KR20200139632A - Curable resin composition, dry film, cured product and printed wiring board - Google Patents

Abstract

It is an object of the present invention to provide a curable resin composition in which the variation in the film thickness of a coating film before and after drying is small even in the case of a thin film and which does not cause a copper show-through phenomenon, wherein the curable resin composition according to the present invention contains a curable resin and an extender pigment. The glossiness of the curable resin composition in a coating film having a film thickness of 12 μm after curing is in the range of 0.5 or more and 40.0 or less at 60°. When 0.3 g of the curable resin composition is mixed with 30 g of propylene glycol monomethyl ether acetate, the average particle diameter (D_50), measured with Microtrac, is 0.1 μm or more and 1.0 μm or less. In addition, the specific surface area (CS) is 10.0 m^2/ml or more.

Description

Curable resin composition, dry film, cured product, and printed wiring board {CURABLE RESIN COMPOSITION, DRY FILM, CURED PRODUCT AND PRINTED WIRING BOARD}

The present invention relates to a curable resin composition. Further, the present invention relates to a dry film, a cured product, and a printed wiring board using the curable resin composition.

Currently, most of the solder resists of printed wiring boards use liquid alkali-developed solder resist ink from the viewpoint of high precision and high density. Specifically, an image is formed by exposing and developing a coating film after printing and drying the ink, and heat curing. It is obtained by

By the way, it is known that roughening of the solder resist layer improves solder adhesion resistance and wiring concealability during solder flow. Further, since the roughened solder resist layer has an appropriate glossiness, good design is obtained. For example, Patent Document 1 proposes that the solder resist layer is reduced in gloss by roughening by adding a gloss remover to the photosensitive resin composition.

In addition, in recent years, from the viewpoint of improving the yield at the time of component mounting, the film thickness of the coating film after drying or curing has become thinner (for example, Patent Document 2). In recent years, more rigorous film thickness management has been required for thin films.

Japanese Laid-Open Patent Publication No. Hei 9-157574 Japanese Laid-Open Patent No. 2004-264560

In general, extender pigments and resins are contained in the curable resin composition for the purpose of reducing warpage during component mounting or improving heat resistance. However, in the curable resin composition, a plurality of components other than extender pigments and resins are mixed in order to satisfy various required characteristics, and therefore, when the mixing state of each component is insufficient, there is a case where a concentration unbalance occurs in the curable resin composition. Therefore, the film thickness of the pre-dry coating film (hereinafter also referred to as the pre-dry coating film) applied to the substrate using the curable resin composition varies. In particular, in the case of a thin film, for example, the metal (copper) wiring of the underlying substrate The problem was the appearance defect caused by "copper reflection" that became uneven and visible. In addition, when the cured coating film (hereinafter, also referred to as a cured coating film) was low gloss, the problem of the appearance defect was more remarkable in the cured coating film. This is presumed to be that the lower the gloss of the coating film is, the more the contrast becomes, and the gloss of the base metal (copper) wiring becomes more uneven, making it easier to see through.

If the film thickness of the pre-drying film is large, the film thickness of the film after drying (hereinafter, also referred to as a dry film) or the film after curing may also increase. Therefore, especially when using an expensive substrate, the film of the pre-drying film When NG is determined based on the size of the thickness deviation and the deviation portion is repaired, the manufacturing process becomes complicated, and there is a concern that productivity may decrease. In addition to the small variation in the film thickness of the coating film after drying, in addition to the small variation in the film thickness of the coating film before drying, it is sometimes considered important.

Accordingly, an object of the present invention is to provide a curable resin composition in which the variation in the film thickness of the pre-dry coating film or the dry coating film is small even in the case of a thin film, and does not cause a copper see-through phenomenon. It is also an object of the present invention to provide a dry film having a resin layer made of a dry coating film of the resin composition, a cured product of the resin composition or the resin layer of the dry film, and a printed wiring board having the cured product. .

As a result of intensive research, the inventors of the present invention found that in the curable resin composition containing powder, in particular, an extender pigment, specifically controlling the value measured using microtracks, not only the value of the average particle diameter (D ₅₀ ), but also the specific surface area ( CS) is also adjusted so that the influence of the powder on the surface of the coating film before or after drying is less, and as a result, the variation in the film thickness of the coating film before or after drying is small even in the case of a thin film, and the curability does not cause copper penetration. It discovered that a resin composition was obtained, and came to complete this invention.

That is, the curable resin composition according to the present invention is a curable resin composition containing a curable resin and an extender pigment,

The glossiness of 60° in the cured coating film having a film thickness of 12 μm after curing of the curable resin composition is in the range of 0.5 to 40.0,

0.3 g of the curable resin composition was mixed with 30 g of propylene glycol monomethyl ether acetate, and the value of the average particle diameter (D ₅₀ ) when measured using Microtrac was 0.1 μm or more and 1.0 μm or less, and the specific surface area (CS) is It is characterized by more than 10.0㎡/ml.

In the embodiment of the present invention, it is preferable that the average spacing (Sm) of the unevenness of the coating film thickness after drying of the curable resin composition is in the range of more than 0 µm and not more than 12.0 µm.

In the embodiment of the present invention, it is preferable that the maximum height (Ry) of the coating film thickness after drying of the curable resin composition is in the range of more than 0 µm and not more than 8.0 µm.

In the embodiment of the present invention, it is preferable that the extender pigment is at least one of silica and barium sulfate.

In an embodiment of the present invention, it is preferable that the silica contains amorphous silica having an oil absorption amount of 180 to 350 ml/100g.

In the embodiment of the present invention, it is preferable that the curable resin contains a carboxyl group-containing resin.

In the embodiment of the present invention, it is preferable that the curable resin contains two or more types of carboxyl group-containing resins.

In an embodiment of the present invention, it is preferable that at least one of the above two or more carboxyl group-containing resins contains a carboxyl group-containing copolymer resin.

A dry film according to another embodiment of the present invention is characterized by comprising a support film and a resin layer comprising a dry coating film of the curable resin composition formed on the support film.

A cured product according to another embodiment of the present invention is characterized in that it is obtained by curing the curable resin composition or the resin layer of the dry film.

A printed wiring board according to another embodiment of the present invention includes the cured product.

According to the present invention, it is to provide a curable resin composition in which there is little variation in the film thickness of the pre-drying coating film or the dry coating film even in the case of a thin film and no copper penetration phenomenon occurs. Further, according to the present invention, it is possible to provide a dry film having a resin layer made of a dry coating film of the resin composition, a cured product of the resin layer of the resin composition or the dry film, and a printed wiring board having the cured product.

Fig. 1 is an explanatory view when the deviation of a dry coating film is measured by step analysis of a surface roughness measuring instrument in Examples.

[Curable resin composition]

The curable resin composition according to the present invention contains a curable resin and an extender pigment. The curable resin composition according to the present invention may further contain a photopolymerization initiator, a sensitizer, a thermosetting catalyst, a colorant, and the like, as long as it satisfies the following physical properties. Further, the curable resin may contain any one of a thermosetting resin, a carboxyl group-containing resin, and a photopolymerizable monomer, or may be a combination of plural types. The curable resin composition according to the present invention satisfies the following physical properties, so that it is possible to obtain a coating film before drying or after drying that has little variation or sagging at the time of application, and a small variation in film thickness even when it is a thin film. It is possible to obtain a cured coating film in which no copper see-through phenomenon occurs. In the present invention, a thin film refers to a case where the thickness of the coating film is usually 20 μm or less before drying and 12 μm or less after drying or after curing.

