KR20220077886A - Etching-resistant ink composition, photocurable film prepared therefrom, and method of manufacturing printed circuit board using same - Google Patents

Abstract

The present invention relates to an ink composition having excellent etching resistance, a photocurable film prepared therefrom, and a method for manufacturing a printed circuit board using the same, and specifically, it is easy to discharge, has a short curing time, and has excellent resistance to etching solution, The present invention relates to an ink composition that readily dissolves in a release solution.

Description

Etching-resistant ink composition, photocurable film prepared therefrom, and method of manufacturing a printed circuit board using the same

The present invention relates to an ink composition having excellent etching resistance, a photocurable film prepared therefrom, and a method for manufacturing a printed circuit board using the same, and specifically, it is easy to discharge, has a short curing time, and has excellent resistance to etching solution, The present invention relates to an ink composition that readily dissolves in a release solution.

In order to manufacture a printed circuit board on which a metal pattern is formed in the past, a non-conductive substrate on which copper foil is formed is prepared, a photoresist dry film is attached on the copper foil, a pattern mask is applied to expose UV to the photoresist layer (photosensitive process) ), removing the unexposed photoresist layer with a developer solution, removing unwanted copper by etching (etching process), and removing the exposed photoresist layer with an alkaline stripping bath (peeling process), A method was adopted that leaves only the desired conductive copper pattern present on the non-conductive substrate.

Recently, electronic parts have become lighter, thinner and smaller, and a new form of composite material combining hard and flexible materials is being developed. However, if the printed circuit board is manufactured using the photoresist dry film, it is insufficient to overcome the step problem occurring in the bonding portion.

In order to solve the above problem, numerous domestic and foreign researchers are conducting research and development on methods such as printing, inkjet printing, or aerosol patterning using UV curable ink instead of photoresist dry film.

The UV curable ink should be photocurable efficiently by UV in the photosensitive process in order to manufacture the above-described printed circuit board, and should have etching resistance because it should not be dissolved in the etching process, and be easily peeled off in the peeling process. Since it should be able to be able to, excellent peelability is required. In addition, for efficient printing and patterning workability, the ejection property should be excellent.

Therefore, there is a need for research and development on an ink composition having excellent rapid curing, etching resistance, peelability and ejection properties.

In order to solve the problems of the prior art, it is an object of the present invention to provide an ink composition excellent in quick curing, etching resistance, releasability and ejection properties. Specifically, an object of the present invention is to provide an ink composition that can be easily and quickly cured by a UV light source, has excellent etching resistance, has a low viscosity, has high ejection properties, and is easily peeled off from a metal pattern through a subsequent peeling process.

Another object of the present invention is to provide a photocurable film manufactured by inkjet printing or patterning in the form of ink, not in the form of a film, and overcoming the problem of step generation, and a printed circuit board using the same.

In order to achieve the above object, the present inventors have continuously studied ink compositions having excellent fast curing, etching resistance, peelability and ejection properties. As a result, a (meth)acrylic monomer having an alicyclic hetero ring, a polyfunctional (meth)acrylic monomer , in the case of an etch-resistant ink composition comprising a (meth)acrylic monomer and a photoinitiator containing a phosphate group, it has a low viscosity, has high ejection property, can be easily and quickly cured by a UV light source, has excellent etching resistance, and is subjected to a subsequent peeling process The present invention was completed by discovering that it is easy to peel from the metal pattern through , and it is possible to efficiently manufacture a printed circuit board.

The present invention provides an etch-resistant ink composition comprising a (meth)acrylic monomer having an alicyclic hetero ring, a polyfunctional (meth)acrylic monomer, a (meth)acrylic monomer including a phosphate group, and a photoinitiator.

According to an embodiment of the present invention, the alicyclic heterocyclic ring of the (meth)acrylic monomer having an alicyclic heterocycle contains 4 to 6 carbon atoms, and one or two selected from the group consisting of nitrogen, oxygen and sulfur. It may be one having a hetero element of.

