KR101688974B1 - Curable resin composition for inkjet printing, solder resist using the same and method for manufacturing the same - Google Patents

Abstract

The present invention relates to a nanosilica dispersion comprising silica particles having a surface-treated siloxane compound and an acrylic monomer; An alicyclic compound having 4 to 20 carbon atoms and containing at least 2 ethylenically unsaturated groups; An aromatic compound having 1 to 10 carbon atoms and containing at least 3 ethylenically unsaturated groups; A polyfunctional aliphatic acrylate compound and a photoinitiator, wherein the content of the nanosilica dispersion is 3 wt% to 20 wt% with respect to the total composition.
The present invention also relates to a solder resist using the curable resin composition for inkjet and a method of manufacturing the solder resist.

Description

TECHNICAL FIELD [0001] The present invention relates to a curable resin composition for an inkjet, a solder resist using the composition, and a method of manufacturing the same. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to a curable resin composition for an ink jet, a solder resist using the same, and a method of manufacturing the same. More specifically, the present invention relates to a curable resin composition for an ink jet, which can exhibit excellent storage stability, electroless plating and mechanical properties while having a low viscosity, a solder resist using the composition, and a process, To a solder resist manufacturing method capable of reducing maintenance cost.

The term "solder" refers to "soldering," and the term "resist" refers to a film that protects the printed circuit board from "any treatment or reaction" during the manufacturing process. Therefore, the solder resist means 'a film which covers a circuit pattern of a printed circuit board and prevents unwanted connection by soldering when the component is mounted', and it has a function of protecting the circuit pattern of the printed circuit board and the insulation between the circuit It is the role that gives.

The circuit pattern of the printed circuit board is formed by corroding the copper foil on the substrate, so that it can be said to be a spiral without insulation coating in principle. As a result, solder bridges may occur when electronic components are mounted on a printed circuit board, and the printed circuit board surface is exposed to molten lead. This leads to a serious defect that prevents the electronic device from operating normally.

In order to prevent such defects, a film that shields other parts except the periphery of a land necessary for soldering the parts is referred to as a solder resist for the purpose of covering a spiral circuit pattern. The solder resist is also referred to as a solder mask by applying the meaning of shielding.

Conventionally, a method of forming a solder resist pattern on a printed circuit board has a limitation in productivity because it must undergo many steps including an exposure step and a development step. Further, in order to ensure the physical properties such as heat resistance and chemical resistance required as the solder resist, the viscosity of the composition including the binder resin such as epoxy resin has been limited.

In order to solve such a problem, a method using an inkjet printer has been proposed so as not to undergo exposure and development processes. However, in order to use the ink as an inkjet ink, the viscosity has to be lowered below a certain level, The solder resist of the printed wiring board can not be used as the inkjet method because the physical properties such as heat resistance and chemical resistance required as the solder resist and the storage stability and electroless plating property required for the inkjet ink may be reduced. And there was no practical solder resist ink usable in an ink jet printer.

Accordingly, development of a curable resin composition for an ink jet capable of exhibiting excellent storage stability, electroless plating and mechanical properties while having a low viscosity is desired.

An object of the present invention is to provide a curable resin composition for an ink jet which has low viscosity and can exhibit excellent storage stability, electroless plating property and mechanical properties.

Further, the present invention is to provide a solder resist using the inkjet curable resin composition.

The present invention also provides a solder resist manufacturing method which can simplify the process, improve the productivity, and reduce the maintenance cost of equipment.

In the present specification, a nanosilica dispersion containing silica particles treated with a siloxane compound on the surface and an acrylic monomer; An alicyclic compound having 4 to 20 carbon atoms and containing at least 2 ethylenically unsaturated groups; An aromatic compound having 1 to 10 carbon atoms and containing at least 3 ethylenically unsaturated groups; A polyfunctional aliphatic acrylate compound, and a photoinitiator, wherein the content of the nanosilica dispersion is 3 wt% to 20 wt% with respect to the total composition.

In this specification, there is also provided a solder resist comprising a cured product of the ink-jet curable resin composition.

The present invention also relates to a method of manufacturing a curable resin composition for inkjet, comprising the steps of: applying the above inkjet curable resin composition onto a substrate with an inkjet printer; And a step of curing the applied resin composition.

Hereinafter, a curable resin composition for an inkjet according to a specific embodiment of the present invention, a solder resist using the same, and a method for producing the same will be described in detail.

In the present specification, the term "(meth) acryloyl group" is meant to include both an acryloyl group and a methacryloyl group. In the present specification, the term "(meth) acryloyloxy group" is meant to include both an acryloyloxy group and a methacryloyloxy group. In the present specification, the term "(meth) acryloyloxyalkyl group" is meant to include both an acryloyloxyalkyl group and a methacryloyloxyalkyl group.

According to an embodiment of the present invention, there is provided a nanosilica dispersion comprising silica particles treated with a siloxane compound on the surface and an acrylic monomer; An alicyclic compound having 4 to 20 carbon atoms and containing at least 2 ethylenically unsaturated groups; An aromatic compound having 1 to 10 carbon atoms and containing at least 3 ethylenically unsaturated groups; A polyfunctional aliphatic acrylate compound, and a photoinitiator, wherein the content of the nanosilica dispersion is 3 wt% to 20 wt% with respect to the total composition.

The present inventors have found that the use of the curable resin composition for inkjet according to one embodiment of the present invention does not include a binder resin such as an epoxy resin and has a low viscosity and exhibits excellent heat resistance and heat resistance comparable to the case of containing a binder resin such as an epoxy resin, It is possible to provide a curable resin composition for an ink jet which can exhibit mechanical properties such as chemical resistance and excellent storage stability and electroless plating property.

