TWI588163B - Acrylate manufacturing method, monomer composition, hardened | cured material, and printed wiring board containing the hardened | cured material - Google Patents

Description

Method for producing poly(meth)acrylate, monomer composition, cured product thereof, and printed wiring board containing the same

The present invention relates to a process for producing a poly(meth)acrylate, and more particularly to a process for producing a (meth)acrylate which polymerizes a monomer having a (meth)acrylonitrile group in the presence of an isocyanate.

Further, the present invention relates to a poly(meth)acrylate obtained by the above production method, a curable composition containing the same, a cured product thereof, and a printed wiring board containing the same.

Poly (meth) acrylate resin (acrylic resin) due to high transparency. Impact resistance, easy to form by heat. Coloring, it is suitable for use as a substitute for inorganic glass, window materials for buildings or vehicles, etc., and is also suitable for use as electrical. Various uses of parts in electronic equipment, daily necessities, and business supplies.

The acrylic resin can be produced by adding a radical generating agent which generates a radical by irradiation of an active energy ray such as an ultraviolet ray or an electron beam to a (meth) acrylate, and undergoing radical polymerization (crosslinking reaction). Alternatively, it may be heated by adding a peroxide to the (meth) acrylate. The radical polymerization is carried out to produce a poly(meth)acrylate.

In the specific example, for example, Patent Document 1 discloses an ultraviolet curable resin composition containing a (meth) acrylate and a photopolymerization initiator. The point described in Patent Document 1 is that the resin composition is cured by irradiating ultraviolet rays to the resin composition with a high pressure mercury lamp.

Further, Patent Document 2 describes a radical-type subsequent composition obtained by heating and hardening a (meth) acrylate in the presence of a hindered amine compound and an organic peroxide, and at a low temperature of 150 ° C or lower. (Meth) acrylate hardens.

Further, Patent Document 3 describes a method of performing photocuring and subsequent thermal hardening on a formulation containing a (meth) acrylate having a hydroxyl group, a blocked isocyanate, and a photopolymerization initiator.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] JP-A-61-31449

[Patent Document 2] Special Opening 2008-94913

[Patent Document 3] No. 2004-513197

However, according to Patent Document 1, polymerization is carried out by using a photoradical generator, whereby the reaction rate is increased, but the degree of hardening is low. The hardened material obtained by this influence cannot obtain the necessary and sufficient adhesion or resistance to medicine Sex.

Further, a peroxide is used in the production of the acrylate of Patent Document 2. Peroxides are dangerous and therefore not easy to handle.

Further, the acrylate may undergo a self-polymerization (homopolymerization) reaction even by simple heating. However, since the acrylonitrile group is relatively stable to heat, heating at about 200 ° C or higher is required. In this case, there is a space for reviewing not only in terms of energy efficiency, but also heat resistance as a substrate using a composition containing an acrylate.

Further, in Patent Document 3, (meth) acrylate is used as a component of polymerization, but it is necessary to have a hydroxyl group. That is, the reaction of the hydroxyl group of the (meth) acrylate with the isocyanate is carried out first, and the homopolymerization of the (meth) acrylate does not occur.

Further, as disclosed in the cited document 3, the isocyanate is a raw material for the production of a urethane or a urea derivative, and is known to easily react with a hydroxyl group, an amine, a phenol, a mercaptan or the like, but with respect to poly(meth)acrylic acid. None of the applications in the ester manufacturing reaction have been reported.

However, an object of the present invention is to provide a method for producing a poly(meth)acrylate which is excellent in physical properties such as adhesion, hardness, chemical resistance, heat resistance and insulation by rapid reaction.

Further, an object of the present invention is to provide a monomer composition for use in a method for producing a poly(meth)acrylate, a cured product thereof, and a printed wiring board containing the same.

In order to solve the above object, the method for producing a poly(meth) acrylate of the present invention is characterized in that a monomer composition obtained by adding a compound having an isocyanate group to a monomer having a (meth) acrylonitrile group is used. The monomer having a (meth) acrylonitrile group is polymerized by heating at 140 ° C to 170 ° C.

According to this method, a poly(meth)acrylate excellent in physical properties such as adhesion, hardness, chemical resistance, heat resistance, and insulating properties can be produced.

Further, according to the present invention, a monomer composition characterized by comprising the produced poly(meth) acrylate can be obtained.

Since this monomer composition does not contain a functional group which reacts at normal temperature, it is excellent in storage stability. The monomer composition of the present invention is suitable for use as a cured product (poly(meth)acrylate) having excellent physical properties such as adhesion, chemical resistance, and heat resistance by thermal curing, photocuring, or both. For example, it is coated with ink or printed wiring board for printing wiring board printing.

According to the production method of the present invention, a monomer having a (meth) acrylonitrile group can be polymerized at a relatively low temperature and in a short time in the presence of an isocyanate, thereby obtaining adhesion, hardness, chemical resistance, and heat resistance. And a cured product of a poly(meth)acrylate excellent in physical properties such as insulating properties and a coating film.