According to an embodiment of the present invention, the polyfunctional (meth)acrylic monomer is dipropylene glycol diacrylate, carboxyethyl acrylate, hydroxypivalic acid neopentyl glycol diacrylate, trimethylolpropane triacrylate and trimethylol. It may be any one or two or more selected from propane trimethacrylate and the like.

According to an embodiment of the present invention, the (meth)acrylic monomer including the phosphate group is 2-hydroxyethyl (meth)acrylate phosphate, 2-methacryloyl oxyethyl phosphate, bis(2-methacryloyl) Oxyethyl) phosphate, 2-acryloyl oxyethyl phosphate, bis(2-acryloyl oxyethyl) phosphate, methyl-(2-methacryloyl oxyethyl) phosphate, ethyl methacryloyl oxyethyl phosphate, methyl It may be any one or two or more selected from acryloyl oxy ethyl phosphate and ethyl acryloyl oxy ethyl phosphate.

According to an embodiment of the present invention, the (meth)acrylic monomer having the alicyclic hetero ring may be included in an amount of 30 to 55% by weight based on the total weight of the etch-resistant ink composition.

According to an embodiment of the present invention, the polyfunctional (meth)acrylic monomer may be included in an amount of 30 to 55% by weight based on the total weight of the etch-resistant ink composition.

According to an embodiment of the present invention, the (meth)acrylic monomer including a phosphate group may be included in an amount of 1 to 10% by weight based on the total weight of the etch-resistant ink composition.

According to an embodiment of the present invention, the photoinitiator may be included in an amount of 5 to 15% by weight based on the total weight of the etch-resistant ink composition.

According to an embodiment of the present invention, the etch-resistant ink composition may have a viscosity value of less than 50 mPa·s at 25°C.

The present invention may provide a photocurable film prepared from the above-described etch-resistant ink composition.

According to an embodiment of the present invention, the photocurable film may have an adhesiveness of 5B or more according to ASTM D 3359 standard.

According to an embodiment of the present invention, the photocurable film may have a peelability test result of 8 minutes or less at 50° C. and 5% NaOH aqueous solution.

The present invention comprises the steps of applying the above-described etching-resistant ink composition to form a predetermined pattern on a copper foil layer of a copper-clad laminate film, and irradiating with light to form a patterned coating layer; etching a region where the coating layer is not formed; and removing the coating layer; may provide a method of manufacturing a printed circuit board comprising a.

According to an embodiment of the present invention, in the step of forming the patterned application layer, thermal curing may be further performed after irradiation with light.

The etching-resistant ink composition according to the present invention includes a (meth)acrylic monomer having an alicyclic hetero ring, a polyfunctional (meth)acrylic monomer, a (meth)acrylic monomer including a phosphate group, and a photoinitiator. It has high properties, can be cured easily and quickly by a UV light source, has excellent etching resistance, and is advantageous in that it is possible to efficiently manufacture a printed circuit board in that it is easy to peel from a metal pattern through a peeling process later.

Hereinafter, the present invention will be described in more detail through embodiments or examples including the accompanying drawings. However, the following specific examples or examples are only a reference for describing the present invention in detail, and the present invention is not limited thereto, and may be implemented in various forms.

Also, unless defined otherwise, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description herein is for the purpose of effectively describing particular embodiments only and is not intended to limit the invention.

Also, the singular forms used in the specification and appended claims may also be intended to include the plural forms unless the context specifically dictates otherwise.

Also, when a part "includes" a certain component, it means that other components may be further included, rather than excluding other components, unless otherwise stated.

In this specification, when it is said that a part of a layer, film, region, plate, etc. is “on” or “on” another part, it is not only when it is “right on” another part, but also when there is another part in between. include

In the present specification, (meth)acrylic includes both acrylic and methacrylic.

Hereinafter, the etching resistant ink composition according to an embodiment of the present invention will be described in more detail.

The present invention provides an etch-resistant ink composition comprising a (meth)acrylic monomer having an alicyclic hetero ring, a polyfunctional (meth)acrylic monomer, a (meth)acrylic monomer including a phosphate group, and a photoinitiator.