Specifically, the curable resin composition for inkjet may include a nanosilica dispersion containing silica particles having a surface-treated siloxane compound and an acrylic monomer. The storage stability and electroless plating ability of the inkjet curable resin composition can be improved by including the nanosilica dispersion containing the silica particles and the acrylic monomer having the surface treated siloxane compound. More specifically, the storage stability means that the quality is maintained without changing the particle diameter of the ink particles, the viscosity of the ink composition, and the appearance even under long-term or high-temperature conditions. The curable resin composition for inkjet, which comprises the nanosilica dispersion containing the silica particles and the acrylic monomer treated with the siloxane compound on the surface thereof, can secure stability for 5 weeks or more at a temperature of 45 ° C at which high temperature discharge proceeds, The stability can be maintained even after a few months. In addition, the electroless plating is a method of plating by a pure chemical reaction with a catalyst rather than an electrical property, and a curable resin composition for an ink jet including a nanosilica dispersion containing silica particles and an acrylic monomer having the siloxane compound treated on the surface thereof It is possible to obtain excellent electroless plating due to improvement of surface hardenability and improvement of adhesion due to reduction of shrinkage ratio. Since the inkjet curable resin composition has excellent electroless plating ability, heat resistance, abrasion resistance, and chemical resistance can be improved through metal treatment on the surface of the inkjet curable resin composition.

The nanosilica dispersion may include silica particles having a surface-treated siloxane compound and an acrylic monomer. Specifically, the nanosilica dispersion may be such that a dispersion containing silica particles having a surface-treated siloxane compound dispersed therein is dispersed on a dispersion medium containing an acrylic monomer. The dispersion quality means a material dispersed in the dispersion medium in the dispersion medium into a particulate phase. Accordingly, the nano silica dispersion and the alicyclic compound having 4 to 20 carbon atoms and containing at least two ethylenic unsaturated groups contained in the inkjet curable resin composition; An aromatic compound having 1 to 10 carbon atoms and containing at least 3 ethylenically unsaturated groups; The miscibility between the polyfunctional aliphatic acrylate compound can be improved.

The silica particles treated with the siloxane compound on the surface may include silica particles in which the siloxane compound is bonded to the surface via a siloxane bond. The siloxane compound means a compound that forms a chain structure through a siloxane bond in which silicon atoms and oxygen atoms are covalently bonded alternately.

Specifically, the silica particles in which the siloxane compound is bound to the surface via a siloxane bond may include a compound represented by the following formula (1).

[Chemical Formula 1]

Wherein R ₁ is hydrogen or a methyl group, R ₂ is hydrogen or a methyl group, R ₃ is hydrogen or a methyl group or a hydroxy group, q is an integer of 1 to 20, a is an integer of 1 or more, Particles.

More specifically, in Formula 1, q is an integer of 2 to 10, a is an integer of 5 to 10, and the silica particles may be a silicon dioxide (SiO ₂ ) compound.

The acrylic monomer contained in the nanosilica dispersion may include at least one compound selected from the group consisting of a monofunctional acrylate compound, a bifunctional acrylate compound and a trifunctional acrylate compound. That is, the acrylic monomer contained in the nanosilica dispersion may include a monofunctional acrylate compound, a bifunctional acrylate compound, a trifunctional acrylate compound, or a mixture of two or more thereof.

Specifically, the monofunctional acrylate compound is preferably a monofunctional acrylate compound in which one functional group selected from the group consisting of a (meth) acryloyl group, a (meth) acryloyloxy group and a (meth) 10 < / RTI > heterocyclic compounds. Examples of the heterocyclic compound having 1 to 10 carbon atoms in which one functional group selected from the group consisting of the (meth) acryloyl group, the (meth) acryloyloxy group and the (meth) acryloyloxy group are substituted are greatly limited For example, a heterocyclic compound having 5 to 9 carbon atoms in which one (meth) acryloyloxyalkyl group is substituted, and the like can be used. Specific examples of the heterocyclic compound having 5 to 9 carbon atoms in which one (meth) acryloyloxyalkyl group is substituted include trimethylolpropane foam acrylate and the like.

The bifunctional acrylate compound is preferably a compound having 1 to 10 carbon atoms in which one functional group selected from the group consisting of a (meth) acryloyl group, a (meth) acryloyloxy group and a (meth) acryloyloxy group is substituted with two Aliphatic compounds; And an aliphatic ether compound having 1 to 10 carbon atoms in which one functional group selected from the group consisting of a (meth) acryloyl group, a (meth) acryloyloxy group and a (meth) acryloyloxy group is substituted, ≪ / RTI >

The examples of the aliphatic compound having 1 to 10 carbon atoms in which one functional group selected from the group consisting of the (meth) acryloyl group, the (meth) acryloyloxy group and the (meth) acryloyloxy group are substituted are greatly limited Alternatively, for example, a linear or branched hydrocarbon compound having 5 to 9 carbon atoms in which two (meth) acryloyloxy groups are substituted can be used. Specific examples of the hydrocarbon compound having 5 to 9 carbon atoms in which the (meth) acryloyloxy group is substituted with 2 are, for example, 1,6-hexanediol diacrylate.

Examples of aliphatic ether compounds having 1 to 10 carbon atoms in which one functional group selected from the group consisting of (meth) acryloyl group, (meth) acryloyloxy group and (meth) acryloyloxy group are substituted are greatly limited For example, an aliphatic ether compound having 5 to 10 carbon atoms in which two (meth) acryloyloxy groups are substituted, and the like can be used. Specific examples of the aliphatic ether compound having 5 to 10 carbon atoms in which the (meth) acryloyloxy group is substituted with two groups include tripropylene glycol diacrylate and the like.