[Properties]

The curable resin composition of the present invention has a glossiness of 60° in a cured coating film having a film thickness of 12 μm after curing within a range of 0.5 to 40.0, preferably 0.8 to 35.0, more preferably 1.0 to 20.0 And more preferably 1.0 or more and 10.0 or less, and particularly preferably 2.0 or more and 6.0 or less.

In addition, glossiness can be measured according to JIS Z 8741. A specific measurement method of glossiness will be described. As a premise, in the case of an incidence angle of 60° on a surface having a refractive index of 1.067, an intensity of light having a reflectance of 10% is assumed to be 100, and an intensity of light having a reflectance of 0% is assumed to be 0. Accordingly, a value of 1/100 of the intensity of light having a reflectance of 10% corresponds to gloss 1. Using a reflectometer under geometric conditions with an incidence angle of 60°, the intensity of light on the surface of the cured coating film provided on the substrate is measured. Then, the glossiness is calculated by dividing the intensity of the obtained light by a value of 1/100 of the intensity of the light having a reflectance of 10% described above. Briefly, using a digital variable angle gloss meter (Micro-Tri-Gloss, manufactured by BYK Gardener), the glossiness of each angle can be measured on the surface of the cured coating film provided on the substrate. In addition, "60 degree glossiness (Gs (60 degree))" is the value of the glossiness when the measurement conditions were set as incident angle = 60 degree and light-receiving angle = 60 degree.

The cured coating film in the present invention refers to a coating film in which the curable resin composition is cured by performing at least one of photocuring and thermal curing. On the other hand, the dry coating film in the present invention refers to a coating film in which the curable resin composition is dried by performing heat drying. As a thermal drying method, the surface is buff-rolled and then printed on a 35 μm-thick 300 mm×150 mm copper foil substrate so that the film thickness is 12 μm after drying, followed by thermal drying using a hot air circulation drying furnace. As a printing plate for screen printing, it is preferable to use a polyester plate of 100 to 200 mesh (with bias), and a polyester plate of 150 to 180 mesh (with bias) from the viewpoint of film thickness adjustment. It is more preferable. As a drying condition, 15 to 90 minutes are mentioned at a temperature of 60-100 degreeC, for example. In addition, DF610 manufactured by Yamato Chemical Co., Ltd. etc. is mentioned as an apparatus.

On the other hand, as a photocuring method, the dry coating film formed as described above is photocured with an active energy ray irradiation, specifically a UV conveyor using a high-pressure mercury lamp. As the irradiation amount, 1,000 to 2,000 mJ/cm 2 is mentioned, for example. Moreover, QRM-2082 manufactured by Oak Seisakusho Co., Ltd. is mentioned as an apparatus.

In addition, as a thermal curing method, on a 35 μm thick 300 mm × 150 mm copper foil substrate with a buff roll polished surface, after curing, the film thickness is 12 μm by screen printing, followed by heat using a hot air circulation drying furnace. Hardens. As the printing plate for screen printing, it is preferable to use a polyester plate of 100 to 200 mesh (with bias) from the viewpoint of adjusting the film thickness, and a polyester plate of 150 to 180 mesh (with bias) is used. It is more preferable. Thermal curing conditions include, for example, 30 to 90 minutes at a temperature of 100 to 220 °C.

As a drying apparatus used at the time of drying or heat curing, DF610 manufactured by Yamato Chemical Co., Ltd. etc. is mentioned. In addition, when measuring the glossiness in the present invention, it is measured using a cured coating film formed without performing a developing step.

In addition, the method of confirming whether the cured coating film is formed in the present invention can be confirmed by the following method. That is, a waste containing isopropyl alcohol (IPA) was placed on the surface of the cured coating film in an environment of 25°C and 50% RH, and a weight of 500 g was placed on it and allowed to stand for 1 minute, and then the waste was removed. , It is judged that the state in which all or part of the resin layer is not adhered to the surface in contact with the cured coating film of the waste is "cured state", that is, the cured coating film has been formed. On the other hand, the method of confirming whether a dry coating film has been formed in the present invention is a condition in which the curable resin composition does not adhere to the finger when the application surface of the curable resin composition is touched with a finger, that is, a dry coating film is formed. Judge.

The curable resin composition of the present invention has an average particle diameter (D ₅₀ ) of 0.1 µm or more and 1.0 µm or less, and from the viewpoint of further suppressing the copper penetration phenomenon, preferably 0.1 µm or more and 0.8 µm or less, and more preferably 0.1 It is not less than µm and not more than 0.5 µm.

In addition, the curable resin composition of the present invention has a specific surface area (CS) of 10.0 m 2 /ml or more, has a lower gloss, and reduces the deviation of the film thickness of the coating film before and after drying even in the case of a thin film, and suppresses the copper penetration phenomenon. In this case, it is preferably 11.5 m 2 /ml or more and 30.0 m 2 /ml or less, and more preferably 13.0 m 2 /ml or more and 25.0 m 2 /ml or less.

If the value of the average particle diameter (D ₅₀ ) as the curable resin composition is 0.1 µm or more and 1.0 µm or less, and the specific surface area (CS) is 10.0 ㎡/ml or more, the deviation of the film thickness of the coating film before or after drying even in the case of a thin film is observed. By making it small, the copper penetration phenomenon can be suppressed. This is not necessarily obvious, but it is estimated as follows. That is, since the specific surface area (CS) is within the above range, the powder contained in the composition maintains a high dispersion state, and as a result, the composition does not cause sagging even when forming a used thin film, and is included The powder has little influence on the surface of the coating film before or after drying, and as a result, it is thought that the copper seepage phenomenon is suppressed even in a low-gloss thin film. However, it is an area of speculation and is not necessarily limited thereto.

In the present invention, the average particle diameter (D ₅₀ ) as the curable resin composition assumes that the powders such as extender pigments contained in the composition are a group of powders, and the particle size distribution is required. That is, when the cumulative curve is obtained with the total volume of one powder group assumed as described above as 100%, the particle diameter at the point at which the cumulative curve becomes 50% is 50% diameter (㎛), and the average particle diameter ( D ₅₀ ). On the other hand, the specific surface area (CS) is the surface area per unit volume when the particle shape in the composition is assumed to be spherical. The above-described average particle diameter (D ₅₀ ) and specific surface area (CS) refer to those calculated by the following measurements, respectively. In addition, the specific surface area (CS) (m2/ml) of the present invention has a different meaning from the specific surface area (m2/g) measured by a BET type or other surface area measuring device. First, prepare the following equipment and equipment.

Particle size distribution meter: Nikkiso Corporation Microtrack MT3300EX

・Circulation device: ASVR manufactured by Nikkiso Co., Ltd.