According to an embodiment of the present invention, the (meth)acrylic monomer having an alicyclic hetero ring may be a (meth)acrylic monomer containing at least one alicyclic hetero ring in a side chain, and having the alicyclic hetero ring ( The alicyclic hetero ring of the meth)acrylic monomer contains 2 to 12 carbon atoms, specifically 3 to 10 carbon atoms, more specifically 4 to 6 carbon atoms, and at the same time nitrogen (N), oxygen (O) and sulfur (S). It may contain one or two heteroatoms selected from the group consisting of, specifically nitrogen and oxygen. Preferably, the (meth)acrylic monomer having an alicyclic hetero ring may be an acryloyl monomer having an alicyclic hetero ring. For example, the (meth)acrylic monomer having the alicyclic hetero ring may be one or a combination of two or more selected from Cyclic trimethylolpropane formal acrylate, Tetrahydrofurfuryl acrylate and 4-Acryloylmorpholine. In the case of an etch-resistant ink composition comprising a (meth)acrylic monomer having the alicyclic hetero ring, it may exhibit a lower viscosity than using an aromatic monomer, prevent shrinkage during curing, implement excellent insulation, and cure Excellent peelability can be realized in the post peeling process.

The polyfunctional (meth)acrylic monomer may contain 1 to 10, specifically, 2 to 7, polymerizable acrylate functional groups, optionally one or two selected from hydroxy, carboxyl, thiol, and amine. It may further contain the above functional groups. Specifically, the polyfunctional (meth)acrylic monomer is, for example, 1,6-hexanediol diacrylate (1,6-Hexanediol Diacrylate), 1,4-butanediol diacrylate (1,4-Butanediol diacrylate), di Propylene glycol diacrylate, carboxyethyl acrylate (2-Carboxyethyl acrylate), hydroxypivalic acid neopentyl glycol diacrylate (HPNDA), tetraethylene diacrylate (Tetraethylene) glycol diacrylate), dipropylene glycol diacrylate, tripropylene glycol diacrylate, polyethylene glycol diacrylate (PEGDA), trimethylolpropane triacrylate, trimethylol It may be one or a combination of two or more selected from propane trimethacrylate, pentaerythritol triacrylate, and dipentaerythritol hexaacrylate, and achieve the target physical properties In order to do this, various combinations of polyfunctional (meth)acrylic monomers may be mixed and used. In the case of the etch-resistant ink composition including the polyfunctional (meth)acrylic monomer, photocuring may be performed quickly and etching resistance may be excellently improved after curing.

According to an embodiment of the present invention, the (meth)acrylic monomer containing a phosphate group may be prepared by reacting a (meth)acrylic monomer containing a hydroxy functional group with phosphate and a phosphate ester, for example, 2- Hydroxyethyl (meth)acrylate phosphate, 2-methacryloyl oxyethyl phosphate, bis(2-methacryloyl oxyethyl) phosphate, 2-acryloyl oxyethyl phosphate, bis(2-acryloyloxy ethyl) phosphate, methyl-(2-methacryloyl oxyethyl) phosphate, ethyl methacryloyl oxy ethyl phosphate, methyl acryloyl oxy ethyl phosphate, ethyl acryloyl oxy ethyl phosphate can In the case of the etching-resistant ink composition including the (meth)acrylic monomer including the phosphate group, excellent peelability may be realized in the peeling process after curing.

According to an embodiment of the present invention, the (meth)acrylic monomer having an alicyclic hetero ring is 20 to 75% by weight, specifically 25 to 65% by weight, more specifically 30 to 55% by weight based on the total weight of the etch-resistant ink composition It may be included in weight %.

According to an embodiment of the present invention, the polyfunctional (meth)acrylic monomer is included in an amount of 20 to 75% by weight, specifically 25 to 65% by weight, more specifically 30 to 55% by weight based on the total weight of the etch-resistant ink composition. can

According to an embodiment of the present invention, the (meth)acrylic monomer including a phosphate group is 1 to 10% by weight, specifically 3 to 8% by weight, more specifically 4 to 7% by weight based on the total weight of the etch-resistant ink composition. may be included.