The trifunctional acrylate compound is an aliphatic (meth) acrylate having 1 to 10 carbon atoms in which one functional group selected from the group consisting of a (meth) acryloyl group, a (meth) acryloyloxy group and a compound; And an aliphatic ether compound having 1 to 20 carbon atoms in which one functional group selected from the group consisting of a (meth) acryloyl group, a (meth) acryloyloxy group and a (meth) acryloyloxy group is substituted, ≪ / RTI >

Examples of aliphatic compounds having 1 to 10 carbon atoms in which one functional group selected from the group consisting of (meth) acryloyl group, (meth) acryloyloxy group and (meth) acryloyloxy group are substituted are very limited For example, a linear or branched hydrocarbon compound having 5 to 9 carbon atoms in which three (meth) acryloyloxy groups are substituted can be used. Specific examples of the hydrocarbon compound having 5 to 9 carbon atoms in which the above (meth) acryloyloxy group is substituted are trimethylolpropane triacrylate and the like.

Examples of the aliphatic ether compound having 1 to 20 carbon atoms in which one functional group selected from the group consisting of the (meth) acryloyl group, the (meth) acryloyloxy group and the (meth) acryloyloxy group are substituted are greatly limited For example, an aliphatic ether compound having 5 to 15 carbon atoms in which three (meth) acryloyloxy groups are substituted, and the like can be used. Specific examples of the aliphatic ether compound having 5 to 15 carbon atoms in which the above (meth) acryloyloxy group is substituted are ethoxylated trimethylolpropane triacrylate and the like.

The particle size of the silica particles treated with the siloxane compound on the surface may be 5 nm to 100 nm, or 10 nm to 50 nm, or 15 nm to 30 nm, or 18 nm to 25 nm. The particle diameter means the diameter of the silica particles.

The content of the silica particles treated on the surface of the siloxane compound may be 40 wt% to 70 wt%, or 45 wt% to 60 wt%, or 48 wt% to 55 wt% with respect to the nanosilica dispersion.

The nanosilica dispersion may have a kinematic viscosity at 25 DEG C of from 150 mPa.s to 3,500 mPa.s or from 160 mPa.s to 3,400 mPa.s or from 170 mPa.s to 3,350 mPa.s have. The dynamic viscosity refers to an absolute size indicating a degree of stickiness of a material in a fluid state against a motion direction. Accordingly, the smaller the kinetic viscosity, the better fluidity of the fluid can be. Examples of the method of measuring the kinetic viscosity are not limited to a wide range, but the NV method or the P / K method can be used. If the kinetic viscosity is excessively larger than 3,500 mPa · s, miscibility of the nanosilica dispersion in the inkjet curable resin composition may be reduced.

In addition, the content of the nanosilica dispersion may be 3 wt% to 20 wt%, or 4 wt% to 12 wt% with respect to the total composition. If the content of the nano silica dispersion is less than 3% by weight based on the total composition, the storage stability and electroless plating ability of the curable resin composition for inkjet may be reduced. In addition, when the content of the nano silica dispersion is more than 20% by weight with respect to the total composition, the viscosity increases and bubbles are generated to make filtration impossible, and dischargeability may become unstable.

On the other hand, the curable resin composition for inkjet may contain an aromatic compound having 1 to 10 carbon atoms and containing an alicyclic compound having 4 to 20 carbon atoms and 2 or more ethylenically unsaturated groups and 3 or more ethylenically unsaturated groups.

The aromatic compounds having 1 to 10 carbon atoms and containing at least two ethylenically unsaturated groups and containing at least 3 alicyclic groups and at least three ethylenically unsaturated groups exhibit a high glass transition temperature to improve the heat resistance of the inkjet curable resin composition And is excellent in chemical resistance and abrasion resistance, thereby contributing to improvement of the mechanical properties of the ink-jet curable resin composition.

The ethylenic unsaturated group means a functional group or an atomic group containing a carbon-carbon double bond. Examples of the ethylenic unsaturated group include, but are not limited to, (meth) acryloyl group, (meth) acryloyl group, A (meth) acryloyloxyalkyl group, or a mixture thereof may be used.

The alicyclic compound having 4 to 20 carbon atoms and containing at least two ethylenically unsaturated groups may be at least one selected from the group consisting of (meth) acryloyl groups, (meth) acryloyloxy groups and (meth) acryloyloxyalkyl groups Cyclic compound having 6 to 15 carbon atoms in which at least two functional groups are substituted. Examples of the polycyclic compound having 6 to 15 carbon atoms are not particularly limited, but examples thereof include norbornane (Bicyclo [2,2,1] heptane), norbornene (Bicyclo [2.2.1] hept- 2-ene, norpinane, Bicyclo [3,1,1] heptane, norpinene, Bicyclo [3,1,1] hept-2-ene), norbornane derivatives, norbornene derivatives, A refractory derivative or a norpinene derivative, and the like. The derivative means a compound in which a hydrogen atom or a specific atomic group in the compound is substituted by another atom or atomic group.

Specifically, a multicyclic compound having 6 to 15 carbon atoms in which at least one functional group selected from the group consisting of (meth) acryloyl group, (meth) acryloyloxy group and (meth) acryloyloxy group is substituted, May comprise a compound of formula (2).

 (2)

In Formula 2,

At least two of R ₅ , R ₆ , R ₇ , R ₈ and R ₉ are functional groups represented by the following formula (3)

And the rest is hydrogen or a straight or branched alkyl group having 1 to 4 carbon atoms,

(3)

In Formula 3,

A is a direct bond or a linear or branched alkylene group having 1 to 20 carbon atoms,

X is a direct bond or oxygen,

R ₁₁ , R ₁₂ and R ₁₃ are each a functional group selected from the group consisting of hydrogen, a methyl group and an ethyl group.

More specifically, the compound of formula (2) is a compound of formula (2) wherein R ₅ , R ₆ At least one of R < ₇ >, R < ₈ >, R < ₈ & R ₉ Lt; / RTI > is a functional group of formula (3).

On the other hand, the aromatic compound having from 1 to 10 carbon atoms and containing at least three ethylenically unsaturated groups may be at least one selected from the group consisting of (meth) acryloyl groups, (meth) acryloyloxy groups and (meth) acryloyloxyalkyl groups And a heteroaromatic compound having 2 to 5 carbon atoms in which at least three functional groups are substituted. The heteroaromatic compound is an annular compound containing a heteroatom, which means that it has aromatic properties.