Next, the measurement conditions are input in the following procedure. Start Microtrack's attached software ("Particle size distribution measurement"), proceed from the SET UP screen, and set the time with the option of setting the measurement conditions. Set zero time is 30sec., measurement is 30sec., and number of times is measured twice. Next, enter the analysis conditions. In the analysis information, the particle refractive index is 1.81 (fixed value: the average value of the refractive indices of all inorganic substances), the transmittance in the characteristics of the particles is transmitted, and the shape is made non-spherical. In addition, PMA (propylene glycol monomethyl ether acetate) is selected from the solvent information, and the solvent refractive index is set to 1.4. Next, enter the scale setting. In the particle diameter range, the minimum particle diameter is set to 0.021 μm and the maximum particle diameter is set to 704 μm. Next, input the sampling system. Set ASVR cleaning times 4 times, flow rate 50%, ultrasonic output 40W, ultrasonic time 300sec. When all measurement conditions are entered, click Save to close the setting of measurement conditions.

Subsequently, the sample is adjusted in the following procedure. 0.3 g of a sample (curable resin composition) is weighed into a screw bottle, and 30 g of propylene glycol monomethyl ether acetate is added little by little using a dropper, and the sample is dissolved by shaking the screw bottle to prepare an adjusted sample. Adjustment samples do not undergo external dispersion or pre-dispersion. Next, the adjustment sample is measured. Click the particle size distribution measurement in the software supplied with MicroTrack to open the sample loading screen. Drop a few drops of the adjusted sample into the sample inlet of the main body using a dropper. When a red indicator bar is displayed on the sample loading screen, an adjusted sample is dropped into the sample inlet until it falls within the range of red to green. When it falls within the green range, the measurement button is pushed to start the measurement. From the adjustment of the sample to the measurement of the adjusted sample, it is carried out within 5 minutes. The values of the cumulative average diameter 50% and the area average diameter (MA), which are displayed as the measurement result, are read, respectively. The value of the cumulative average diameter of 50% is taken as the value of the average particle diameter (D ₅₀ ) measured by microtrack. In addition, CS = 6/MA is calculated. The calculated value of CS is taken as the value of the specific surface area measured by microtrack.

In addition, MA is calculated by the following formula.

(a _i : surface area per particle, d _i : particle diameter per particle, v _i : volume per particle)

In order to make the value of the average particle diameter (D ₅₀ ) as the curable resin composition be 0.1 μm or more and 1.0 μm or less, and the specific surface area (CS) is 10.0 m 2 /ml or more, a known and common method can be applied. For example, the composition And optimizing the selection of the components in the composition, the blending amount thereof, and the dispersion method of the powder or resin in the composition.

In the curable resin composition of the present invention, the average spacing (Sm) of the irregularities of the coating film thickness after drying is preferably in the range of more than 0 µm and 12.0 µm or less, more preferably in the range of 1.0 µm or more and 11.0 µm or less, and further It is preferably in the range of 2.0 µm or more and 8.0 µm or less.

In the curable resin composition of the present invention, the maximum height (Ry) of the thickness of the coating film after drying is preferably in the range of more than 0 µm and not more than 8.0 µm, more preferably in the range of 0.1 µm or more and 6.5 µm or less, and more preferably Is in the range of 0.2 µm or more and 2.5 µm or less.

When the average interval (Sm) and the maximum height (Ry) of the irregularities of the coating film thickness after drying of the curable resin composition are within the above numerical range, the variation in film thickness becomes smaller. Although this is not necessarily clear, it is thought as follows. That is, the surface condition of the dry coating film is also stable in that the average interval and maximum height of the irregularities of the coating film thickness are constant, and as a result, the cured coating film is low-gloss, and the deviation is small even in the case of a thin film, and further suppresses the copper seepage phenomenon. I think it is. In the present invention, the average interval (Sm) and maximum height (Ry) of the irregularities of the coating film thickness are measured after drying, and then allowed to stand at room temperature for 30 minutes.

In the present invention, the above-described "average spacing of irregularities (Sm)" and "maximum height (Ry)" mean values measured by a measuring device conforming to JIS B0601-1994, respectively. Hereinafter, a specific measurement method will be described. The average spacing (Sm) and the maximum height (Ry) of the irregularities can be measured using a shape measurement laser microscope (eg, VK-X100 manufactured by Keyence Corporation). After starting the shape measurement laser microscope (copper VK-X100) body (control unit) and the VK observation application (VK-H1VX manufactured by Keyence Corporation), a sample (dry coating formed on a substrate, etc.) to be measured on the xy stage Put it on. Turn the lens revolver of the microscope unit (VK-X110 manufactured by Keyence Corporation) to select an objective lens with a magnification of 10 times, and adjust the focus and brightness approximately in the image observation mode of the VK observation application (VK-H1VX). . Operate the x-y stage so that the part you want to measure on the sample surface is in the center of the screen. The objective lens with a magnification of 10 times is changed to a magnification of 50 times, and the autofocus function of the image observation mode of the VK observation application (VK-H1VX) focuses on the surface of the sample. By selecting the simple mode of the shape measurement tab of the VK observation application (VK-H1VX) and pressing the measurement start button, the surface shape of the sample can be measured and a surface image file can be obtained. After starting up the VK analysis application (VK-H1XA manufactured by Keyence Corporation) and displaying the obtained surface image file, tilt correction is performed.

In addition, the observation measurement range (horizontal) in the measurement of the surface shape of the sample is 270 µm. Display the line roughness window, select JIS B0601-1994 in the parameter setting area, select a horizontal line from the measurement line button, display a horizontal line in an arbitrary place in the surface image, and press the OK button to The values of the average spacing (Sm) (µm) and the maximum height (Ry) (µm) are obtained. Further, horizontal lines were displayed at four other locations in the surface image, and values of the average spacing (Sm) (µm) and maximum height (Ry) (µm) of the respective uneven surfaces were obtained. The average value of the obtained five numerical values is calculated, and the average interval (Sm) value of the uneven surface of the sample surface and the maximum height (Ry) value are used.

In addition, since Sm and Ry of the dry coating film are generally smoother than the surface of the cured film, the values of Sm and Ry are not affected by the type of the substrate. As the substrate, a known conventional one can be used, but it is preferable to use a glass substrate.

A known conventional technique can be applied to make the coating film thickness after drying of the curable resin composition within the range of the average interval (Sm) and the maximum height (Ry) of the specific irregularities described above, for example, components such as organic solvents in the composition. And optimizing the selection, the blending amount, and dispersion method, or combinations of the above-described contents. In addition, to make the glossiness of 60° in the cured coating film having a coating film thickness of 12 µm of the curable resin composition within a specific range, similarly well-known and common techniques can be applied, for example, a coarse extender pigment having an average particle diameter. And mixing of a plurality of resins having poor compatibility or the like.

Hereinafter, each component constituting the curable resin composition according to the present invention will be described.

[Curable resin]

Examples of the curable resin include a thermosetting resin that contributes to a thermosetting reaction by heating, a photocurable resin that contributes to a photocuring reaction by irradiation with light, and a photocurable thermosetting resin that contributes to any reaction.

Here, the curable resin preferably contains a thermosetting resin and a photocurable resin, and even when any curable resin is contained, the thermosetting resin includes a carboxyl group-containing resin and a plurality of cyclic ether groups or cyclic thioether groups in the molecule. It is more preferable to contain the compound.

The blending amount of the curable resin is, in terms of solid content per total amount of the curable resin composition, preferably 20 to 80% by mass, more preferably 25 to 75% by mass, and still more preferably 50 to 70% by mass. When the blending amount of the curable resin is within the above range, a more excellent cured product can be obtained. Hereinafter, each curable resin is demonstrated.

