (meth)acrylate represented by the said General formula (1) can be synthesize|combined by making the compound represented by the following general formula (4) and anhydrous (meth)acrylic acid react, for example in presence of an alkali catalyst.

<Formula 6>

(Wherein, R ⁵ to R ⁷ , AO, m, n, p, r and s are the same as above.)

Examples of the alkali catalyst include sodium amide, triethylamine, tributylamine, trioctylamine, pyridine, dimethylaminopyridine, N,N-dimethylaniline, 1,5-diazabicyclo[4,3,0]nonene- 5 (DBN), 1,8-diazabicyclo [5,4, 0] undecene-7 (DBU), sodium hydroxide, potassium hydroxide, sodium hydride, sodium phosphate, potassium phosphate, sodium carbonate, potassium carbonate, silver oxide, sodium methoxide and potassium t-butoxide; and the like.

As (meth)acrylate represented by the said General formula (2), the (meth)acrylate represented by following formula (5) is mentioned, for example.

<Formula 7>

[0031] The (meth)acrylate represented by the general formula (2) can be synthesized by, for example, reacting a compound represented by the following general formula (6) with anhydrous (meth)acrylic acid in the presence of an alkali catalyst .

<Formula 8>

(Wherein, R ⁵ to R ⁷ , AO, m, n, p, r and s are the same as above.)

Examples of the alkali catalyst include those described above.

<Curable resin composition>

Curable resin composition of this invention contains at least 1 sort(s) of said (meth)acrylate X, a base polymer, a polymerization initiator, and a solvent.

Although content in particular of the said (meth)acrylate X in the said curable resin composition is not restrict|limited, From a viewpoint of lowering the water absorption of the hardened|cured material obtained and a viewpoint of film forming property, it is 20 - with respect to 100 mass parts of said base polymers It is preferable that it is 100 mass parts, More preferably, it is 20-80 mass parts, More preferably, it is 20-40 mass parts.

The base polymer is not particularly limited, and for example, poly(meth)acrylic resin, polyurethane-based resin, polyvinyl-based resin, polystyrene-based resin, polyethylene-based resin, polypropylene-based resin, polyimide-based resin, polyamide-based resin, polyacetal Resin, polycarbonate resin, polyester resin, epoxy resin, phenol resin, urea resin, melamine resin, polyphenylene ether resin, polyphenylene sulfide resin, polyether sulfone resin resin and polyether ether ketone type resin etc. are mentioned, These can be used individually or in combination of 2 or more types. Among these, it is preferable to use poly(meth)acrylic-type resin.

The monomer forming the poly (meth) acrylic resin is not particularly limited, and for example, alkyl (meth) acrylate, alkoxy group-containing (meth) acrylate, alicyclic group-containing (meth) acrylate, aryl group containing (meth)acrylate, hydroxyl group containing (meth)acrylate, epoxy group containing (meth)acrylate, and carboxyl group containing (meth)acrylate, etc. are mentioned. These can be used individually or in combination of 2 or more types.

Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, tert-butyl (meth) acrylate, sec-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) Acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) Acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, isostearyl (meth) acrylate, eicosyl (meth) acrylic a rate, behenyl (meth)acrylate, and tetrahydrofurfuryl (meth)acrylate, etc. are mentioned. These can be used individually or in combination of 2 or more types.

Examples of the alkoxy group-containing (meth)acrylate include 2-methoxyethyl (meth)acrylate, methoxyethylene glycol (meth)acrylate, 2-ethoxyethyl (meth)acrylate, and ethyl carbitol (ethyl carbitol). ) (meth)acrylate, etc. are mentioned. These can be used individually or in combination of 2 or more types.

As the alicyclic group-containing (meth)acrylate, for example, cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicy Clopentenyl (meth)acrylate, and adamantyl (meth)acrylate, etc. are mentioned. These can be used individually or in combination of 2 or more types.

As the aryl group-containing (meth)acrylate, for example, an aryl group-containing (meth)acrylic having 6 to 15 carbon atoms, such as phenyl (meth)acrylate, benzyl (meth)acrylate, and phenoxyethyl (meth)acrylate rate etc. are mentioned. These can be used individually or in combination of 2 or more types.