Further, since the monomer composition of the present invention does not undergo polymerization reaction at normal temperature, it can be stored in a stable manner in a single liquid type. Monomer composition The material is applied to a printed wiring board, and is cured by an insulating material for a printed wiring board having excellent physical properties such as adhesion, hardness, chemical resistance, heat resistance, and insulating properties, and is applied as a coloring pigment or the like. Printing use of printed wiring boards for ink compositions.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a graph showing the differential scanning calorimetry curves of the monomer composition of the present invention and the comparative material.

Fig. 2 is a graph showing changes in absorbance obtained by infrared spectroscopy when the monomer composition of the present invention is heated to different temperatures.

The present invention uses a mixture of a monomer having a (meth) acrylonitrile group (also referred to as a (meth) acrylate) and an isocyanate as a monomer composition, by heating it at a specific temperature for a specific time, thereby A monomer having a (meth) acrylonitrile group is polymerized to produce a poly(meth) acrylate.

Further, the homopolymerization of (meth) acrylate is usually carried out by heating at 200 ° C or higher, but the monomer composition of the present invention is heated at 140 ° C to 170 ° C, preferably 150 ° C to 170 ° C. 15 seconds to 1000 seconds, and the (meth) acrylate contained therein is polymerized. When the temperature is less than 140 ° C, the polymerization of (meth) acrylate is insufficient, and when it exceeds 170 ° C, the possibility of adversely affecting the heat of the substrate to which the monomer composition is applied may occur. By heating at 140 ° C ~ 170 ° C for 15 seconds ~ In the case of 1000 seconds, substantially all of the double bonds of the (meth) acrylonitrile group are broken, and the monomer having a (meth) acrylonitrile group is crosslinked.

The poly(meth) acrylate formation reaction in the present invention is considered to be such that if the isocyanate is heated in a state in which the (meth) acrylate is coexistent, the presence of the (meth) acrylonitrile group promotes the trimerization reaction of the isocyanate. Further, the isocyanate trimerization reaction increases the activity of the (meth) acrylonitrile group.

Further, in the present invention, the monomer having a (meth) acrylonitrile group preferably does not have a functional group capable of reacting with an isocyanate. Generally, an isocyanate is reacted with a compound having a hydrogen atom which is active for isocyanate such as OH or NH ₂ , but does not react with a (meth) acryl group of (meth) acrylate. Therefore, when (meth) acrylate is reacted with an isocyanate, a (meth) acrylate such as (meth) acrylate having an active hydrogen atom can be used.

However, since the polymerization of (meth) acrylate is preferred, the method or monomer composition of the present invention preferably does not contain a compound having a functional group reactive with isocyanate, even as other components.

Further, it is considered that the heat generated locally by the isocyanate trimerization reaction also contributes to the polymerization of the (meth) acrylate.

The coating film obtained from the reaction product obtained by the reaction mechanism of the present invention has extremely excellent physical properties such as high adhesion, chemical resistance, and heat resistance, and thus can be used extremely effectively in various applications.

Further, the trimerization of the isocyanate forms an isocyanurate having a triazine ring structure. a coating consisting of a compound containing a triazine ring structure Since a film or a cured material is excellent in heat resistance and insulation, it is also useful as a heat resistant material and an insulating material.

Further, when a trifunctional or higher isocyanate is used, a network structure having a triazine skeleton is also formed. A material having such a network structure has an effect of improving heat resistance, chemical resistance, and the like of a coating film and a cured product containing the same.

Thus, according to the method of the present invention, a reaction mixture containing a terpolymer of poly(meth)acrylate and isocyanate or the like is produced, and the reaction mixture is hardened to constitute excellent hardness, chemical resistance, heat resistance and insulation. Coating film.

[Monomer having (meth)acrylonitrile group]

In the present invention, the monomer having a (meth) acrylonitrile group has one or more (meth) acrylonitrile groups in one molecule. Further, the monomer having a (meth) acrylonitrile group is preferably a compound having no functional group reactive with isocyanate.

Here, the functional group reactive with isocyanate is a functional group having an active hydrogen atom, and examples thereof include an OH group, an NH group, an NH ₂ group, an SH group, and a COOH group. The monomer having a (meth) acrylonitrile group used in the present invention preferably does not have such a functional group.

The (meth) acrylate used in the present invention is exemplified by, for example, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, butyl (meth)acrylate, stearyl (meth)acrylate, Tridecyl (meth)acrylate, lauryl (meth)acrylate, isobornyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, ( Methyl)acrylic acid 2- Monofunctional (meth) acrylate such as phenoxyethyl ester, and 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1, 6-hexanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, tricycloanthracene a difunctional (meth) acrylate such as alkane dimethanol di(meth) acrylate or neopentyl glycol diacrylate, or a trifunctional (meth) acrylate such as trimethylolpropane triacrylate, and A polyfunctional (meth) acrylate compound of a tetrafunctional or higher (meth) acrylate such as trimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate or dipentaerythritol hexaacrylate.