In the case of an etch-resistant ink composition containing a (meth)acrylic monomer having an alicyclic hetero ring that satisfies the above-described content range, a polyfunctional (meth)acrylic monomer and a (meth)acrylic monomer including a phosphate group, the low viscosity It is preferable in that it can implement excellent ejection property, fast photocuring property, and excellent etching resistance, and at the same time exhibit excellent peelability with respect to the stripping solution.

According to an embodiment of the present invention, the photoinitiator may be activated by light energy such as radiation or ultraviolet light to activate the double bond of the above-described acrylate-based monomer to initiate a curing reaction. Non-limiting examples of the photoinitiator include alpha-ketone compounds, acetophenone compounds, ketal compounds, aromatic sulfonyl chloride compounds, photoactive oxime compounds, benzophenone compounds, thioxanthone compounds, camphorquinone compounds , one or more selected from the group consisting of , halogenated ketone-based compounds, acyl phosphinoxide-based compounds, acyl phosphonate-based compounds, etc. may be used, and specifically, may be a photoinitiator that absorbs a wavelength region of 235 to 293 nm, , more specifically, one or two or more selected from 2-isopropylthioxanthone (ITX), TPO-L (Ethyl (2, 4, 6-trimethylbenzoyl) phebylphophineoxide), Ethyl 4-dimethyaminobenzoate (EPD), and 1-hydroxy-cyclohexylphenyl ketone It may be a combination, but is not limited thereto. The photoinitiator may be included in an amount of 0.1 to 20 wt%, specifically 1 to 15 wt%, more specifically 5 to 15 wt%, based on the total weight of the etch-resistant ink composition.

According to an embodiment of the present invention, the etch-resistant ink composition may have a viscosity value at 25° C. of less than 100 mPa·s, preferably less than 50 mPa·s, more preferably 1 to 35 mPa·s. When the above viscosity range is satisfied, it has an advantage that it is very easy to print a pattern on the copper foil layer because it exhibits excellent discharge property according to a low viscosity.

The present invention may provide a photocurable film prepared from the above-described etch-resistant ink composition. Specifically, a cured photocurable film may be prepared by irradiating light to the etching resistant ink composition, and the photocurable film may be prepared in various forms depending on a method of applying the composition. If the etching-resistant ink composition is printed in a specific pattern and irradiated with light, it is cured according to the printed pattern to produce a patterned photocurable film. In addition, the photocurable film may be prepared by additionally performing thermal curing for 30 minutes or less, preferably 1 second to 10 minutes or less at a temperature of 60 to 100 ℃, preferably 70 to 90 ℃ after irradiating light . The thickness of the film may be 0.1 to 100 μm, preferably 1 to 50 μm, but is not limited thereto.

According to an embodiment of the present invention, the photocurable film may exhibit rapid photocurability and excellent etching resistance. The photocurability can be evaluated by irradiating light until the stickiness disappears and measuring the time taken for curing, and the etching resistance can be evaluated by immersing the sample for a certain period of time (1 to 10 minutes) in a commonly used etching solution. It can be evaluated by the extent to which it occurs. In addition, the adhesion can measure the cross cut adhesion according to the ASTM D 3359 standard. Specifically, when the adhesion is 5B or more, the adhesion can be evaluated as excellent, and the peelability is the photocurable film at 50 ° C., 5% NaOH The time until the film is peeled off from the copper foil by immersion in an aqueous solution may be measured, and the specifically measured peelability test result is 10 minutes or less, preferably 8 minutes or less, more preferably 5 minutes or less, or 2 It may be less than or equal to minutes, and although the upper limit is not particularly limited, it may be greater than or equal to 1 second. The photocurability, etching resistance, and peelability described above can be adjusted according to the intensity of light used to prepare the photocurable film, and in an embodiment of the present invention, select and use a light intensity in the range of 10 to 25 mW/cm2 did

According to the present invention, a printed circuit board can be manufactured by using the above-described etching-resistant ink composition, and the printed circuit board can be used without much limitation as long as it is commonly used or a known method. Specifically, a photosensitive (photocuring) process step of preparing a non-conductive substrate on which a copper foil layer is formed, forming a pattern on the copper foil layer using the above-described etching-resistant ink composition, and photocuring by exposing a UV light source is performed. can Then, an etching process is performed to remove an unwanted copper foil by etching an area in which the etch-resistant ink composition does not form a pattern, and finally a peeling process is performed to remove the cured ink composition, so that on the non-conductive substrate A printed circuit board on which a conductive copper foil pattern is formed can be manufactured.