Examples of the hydroxyl group-containing (meth)acrylate include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 6-hydroxyhexyl (meth)acrylate. ) acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, and 12-hydroxylauryl (meth)acrylate. These can be used individually or in combination of 2 or more types.

Examples of the epoxy group-containing (meth)acrylate include glycidyl (meth)acrylate and epoxycyclohexyl (meth)acrylate. These can be used individually or in combination of 2 or more types.

Examples of the carboxyl group-containing (meth)acrylate include acrylic acid, methacrylic acid, carboxyethyl (meth)acrylate, carboxybutyl (meth)acrylate, and carboxypentyl (meth)acrylate. These can be used individually or in combination of 2 or more types.

In addition, 2-(meth)acryloyloxyethyl succinic acid, maleic acid, itaconic acid, maleic anhydride, itaconic anhydride, vinyl acetate, vinyl propionate, styrene, α-methylstyrene, N-vinylcaprolactam, cyclohexyl maleate Mide, phenylmaleimide, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, n-butylmaleimide, laurylmaleimide, and a silicone-containing monomer may be used as the copolymerization monomer. These can be used individually or in combination of 2 or more types.

From the viewpoint of lowering the water absorption of the cured product, it is preferable to use 20% by mass or more of the alicyclic group-containing (meth)acrylate with respect to all the monomers forming the poly(meth)acrylic resin, and more preferably 30% by mass or more. From the same viewpoint, it is preferable to use 10 mass% or more of aryl group-containing (meth)acrylate with respect to all the monomers forming the poly(meth)acrylic resin, more preferably 20 mass% or more. Moreover, from the same viewpoint, it is preferable to use 5 mass % or more of a carboxyl group-containing monomer with respect to all the monomers which form a poly(meth)acrylic-type resin, and it is more preferable to use 10 mass % or more.

Although the weight average molecular weight in particular of the said poly (meth)acrylic resin is not restrict|limited, When it contains in curable resin composition, it becomes easy to form a fine pattern (hereafter, resolution is good), 5000 from a viewpoint It is preferable that it is -100000, More preferably, it is 10000-30000. Also regarding the weight average molecular weight of other types of base polymers, the above range is preferable. The weight average molecular weight of the base polymer containing the poly(meth)acrylic resin is a value in terms of polystyrene measured using gel permeation chromatography (GPC), and is a value measured in accordance with JIS 7252-4. The weight average molecular weight described in the Examples described later is also a value calculated according to the description on this page.

Although the acid value of the poly(meth)acrylic resin is not particularly limited, from the viewpoint of resolution, it is preferably 10 to 200 (mgKOH/g), more preferably 30 to 100 (mgKOH/g). .

It is preferable to use a photoinitiator as a polymerization initiator. The photopolymerization initiator is not particularly limited, and examples thereof include benzoin and its alkyl ethers such as benzoin, benzoin methyl ether, and benzoin ethyl ether; acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, and 1,1-dichloroacetophenone; anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone; thioxanthone such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone; 2-Methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone -One; Acyl phosphine oxides, xanthones, etc. are mentioned. These photoinitiators may be used independently and may use 2 or more types together.

The content of the photoinitiator is not particularly limited, but is preferably 1 part by weight or more, more preferably 5 parts by weight or more, and preferably 15 parts by weight or less, based on 100 parts by weight of all polymerizable raw materials in the curable resin composition. and more preferably 10 parts by weight or less.

The said curable resin composition may contain a photoinitiation adjuvant. Examples of the photopolymerization initiation adjuvant include 1,3,5-tris(3-mercaptopropionyloxyethyl)-isocyanurate, 1,3,5-tris(3-mercaptobutyloxyethyl)-isocyanurate. Trifunctional thiol compounds, such as the rate (The Showa Denko company make, Karenz MT (trademark) NR1), and trimethylolpropane tris(3-mercaptopropionate); tetrafunctional thiol compounds such as pentaerythritol tetrakis (3-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptobutyrate) (the Showa Denko make, Karenz MT (registered trademark) PEI); Polyfunctional thiols, such as 6 functional thiol compounds, such as dipentaerythritol hexakis (3-propionate), are mentioned. These photoinitiation adjuvants may be used independently and may use 2 or more types together.