The product name sold by the (meth) acrylate compound is, for example, NEOMA DA-600 (manufactured by Sanyo Chemical Industries, Ltd.), ARONIX M-309, M-7100, M309 (manufactured by Toagosei Co., Ltd.), A-DCP (Xinzhongcun) Chemical Industry Co., Ltd.), 1.6HX-A (manufactured by Kyoei Chemical Industry Co., Ltd.), FA-125 (manufactured by Hitachi Chemical Co., Ltd.), and the like.

The monomer having a (meth) acrylonitrile group may be used alone or in combination of two or more.

In the present invention, a monomer containing a polyfunctional (meth) acrylonitrile group is preferably used, and in particular, a monomer having a trifunctional or higher (meth) acrylonitrile group is preferably used, whereby a substrate such as a substrate is coated. The monomer composition of the present invention is excellent in heat resistance, hardness, and chemical resistance of the cured product (cured film after curing) obtained by curing.

[compound containing isocyanate group]

In the present invention, an aliphatic/alicyclic isocyanate, an aromatic isocyanate, and a blocked isocyanate can be used as the isocyanate group-containing compound.

Polyfunctional isocyanates are preferably used in the present invention. When a polyfunctional isocyanate is used, since it has a network structure which has a triazine skeleton, heat resistance, chemical resistance, etc. are further improved.

The amount of the aliphatic/alicyclic isocyanate and the aromatic isocyanate to be added is 2 to 100 parts by mass, preferably 2 to 50 parts by mass, per 100 parts by mass of the monomer having a (meth) acrylonitrile group.

Further, the amount of the blocked isocyanate is from 2 to 200 parts by mass based on 100 parts by mass of the monomer having a (meth) acrylonitrile group. When it is less than 2 parts by mass, sufficient thermosetting property cannot be obtained, and adhesion, chemical resistance, and heat resistance cannot be obtained. When the amount is more than 200 parts by mass, the content of the acrylonitrile-based monomer decreases, and the ultraviolet curability is deteriorated.

The above aliphatic/alicyclic isocyanate compound is, for example, 1,6-hexamethylene diisocyanate (HDI or HDMI), isophorone diisocyanate (IPDI), methylcyclohexane 2,4-(2,6 )-Diisocyanate (hydrogenated TDI), 4,4'-methylenebis(cyclohexyl isocyanate) (hydrogenated MDI), 1,3-(isocyanatemethyl)cyclohexane (hydrogenated XDI), norbornene II Isocyanate (NDI), diazonic acid diisocyanate (LDI), trimethylhexamethylene diisocyanate (TMDI), dimer acid diisocyanate (DDI), N, N', N"- cis (6-isocyanate, Hexamethylene) uret and the like.

The aromatic isocyanate compound may, for example, be toluene diisocyanate (TDI) or 4,4'-diphenylmethane diisocyanate (MDI). Xylene diisocyanate (XDI) and the like.

In the present invention, any of the isocyanates may be used alone or in combination of two or more.

Further, a trimer of 1,6-hexamethylene diisocyanate or a terpolymer of isophorone diisocyanate may also be used.

Further, in view of the single liquefaction of the monomer composition in the production method of the present invention and the residence time, the isocyanate compound is preferably blocked isocyanate blocked by a conventional blocking agent (blocking agent). .

The product names sold by the blocked isocyanate are, for example, BI7961, BI7992 (all manufactured by Baxenden), MF-K60X (made by Asahi Kasei Chemicals Co., Ltd.), VPLS2253, BL4265SN (all manufactured by Bayer Urethane Co., Ltd.).

[blocking agent]

Examples of the blocking agent include alcohols such as ethanol, n-propanol, isopropanol, tert-butanol, and isobutanol, and phenols such as phenol, chlorophenol, cresol, xylenol, and p-nitrophenol. , p-tert-butylphenol, p-t-butylphenol, p-second amyl phenol, p-octyl phenol, p-nonyl phenol and other alkyl phenols, 3-hydroxypyridine, 8-hydroxyl Quinoline, 8-hydroxyquinaldine (quinaldine) contains basic nitrogen-containing compounds, active methylene compounds such as diethyl malonate, ethyl acetoxyacetate, etidylacetone, acetamide, propylene oxime Amines such as amines and acetanilides, sulfoximines such as amber succinimide and maleimide, imidazoles such as 2-ethylimidazole and 2-ethyl-4-methylimidazole, pyrazole, 3-methylpyrazole, 3,5-di Pyrazoles such as methylpyrazole, indoleamines such as 2-pyrrolidone and ε-caprolactam, ketones or aldehydes such as acetone oxime, methyl ethyl ketone oxime, cyclohexanone oxime, acetaldoxime The cockroaches, such as ethyl imine, bisulfite, and the like.

The blocked isocyanate is preferably a blocked isocyanate which is blocked with at least one of an active methylene compound or a pyrazole, more preferably diethyl malonate and 3,5-dimethylpyrazole. At least one of the blocked isocyanates to be blocked is preferably a blocked isocyanate blocked with 3,5-dimethylpyrazole.