[Thermosetting resin]

Any known thermosetting resin can be used. When the curable resin composition contains a thermosetting resin, the heat resistance of the cured coating film can be improved. Examples of thermosetting resins include amino resins such as melamine resins, benzoguanamine resins, melamine derivatives, and benzoguanamine derivatives, isocyanate compounds, block isocyanate compounds, cyclocarbonate compounds, epoxy compounds, oxetane compounds, episulfide resins, Known thermosetting resins, such as bismaleimide and carbodiimide resin, can be used. Particularly preferred is a thermosetting resin having a plurality of cyclic ether groups or cyclic thioether groups (hereinafter, abbreviated as cyclic (thio) ether groups) in the molecule. Thermosetting resins may be used alone or in combination of two or more.

The thermosetting resin having a plurality of cyclic (thio) ether groups in the molecule is a compound having a plurality of cyclic (thio) ether groups of 3, 4 or 5 membered rings in the molecule, and for example, a compound having a plurality of epoxy groups in the molecule, that is, A polyfunctional epoxy compound, a compound having a plurality of oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound, a compound having a plurality of thioether groups in the molecule, that is, an episulfide resin, may be mentioned.

Such epoxy resins include, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol. A novolak type epoxy resin, a novolac type epoxy resin of bisphenol A, a biphenyl type epoxy resin, a naphthalene type epoxy resin, a dicyclopentadiene type epoxy resin, a triphenylmethane type epoxy resin, and the like.

Commercially available epoxy resins include, for example, jER 828, 806, 807, YX8000, YX8034, 834 manufactured by Mitsubishi Chemical Corporation, YD-128, YDF-170 manufactured by Nittetsu Chemical & Matterial Corporation, ZX-1059, ST-3000, EPICLON 830, 835, 840, 850, N-730A, N-695 manufactured by DIC Corporation, and RE-306 manufactured by Nippon Kayaku Corporation.

Examples of the polyfunctional oxetane compound include bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3-ethyl-3-oxetanylmethoxy)methyl]ether, 1,4 -Bis[(3-methyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, (3-methyl-3-oxeta Nyl)methylacrylate, (3-ethyl-3-oxetanyl)methylacrylate, (3-methyl-3-oxetanyl)methylmethacrylate, (3-ethyl-3-oxetanyl)methylmethacrylate In addition to polyfunctional oxetanes such as acrylates or their oligomers or copolymers, oxetane alcohol and novolac resins, poly(p-hydroxystyrene), cardo type bisphenols, calixarenes , Calixresorcin arenes, or etherified products with a resin having a hydroxyl group such as silsesquioxane. In addition, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth)acrylate, etc. are also mentioned.

Examples of the compound having a plurality of cyclic thioether groups in the molecule include bisphenol A episulfide resins. Further, an episulfide resin obtained by substituting a sulfur atom for an oxygen atom in the epoxy group of a novolak type epoxy resin can also be used using the same synthesis method.

Examples of amino resins such as melamine derivatives and benzoguanamine derivatives include methylolmelamine compounds, methylolbenzoguanamine compounds, methylolglycoluril compounds, and methylolurea compounds.

As the isocyanate compound, a polyisocyanate compound can be blended. Polyisocyanate compounds include 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m- Aromatic polyisocyanates such as xylylene diisocyanate and 2,4-tolylene dimer; Aliphatic polyisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate) and isophorone diisocyanate; Alicyclic polyisocyanates such as bicycloheptane triisocyanate; And the adduct body, biuret body and isocyanurate body of the isocyanate compound mentioned above.

As the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent can be used. As an isocyanate compound which can react with an isocyanate blocking agent, the polyisocyanate compound etc. mentioned above are mentioned, for example. As an isocyanate blocking agent, For example, a phenol type blocking agent; Lactam-based blocking agents; Active methylene-based blocking agents; Alcohol-based blocking agents; Oxime block agents; Mercaptan-based blocking agents; Acid amide block agents; Imide-based blocking agents; Amine block agents; Imidazole-based blocking agents; And immigration block systems.

The blending amount of the thermosetting resin is preferably 0.5 to 2.5 mol, and more preferably, the number of functional groups of the thermosetting component to react with respect to 1 mol of carboxyl group contained in the carboxyl group-containing resin when the composition contains a carboxyl group-containing resin described later. It is 0.8 ~ 2.0㏖.

As the thermosetting component, it is preferable to contain an alkali-soluble resin having an alkali-soluble group from the viewpoint of imparting alkali developability to the composition. Examples of the alkali-soluble resin include a compound having two or more phenolic hydroxyl groups, a carboxyl group-containing resin, a compound having a phenolic hydroxyl group and a carboxyl group, and a compound having two or more thiol groups. Among them, since the adhesion to the base is improved, a carboxyl group-containing resin or a phenol resin is preferable, and since developability is particularly excellent, a carboxyl group-containing resin is more preferable. Hereinafter, a carboxyl group-containing resin will be described.

[Carboxyl group-containing resin]

As the carboxyl group-containing resin, various conventionally known resins having a carboxyl group in the molecule can be used. The carboxyl group-containing resin may or may not have an ethylenically unsaturated double bond in the molecule, but a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond in the molecule is particularly preferable from the viewpoint of photocurability and development resistance. This case corresponds to a photocurable thermosetting resin. Further, when the photocurable composition of the present invention contains a carboxyl group-containing resin, it may be used not only for alkali development but also for non-alkali development. It is preferable that the ethylenically unsaturated double bond is derived from acrylic acid or methacrylic acid or a derivative thereof. In the case of using only a carboxyl group-containing resin having no ethylenically unsaturated double bond, in order to make the composition photocurable, it is necessary to use a compound having a plurality of ethylenically unsaturated groups, that is, a photopolymerizable monomer in the molecule described later. As a specific example of the carboxyl group-containing resin, the following compounds (all oligomers and polymers may be used) are mentioned.

(1) Carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth)acrylic acid with an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth)acrylate, and isobutylene (lower alkyl Examples of the (meth)acrylate include methyl (meth)acrylate).

(2) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates, and carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, and polycarbonate-based polyols and polyether-based polyols , Polyester-based polyol, polyolefin-based polyol, acrylic polyol, bisphenol A-based alkylene oxide adduct diol, carboxyl group-containing urethane resin by polyaddition reaction of a diol compound such as a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group .

(3) Diisocyanate and bifunctional epoxy resins such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, non-ylenol type epoxy resin, and nonphenol type epoxy resin. A photosensitive urethane resin containing a carboxyl group by a polyaddition reaction of a (meth)acrylate or a partially modified acid anhydride thereof, a carboxyl group-containing dialcohol compound, and a diol compound.

(4) During synthesis of the resin of (2) or (3) above, a compound having one hydroxyl group and one or more (meth)acryloyl groups is added in a molecule such as hydroxyalkyl (meth)acrylate, and the terminal (meth) ) Photosensitive urethane resin containing acrylated carboxyl groups.

(5) During the synthesis of the resin of (2) or (3), a compound having one isocyanate group and one or more (meth)acryloyl groups in the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate A photosensitive urethane resin containing a carboxyl group that was added to the terminal (meth)acrylated.

(6) A photosensitive resin containing a carboxyl group in which (meth)acrylic acid is reacted with a bifunctional or higher polyfunctional (solid) epoxy resin, and a dibasic anhydride is added to a hydroxyl group present in the side chain.