The said curable resin composition may contain a thermal-polymerization initiator. As the thermal polymerization initiator, for example, cumene hydroperoxide, diisopropylbenzene peroxide, di-t-butyl peroxide, lauryl peroxide, benzoyl peroxide, t-butyl peroxyisopropyl carbonate, t-butyl peroxy organic peroxides such as -2-ethylhexanoate and t-amylperoxy-2-ethylhexanoate; 2,2'-azobis(isobutyronitrile), 1,1'-azobis(cyclohexanecarbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl 2,2 Azo compounds, such as '-azobis (2-methylpropionate), etc. are mentioned. These thermal-polymerization initiators may be used independently and may use 2 or more types together.

Examples of the solvent include ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, and 3-methoxybutyl acetate; alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether, and propylene glycol monomethyl ether; aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; Chloroform, dimethyl sulfoxide, etc. are mentioned. These solvents may be used independently and may use 2 or more types together. In addition, content in particular of a solvent is not restrict|limited, What is necessary is just to adjust suitably according to the optimal viscosity at the time of using this composition, etc.

The said curable resin composition may contain polyfunctional monomers other than the said (meth)acrylate X further. The polyfunctional monomer is not particularly limited, and for example, polyfunctional aromatic vinyl-based monomers such as divinylbenzene, diallyl phthalate, and diallylbenzene phosphonate; (di) ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol di(meth)acrylate, Pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipenta Polyfunctional (meth)acrylates, such as tri(meth)acrylate of erythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and tris(hydroxyethyl) isocyanurate, etc. are mentioned. . Among these, (di)pentaerythritol tetra(meth)acrylate, (di)pentaerythritol penta(meth)acrylate, (di)pentaerythritol hexa(meth)acrylate, and tris(hydroxyethyl)iso The tri(meth)acrylate of cyanurate is preferable. These polyfunctional monomers may be used independently and may use 2 or more types together.

The content of the polyfunctional monomer in the curable resin composition is not particularly limited, but is preferably 20 to 100 parts by mass based on 100 parts by mass of the base polymer, more preferably from the viewpoint of lowering the water absorption of the obtained cured product and from the viewpoint of film forming properties. Preferably it is 20-50 mass parts, More preferably, it is 20-40 mass parts.

The said curable resin composition may contain an epoxy resin further. This epoxy resin is different from the epoxy resin which can be used as a base polymer mentioned above, It is an epoxy resin whose molecular weight is smaller than the said epoxy resin. Accordingly, the curable resin composition includes an epoxy-based resin as a base polymer, and may also contain an epoxy resin. The epoxy resin is typically a low molecular weight resin having an epoxy skeleton, an oligomer, and a monomer, and has a weight average molecular weight of about 1000 or less. The epoxy resin is not particularly limited, and for example, a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a glycidyl ether type epoxy compound, a glycidyl ester type epoxy compound, a biphenyl type epoxy compound, a phenol novolak type epoxy compound, cresol novolac-type epoxy compound, bisphenol A novolak-type epoxy compound, aliphatic polyglycidyl ether compound, cyclic aliphatic epoxy compound, polymer of a monomer having an epoxy group, and a monomer having an epoxy group and another monomer an epoxy compound having a coalescence and a siloxane bonding site; and the like. These epoxy resins may be used independently and may use 2 or more types together.

The content of the epoxy resin in the curable resin composition is not particularly limited, but from the viewpoint of lowering the water absorption of the obtained cured product and the film forming property, it is preferably 10 to 100 parts by mass based on 100 parts by mass of the base polymer, more preferably is 10 to 50 parts by mass, more preferably 10 to 30 parts by mass.

The said curable resin composition may contain radically polymerizable oligomers, such as unsaturated polyester, an epoxy acrylate, a urethane acrylate, and a polyester acrylate further.