The above-mentioned blocking agent may be used singly or in combination of two or more kinds, or a plurality of blocked isocyanates which may be blocked by a single or two or more kinds of blocking agents.

[Photopolymerization initiator]

Further, the monomer composition used in the present invention may further comprise a photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it can be polymerized by irradiation with an energy ray, and a radical polymerization initiator can be used.

The photoradical polymerization initiator can be used as long as it is a radical generated by light, laser, electron beam or the like, and a compound which initiates radical polymerization. The photoradical polymerization initiator is exemplified by benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether; Ethyl ketone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, etc. Ketones; 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4- Amino acetophenones such as morpholinylphenyl)-butan-1-one, N,N-dimethylaminoacetophenone, etc.; 2-methylindole, 2-ethylhydrazine, 2- Terpenes such as tert-butyl hydrazine and 1-chloroindole; 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4 - thioxanthones such as diisopropyl thioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; 2,4,5-triaryl imidazole dimer; a thiol compound such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole or 2-mercaptobenzothiazole; 2,4,6-para-s-triazine, 2,2 , organic halogen compounds such as 2-tribromoethanol and tribromomethyl ether; benzophenones or xanthone such as benzophenone and 4,4'-bisdiethylaminobenzophenone; , 4,6-trimethylbenzimidyldiphenylphosphine oxide, and the like.

The above photoradical initiators may be used singly or in combination of plural kinds.

Further, in addition to these, ethyl N,N-dimethylaminobenzoate, isoamyl N,N-dimethylaminobenzoate, and amyl 4-dimethylaminobenzoate may be used. A photoinitiator such as a tertiary amine such as triethylamine or triethanolamine. In addition, in order to promote the photoreaction, a titanium oxide (titanocene) compound such as CGI-784 (manufactured by BASF Corporation, Japan) having absorption in the visible light region may be added to the photoradical polymerization initiator. Further, the component to be added to the photoradical polymerization initiator is not limited to these, as long as it absorbs light in the ultraviolet light or visible light region, and radically polymerizes an unsaturated group such as a (meth) propyl fluorenyl group. Further, it is not limited to a photopolymerization initiator, a photoinitiator, and may be used singly or in combination of several kinds.

The amount of the photopolymerization initiator to be added is 0.5 to 15 parts by mass, more preferably 0.5 to 10 parts by mass, even more preferably 1 to 10 parts by mass, per 100 parts by mass of the monomer having a (meth) acrylonitrile group.

The name of the product sold by the photopolymerization initiator is, for example, Irgacure 907 or Irgacure 127 (all manufactured by BASF Corporation of Japan).

[Other additives]

The monomer composition of the present invention may contain defoaming as needed. Advection agent, thixotropic agent. Additives such as tackifiers, coupling agents, dispersants, and flame retardants.

Defoamer. The advection agent can use polyfluorene oxide, modified polyoxane, mineral oil, vegetable oil, aliphatic alcohol, fatty acid, metal soap, fatty acid decylamine, polyoxyalkylene glycol, polyoxyalkylene alkyl ether, polyoxyalkylene A compound such as an alkyl fatty acid ester or the like.

Thixotropic agent. As the tackifier, kaolin, smectite, montmorillonite, bentonite, talc, mica, zeolite, etc., or mineral fine particles of cerium oxide, cerium, amorphous inorganic particles, polyamido-based additives, and upgrading can be used. Urea-based additives, wax-based additives, and the like.

By adding defoaming. Advection agent, thixotropic agent. The tackifier can adjust the surface properties of the cured product and the properties of the composition.