Specifically, a heteroaromatic compound having 2 to 5 carbon atoms in which at least one functional group selected from the group consisting of (meth) acryloyl group, (meth) acryloyloxy group and (meth) acryloyloxy group is substituted, Lt; / RTI > may comprise a compound of formula (4).

 [Chemical Formula 4]

In Formula 4,

At least one of Y ₁ , Y ₂ and Y ₃ is nitrogen and the others are carbon,

R ₂₁ , R ₂₂ and R ₂₃ are each a functional group represented by the following formula (3)

(3)

In Formula 3,

A is a direct bond or a linear or branched alkylene group having 1 to 20 carbon atoms,

X is a direct bond or oxygen,

R ₁₁ , R ₁₂ and R ₁₃ are each a functional group selected from the group consisting of hydrogen, a methyl group and an ethyl group.

The glass transition temperature of the alicyclic compound having 4 to 20 carbon atoms and containing at least two ethylenically unsaturated groups may be 150 to 220 캜, and the glass transition of the aromatic compound having 1 to 10 carbon atoms including the ethylenically unsaturated group of 3 or more The temperature may be between 250 [deg.] C and 300 [deg.] C. The glass transition temperature is determined by annealing the alicyclic compound having 4 to 20 carbon atoms containing the two ethylenically unsaturated groups or the aromatic compound having 1 to 10 carbon atoms containing the 3 ethylenically unsaturated groups at 300 DEG C for 5 minutes , And then cooled to room temperature, and then subjected to a second scan at a heating rate of 10 ° C / min. If the glass transition temperature of the alicyclic compound having 4 to 20 carbon atoms containing the two ethylenically unsaturated groups or the aromatic compound having 1 to 10 carbon atoms containing the 3 ethylenically unsaturated groups is too low, It may be difficult to ensure sufficient heat resistance.

The alicyclic compound having 4 to 20 carbon atoms and containing at least two ethylenically unsaturated groups may be contained in an amount of 20% by weight to 50% by weight or 25% by weight to 40% by weight based on the inkjet curable resin composition. The aromatic compound having 1 to 10 carbon atoms containing at least 3 ethylenically unsaturated groups may be contained in an amount of 5 to 20% by weight or 7 to 15% by weight based on the inkjet curable resin composition .

A weight ratio of an alicyclic compound having 4 to 20 carbon atoms and at least 2 ethylenically unsaturated groups and an aromatic compound having 1 to 10 carbon atoms containing 3 or more ethylenically unsaturated groups is 2: 1 to 10: 1, or 2.2: 1 to 5 : 1, or 2.5: 1 to 4: 1, or 2.8: 1 to 3.5: 1. When the weight ratio between the alicyclic compound having 4 to 20 carbon atoms and 2 to 10 carbon atoms and the aromatic compound having 1 to 10 carbon atoms containing 3 or more ethylenically unsaturated groups is less than 2: 1, the curing If the weight ratio between the alicyclic compound having 4 to 20 carbon atoms and 2 to 10 ethylenically unsaturated groups and the aromatic compound having 1 to 10 carbon atoms containing 3 or more ethylenically unsaturated groups is more than 10: The viscosity of the curable resin composition for inkjet can be excessively increased.

The curable resin composition for inkjet may include a polyfunctional aliphatic acrylate compound. In addition, the polyfunctional aliphatic acrylate compound may include a bifunctional aliphatic acrylate compound or a tetrafunctional aliphatic acrylate compound.

Examples of the bifunctional aliphatic acrylate compound include, but are not limited to, for example, a (meth) acryloyloxy group, a (meth) acryloyloxy group and a An aliphatic compound having 1 to 10 carbon atoms in which two functional groups are substituted can be used.

Examples of the aliphatic compound having 1 to 10 carbon atoms in which one functional group selected from the group consisting of the (meth) acryloyl group, the (meth) acryloyloxy group and the (meth) acryloyloxy group are substituted are very limited For example, a linear or branched hydrocarbon compound having 5 to 9 carbon atoms in which two (meth) acryloyloxy groups are substituted can be used. Specific examples of the hydrocarbon compound having 5 to 9 carbon atoms in which the (meth) acryloyloxy group is substituted with 2 are, for example, 1,6-hexanediol diacrylate.

Examples of the tetrafunctional aliphatic acrylate compound include, but are not limited to, a (meth) acryloyl group, a (meth) acryloyloxy group and a (meth) acryloyloxyalkyl group. An aliphatic compound having 1 to 10 carbon atoms substituted with four functional groups can be used.

Examples of aliphatic compounds having 1 to 10 carbon atoms in which one functional group selected from the group consisting of (meth) acryloyl group, (meth) acryloyloxy group and (meth) acryloyloxy group are substituted are greatly limited For example, a linear or branched hydrocarbon compound having 3 to 7 carbon atoms in which (meth) acryloyloxy groups are substituted can be used. Specific examples of the hydrocarbon compound having 3 to 7 carbon atoms in which the above (meth) acryloyloxy group is substituted are pentaceritriol tetraacrylate and the like.

The weight ratio of the bifunctional aliphatic acrylate compound and the tetrafunctional aliphatic acrylate compound may be 0.5: 1 to 1.5: 1, or 0.7: 1 to 1.3: 1, or 0.9: 1 to 1.1: 1. The curable resin composition for inkjet has a weight ratio of the bifunctional aliphatic acrylate compound and the tetrafunctional aliphatic acrylate compound within the specific range described above and therefore the inkjet curable resin composition has a low viscosity and excellent heat resistance, Chemical and mechanical properties.