Specifically, the present invention comprises the steps of applying the above-described etching-resistant ink composition to form a predetermined pattern on the copper foil layer of the copper-clad laminate film, and irradiating light to form a patterned coating layer; etching a region where the coating layer is not formed; and removing the coating layer; may provide a method of manufacturing a printed circuit board comprising a.

The copper-clad laminated film may be a film in which a copper-clad layer is formed on a non-conductive substrate, and the non-conductive substrate may be used without significant limitation as long as it is a commonly used or known non-conductive substrate.

The method of applying the etch-resistant ink composition may be performed by selecting a commonly used or known method, and specifically spin coating, printing, inkjet printing, or aerosol patterning may be used, but is not limited thereto.

The light source used in the light irradiation is not particularly limited as long as it is a light source in a wavelength region in which the etching-resistant ink composition can be cured, and a light source used in a photosensitive process for manufacturing a printed circuit board can be used. . Specifically, a UV lamp having a wavelength range of 230 to 330 nm may be used, but is not limited thereto. In addition, in the step of forming the patterned application layer by irradiating light, a pattern mask may be used, and the patterned application layer may be formed by printing the pattern as described above, but if it is a commonly used or known method, it is greatly limited can be used without

According to an embodiment of the present invention, in the step of forming the patterned coating layer, after light irradiation at a temperature of 60 to 100 ℃, preferably 70 to 90 ℃ for 30 minutes or less, preferably for 1 second to 20 minutes or less It may be to further perform thermal curing. As the thermosetting process is further performed, adhesiveness may be further improved to have excellent etching resistance. In addition, it may optionally include a step of removing the uncured ink composition by not irradiating with light.

The step of etching the area where the coating layer is not formed is a step of etching the remaining copper foil portion except for the patterned coating layer using an etching solution, and the etching solution may be commonly used or known. and specifically, an oxidizing agent for copper, for example, hydrogen peroxide, ammonium persulfate and/or hydrochloric acid/sodium chlorate aqueous solution, etc. may be used, but is not limited thereto.

Subsequently, the step of removing the patterned coating layer is a step of peeling the coating layer cured by light irradiation from the copper foil using a peeling solution, and the peeling solution can peel the coating layer from the copper foil and is commonly used or As long as it is known, it can be used without significant restrictions. In one embodiment of the present invention, an alkaline solution, specifically, 1 to 10% NaOH aqueous solution is used, but is not limited thereto. The coating layer formed by using the etch-resistant ink composition according to an embodiment of the present invention can be easily peeled off, so that workability in the manufacturing process can be improved more efficiently. A printed circuit board on which a desired copper foil pattern is formed can be manufactured through the above-described steps.

Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples. However, the following examples and comparative examples are merely examples for explaining the present invention in more detail, and the present invention is not limited by the following examples and comparative examples.

[Method of measuring physical properties]

1) Photocurability evaluation: Based on the following evaluation criteria, the photocuring time until curing of 5 levels is recorded in Table 2 below.

- Uncured: 1

-Only partly hardened: 2

-Cured, but unreacted monomer comes out : 3

-There is stickiness, but nothing comes out : 4

-No stickiness: 5

2) Adhesion evaluation: Record the curing time according to the light intensity until the adhesive evaluation result is 5B (the cut surface is clean and the square of the grid is not separated) by cross-cutting according to ASTM D 3359 standard. 2 is shown.

3) Etching resistance evaluation: The photocurable films prepared in Examples and Comparative Examples were immersed in hydrochloric acid/sodium chlorate aqueous solution, which is an etching solution at 50° C., for 5 minutes to evaluate etching resistance. When the photocurable film was immersed in the etching solution and then rubbed with a cotton swab, the curing time according to the light intensity until the evaluation result of the state in which the sample was not damaged was recorded and shown in Table 2 below.