The coupling agent may be an alkoxy group having a methoxy group, an ethoxy group or an ethenyl group, and has a vinyl group, a methacryl group, an acryl group, an epoxy group, a cyclic epoxy group, a decyl group, an amine group, and a diamine. Base, acid anhydride, urea group, sulfur An ether group, an isocyanate group or the like as a reactive functional group such as vinyl ethoxy decane, vinyl trimethoxy decane, vinyl. A vinyl decane compound such as β-methoxyethoxy decane or γ-methyl propylene methoxy propyl trimethoxy decane, γ-aminopropyltrimethoxy decane, N-β-(amine Benzyl) γ-aminopropyltrimethoxydecane, N-β-(aminoethyl)γ-aminopropylmethyldimethoxydecane, γ-ureidopropyltriethoxydecane Equivalent decane compound, γ-glycidoxypropyltrimethoxydecane; β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, γ-glycidoxypropylmethyl An epoxy-based decane compound such as diethoxysilane or a fluorenyl decane compound such as γ-mercaptopropyltrimethoxydecane or a phenylamino decane compound such as N-phenyl-γ-aminopropyltrimethoxydecane Etane coupling agent, isopropyl triisostearate, titanylbis(di-dodecylphosphite) titanate, bis(dioctylpyrophosphate)oxylate B Acid ester titanate, isopropyl tri-dodecylbenzenesulfonyl titanate, isopropyl tris(dioctyl pyrophosphate) titanate, tetraisopropyl bis(dioctylphosphite) Ester) titanate, tetrakis(1,1-diallyloxymethyl-1-butyl Bis-(di-dodecyl)phosphite titanate, bis(dioctyl pyrophosphate) extended ethyl titanate, isopropyl trioctadecyl titanate, isopropyldimethylpropene Isostearyl phthalocyanate, isopropyl tristearyl bis propylene titanate, isopropyl tris(dioctyl phosphate) titanate, isopropyl triisopropyl phenyl phenyl a titanate coupling agent such as titanate, diisopropylphenyl phenyloxyacetate titanate or diisostearate ethyl ethyl titanate, a compound containing an ethylenically unsaturated zirconate, a compound containing a neoalkoxy zirconate, a neoalkoxy neodecyl zirconate, a neoalkoxy(dodecyl)benzenesulfonyl zirconate, a neoalkoxy ginate Octyl phosphate Ester zirconate, neoalkoxy (dioctyl) pyrophosphate zirconate, neoalkoxy (ethylidene diamine) ethyl zirconate, neoalkoxy (m-amine) Phenyl zirconate, tetrakis(2,2-diallyloxymethyl)butyl, bis(di-tridecyl)phosphite zirconate, neopentyl (diallyl) Oxyl, ginsengyl zirconate, neopentyl (diallyl)oxy, tris(dodecyl)benzenesulfonyl zirconate, neopentyl (diallyl) oxygen , tris(dioctyl)phosphite zirconate, neopentyl (diallyl)oxy, tris(dioctyl)pyrophosphate zirconate, neopentyl (diallyl)oxy , tris(N-extended ethyldiamine)ethylzirconate, neopentyl (diallyl)oxy, tris(m-amino)phenylzirconate, neopentyl (diene) Propyl)oxy, trimethylpropenyl zirconate, neopentyl (diallyl)oxy, tripropenyl zirconate, neopentyl (diallyl)oxy, di-pair Amido benzhydryl zirconate, dipentyl (diallyl)oxy, tris(3-indenyl)propenyl zirconate, 2,2-bis(2-propionatemethyl) Zirconium oxychloride (IV), cyclic bis[2,2-(bis 2-propionate methyl)butyrate]-phosphate phosphate-O, O Zirconate coupling agent, diisobutyl (oil acyl) acetyl acetate aluminum acetyl group, an alkyl group acetyl acetyl aluminum diisopropyl ester and the like aluminate-based coupling agents.

As the dispersing agent, a polymeric dispersant such as a polycarboxylic acid-based, a naphthalenesulfonic acid formalin condensation system, a polyethylene glycol, a polycarboxylic acid partial alkyl ester system, a polyether system, or a polyalkylene polyamine system can be used. A low molecular weight dispersant such as a sulfonic acid system, a quaternary ammonium system, a higher alcohol alkylene oxide system, a polyol ester system or an alkyl polyamine system.

As the flame retardant, a hydrated metal system such as aluminum hydroxide or magnesium hydroxide, red phosphorus, ammonium phosphate, ammonium carbonate, zinc borate, zinc stannate, molybdenum compound, bromine compound, chlorine compound, phosphate, or phosphorus may be used. Polyol, Phosphine-containing amine, melamine cyanurate, melamine compound, triazine compound, hydrazine compound, hydrazine polymer, and the like.

Further, an organic binder component may be added to the monomer composition of the present invention. Further, in order to adjust the polymerization rate or the degree of polymerization, a polymerization inhibitor or a polymerization retarder may be added.

In the monomer composition of the present invention, a coloring pigment, a dye or the like may be added depending on the purpose of coloring. Colored pigments, dyes, and the like can be used as a conventional one represented by a color index.

For example, Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60, Solvent Blue 35, 63, 68, 70, 83, 87, 94, 97, 122, 136 , 67, 70, Pigment Green 7, 36, 3, 5, 20, 28, Solvent Yellow 163, Pigment Yellow 24, 108, 193, 147, 199, 202, 110, 109, 139, 179, 185, 93, 94 , 95, 128, 155, 166, 180, 120, 151, 154, 156, 175, 181, 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62: 1, 65 , 73, 74, 75, 97, 100, 104, 105, 111, 116, 167, 168, 169, 182, 183, 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126 , 127, 152, 170, 172, 174, 176, 188, 198, Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61 , 63, 64, 71, 73, Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114 1,146,147,151,170,184,187,188,193,210,245,253,258,266,267,268,269,37,38,41,48:1,48:2,48:3 48:4, 49: 1, 49:2, 50:1, 52:1, 52:2, 53:1, 53:2, 57:1, 58:4, 63:1, 63:2, 64:1, 68, 171, 175, 176, 185, 208, 123, 149, 166, 178, 179, 190, 194, 224, 254, 255, 264, 270, 272, 220, 144, 166, 214, 220, 221, 242, 168, 177, 216, 122, 202, 206, 207, 209, solvent red 135, 179, 149, 150, 52, 207, pigment violet 19, 23, 29, 32, 36, 38, 42, solvent violet 13, 36, Pigment brown 23, 25, pigment black 1, 7 and so on. These colored pigments. The dye or the like is preferably added in an amount of 0.01 to 5 parts by mass based on 100 parts by mass of the monomer composition. Further, when the monomer composition of the present invention is used for marking, a rutile-type or anatase-type titanium oxide is preferably added in order to ensure visibility. In this case, it is preferred to add 1 to 20 parts by mass based on 100 parts by mass of the monomer composition. These colored pigments. The dyes may be used singly or in combination of two or more.