The curable resin composition for inkjet may include a photoinitiator. The photoinitiator may serve to generate radicals by irradiation with heat or active energy ray to improve the curability of the curable resin composition for inkjet. Examples of the photoinitiator include, but are not limited to, benzoin and its alkyl ethers, acetophenones, anthraquinones, thioxanthones, ketals, benzophenones,? -Aminoacetophenones, Phosphine oxides, oxime esters, and the like. The photoinitiator may be contained in an amount of 0.1 wt% to 20 wt%, or 5 wt% to 10 wt% based on the inkjet curable resin composition.

The inkjet curable resin composition may further include an organic solvent in an amount of 10% by weight to 95% by weight based on the weight of the entire inkjet curable resin composition.

Examples of the organic solvent include, but are not limited to, ketones such as methyl ethyl ketone and cyclohexanone; Aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; Methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol diethyl ether, tripropylene glycol monomethyl ether, etc. Of glycol ethers; Esters such as ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate and propylene carbonate; Aliphatic hydrocarbons such as octane and decane; Petroleum ether such as petroleum ether, petroleum naphtha and solvent naphtha may be used alone or in combination of two or more.

The inkjet curable resin composition may further comprise additives including a pigment, a dispersant, an antioxidant, a photopolymerization accelerator, a surface modifier, or a mixture of two or more thereof. Examples of the inorganic pigments include cobalt oxide, aluminum oxide, titanium dioxide, zinc sulfide, bismuth sulfate, and the like. Examples of the inorganic pigments include, but are not limited to, Examples of the organic pigments are not particularly limited, and for example, an anthraquinone type, a perylene type, a disazo type, an isoindoline type, a phthalocyanine type and the like can be used. The pigment may be contained in an amount of 1 wt% to 20 wt%, or 10 wt% to 15 wt% based on the inkjet curable resin composition.

The dispersing agent may be used in a variety of commonly used dispersing agents without limitation, and may be contained in an amount of 0.1 wt% to 5 wt%, or 1 wt% to 2 wt% based on the inkjet curable resin composition.

The photopolymerization accelerator accelerates the polymerization reaction and is not particularly limited. For example, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylamino Tertiary amines such as benzoate, triethylamine and triethanolamine, and the like can be used. The photopolymerization accelerator may be contained in an amount of 0.1 wt% to 5 wt%, or 0.5 wt% to 2 wt% based on the inkjet curable resin composition.

The ink-jetting curable resin composition obtained by blending the above components can be mixed and dispersed by using a dispersing machine such as a stirrer or a dispersing machine such as a roll mill, a sand mill, a ball mill, a bead mill or an attritor until uniform have.

The initial viscosity of the ink-jet curable resin composition may be 100 mPa s or less at 25 ° C, or 30 mPa s to 60 mPa s, at 45 ° C at 20 mPa s or less, or 7 mPa s to 15 mpa.multidot.s have. The initial viscosity refers to the viscosity immediately after the completion of the production of the ink-jet curable resin composition. The initial viscosity of the inkjet curable resin composition must be lowered to a certain level or less to be applied by an inkjet printer. If the initial viscosity of the ink-jet curable resin composition is more than 100 mPa · s at 25 ° C. or more than 20 mPa · s at 40 ° C., the viscosity of the ink-jet curable resin composition may increase, Can be degraded.

The viscosity change rate of the ink-jet curable resin composition at 45 ° C may be 10% or less, or 1% to 10%, or 1.5% to 7%, or 1.8% to 6%. The viscosity change rate can be obtained by the following equation (1).

[Equation 1]

Viscosity change rate (%) = (viscosity of ink-jet curable resin composition after storage at 45 占 폚 for 5 weeks-initial viscosity of ink-jet curable resin composition at 45 占 폚) / initial viscosity of ink-jet curable resin composition X100

The viscosity of the ink-jet curable resin composition after storage for 5 weeks at a temperature of 45 ° C, the initial viscosity of the ink-jet curable resin composition at a temperature of 45 ° C was maintained at 45 ° C for 5 weeks, Means the absolute value of the difference between the initial viscosity of the curable resin composition for ink-jet at a temperature of 45 캜 and the viscosity of the curable resin composition for inkjet.

When the curable resin composition for inkjet is stored at a temperature of 45 ° C for a long period of time, an increase or decrease may occur based on the initial viscosity. If the viscosity change rate is excessively increased, stability with respect to the temperature of the curable resin composition for ink jet is decreased, and it may be difficult to use the ink jet according to high temperature discharge.

According to another embodiment of the present invention, a solder resist containing a cured product of the ink-jet curable resin composition may be provided.

Wherein the solder resist comprises: a nanosilica dispersion containing silica particles and an acrylic monomer having a surface treated with a siloxane compound; An alicyclic compound having 4 to 20 carbon atoms and containing at least 2 ethylenically unsaturated groups; An aromatic compound having 1 to 10 carbon atoms and containing at least 3 ethylenically unsaturated groups; And a polyfunctional aliphatic acrylate compound; and a cross-linking between two or more compounds selected from the group consisting of a polyfunctional aliphatic acrylate compound and a polyfunctional aliphatic acrylate compound.

The weight ratio of the alicyclic compound having 4 to 20 carbon atoms containing at least two ethylenically unsaturated groups and the aromatic compound having 1 to 10 carbon atoms containing at least 3 ethylenically unsaturated groups is 2: 1 to 10: 1, or 2: 5: 1.

According to another embodiment of the present invention, there is provided a method of manufacturing an inkjet curable resin composition, And a step of curing the applied resin composition.

As described above, the method of manufacturing the solder resist does not require a complicated process such as an alkaline developing type solder resist by using the inkjet curable resin composition, but is applied to a specific portion by a specific amount using an inkjet printer , The process can be simplified, the productivity can be improved, and the maintenance cost of the equipment can be reduced.

As the ink jet printer, an on-demand or piezo ink jet printer may be used, and preferably a piezoelectric ink jet printer may be used. The above-mentioned piezo system means a system which utilizes the property of generating electricity on the surface of a crystal (crystal, tourmaline, etc.) when pressure is applied in a specific direction.