4) Peelability evaluation: Specimens for which etching resistance was evaluated for the photocurable films prepared in Examples and Comparative Examples were immersed in a 5% NaOH aqueous solution, which is a peeling solution, under a temperature condition of 50° C., and the time until all the specimens were peeled off measured.

5) Viscosity: The ink compositions prepared in Examples and Comparative Examples were measured at a temperature of 25±1° C. with an AND vibration low-viscosity viscometer.

[Examples 1 to 5 and Comparative Examples 1 to 6]

An etch-resistant ink composition was prepared according to Table 1 (Examples 1 to 2 and Comparative Examples 1 to 3), and the prepared ink composition was bar-coated and coated to a thickness of 30 μm, and then light with a UV LED lamp of 365 nm A photocurable film was prepared on a CCL substrate by curing (Examples 3 to 4 and Comparative Examples 4 to 6), and the light intensity and light irradiation time (3 sec, 5 sec, 10 sec, 15 sec) were measured according to Table 2 below. The test was carried out by adjusting.

In addition, the photocurable film prepared according to Example 4 was thermally cured in an oven at 80° C. for 10 minutes to prepare a photocurable film according to Example 5.

(weight%) ACMO TMPTA HMP ITX Viscosity (cP) Example 1 41.86 40.81 5.09 12.24 33 Example 2 52.30 30.36 5.09 12.24 29 Comparative Example 1 - 82.7 5.09 12.21 88 Comparative Example 2 82.7 - 5.09 12.21 25 Comparative Example 3 44.12 43.01 - 12.87 31

- ACMO: Acryloylmorphonile

- TMPTA : Trimethylol propane triacrylate

- HMP : 2-Hydroxyethyl methacrylate phosphate

- ITX: 2-isopropylthioxanthone

physical properties light intensity
[mW/cm2] Example 3 Example 4 Example 5 Comparative Example 4 Comparative Example 5 Comparative Example 6 ink composition Example 1 Example 2 Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 photocuring time 10.84 10 seconds 10 seconds 10 seconds 10 seconds 15 seconds 10 seconds 18.45 10 seconds 10 seconds 10 seconds 5 seconds 15 seconds 10 seconds 24.3 3 seconds 3 seconds 3 seconds 3 seconds 10 seconds 3 seconds adhesion 10.84 10 seconds 10 seconds 10 seconds 15 seconds 15 seconds 10 seconds 18.45 10 seconds 10 seconds 5 seconds 10 seconds 15 seconds 10 seconds 24.3 3 seconds 3 seconds 3 seconds 10 seconds 10 seconds 3 seconds Etch resistance 10.84 5 seconds 5 seconds 5 seconds 15 seconds 15 seconds 10 seconds 18.45 5 seconds 5 seconds 3 seconds 10 seconds 15 seconds 10 seconds 24.3 3 seconds 3 seconds 3 seconds 10 seconds 10 seconds 5 seconds peelability
(5 seconds) 10.84 23 seconds 37 seconds 31 seconds 54 seconds 42 seconds 2 minutes and 6 seconds 18.45 1 minute 40 seconds 4 minutes 52 seconds 4 minutes and 56 seconds 6 minutes and 10 seconds 5 minutes and 34 seconds 8 minutes 40 seconds 24.3 1 minute 18 seconds 5 minutes and 26 seconds 5 minutes 10 seconds 9 minutes and 39 seconds 8 minutes 41 seconds 15 minutes 7 seconds

As shown in Tables 1 and 2, the etch-resistant ink composition prepared in Examples exhibited a viscosity of 50 or less to realize excellent ejection properties, and furthermore, compared to Comparative Examples, faster photocuring time, etching resistance, and peelability were achieved. It was confirmed that the In particular, all of the examples can be photocured at an irradiation time of 10 seconds or less, preferably 5 seconds or less, and photocuring can be made in just 3 seconds under the condition that the light intensity is 24.3 mW/cm 2 , and the peelability is also 8 minutes , preferably in 6 minutes or less, especially in the case of Example 1, it was confirmed that the results were within 2 minutes.