Further, in the monomer composition of the present invention, a solvent for viscosity adjustment may be used, but in order to prevent a decrease in film thickness after hardening, the amount of addition is preferably small. Also, it is better not to contain a solvent for adjusting the viscosity.

When the monomer composition of the present invention contains a photopolymerization initiator, the (meth) acrylate can be photocured by irradiation with an active energy ray such as an ultraviolet ray, an electron beam or a chemical line, and then heated as described above (methyl) ) acrylate polymerization.

As a result, the monomer composition applied to the substrate such as the substrate is cured by light irradiation, and then thermally cured in two stages by heating to improve workability and general characteristics of the cured product.

In the present invention, when the monomer composition is formally hardened, A heating means such as a hot air furnace, an electric furnace, an infrared heating furnace or the like is used.

The poly(meth)acrylate produced by the production method of the present invention can be applied to various applications because of its excellent transparency, plasticity, impact resistance, adhesion, chemical resistance, heat resistance, and insulation properties. For example, it can be applied to electricity in addition to window materials such as buildings or vehicles. Among electronic equipment, daily necessities, and office supplies, it is particularly suitable for products requiring impact resistance, adhesion, chemical resistance, heat resistance, and insulation, such as printed wiring boards.

Further, the present invention is not limited to the configurations and examples of the above embodiments, and various modifications can be made within the scope of the spirit of the invention.

[Examples]

I. Thermal hardening test

[Examples 1 to 11 and Comparative Examples 1 to 4]

The components were blended in the proportions shown in Table 1, and the monomer composition and the comparative monomer composition of the present invention were obtained by stirring with a dissolving machine.

[gelling time measurement]

The monomer composition of the present invention was heated at a specific temperature shown below using a gelation tester (gelation tester manufactured by Nisshin Scientific Co., Ltd.), and the time until gelation was measured. The results are shown in Table 1.

Example 1~8: 150 ° C

Example 9-11: 170 ° C

Comparative Example 1:150 ° C

Comparative Example 2~4: 170 °C

The amount of each material in the table is in parts by mass.

The gelation time refers to the time from the start of heating of the monomer composition to the time when the material loses fluidity and solidifies (measured in a gelation tester in seconds).

Further, the details of the materials described in Table 1 are as follows.

Acrylate 1: Trimethylolpropane triacrylate (TMPTA) manufactured by East Asia Synthesis Co., Ltd. M-309

Acrylate 2: Tricyclodecane Dimethanol Diacrylate A-DCP manufactured by Xinzhongcun Chemical Co., Ltd.

Acrylate 3:1,6-hexanediol diacrylate manufactured by Kyoeisha Chemical Co., Ltd. 1,6-HX-a

Acrylate 4: Neopentyl glycol diacrylate manufactured by Hitachi Chemical Co., Ltd. FA-125M

Isocyanate 1: m-xylene diisocyanate

Isocyanate 2: isophorone diisocyanate

Isocyanate 3:1,6-hexamethylene diisocyanate

Blocked isocyanate 1: BI7961 solid content 70% NCO part manufactured by Baxenden Company 10.2%

A uret that capped 1,6-hexamethylene diisocyanate with dimethylpyrazole.

Urea form of 1,6-hexamethylene diisocyanate

Dimethylpyrazole

Blocked isocyanate 2: manufactured by Baxenden BI7992 solid content 70% NCO parts 9.2%

A trimer of 1,6-hexamethylene diisocyanate is capped with methyl carbamide and (active methylene compound) diethyl malonate.

Terpolymer of 1,6-hexamethylene diisocyanate

Diethyl malonate

Blocked Isocyanate 3: MF-K60X manufactured by Asahi Kasei Chemicals Co., Ltd.

Solid content 60% NCO share 6.6%

A person who capped 1,6-hexamethylene diisocyanate with an active methylene compound.

Blocked isocyanate 4: VPLS2253 manufactured by Bayer Urethane

Solid content 75% NCO share 10.5%

A trimer of 1,6-hexamethylene diisocyanate is capped with dimethylpyrazole.

Blocked isocyanate 5: manufactured by Bayer Urethane, BL4265SN

Solid content 65% NCO parts 8.1%

A terpolymer of isophorone diisocyanate terminated with methyl ethyl ketone oxime.