As the substrate, a printed wiring board or the like formed with a circuit can be used.

On the other hand, the step of curing the applied resin composition includes a photo-curing step; And a heat curing step.

The photo-curing step may have an exposure dose of 150 mJ / cm2 to 250 mJ / cm2, or 180 mJ / cm2 to 220 mJ / cm2. As the light source, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a xenon lamp or a metal halide lamp can be used.

The thermosetting step may be performed at 100 ° C to 200 ° C, or 140 ° C to 160 ° C for 30 minutes to 90 minutes, or 40 minutes to 70 minutes. In addition, the thermosetting step may be performed in a hot air circulating type drying furnace. Through the above-mentioned thermosetting step, a resist pattern containing a cured product having excellent heat resistance can be obtained.

According to the present invention, it is possible to provide a curable resin composition for an ink jet which can exhibit excellent storage stability, electroless plating property and mechanical properties while having a low viscosity, a solder resist using the same, and a process, A solder resist manufacturing method capable of reducing maintenance cost can be provided.

The invention will be described in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

< Example  1 to 2 and Comparative Example  1 to 2: For Inkjet  Curable resin composition and Solder resist  Manufacturing>

(1) Preparation of curable resin composition for inkjet

The reactants were mixed at a rate of 2,000 rpm at a temperature of 45 ° C for 1.5 hours using a stirrer in the contents shown in Table 1 below, and dispersed for 3 hours using zirconia beads having a particle size of 0.2 μm by adding a pigment and a dispersant. Then, an additive such as an antioxidant, a photopolymerization accelerator, and a surface conditioner was added thereto, followed by filtration through a 1 占 퐉 filter to prepare a curable resin composition for an ink jet.

(2) Manufacture of solder resist

The ink-jet curable resin composition was applied to a piezoelectric type printhead and coated on a printed wiring board 1.6T FR-4 (150 mm x 95 mm) with a solder resist pattern. Then, the solder resist solution applied on the printed wiring board was irradiated with ultraviolet rays at a dose of 200 mJ / cm 2 using a mercury lamp, and photo-curing was performed. After the photo-curing, the solder resist was prepared by conducting thermal curing at a temperature of 150 ° C for 60 minutes in a hot air circulating type drying furnace.

< Experimental Example  : Example  And In the comparative example  Obtained For Inkjet  Curable resin composition and Solder resist  Measurement of physical properties>

The physical properties of the ink-jet curable resin composition and the solder resist obtained in the above Examples and Comparative Examples were measured by the following methods, and the results are shown in Table 1.

1. Storage stability

1-1. Particle size (탆)

The curable resin composition for inkjet was stored at 45 캜 for 5 weeks, and then the maximum particle diameter of the particles contained in the solder resist composition was measured according to laser diffraction (using ethyl alcohol as a solvent) using a particle size analyzer MS3000 manufactured by Malvern Respectively.

1-2. Viscosity change rate (%)

The specific gravity of the ink-jet curable resin composition after storage for 45 days at an initial temperature of 45 ° C for 5 weeks was measured using a densitometer, and the kinematic viscosity was measured using a Canon Pen Scue viscometer to measure the viscosity of the inkjet curable resin composition Respectively.

The viscosity change rate was measured based on the initial viscosity of the ink-jet curable resin composition. The viscosity change rate can be obtained through the following equation (1).

[Equation 1]

Viscosity change rate (%) = (viscosity of ink-jet curable resin composition after storage at 45 占 폚 for 5 weeks-initial viscosity of ink-jet curable resin composition at 45 占 폚) / initial viscosity of ink-jet curable resin composition X100

The viscosity of the ink-jet curable resin composition after storage for 5 weeks at a temperature of 45 ° C, the initial viscosity of the ink-jet curable resin composition at a temperature of 45 ° C was maintained at 45 ° C for 5 weeks, Means the absolute value of the difference between the initial viscosity of the curable resin composition for ink-jet at a temperature of 45 캜 and the viscosity of the curable resin composition for inkjet.

1-3. Precipitation and separation

After the curable resin composition for ink jet was stored at 45 캜 for 5 weeks, it was visually observed whether it was precipitated or separated.

OK: no precipitation and separation observed

NG: precipitation and separation observed

2. Adhesion

The adhesive force of the solder resist was measured according to the test method of ASTM D3359.

3. Pencil hardness (H)

The pencil hardness of the solder resist was measured according to the test method of JIS K-5600-5

4. Chemical resistance

According to the JIS-C-5016 test method, the state of the coating film after the solder resist was immersed in 10 vol% hydrochloric acid for 10 minutes was evaluated.

4-1. Solvent resistance

According to the JIS-C-5016 test method, the solder resist was immersed in isopropyl alcohol for 5 minutes, and the state of the film under the following criteria was evaluated.

OK: No swelling, discoloration, peeling on solder resist

NG: Swelling, discoloration, and peeling were observed on the solder resist.

4-2. Acid resistance

According to the JIS-C-5016 test method, the solder resist was immersed in 2N hydrochloric acid for 5 minutes, and the state of the film under the following criteria was evaluated.

OK: No swelling, discoloration, peeling on solder resist

NG: Swelling, discoloration, and peeling were observed on the solder resist.

4-3. My alkalinity

According to the JIS-C-5016 test method, the solder resist was immersed in 2N sodium hydroxide for 5 minutes, and the state of the coating film was evaluated under the following criteria.

OK: No swelling, discoloration, peeling on solder resist

NG: Swelling, discoloration, and peeling were observed on the solder resist.

5. Heat resistance

According to the test method of JSTD-003, the solder resist was immersed in a solder bath of 260 deg. C for 5 seconds, and then subjected to a peeling test using a scotch tape to evaluate the film state under the following criteria.