[0058] The curable resin composition, in the range not impairing the effects of the present invention, an adhesion imparting agent, a coating property improving agent, a dye, a pigment, an antifoaming agent (消泡劑), a coupling agent, a leveling agent, a sensitizer, a mold release agent, You may contain well-known additives, such as a lubricant, a plasticizer, antioxidant, a ultraviolet absorber, a flame retardant, a thickener, and a dispersing agent.

Although the solid content concentration in particular of the said curable resin composition is not restrict|limited, From a viewpoint of the film forming property of the hardened|cured material obtained, it is preferable that it is 10-60 mass %, More preferably, it is 20-50 mass %.

<Cured material>

The hardened|cured material of this invention is obtained by hardening the said curable resin composition. As a method for producing the cured product, for example, the curable resin composition is poured into a molding die (resin die), or the curable resin composition is coated on a substrate (substrate) or various layers to form a desired shape. and a method of curing the curable resin composition by irradiating and/or heating light (eg, ultraviolet rays). The conditions of hardening are adjusted suitably according to the said curable resin composition to be used.

The cured product of the present invention has a very low water absorption and is characterized in that it can maintain high insulation properties for a long time under high temperature and high humidity. It is preferable that the water absorption of the said hardened|cured material is 1 % or less, More preferably, it is 0.9 % or less, More preferably, it is 0.8 % or less.

Although the use in particular of the hardened|cured material of this invention is not restrict|limited, It can use suitably as a member (for example, insulating film, insulating film resist, insulating sheet, insulating layer, etc.) which requires insulation. Applications include, for example, semiconductor devices/integrated circuits (ICs, etc.), discrete semiconductors (diodes, transistors, thermistors, etc.), LEDs (LED lamps, chip LEDs, light-receiving elements, optical semiconductor lenses), sensors (temperature sensors, optical sensors, etc.) , magnetic sensors), passive components (high-frequency devices, resistors, capacitors, etc.), mechanical parts (connectors, switches, relays, etc.), automobile parts (circuit systems, control systems, sensors, lamp seals, etc.), adhesives and adhesives (optical parts, optical disks, pickup lenses, etc.), a surface protection film, and an optical film.

[Example]

Hereinafter, the present invention will be described with reference to Examples, but the present invention is by no means limited by these Examples.

<Preparation of base polymer>

Preparation 1-1

20.0 g of methacrylic acid, 34.1 g of dicyclopentanyl methacrylate, and 21.0 g of benzyl acrylate were placed in a glass flask equipped with a heating cooling and stirring device, a reflux cooling tube, and a nitrogen introduction tube. After replacing the gas phase part in the system with nitrogen, 4.8 g of 2,2'-azobis(isobutyronitrile) was added, heated to 80° C., and reacted at the same temperature for 8 hours. . Then, 20.3 g of 3,4-epoxycyclohexylmethyl methacrylate, 0.2 g of triphenylphosphine, and 0.1 g of methoxyhydroquinone were added. After replacing the gaseous phase in the system with air, it was heated to 100° C. and reacted at the same temperature for 20 hours to obtain a base polymer (A-1). The acid value in terms of solid content of the obtained base polymer was 73.3. Moreover, the weight average molecular weight (Mw) by GPC of the obtained base polymer was 14,000.

Preparation 1-2

To a glass flask equipped with a heating cooling and stirring device, a reflux cooling tube and a nitrogen introduction tube, methacrylic acid 2.6 g, dicyclopentanyl methacrylate 13.1 g, 3,4-epoxycyclohexylmethyl methacrylate 8.3 g, cyclo 72.3 g of hexanone was added. After replacing the gas phase part in the system with nitrogen, 3.6 g of 2,2'-azobis(2,4-dimethylvaleronitrile) was added, heated to 65° C., and reacted at the same temperature for 13 hours to make the base polymer ( A-2) was obtained. The acid value in terms of solid content of the obtained base polymer was 52.6. Moreover, the weight average molecular weight (Mw) by GPC of the obtained base polymer was 5,400.