(7) Carboxyl group-containing photosensitivity obtained by reacting (meth)acrylic acid with a polyfunctional epoxy resin epoxidized with epichlorohydrin and adding a dibasic anhydride to the hydroxyl group of a bifunctional (solid) epoxy resin. Suzy.

(8) Dicarboxylic acid such as adipic acid, phthalic acid, and hexahydrophthalic acid is reacted with a bifunctional oxetane resin, and two such as phthalic anhydride, tetrahydro phthalic anhydride, and hexahydro phthalic anhydride are reacted with the primary hydroxyl group produced. Carboxyl group-containing polyester resin to which basic acid anhydride was added.

(9) Compounds having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, such as p-hydroxyphenethyl alcohol, in an epoxy compound having a plurality of epoxy groups in one molecule, and unsaturation such as (meth)acrylic acid Carboxyl group obtained by reacting a group-containing monocarboxylic acid and reacting polybasic acid anhydrides such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and adipic acid with respect to the alcoholic hydroxyl group of the obtained reaction product. Containing photosensitive resin.

(10) A monocarboxylic acid containing an unsaturated group is reacted with a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide and propylene oxide, and polybasic acid anhydride is added to the reaction product. Carboxyl group-containing photosensitive resin obtained by reaction.

(11) A monocarboxylic acid containing an unsaturated group is reacted with a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate and propylene carbonate, and polybasic acid anhydride is added to the reaction product obtained. Carboxyl group-containing photosensitive resin obtained by reaction.

(12) Carboxyl group-containing photosensitive resin obtained by adding a compound having one epoxy group and one or more (meth)acryloyl groups in one molecule to the resins (1) to (11).

Among these, it is preferable that the curable resin contains two or more types of carboxyl group-containing resins. Further, it is preferable that at least one of the above two or more types of carboxyl group-containing resins is a carboxyl group-containing copolymer resin from the viewpoint of uniform dispersion while lowering the gloss. This is estimated as follows. In other words, since the carboxyl group-containing copolymer resin has poor compatibility, it takes a dissociated structure dispersed in other carboxyl group-containing resins among the coating film formed of the curable resin composition, and the incident light is diffusely reflected due to the difference in these refractive indices. It is thought to produce an effect. On the other hand, in the case of addition of the carboxyl group-containing copolymer resin, even if it is a blend with a small amount of extender pigments, it is considered that the copper impregnation phenomenon can be further suppressed because it can be uniformly dispersed while reducing gloss.

As a carboxyl group-containing copolymer resin, the resin of (1) and the copolymer resin in (12) are mentioned. As the resin of (12), in addition to the carboxyl group-containing resin obtained by copolymerization of (meth)acrylic acid and methyl (meth)acrylate, glycidyl methacrylate or 3,4-epoxycyclohexylmethyl (meth)acrylate, etc. It is preferably a carboxyl group-containing photosensitive resin obtained by adding a (meth)acrylate having an alicyclic epoxy group.

Moreover, it is preferable as the resin to be combined with the carboxyl group-containing copolymer resin from the viewpoint of being uniformly dispersed while lowering the gloss. Combinations with resins other than the carboxyl group-containing copolymer resin are preferred. Specifically, resins other than the resins of (2) to (11) and the copolymerization resin of (12) are exemplified, and among them, other than the resin of (6), (10) and (11), and the copolymer resin of (12) The resin of is more preferable.

In addition, in the present specification, (meth)acrylate is a generic term for acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.

The carboxyl group-containing resin that can be used in the present invention is not limited to those listed above. In addition, the carboxyl group-containing resins listed above may be used singly or in combination of multiple types.

In the present invention, when using a weakly alkaline developer such as an aqueous sodium carbonate solution, when considering the drawability of the resist pattern and the developability, the acid value of the carboxyl group-containing resin is preferably in the range of 30 to 150 mgKOH/g, and 50 to 120 mg. It is more preferable that it is a range of KOH/g. As the acid value of the carboxyl group-containing resin increases, the developability is improved, but since dissolution of the exposed portion by the developer proceeds, the exposed portion and the unexposed portion may be dissolved and peeled with a developer without distinction.

The weight average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, but is generally in the range of 2,000 to 150,000, and preferably in the range of 5,000 to 100,000. By using a carboxyl group-containing resin having a weight average molecular weight of 2,000 or more, resolution and tack-free performance can be improved. Moreover, developability and storage stability can be improved by using a carboxyl group-containing resin having a weight average molecular weight of 150,000 or less. The weight average molecular weight can be measured by gel permeation chromatography (GPC).

The blending amount of the carboxyl group-containing resin is, in terms of solid content per total amount of the curable resin composition, preferably 20 to 80% by mass, more preferably 20 to 75% by mass, and still more preferably 20 to 50% by mass. By setting it as 20 mass% or more, the strength of a cured coating film can be improved. Moreover, by setting it as 80 mass% or less, the viscosity of a curable resin composition becomes suitable and workability improves.

In addition, when the carboxyl group-containing resin contains a carboxyl group-containing copolymer resin, the blending amount of the carboxyl group-containing copolymer resin is 5 to 90% by mass based on 100 parts by mass of the carboxyl group-containing resin in terms of solid content in terms of lower gloss and suppression of copper seepage. Is preferable, 10 to 70 mass% is more preferable, and 15 to 50 mass% is more preferable.

[Photocurable resin]

The photocurable resin is a compound having an ethylenically unsaturated group, and includes polymers, oligomers, and monomers, and a mixture thereof may be used. By including a photocurable resin, the strength of a cured film can be improved. Photocurable resins may be used alone or in combination of two or more.

As the compound having an ethylenically unsaturated group, a known and commonly used photopolymerizable oligomer, photopolymerizable monomer, or the like can be used. Among these, it is preferable to use a photopolymerizable monomer from the viewpoint of further imparting crosslinkability and curability of the cured coating film.

Photopolymerizable oligomers are oligomers having ethylenically unsaturated double bonds. Examples of the photopolymerizable oligomer include unsaturated polyester oligomers and (meth)acrylate oligomers. (Meth) acrylate oligomers include epoxy (meth) acrylates such as phenol novolac epoxy (meth) acrylate, cresol novolac epoxy (meth) acrylate, bisphenol-type epoxy (meth) acrylate, and urethane (meth) Acrylate, epoxy urethane (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, polybutadiene-modified (meth)acrylate, and the like.

The photopolymerizable monomer is a monomer having an ethylenically unsaturated double bond. Examples of such photopolymerizable monomers include alkyl (meth)acrylates such as 2-ethylhexyl (meth)acrylate and cyclohexyl (meth)acrylate; Hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; Mono or di(meth)acrylates of alkylene oxide derivatives such as ethylene glycol, propylene glycol, diethylene glycol, and dipropylene glycol; Polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, and trishydroxyethyl isocyanurate, or poly(meth)acrylates of ethylene oxide or propylene oxide adducts thereof; (Meth)acrylates of ethylene oxide or propylene oxide adducts of phenols such as phenoxyethyl (meth)acrylate and polyethoxydi (meth)acrylate of bisphenol A; (Meth)acrylates of glycidyl ether, such as glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, and triglycidyl isocyanurate; And melamine (meth)acrylate. The photopolymerizable monomer may be used singly or in combination of two or more.