OK: Solder resist does not come off by Scotch tape

NG: Solder resist comes off by Scotch tape

6. Electroless Plating property

Using the electroless nickel plating bath and the electroless gold plating bath at a conveyer speed of 2.5 m / min, the solder resist was plated with nickel 3.745 mu m and gold 0.056 mu m, and the peeling of the cured coating film or the permeation of plating Respectively.

OK: Solder resist does not peel off or plunge.

NG: Solder resist peeling off or plated

The compositions of the solder res of the above Examples and Comparative Examples and the results of the experimental examples are shown in Tables 1 and 2 below.

Composition of solder resist in Examples and Comparative Examples and Results of Experimental Example (unit:% by weight) division Example 1 Example 2 Comparative Example 1 Comparative Example 2 Tris (2-hydroxyethyl) isocyanurate trimethacrylate (THEICTA) 10 10 10 10 Tricyclodecane dimethanol diacrylate (TCDDA) 30 30 30 30 Pentacyceritol tetraacrylate (PETRA) 10 10 10 10 1,6-hexanediol diacrylate (HDDA) 10 10 - 10 Dipropylene glycol diacrylate (DPGDA) - - 20 - 4-hydroxybutyl acrylate (4HBA) 20 20 20 20 Nano silica dispersion 5 10 - 2.5 Initial viscosity (mPa · s) 12.4 14.5 28.1 19.3 Storage stability Particle size (탆) 0.18 0.17 0.64 0.38 Viscosity change rate (%) 5 2 20 12 Precipitation and separation OK OK NG NG Adhesion 100/100 100/100 100/100 100/100 Pencil hardness 6H 7H 5H 5H Chemical resistance OK OK OK OK Heat resistance OK OK OK OK Electroless plating property OK OK NG NG

 As shown in Table 1, the curable resin composition for inkjet according to Examples 1 and 2 contained 5 wt% and 10 wt% of the nanosilica dispersions, respectively, and therefore, even after storage at 45 ° C for 5 weeks, Can be kept as low as less than 0.2 μm, and the rate of change in viscosity is less than 10%, and precipitation and separation do not occur, indicating excellent storage stability. On the other hand, in the case of Comparative Examples 1 and 2, the content of the nanosilica dispersion was not sufficient, and after storage for 5 weeks at 45 ° C, the particle size exceeded 0.3 μm, the viscosity change rate exceeded 10% It can be confirmed that the storage stability is not sufficiently secured.

In addition, in the case of the ink-jet curable resin compositions of Examples 1 and 2, excellent electroless plating performance was exhibited due to the inclusion of 5 wt% and 10 wt% of the nanosilica dispersion, respectively, while the content of the nanosilica dispersion was It can be confirmed that the electroless plating ability is not sufficiently secured in Comparative Examples 1 and 2 which are not sufficient.

In addition, in the case of the ink-jet curable resin compositions of Examples 1 and 2, the mechanical properties such as adhesive force, pencil hardness, chemical resistance and heat resistance were comparable to those of Comparative Examples It can be seen that this is implemented at an equivalent level.

Thus, the curable resin composition for inkjet according to Examples 1 and 2 contains a specific amount of nanosilica dispersion and exhibits excellent storage stability, so that it can be stored for a long period of time, . In addition, it can have excellent electroless plating properties, and heat resistance, abrasion resistance, and chemical resistance can be improved through metal treatment on the surface of the ink-jet curable resin composition.

Claims (25)

A nanosilica dispersion containing silica particles and an acrylic monomer having a siloxane compound surface-treated;
An alicyclic compound having 4 to 20 carbon atoms and containing at least 2 ethylenically unsaturated groups;
An aromatic compound having 1 to 10 carbon atoms and containing at least 3 ethylenically unsaturated groups; Polyfunctional aliphatic acrylate compounds; And
A photoinitiator,
Wherein the silica particles treated with the siloxane compound on the surface thereof comprise a compound represented by the following formula (1)
Wherein the content of the nano-silica dispersion is 3 wt% to 20 wt% with respect to the total composition.
[Chemical Formula 1]

In Formula 1,
R ₁ is hydrogen or a methyl group,
R ₂ is hydrogen or a methyl group,
R ₃ is hydrogen or a methyl group or a hydroxy group,
q is an integer of 1 to 20,
a is an integer of 1 or more,
Silica means silica particles.
delete delete The method according to claim 1,
Wherein the acrylic monomer contained in the nanosilica dispersion comprises at least one compound selected from the group consisting of a monofunctional acrylate compound, a bifunctional acrylate compound and a trifunctional acrylate compound.
5. The method of claim 4,
The monofunctional acrylate compound is a (meth) acryloyl group having 1 to 10 carbon atoms substituted with one functional group selected from the group consisting of a (meth) acryloyl group, a (meth) acryloyloxy group and a Ring compounds,
The bifunctional acrylate compound is an aliphatic compound having 1 to 10 carbon atoms in which one functional group selected from the group consisting of a (meth) acryloyl group, a (meth) acryloyloxy group and a (meth) acryloyloxy group is substituted. compound; And an aliphatic ether compound having 1 to 10 carbon atoms in which one functional group selected from the group consisting of a (meth) acryloyl group, a (meth) acryloyloxy group and a (meth) acryloyloxy group is substituted, , &Lt; / RTI &gt;
The trifunctional acrylate compound is an aliphatic (meth) acrylate having 1 to 10 carbon atoms in which one functional group selected from the group consisting of a (meth) acryloyl group, a (meth) acryloyloxy group and a compound; And an aliphatic ether compound having 1 to 20 carbon atoms in which one functional group selected from the group consisting of a (meth) acryloyl group, a (meth) acryloyloxy group and a (meth) acryloyloxy group is substituted, And at least one compound selected from the group consisting of the following compounds.
The method according to claim 1,
Wherein the silica particles treated with the siloxane compound have a particle diameter of 5 nm to 100 nm.
The method according to claim 1,
Wherein the content of the silica particles treated on the surface of the siloxane compound is 40% by weight to 70% by weight with respect to the dispersion of the nano silica.
The method according to claim 1,
Wherein the weight ratio between the alicyclic compound having 4 to 20 carbon atoms and the aromatic compound having 1 to 10 carbon atoms containing 3 or more ethylenically unsaturated groups is 2: 1 to 10: 1, and the curable resin composition for inkjet .
The method according to claim 1,
The alicyclic compound having 4 to 20 carbon atoms and containing at least two ethylenically unsaturated groups,
(Meth) acryloyl group, a (meth) acryloyloxy group, and a (meth) acryloyloxy group. .
10. The method of claim 9,
The polycyclic compound having 6 to 15 carbon atoms may be selected from the group consisting of norbornane (Bicyclo [2,2,1] heptane), norbornene, Bicyclo [2.2.1] hept-2-ene, norpinane, [3,1,1] heptane), norpinene, Bicyclo [3,1,1] hept-2-ene, norbornane derivatives, norbornene derivatives, nophenan derivatives and nopinene derivatives A curable resin composition for inkjet, comprising at least one compound.
10. The method of claim 9,
The polycyclic compound having 6 to 15 carbon atoms in which one functional group selected from the group consisting of the (meth) acryloyl group, the (meth) acryloyloxy group and the (meth) acryloyloxy group is substituted is represented by the following formula A curable resin composition for inkjet comprising:
(2)