Terpolymer of isophorone diisocyanate

Methyl ethyl ketone oxime

By the gelation time measurement, the compositions of Examples 1 to 8 were known to be polymerized at 150 ° C for 21 seconds to 590 seconds.

On the other hand, Comparative Example 1 containing no isocyanate did not cause gelation even in the test of 1000 seconds or more.

Further, the compositions of Examples 9 to 11 also gelled at a maximum of 926 seconds, and the polymerization reaction was completed. On the other hand, in Comparative Examples 2 to 4, gelation did not occur even if the test was performed for 2000 seconds or more longer than this. From this, it is understood that the reaction occurs at a low temperature in the coexistence of the acrylonitrile group and the isocyanate, but the reaction does not occur in the absence of the isocyanate.

[Measurement of DSC data]

For the compositions of Example 1 and Comparative Example 1, EXSTAR manufactured by SEIKO Instruments Co., Ltd. was used to carry out differential scanning calorimetry (DSC). The resulting DSC curve is shown in Figure 1.

As a result, the exothermic peak of the composition of trimethylolpropane triacrylate and isocyanate (m-xylylene diisocyanate) obtained in Example 1 was higher than that of the trimethylolpropane triacrylate obtained in Comparative Example 1. The peak position is shifted to the low temperature side, and it can be seen that it can be hardened at a low temperature.

As a result of the DSC measurement, the peaks of the polymerization which can be produced in Example 1 and Comparative Example 1 are indirectly shown, and since the gelation time measurement result is consistent, the conclusion that the acrylate polymerization occurs due to gelation can be made. .

[Measurement of Infrared Spectrophotometry]

With respect to the composition of Example 1, the absorbance was measured by IR Spectroscopy using Spectrum 100 manufactured by Perkin Elmer Co., Ltd., Japan. Also, smiths Dura Sampl IRII was used as the MICRO ATR unit.

The measurement was first carried out by applying the composition of Example 1 to two KBr plates by scraping, one of which was heated in air at 80 ° C for 30 minutes (sample 1), and the other piece was heated in air at 150 ° C for 30 minutes. (Sample 2) was carried out.

The IR image obtained for sample 1 is in the upper half of Figure 2, The IR pattern obtained for sample 2 is shown in the lower half of Figure 2.

Comparing the IR patterns of Samples 1 and 2, it was revealed that the peak near 2260 cm ^{-1 of the} isocyanate group was remarkable in Sample 1 (heating at 80 ° C), but was significantly reduced in Sample 2 (heating at 150 ° C).

Further, the peak near 1406 cm ^{-1 of the} acrylonitrile group was also remarkable in the sample 1 (heating at 80 ° C), but was significantly reduced in the sample 2 (heating at 150 ° C).

From this, it is understood that the isocyanate and the acrylic acid are heated and consumed.

In addition, a peak of a carbonyl group near 1721 cm ^{-1 was} observed, and sample 2 (heated at 150 ° C) was increased more than sample 1 (heated at 80 ° C).

This teaches that the isocyanate groups are trimerized to form a carbonyl group.

Combining the measurement results shown in FIG. 1 and FIG. 2, it can be said that the isocyanate is trimmed by heating in the state in which the isocyanate and the acrylate coexist, and the acrylate is produced along with the reaction of the trimerization. polymerization.

II. Photothermal heat hardening test

[Examples 12, 13, and Comparative Example 5]

I. UV irradiation step

The components were blended in the proportions shown in Table 2, and stirred with a dissolving machine to obtain a monomer composition of the present invention and a comparative monomer composition.

Further, the details of the materials described in Table 2 are as follows.

Acrylate 1: Trimethylolpropane triacrylate (TMPTA)

East Asia Synthesis Company manufactures M-309

Photopolymerization initiator 1: Irgacure 907 manufactured by BASF Corporation, Japan

Photopolymerization initiator 2: Irgacure 127 manufactured by BASF Corporation, Japan

Isocyanate 1: m-xylene diisocyanate

Blocked isocyanate 2: blocked isocyanate 2: BI7992 manufactured by Baxenden

Solid component 70% NCO part 9.2% (trimer of 1,6-hexamethylene diisocyanate blocked with active methylene compound)

Advection agent: BYK-307 manufactured by BYK Chemie, Japan

[Production of test sample]

A. UV irradiation sample: FR-4/10μ

A plurality of FR-4 copper-clad laminates (substrates) of 150 mm × 95 mm × 1.6 mm were coated on the 150 mm × 95 mm × 1.6 mm by using a bar coater to form the monomer composition of the present invention and the comparative monomer composition to a thickness of 10 μm. Become an unhardened sample for each test. These uncured samples were irradiated with ultraviolet rays having a cumulative light amount of 150 mJ/cm ² by a high pressure mercury lamp.

Each of the samples (ultraviolet irradiation sample: FR-4/10 μ) after the ultraviolet irradiation step was subjected to the following adhesion test, pencil hardness test, chemical resistance test, and heat resistance test. The test results are shown in Table 3.