Furthermore, it was confirmed that all of the Examples had excellent etching resistance under the irradiation time condition of 5 seconds or less, and it was confirmed that Example 5 exhibited more improved etching resistance by additionally performing thermal curing.

Through this, it can be confirmed that the etching-resistant ink composition according to an embodiment of the present invention has a fast curing time and excellent etching resistance, and at the same time has excellent peelability, so that more improved workability can be realized in the printed circuit board manufacturing process. there was.

As described above, the present invention has been described with reference to specific matters and limited examples and drawings, but these are only provided to help a more general understanding of the present invention, and the present invention is not limited to the above embodiments, and the present invention is not limited to the above embodiments. Various modifications and variations are possible from these descriptions by those of ordinary skill in the art.

Therefore, the spirit of the present invention should not be limited to the described embodiments, and not only the claims to be described later, but also all those with equivalent or equivalent modifications to the claims will be said to belong to the scope of the spirit of the present invention. .

Claims (14)

An etch-resistant ink composition comprising a (meth)acrylic monomer having an alicyclic hetero ring, a polyfunctional (meth)acrylic monomer, a (meth)acrylic monomer including a phosphate group, and a photoinitiator. According to claim 1,
The alicyclic heterocyclic ring of the (meth)acrylic monomer having the alicyclic heterocyclic ring contains 4 to 6 carbon atoms and has one or two heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur, etching resistant ink composition. The method of claim 1,
The polyfunctional (meth)acrylic monomer is any one selected from dipropylene glycol diacrylate, carboxyethyl acrylate, hydroxy pivalic acid neopentyl glycol diacrylate, trimethylolpropane triacrylate and trimethylolpropane trimethacrylate One or more etch resistant ink compositions. According to claim 1,
The (meth)acrylic monomer containing the phosphate group is 2-hydroxyethyl (meth)acrylate phosphate, 2-methacryloyl oxyethyl phosphate, bis(2-methacryloyloxyethyl) phosphate, 2-acryloyl yloxyethyl phosphate, bis(2-acryloyl oxyethyl) phosphate, methyl-(2-methacryloyl oxyethyl) phosphate, ethyl methacryloyl oxyethyl phosphate, methyl acryloyl oxyethyl phosphate and ethyl acrylic Any one or two or more etch-resistant ink compositions selected from loyl oxy ethyl phosphate. According to claim 1,
The (meth)acrylic monomer having the alicyclic hetero ring is included in an amount of 30 to 55% by weight based on the total weight of the etching resistant ink composition. The method of claim 1,
The polyfunctional (meth)acrylic monomer is included in an amount of 30 to 55% by weight based on the total weight of the etching resistant ink composition. According to claim 1,
The (meth)acrylic monomer including a phosphate group is included in an amount of 1 to 10% by weight based on the total weight of the etching resistant ink composition. According to claim 1,
The photoinitiator is an etch-resistant ink composition comprising 5 to 15% by weight based on the total weight of the etch-resistant ink composition. The method of claim 1,
The etch-resistant ink composition has a viscosity value of less than 50 mPa·s at 25°C. 10. A photocurable film prepared from the etch-resistant ink composition of any one of claims 1 to 9. 11. The method of claim 10,
The photocurable film is a photocurable film having an adhesiveness of 5B or more according to ASTM D 3359 standard. 11. The method of claim 10,
The photocurable film is a photocurable film having a peelability test result value of 8 minutes or less in 50 ℃, 5% NaOH aqueous solution. 10. A method comprising: applying the etching-resistant ink composition of any one of claims 1 to 9 to form a predetermined pattern on the copper foil layer of the copper-clad laminate film, and irradiating with light to form a patterned coating layer;
etching a region where the coating layer is not formed; and
removing the coating layer;
A method of manufacturing a printed circuit board comprising a. 13. The method of claim 12,
In the step of forming the patterned coating layer, the method of manufacturing a printed circuit board to further perform thermal curing after light irradiation.