In Formula 2,
At least two of R ₅ , R ₆ , R ₇ , R ₈ and R ₉ are functional groups represented by the following formula (3)
And the rest is hydrogen or a straight or branched alkyl group having 1 to 4 carbon atoms,
(3)

In Formula 3,
A is a direct bond or a linear or branched alkylene group having 1 to 20 carbon atoms,
X is a direct bond or oxygen,
R ₁₁ , R ₁₂ and R ₁₃ are each a functional group selected from the group consisting of hydrogen, a methyl group and an ethyl group.
12. The method of claim 11,
The compound of formula (2) is a compound of formula (2) wherein R ₅ , R ₆ At least one of R &lt; ₇ &gt;, R &lt; ₈ &gt;, R &lt; ₈ & R ₉ Wherein at least one of the functional groups is a functional group of the above formula (3).
The method according to claim 1,
The aromatic compound having from 1 to 10 carbon atoms and containing at least three ethylenically unsaturated groups,
(Meth) acryloyl group, a (meth) acryloyloxy group, and a (meth) acryloyloxy group, which is substituted with at least one functional group selected from the group consisting of .
14. The method of claim 13,
The heteroaromatic compound having 2 to 5 carbon atoms in which one functional group selected from the group consisting of the (meth) acryloyl group, the (meth) acryloyloxy group and the (meth) acryloyloxy group is substituted is represented by the following formula A curable resin composition for inkjet comprising:
[Chemical Formula 4]

In Formula 4,
At least one of Y ₁ , Y ₂ and Y ₃ is nitrogen and the others are carbon,
R ₂₁ , R ₂₂ and R ₂₃ are each a functional group represented by the following formula (3)
(3)

In Formula 3,
A is a direct bond or a linear or branched alkylene group having 1 to 20 carbon atoms,
X is a direct bond or oxygen,
R ₁₁ , R ₁₂ and R ₁₃ are each a functional group selected from the group consisting of hydrogen, a methyl group and an ethyl group.
The method according to claim 1,
Wherein the polyfunctional aliphatic acrylate compound comprises a bifunctional aliphatic acrylate compound or a tetrafunctional aliphatic acrylate compound.
16. The method of claim 15,
Wherein the weight ratio of the bifunctional aliphatic acrylate compound and the tetrafunctional aliphatic acrylate compound is 0.5: 1 to 1.5: 1.
The method according to claim 1,
At least one additive selected from the group consisting of a pigment, a dispersant, an antioxidant, a photopolymerization accelerator, and a surface modifier.
The method according to claim 1,
Wherein the initial viscosity of the ink-jet curable resin composition is from 10 to 20 mPa · s at 45 캜.
The method according to claim 1,
A curable resin composition for inkjet, wherein the viscosity change ratio at 45 캜 according to the following formula (1) is 10% or less:
[Equation 1]
Viscosity change rate (%) = (viscosity of ink-jet curable resin composition after storage at 45 占 폚 for 5 weeks-initial viscosity of ink-jet curable resin composition at 45 占 폚) / initial viscosity of ink-jet curable resin composition X100
The viscosity of the ink-jet curable resin composition after storage for 5 weeks at a temperature of 45 ° C, the initial viscosity of the ink-jet curable resin composition at a temperature of 45 ° C was maintained at 45 ° C for 5 weeks, Means the absolute value of the difference between the initial viscosity of the curable resin composition for ink-jet at a temperature of 45 캜 and the viscosity of the curable resin composition for inkjet.
A solder resist comprising the cured product of the ink-jet curable resin composition of claim 1.
21. The method of claim 20,
A nanosilica dispersion containing silica particles and an acrylic monomer having the siloxane compound treated on the surface thereof; An alicyclic compound having 4 to 20 carbon atoms and containing at least 2 ethylenically unsaturated groups; An aromatic compound having 1 to 10 carbon atoms and containing at least 3 ethylenically unsaturated groups; And a polyfunctional aliphatic acrylate compound; and a cross-linking between two or more compounds selected from the group consisting of a polyfunctional aliphatic acrylate compound and a polyfunctional aliphatic acrylate compound.
Applying the ink-jet curable resin composition of claim 1 onto a substrate with an inkjet printer; And
And curing the applied resin composition.
23. The method of claim 22,
Wherein the step of curing the applied resin composition comprises:
Photocuring step; And a thermosetting step.
24. The method of claim 23,
Wherein the photo-curing step has an exposure dose of 150 mJ / cm2 to 250 mJ / cm2.
24. The method of claim 23,
Wherein the thermosetting step is performed at 100 占 폚 to 200 占 폚 for 30 minutes to 90 minutes.