B. Ultraviolet radiation. Heating sample: FR-4/10μ

The sample was irradiated with ultraviolet rays at 150 ° C in a hot air circulating drying oven: FR-4/10μ for 30 minutes to obtain ultraviolet irradiation. Heated sample (UV irradiation. Heating sample: FR-4/10μ). The sample was subjected to the following adhesion test, pencil hardness test, chemical resistance test, and heat resistance test, and the test results are shown in Table 4.

C. Ultraviolet radiation. Heating sample: B sample / 40μ

The monomer composition and the comparative monomer composition of the present invention were applied to a comb-type electrode sample (substrate) of the IPC B-25 test pattern so as to have a thickness of 40 μm, and irradiated with ultraviolet rays in the same manner as above, followed by the above The same heating is carried out to obtain ultraviolet radiation. Heated sample: B sample / 40μ. The insulation test described below was carried out.

The characteristic test shown below was carried out for each of the above samples.

[1. Adhesion test]

On the surface of the coating film of each sample, 11 slits were cut out at intervals of 1 mm with a dicing blade at a distance of 1 mm, and scotch tape was attached to 100 cutting blocks surrounded by longitudinal and transverse slits on the surface of the coating film to perform peeling. And the investigation did not follow The number of cutting blocks of the coating film which was peeled off by the tape and remained on the FR-4.

[2. Pencil hardness test]

Each sample was prepared, and a pencil hardness test was performed using Hi-uni manufactured by Mitsubishi Pencil in accordance with JIS K5400.

Specifically, the wood portion of the pencil is removed to make the core 5 to 6 mm in length. A pencil that was ground to the smoothness of the front end of the core to obtain a circular cross section was used. The pencil was held at an angle of 45 degrees with respect to the surface of the sample, and the weight applied to the surface of the sample was set to 1 kg, and the coating film was drawn at an angle of 45 degrees. The maximum hardness of the pencil whose coating film did not reach the substrate is shown in Table 2.

[3. Chemical resistance test]

Each sample was immersed in a 10% aqueous sulfuric acid solution for 30 minutes at room temperature, taken out and washed with water. dry. The state of the coating film was visually evaluated for each sample after drying, and then peeled off by CELLOTAPE (registered trademark), and evaluated as follows.

○: The state of the coating film is completely unchanged.

×: The coating film bulges and peels off. Moreover, it is transferred to CELLOTAPE (registered trademark) and peeled off.

[4. Heat resistance test]

A rosin-based flux (SF-270 manufactured by SANWA Chemical Co., Ltd.) was applied to each sample, and immersed in a solder bath at 260 ° C for 10 seconds. Self-solder layer Each sample was taken out and naturally cooled, washed with propylene glycol monomethyl ether acetate, and dried. After the test was repeated three times, the state of the coating film of each test piece was visually evaluated, and peeling was performed by CELLOTAPE (registered trademark), and the evaluation was performed as follows.

○: The film state is completely unchanged.

△: There was no change in visual observation, but there were some peeling off by CELLOTAPE (registered trademark).

×: The coating film bulges and peels off. Moreover, it is transferred to CELLOTAPE (registered trademark) and peeled off.

[5. Insulation test]

The insulation resistance value was measured by applying a bias voltage of 500 V DC to the sample of ultraviolet irradiation previously described: B sample / 40 μ. Evaluation was performed as follows.

○: Insulation resistance value ≧100GΩ

×: Insulation resistance value <100GΩ

A. For UV irradiation samples: FR-4/10μ test results (adhesion test, pencil hardness test, chemical resistance test and heat resistance test)

B. For ultraviolet radiation. Heating sample: FR-4/10μ test results (adhesion test, pencil hardness test, chemical resistance test and heat test)

C. For ultraviolet radiation. Heating sample: B sample / 40μ test result (insulation test)

-: Not evaluated

The coating film obtained by the manufacturing method of the present invention can be understood from the above Table 4. The cured product has excellent properties such as adhesion, hardness, chemical resistance, heat resistance, and insulation.

Further, the present invention is not limited to the configurations and examples of the above embodiments, and various changes can be made within the spirit of the invention.

Claims (5)

A method for producing a poly(meth) acrylate, which comprises a monomer obtained by adding a compound having an isocyanate group to a monomer having a (meth) acrylonitrile group but having no functional group reactive with isocyanate The composition is heated at 140 ° C to 170 ° C to polymerize the aforementioned monomer having a (meth)acryl fluorenyl group but having no functional group reactive with isocyanate. The method of claim 1, wherein the photopolymerization initiator is further added to the monomer composition, and the monomer having the (meth) acrylonitrile group is photocured by irradiation of an active energy ray. Heating causes the aforementioned monomer having a (meth) acrylonitrile group to be polymerized. A monomer composition characterized by (i) a monomer having a (meth)acryl fluorenyl group but having no functional group reactive with isocyanate, (ii) a compound having an isocyanate group, and (iii) photopolymerization Starting agent. A cured product characterized by hardening a monomer composition as claimed in claim 3. A printed wiring board characterized by having a cured product as claimed in claim 4.