Preparation 1-3

To a glass flask equipped with a heating cooling and stirring device, a reflux cooling tube and a nitrogen introduction tube, methacrylic acid 2.6 g, dicyclopentanyl acrylate 12.9 g, 3,4-epoxycyclohexylmethyl methacrylate 8.6 g, cyclohexa 72.3 g of rice paddy was added. After replacing the gas phase part in the system with nitrogen, 3.6 g of 2,2'-azobis(2,4-dimethylvaleronitrile) was added, heated to 65° C., and reacted at the same temperature for 13 hours to make the base polymer ( A-3) was obtained. The acid value in terms of solid content of the obtained base polymer was 68.8. Moreover, the weight average molecular weight (Mw) by GPC of the obtained base polymer was 7,300.

Preparation Example 1-4

2.3 g of methacrylic acid, 13.3 g of dicyclopentanyl acrylate, 8.5 g of glycidyl methacrylate, and 72.3 g of cyclohexanone were placed in a glass flask equipped with a heating cooling and stirring device, a reflux cooling tube and a nitrogen introduction tube. . After replacing the gas phase part in the system with nitrogen, 3.6 g of 2,2'-azobis(2,4-dimethylvaleronitrile) was added, heated to 65° C., and reacted at the same temperature for 13 hours to make the base polymer ( A-4) was obtained. The acid value in terms of solid content of the obtained base polymer was 42.7. Moreover, the weight average molecular weight (Mw) by GPC of the obtained base polymer was 7,200.

Preparation 1-5

3.0 g of methacrylic acid, 14.1 g of dicyclopentanyl acrylate, 6.9 g of glycidyl methacrylate, and 72.3 g of cyclohexanone were placed in a glass flask equipped with a heating cooling and stirring device, a reflux cooling tube and a nitrogen introduction tube. . After replacing the gas phase part in the system with nitrogen, 3.6 g of 2,2'-azobis(2,4-dimethylvaleronitrile) was added, heated to 65° C., and reacted at the same temperature for 13 hours to make the base polymer ( A-5) was obtained. The acid value in terms of solid content of the obtained base polymer was 57.8. In addition, the weight average molecular weight (Mw) by GPC of the obtained base polymer was 7,100.

Preparation 1-6

9.8 g of methacrylic acid, 20.3 g of dicyclopentanyl methacrylate, and 55.8 g of cyclopentanone were put in the glass flask provided with the heating cooling and stirring apparatus, the reflux cooling tube, and the nitrogen introduction tube. After replacing the gaseous phase in the system with nitrogen, 2.7 g of 2,2'-azobis(isobutyronitrile) was added, heated to 80° C., and reacted at the same temperature for 8 hours. Then, it heated to 100 degreeC, and made it react at the same temperature for 2 hours. Then, 11.3 g of glycidyl methacrylate, 0.02 g of methoxyhydroquinone, 0.001 g of 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical (BTOX), 0.1 g of dimethylbenzylamine was added. After replacing the gaseous phase in the system with air, the mixture was heated to 100° C. and reacted at the same temperature for 20 hours to obtain a base polymer (A-6). The acid value in terms of solid content of the obtained base polymer was 47.5. Moreover, the weight average molecular weight (Mw) by GPC of the obtained base polymer was 7,900.

<Production of (meth)acrylate>

Preparation 2-1

10.0 g of Adamantate E201 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), 6.2 g of methacrylic anhydride, 0.3 g of dimethylaminopyridine, and 24.3 g of toluene were added to a glass flask equipped with a heating cooling and stirring device, a reflux cooling tube and a nitrogen introduction tube. . After replacing the gas phase in the system with air, it was heated to 90° C. and reacted at the same temperature for 12 hours. Then, 100.0 g of methanol was added, and the precipitated solid was separated by filtration, and it dried and obtained the methacrylate (C-1) represented by following formula (3).

<Formula 9>

Preparation 2-2

10.0 g of Adamantate E201 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), 3.5 g of acrylic acid, 0.3 g of dimethylaminopyridine, and 24.3 g of toluene were placed in a glass flask equipped with a heating/cooling and stirring device, a reflux cooling tube and a nitrogen introduction tube. After replacing the gas phase in the system with air, it was heated to 90° C. and reacted at the same temperature for 12 hours. Then, 100.0 g of methanol was added, the precipitated solid was separated by filtration, and it dried and obtained the acrylate (C-3) represented by following formula (7).