The blending amount of the photocurable resin is, in terms of solid content per total amount of the curable resin composition, preferably 3 to 20% by mass, more preferably 5 to 15% by mass. When the blending amount of the photopolymerizable monomer is 3% by mass or more, the photocurability is good, and pattern formation is facilitated by alkali development after irradiation with active energy rays. On the other hand, in the case of 20% by mass or less, halation is difficult to occur, and good resolution is easily obtained.

[Extender Pigment]

The extender pigment of the present invention refers to a pigment having a refractive index of 1.40 or more and, for example, silica such as amorphous silica, crystalline silica, fused silica, and spherical silica, talc, boehmite, hydrotalcite, slaked lime, calcium hydroxide, calcium carbonate, sulfuric acid. Calcium, potassium carbonate, magnesium carbonate, clay, mica powder, aluminum oxide, aluminum hydroxide, barium sulfate, copper sulfide, alumina, zinc oxide, iron, zinc sulfide, zirconium oxide, chromium oxide, cadmium oxide, cadmium sulfide, titanium oxide, And copper oxide. Among these, silica and barium sulfate are preferable from the viewpoint of dispersibility. One type of extender pigment may be used alone, or two or more types of extender pigments may be used in combination. By containing an extender pigment, heat resistance can be improved, or variation at the time of application can be reduced. Further, from the viewpoint of lowering the gloss, aluminum silicate or the like containing SiO ₂ and Al ₂ O ₃ as main components may be used.

The presence or absence of the surface treatment of the extender pigment is not particularly limited, but a surface treatment for enhancing dispersibility may be performed. Aggregation can be suppressed by using a surface-treated extender pigment. The surface treatment method of the extender pigment is not particularly limited, and a known conventional method may be used, but the surface of the inorganic extender pigment is treated with a surface treatment agent having a curable reactive group, for example, a coupling agent having a curable reactive group as an organic group. It is desirable.

The extender pigment may preferably have an average particle diameter of 10 µm or less, but more preferably 0.1 to 2.0 µm, more preferably 0.15 to 1.0 µm, in particular, except for amorphous silica described later from the viewpoint of dispersibility. It is preferably 0.2 to 0.9 μm. The average particle diameter of the extender pigment is an average particle diameter (D ₅₀ ) including not only the particle diameter of the primary particles but also the particle diameter of the secondary particles (aggregates), and is a value of D ₅₀ measured by a laser diffraction method. As a measuring device by laser diffraction method, Nikkiso Corporation Microtrac MT3300EXII is mentioned. Further, the maximum particle diameter (D ₁₀₀ ) and the particle diameter (D ₁₀ ) can be measured in the same manner with the above apparatus. In addition, the value of each particle diameter of the extender pigment mentioned above shall refer to the value measured in the above manner of the extender pigment before adjusting (pre-stirring, kneading) the curable resin composition.

The blending amount of the extender pigment, in terms of solid content per total amount of the curable resin composition, is preferably 20 to 80% by mass, more preferably 25 to 75% by mass, and still more preferably 30 to 50% by mass. Since the blending amount of the extender pigment is within the above range, the cured product can be made high strength.

The curable resin composition of the present invention preferably contains amorphous silica having an oil absorption amount of 180 to 350 ml/100 g from the point that the cured coating film becomes lower gloss. The reason why the cured coating film becomes low-gloss by using the amorphous silica is estimated as follows. That is, the amorphous silica in which the oil absorption amount is within a predetermined range is porous, and as a result of the amorphous silica or other extender pigments becoming more dense due to oil absorption of an organic solvent during curing or drying, the glossiness of the formed cured coating film Is estimated to be lower than. The oil absorption is more preferably 200 ~ 300ml / 100g. In addition, in the present invention, the oil absorption is measured in accordance with "JIS K5101-13-1: 2004 Pigment Test Method-Part 13: Oil Absorption-Section 1: Refined Linseed Oil Method".

As the amorphous silica, a conventionally known one can be used, and may be synthetic or natural. In addition, even if surface treatment is performed, it is not necessary to perform it. The type of surface treatment is the same as the extender pigment. Products include ACEMATT 82, ACEMATT 790, ACEMATT OK 412, and ACEMATT OK 500 (all manufactured by EVONIK DEGUSSA).

The average particle diameter of the amorphous silica may preferably be 3 to 10 µm, and more preferably 4 to 8 µm, in that the cured coating film has a lower gloss. In addition, the average particle diameter in this section was measured as a curable resin composition in a state before kneading. In addition, the method of measuring the average particle diameter is the same as that of the extender pigment.

When the amorphous silica is included in the extender pigment, the blending amount of the amorphous silica is uniformly dispersed while making the cured coating film more low gloss, and is preferably 5 to 90 parts by mass, based on 100 parts by mass of the extender pigment in terms of solid content. , More preferably, it is 10 to 70 parts by mass, and even more preferably 12 to 50 parts by mass. In addition, when the extender pigment contains an extender pigment different from the amorphous silica, barium sulfate is preferable from the viewpoint of uniform dispersion while making the cured coating film more low gloss.

The curable resin composition of the present invention may contain the following optional components.

[Photopolymerization initiator]

The photoinitiator is for reacting a carboxyl group-containing resin or a photopolymerizable monomer by exposure. Any known photopolymerization initiator can be used. A photoinitiator may be used individually by 1 type, and may be used in combination of 2 or more types.

Specifically as a photoinitiator, for example, bis-(2,6-dichlorobenzoyl)phenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, bis-( 2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-1-naphthylphosphine oxide, bis-(2,6-dimethoxybenzoyl)phenylphosphine oxide , Bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide, bis-( Bisacylphosphine oxides such as 2,4,6-trimethylbenzoyl)-phenylphosphine oxide; 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphinic acid methyl ester, 2-methylbenzoyldiphenylphosphine oxide, blood Monoacylphosphine oxides such as isopropyl ester of valeoylphenylphosphinic acid and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; Ethyl phenyl (2,4,6-trimethylbenzoyl) phosphinate, 1-hydroxy-cyclohexylphenylketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl -1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one And hydroxyacetophenones such as 2-hydroxy-2-methyl-1-phenylpropan-1-one; Benzoins, such as benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, and benzoin n-butyl ether; Benzoin alkyl ethers; Benzophenones such as benzophenone, p-methylbenzophenone, Michler's ketone, methylbenzophenone, 4,4'-dichlorobenzophenone, and 4,4'-bisdiethylaminobenzophenone; Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl- 1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2- Acetophenones such as (dimethylamino)-2-[(4-methylphenyl)methyl)-1-[4-(4-morpholinyl)phenyl]-1-butanone and N,N-dimethylaminoacetophenone; Thioxanthone, 2-ethyl thioxanthone, 2-isopropyl thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2-chloro thioxanthone, 2,4-di Thioxanthones such as isopropyl thioxanthone; Anthraquinones such as anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, and 2-aminoanthraquinone; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzoic acid esters such as ethyl-4-dimethylaminobenzoate, 2-(dimethylamino)ethylbenzoate, and p-dimethyl benzoic acid ethyl ester; 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H- Oxime esters such as carbazol-3-yl]- and 1-(O-acetyloxime); Bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, bis(cyclopentadienyl)- Titanocenes such as bis[2,6-difluoro-3-(2-(1-pil-1-yl)ethyl)phenyl]titanium; Phenyl disulfide 2-nitrofluorene, butyroin, anisoin ethyl ether, azobisisobutyronitrile, tetramethylthiuram disulfide, etc. are mentioned.