<Formula 10>

<Preparation of curable resin composition>

Example 1

21.4 mass% of the base polymer (A-1), 6.4 mass% of dipentaerythritol hexaacrylate (B-1) as a polyfunctional monomer, 6.4 mass% of the methacrylate (C-1), dicyclopenta as an epoxy resin Dienedimethanol diglycidyl ether (D-1) 4.3% by mass, photopolymerization initiator (manufactured by IGM Resins B.V., Omnirad 379EG) 1.2% by mass, 3-glycidoxypropylmethyldiethoxysilane (Shin-Etsu) as an adhesive imparting agent ) manufactured by Chemical Industry Co., Ltd., KBM-403) 0.3 mass%, and 60 mass% of propylene glycol monomethyl ether acetate (PGMEA) as a solvent were mixed under light blocking to prepare a curable resin composition (solid content concentration: about 40 mass%) did.

Example 2, Comparative Examples 1-4

A curable resin composition (solid content concentration: about 40 mass %) was prepared in the same manner as in Example 1 except that the raw materials shown in Table 1 were used in the compounding amounts shown in Table 1.

Example 3, Comparative Examples 5 and 6

A curable resin composition (solid content concentration: about 35 mass %) was prepared in the same manner as in Example 1 except that the raw materials shown in Table 2 were used in the amounts shown in Table 2.

Examples 4-6, Comparative Example 7

A curable resin composition (solid content concentration: about 35 mass %) was prepared in the same manner as in Example 1 except that the raw materials shown in Table 3 were used in the compounding amounts shown in Table 3.

The raw materials described in Tables 1 to 4 are as follows.

Base polymer (A-1): the base polymer prepared in Preparation Example 1-1

Base polymer (A-2): the base polymer prepared in Preparation Example 1-2

Base polymer (A-3): the base polymer prepared in Preparation Example 1-3

Base polymer (A-4): the base polymer prepared in Preparation Example 1-4

Base polymer (A-5): the base polymer prepared in Preparation Example 1-5

Base polymer (A-6): the base polymer prepared in Preparation Example 1-6

-Polyfunctional monomer (B-1): dipentaerythritol hexaacrylate

·Methacrylate (C-1): methacrylate prepared in Preparation Example 2-1

Acrylate (C-2): dimethylol-tricyclodecane diacrylate

Acrylate (C-3): the acrylate prepared in Preparation Example 2-2

Acrylate (C-4): an acrylate represented by the following formula (8)

<Formula 11>

Epoxy resin (D-1): dicyclopentadienedimethanol diglycidyl ether

・Epoxy resin (D-2): VG3101L manufactured by Techmore

·Photoinitiator (E-1): Omnirad 379EG manufactured by IGM Resins B.V.

・Photoinitiator (E-2): Irgacure OXE01 manufactured by BASF Japan

·Adhesiveness imparting agent (F-1): 3-glycidoxypropylmethyldiethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403)

Adhesion imparting agent (F-2): a reaction product of isocyanate propyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM9007) and urea propyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd., T1915) (International Publication No. WO2014/104195) It was prepared according to Example 1 described in.)

·Polymerization inhibitor: methoxyhydroquinone

·Surfactant: silicone oil (manufactured by Toray Dow Corning, FZ2122)

PGMEA: Propylene glycol monomethyl ether acetate

<Evaluation of resolution>

Examples 1 and 2, Comparative Examples 1-4

On a glass substrate, after apply|coating each prepared curable resin composition uniformly with a spin coater, it dried at 90 degreeC for 2 minute(s) on a hotplate. With respect to the obtained coating film, 300 mJ/cm<2> of light from an ultra-high pressure mercury lamp was irradiated through the mask which has the light-shielding part of a hole pattern (illuminance is 30 mW in i-line conversion). In addition, the space|interval (exposure gap) of a mask and a board|substrate was 50 micrometers. Then, development was performed using a 2.38% aqueous TMAH solution. After washing with water, it was baked at 230 degreeC for 30 minutes, and the resist pattern with a film thickness of 8 micrometers was produced. According to the size of the resolved through hole, the resolution was evaluated according to the following criteria. A result is shown in Table 1.

A: The size of the resolved through-hole is 30㎛ or less in diameter

B: The size of the resolved through-hole is more than 30㎛ diameter and less than 50㎛

C: The size of the resolved through hole is 50㎛ or more in diameter

<Evaluation of insulation>

Examples 1 and 2, Comparative Examples 1-4

A glass substrate having a predetermined copper wiring pattern was prepared. After uniformly apply|coating each prepared curable resin composition to the glass substrate with copper wiring with a spin coater, it dried at 90 degreeC for 2 minute(s) on a hotplate. About the obtained coating film, light was shielded on the electrode top of both ends of copper wiring, and 300 mJ/cm<2> of light from an ultra-high pressure mercury lamp was irradiated (illuminance is 30 mW in i-line conversion). Thereafter, development was performed using a 2.38% aqueous TMAH solution. After washing with water, it baked at 230 degreeC for 30 minutes, and formed the cured film with a film thickness of 8 micrometers. This substrate was used as an evaluation substrate. The obtained board|substrate was put into the HAST evaluation apparatus (made by ESPEC), and the test was done under the conditions of a temperature of 130 degreeC, a humidity of 85%, and an applied voltage of 12V. Insulation fell, the resistance value measured the time less than 10 ⁶ ohms, and the following criteria evaluated insulation. A result is shown in Table 1.

A: The resistance value is less than 10 ⁶ Ω for more than 100 hours

B: The time for which the resistance value is less than 10 ⁶ Ω is 80 hours or more and less than 100 hours

C: The time for which the resistance value is less than 10 ⁶ Ω is more than 50 hours and less than 80 hours.

D: Less than 50 hours for resistance value below 10 ⁶ Ω

<Measurement of water absorption rate>

Examples 1 and 2, Comparative Examples 1-4

On a glass substrate, after apply|coating each curable resin composition prepared in Examples 1 and 2 and Comparative Examples 1-4 uniformly with a spin coater, it dried at 90 degreeC for 2 minute(s) on a hotplate. 300 mJ/cm<2> of light from an ultra-high pressure mercury lamp was irradiated with respect to the whole surface of the obtained coating film (illuminance was 30 mW in i-line conversion). Then, development was performed using a 2.38% aqueous TMAH solution. After washing with water, it baked at 230 degreeC for 30 minutes, and formed the cured film with a film thickness of 8 micrometers. After immersing the obtained board|substrate in 23 degreeC water for 24 hours, the water content in the cured film was measured using Tg-DTA, and the water absorption (%) was calculated|required. A result is shown in Table 1.

<Measurement of ion-migration>

Example 3, Comparative Examples 5 and 6

A first substrate (copper wiring width: 1500 µm, inter-wiring distance: 350 µm, wiring film thickness: 35 µm) having a copper wiring pattern conforming to IPC-B24 specified in ISO 9455-17 was prepared. After each curable resin composition was uniformly apply|coated to the said board|substrate which protected the electrodes provided at the both ends of a copper wiring with a spin coater, respectively, it dried at 100 degreeC for 2 minute(s) on a hotplate. The obtained coating film was irradiated with light from an ultra-high pressure mercury lamp at 1000 mJ/cm 2 (illuminance was 20 mW in terms of i-line). Then, it baked at 120 degreeC for 45 minutes, the cured film with a film thickness of 35 micrometers was formed, and it was set as each evaluation board|substrate. The obtained evaluation substrate was put into a migration tester (manufactured by Kusumoto Kasei Co., Ltd., SIR13-SLIM), and the test was performed under the conditions of a temperature of 85° C., a humidity of 85% and an applied voltage of 100 V, and the change in resistance value with time ( chronology) was evaluated. A result is shown in Table 2.