Commercially available products of α-aminoacetophenone-based photoinitiators include Omnirad 907, 369, 369E, 379 manufactured by IGM Resins. Further, as a commercial item of the acylphosphine oxide-based photopolymerization initiator, Omnirad TPO, 819 manufactured by IGM Resins, and the like can be mentioned. Commercially available products of oxime ester photopolymerization initiators include Irgacure OXE01, OXE02 manufactured by BASF Japan Co., Ltd., N-1919 manufactured by ADEKA Co., Ltd., Adeka Acruze NCI-831, NCI-831E, and Dientz New Chiria by Changzhou Qianli And TR-PBG-304 manufactured by Changzou tronly new electronic materials co, ltd.

Other Japanese Published Patent No. 2004-359639, Japanese Published Patent No. 2005-097141, Japanese Published Patent No. 2005-220097, Japanese Published Patent No. 2006-160634, Japanese Published Patent No. 2008-094770 The carbazole oxime ether compounds described in Japanese Unexamined Publication No. 2008-509967, Japanese Unexamined Patent No. 2009-040762, and Japanese Unexamined Patent No. 2011-80036 may be mentioned.

The blending amount of the photoinitiator is in terms of solid content per total amount of the curable resin composition, preferably 0.1 to 10% by mass, and more preferably 1 to 5% by mass. When the blending amount of the photopolymerization initiator is 0.1% by mass or more, the photocurability of the curable resin composition becomes good, and the coating film properties such as chemical resistance are also good. On the other hand, in the case of 10% by mass or less, light absorption on the surface of the resist film (cured coating film) becomes good, and the deep curing property is hardly lowered.

You may use a photoinitiation aid or a sensitizer in combination with the above photoinitiator. Examples of the photo-initiating aid or sensitizer include a benzoin compound, an anthraquinone compound, a thioxanthone compound, a ketal compound, a benzophenone compound, a tertiary amine compound, and a xanthone compound. In particular, thioxanthone compounds such as 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2-chloro thioxanthone, 2-isopropyl thioxanthone, and 4-isopropyl thioxanthone are used. It is desirable. By including the thioxanthone compound, it is possible to improve the deep curing properties. Although these compounds can be used as a photoinitiator in some cases, it is preferable to use it in combination with a photoinitiator. Moreover, a photoinitiation aid or a sensitizer may be used individually by 1 type, and may use 2 or more types together.

In addition, since these photoinitiators, photoinitiation aids, and sensitizers absorb specific wavelengths, the sensitivity is lowered in some cases, and thus functions as an ultraviolet absorber in some cases. However, these are not used only for the purpose of improving the sensitivity of the resin composition. If necessary, it is possible to increase the photoreactivity of the surface by absorbing light of a specific wavelength, change the line shape and opening of the resist pattern into vertical, tapered, and reverse tapered shapes, and improve the accuracy of the line width and opening diameter. have.

[Thermal curing catalyst]

A thermosetting catalyst can be blended into the curable resin composition of the present invention. As a thermosetting catalyst, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole , Imidazole derivatives such as 1-cyanoethyl-2-phenylimidazole and 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; Amines such as dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N, and N-dimethylbenzylamine Hydrazine compounds such as compounds, adipic acid dihydrazide, and sebacic acid dihydrazide; And phosphorus compounds such as triphenylphosphine. In addition, commercially available ones include, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all brand names of imidazole-based compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., and U manufactured by San Apro Co., Ltd. -CAT 3513N (trade name of a dimethylamine compound), DBU, DBN, and U-CAT SA 102 (both bicyclic amidine compounds and salts thereof), and the like. In particular, it is not limited thereto, and any one that promotes the reaction of at least one of an epoxy group and oxetanyl group and a carboxyl group, or a thermosetting catalyst of an epoxy resin or an oxetane compound, or a mixture of two or more It doesn't matter if you use it.

In addition, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-tri Azine, 2-vinyl-4,6-diamino-S-triazine/isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine/isocyanuric acid adduct S-triazine derivatives such as may be used, and preferably, a compound that functions also as an adhesive imparting agent is used in combination with a thermosetting catalyst. The thermosetting catalyst may be used singly or in combination of two or more.

The blending amount of the thermosetting catalyst is, in terms of solid content per total amount of the curable resin composition, preferably 0.1 to 5 parts by mass, more preferably 1 to 3 parts by mass.

[coloring agent]

A colorant can be blended into the curable resin composition of the present invention. The colorant is not particularly limited, and known colorants such as red, blue, green, and sulfur may be used, and any of pigments, dyes, and pigments may be used. However, from the viewpoint of reducing the environmental load and having little influence on the human body, halogen It is preferably a colorant that does not contain.

Red colorants include mono-azo, disazo, azo lake, benzimidazolone, perylene, diketo-pyrrolo-pyrrole, condensed azo, anthraquinone, quinaclidone, etc. In particular, the following color-index (CI; issued by The Society of Dyersand Colourists) numbers are given.

Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146 , 147, 151, 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269, and the like. In addition, Pigment Red 37, 38, 41, etc. are mentioned as a disazo-based red colorant. In addition, as a mono azo lake-based red colorant, Pigment Red 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, and the like. Further, as the benzimidazolone-based red colorant, Pigment Red 171, 175, 176, 185, 208, and the like may be mentioned. Further, examples of the perylene-based red colorants include Solvent Red 135, 179, Pigment Red 123, 149, 166, 178, 179, 190, 194, 224, and the like. Moreover, Pigment Red 254, 255, 264, 270, 272, etc. are mentioned as a diketopyrrolopyrrole type red colorant. In addition, Pigment Red 220, 144, 166, 214, 220, 221, 242, etc. are mentioned as a condensed azo-based red colorant. In addition, Pigment Red 168, 177, 216, Solvent Red 52, 149, 150, 207, etc. are mentioned as an anthraquinone-based red colorant. Moreover, Pigment Red 122, 202, 206, 207, 209, etc. are mentioned as a quinacridone type red colorant.

Examples of blue colorants include phthalocyanine-based and anthraquinone-based compounds, and pigment-based compounds classified as pigments. For example, Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60. As the dye system, Solvent Blue 35, 63, 67, 68, 70, 83, 87, 94, 97, 122, 136, etc. may be used. In addition to the above, a metal substituted or unsubstituted phthalocyanine compound can also be used.

Examples of the yellow colorant include mono-azo-based, disazo-based, condensed azo-based, benzimidazolone-based, isoindolinone-based, and anthraquinone-based, for example, Solvent Yellow 163, as an anthraquinone-based yellow colorant, Pigment Yellow 24, 108, 193, 147, 199, 202, etc. are mentioned. Pigment Yellow 110, 109, 139, 179, 185, etc. are mentioned as an isoindolinone type yellow colorant. Pigment Yellow 93, 94, 95, 128, 155, 166, 180, etc. are mentioned as a condensed azo yellow colorant. Pigment Yellow 120, 151, 154, 156, 175, 181, etc. are mentioned as a benzimidazolone yellow colorant. In addition, as a mono azo yellow colorant, Pigment Yellow 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, etc. are mentioned. In addition, Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198, etc. Can be lifted.