Examples 4-6, Comparative Example 7

Except for using a second substrate having a copper wiring pattern (copper wiring width: 100 µm, inter-wiring distance: 100 µm, wiring film thickness: 0.1 µm) and adjusting the film thickness of the cured film to 6 µm, In the same manner, each evaluation substrate was produced. The change with time of the resistance value was evaluated by carrying out the test similarly to the above except having set the applied voltage to 12V. A result is shown in Table 3.

<Measurement of dielectric constant>

100 parts by mass of each monomer of the methacrylate (C-1), the acrylate (C-2), or the acrylate (C-4), 3 parts by mass of a photopolymerization initiator (manufactured by BASF Japan, Irgacure OXE04); and a solvent (cyclohexanone/propylene glycol monomethyl ether acetate = 75/25) were mixed under light blocking to prepare each monomer composition (solid content concentration: 45 mass%). On an ITO substrate (manufactured by EHC, 10 cm x 10 cm), each prepared monomer composition was uniformly applied with a spin coater, and then dried on a hot plate at 90° C. for 90 seconds to form a coating film. And 90 mJ/cm<2> of light of an ultra-high pressure mercury lamp was irradiated to the obtained coating film (illuminance is 30 mW in i-line conversion), After that, it baked at 230 degreeC for 30 minutes, and obtained the cured film. Then, the ITO substrate on which the cured film was formed was cut to a size of 2.5 cm x 5 cm, and a metal mask having an opening on the cured film was attached with a polyimide tape, and on the cured film in the opening using a gold vapor deposition machine. Gold was deposited 6 times to form a gold electrode (3 mm x 3 mm, film thickness: 1500 ANGSTROM ) to prepare a sample for measuring the relative dielectric constant.

With respect to the produced sample, using an impedance analyzer (manufactured by KEYSIGHT TECHNOLOGIES, E4990A), capacitance was measured under the following measurement conditions, and relative dielectric constant was calculated. A result is shown in Table 4.

<Measurement conditions>

·Resonance measurement jig: 16047E

Start : 1kHz

End: 1000kHz

500mV

<Calculation method for dielectric constant>

The value of "C (capacitance)" was acquired by the impedance analyzer. The relative permittivity was calculated by the following formula.

ε _r =Cd/ε ₀ S

ε _r : relative permittivity

ε ₀ : permittivity of vacuum

C: capacitance [pF]

S: electrode area [m2]

d: film thickness [m]

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Industrial Applicability]

The cured product obtained from the curable resin composition of the present invention can be suitably used as a member (eg, an insulating film, an insulating film resist, an insulating sheet, an insulating layer, etc.) required to have insulating properties.

Claims (7)

(meth)acrylate represented by the following general formula (1) or (2).
<Formula 1>

(Wherein, R ¹ to R ⁴ are each independently H or a methyl group, R ⁵ to R ⁷ are each independently a halogen group, an alkyl group, an alkoxy group or an aromatic group, and AO is an ethyleneoxy group, or a propyleneoxy group , m and n are each independently an integer of 0-5, p is an integer of 0-2, and r and s are each independently an integer of 0-15.)
<Formula 2>

(Wherein, R ¹ to R ⁴ are each independently H or a methyl group, R ⁵ to R ⁷ are each independently a halogen group, an alkyl group, an alkoxy group or an aromatic group, and AO is an ethyleneoxy group, or a propyleneoxy group , m and n are each independently an integer of 0-5, p is an integer of 0-2, and r and s are each independently an integer of 0-15.) A curable resin composition comprising at least one of the (meth)acrylate according to claim 1, a base polymer, a polymerization initiator, and a solvent. 3. The method of claim 2,
Curable resin composition whose content of the said (meth)acrylate is 20-100 mass parts with respect to 100 mass parts of base polymers. 4. The method of claim 2 or 3,
Curable resin composition containing a polyfunctional monomer. 5. The method according to any one of claims 2 to 4,
A curable resin composition containing an epoxy resin. The hardened|cured material by which the curable resin composition in any one of Claims 2-5 was hardened|cured. 7. The method of claim 6,
A cured product having a water absorption rate of 1% or less.