In addition, colorants such as purple, orange, brown, and black may be added. Specifically, Pigment Black 1, 6, 7, 8, 9, 10, 11, 12, 13, 18, 20, 25, 26, 28, 29, 30, 31, 32, Pigment Violet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36, CI Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63 , 64, 71, 73, PigmentBrown 23, 25, carbon black, and the like.

The blending amount of the colorant is, in terms of solid content per total amount of the curable resin composition, preferably 0.1 to 2.0 mass%, and more preferably 0.3 to 1.5 mass%.

[Organic solvents]

The curable resin composition of the present invention can contain an organic solvent for the purpose of preparing the composition or adjusting the viscosity when applied to a substrate or film. Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; Aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; Cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methylcarbitol, butylcarbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether Glycol ethers such as acetate and tripropylene glycol monomethyl ether; Ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, diethylene glycol monoethyl ether acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, propylene carbonate, etc. Esters of; Aliphatic hydrocarbons such as octane and decane; Known and common organic solvents, such as petroleum solvents such as petroleum ether, petroleum naphtha, and solvent naphtha, can be used. Among these, when the curable resin composition in the present invention uses a porous one such as amorphous silica, esters are preferable from the viewpoint of lowering the glossiness of the formed cured coating film as a result of easy absorption on the silica surface during curing or drying. And diethylene glycol monoethyl ether acetate is more preferable. These organic solvents may be used alone or in combination of two or more.

The blending amount of the organic solvent is not particularly limited, and can be appropriately set according to the intended viscosity so that the curable resin composition can be easily prepared.

[Other additive ingredients]

In addition to the curable resin composition of the present invention, if necessary, a photo-initiation aid, a cyanate compound, an elastomer, a mercapto compound, a urethanization catalyst, a thixotropic agent, an adhesion promoter, a block copolymer, a chain transfer agent, a polymerization inhibitor, and a freezing agent (銅害) At least one kind of anti-foaming agent, anti-oxidant, rust inhibitor, thickener such as finely divided silica, organic bentonite, montmorillonite, silicone-based, fluorine-based, polymer-based, and leveling agent, imidazole-based, thiazole-based and triazole-based Components such as flame retardants such as phosphorus compounds such as silane coupling agents, phosphinates, phosphoric acid ester derivatives, and phosphazene compounds may be blended. Those known in the field of electronic materials can be used.

The curable resin composition of the present invention may be used after forming a dry film.

[How to prepare]

In the preparation of the curable resin composition of the present invention, each component is weighed and blended, followed by preliminary stirring with a stirrer. Subsequently, it can be prepared by dispersing each component in a kneader and kneading.

Examples of the kneading machine include a bead mill, a ball mill, a sand mill, a three roll mill, and a two roll mill. Among these, it is preferable to use a bead mill from the viewpoint of having a lower gloss, further reducing the variation in the film thickness of the coating film before or after drying, and suppressing the copper seepage phenomenon. Dispersion conditions, such as the kind and particle diameter of beads of the bead mill, can be appropriately set according to the target viscosity, but examples of the kinds of beads include zirconia beads and alumina beads. The particle diameter of the beads is, for example, in the range of φ0.015 to 2.0 mm. Among these, the range of φ0.3 to 1.5 mm is more preferable. The filling rate of the beads is 50 to 95%, and the rotational speed of the rotor is preferably 800 to 1300 rpm. In addition, the viscosity of the composition at the time of adding a bead mill is preferably 200 dPa·s or less from the viewpoint of improving dispersibility and lowering the gloss of the cured coating film as the target viscosity. On the other hand, 50 dPa·s or more is preferable as the lower limit. The viscosity of the present invention is 50° C., 100 rpm, 30 seconds, according to the method of measuring viscosity using a 10-conical-plate rotary viscometer of JIS Z 8803:2011, and 3°×R9.7 as a cone rotor. It is a value measured by the used cone plate type viscometer (TVE-33H, manufactured by Tokisankyo Corporation).

On the other hand, dispersion conditions, such as the rotation ratio of each roll of the three-roll mill, can also be appropriately set according to the target viscosity.

Further, in order to further improve the dispersibility, the raw material may be weighed and blended into a slurry using a kneader such as a bead mill or a three-roll mill, and then pre-stirred with a stirrer. When the raw material is slurried, it is preferable to weigh and mix a lubricant dispersant such as a silane coupling agent, and then knead it by a bead mill or the like. Subsequently, it may be prepared by dispersing each component including those obtained by slurrying in a kneader as described above, and kneading with a bead mill or the like.

[Usage]

The curable resin composition according to the present invention is useful for forming a pattern layer as a permanent film of a printed wiring board such as a solder resist, a coverlay, and an interlayer insulating layer, and is particularly useful for forming a solder resist. In addition, since the curable resin composition of the present invention can form a cured product having excellent film strength even with a thin film, a pattern on a printed wiring board that is required to be thinned, for example, a package substrate (printed wiring board used in a semiconductor package) It can also be preferably used for layer formation. In addition, the cured product obtained from the curable resin composition of the present invention can be preferably used for a flexible printed wiring board because of its excellent flexibility.

In addition, the curable resin composition of the present invention can be used not only for forming the pattern layer of the cured coating film, but also for not forming the pattern layer, for example, for mold applications (sealing applications).

[Dry film]

The curable resin composition of the present invention may be in the form of a dry film including a support (carrier) film and a resin layer comprising a dry coating film of the curable resin composition formed on the support film. In dry film formation, the curable resin composition of the present invention is diluted with the organic solvent and adjusted to an appropriate viscosity, and comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater, gravure coater, spray coater The film can be obtained by coating it with a uniform thickness on the carrier film by using the same, and drying for 1 to 30 minutes at a temperature of usually 50 to 130°C. There is no particular limitation on the thickness of the coating film, but in general, the thickness after drying is appropriately selected in the range of 1 to 150 µm, preferably 5 to 60 µm. By using the curable resin composition of the present invention, it is possible to reduce the variation of the coating film before drying, so that even if the resin layer made of the dry coating is a thin film, the variation can be reduced. For example, it may be in the form of a dry film including a thin resin layer of 12 μm or less.

Any known support film can be used without particular limitation. For example, a thermoplastic resin such as a polyester film such as polyethylene terephthalate or polyethylene naphthalate, a polyimide film, a polyamideimide film, a polypropylene film, or a polystyrene film. The formed film can be preferably used. Among these, polyester films are preferred from the viewpoints of heat resistance, mechanical strength, and handling properties. Further, a laminate of such a film can also be used as a supporting film.

In addition, the thermoplastic resin film as described above is preferably a film stretched in a uniaxial or biaxial direction from the viewpoint of improving mechanical strength.

The thickness of the supporting film is not particularly limited, but may be, for example, 10 μm to 150 μm.

After forming a resin layer consisting of a dry coating film of the curable resin composition of the present invention on the support film, for the purpose of preventing dust from adhering to the surface of the resin layer, etc., peelable protection (cover ) It is preferable to laminate the film. As a peelable protective film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, etc. can be used. When peeling the protective film, the resin layer is more adherent than the resin layer and the support film. It is sufficient if the adhesive strength of the protective film is smaller.

The thickness of the protective film is not particularly limited, but may be, for example, 10 μm to 150 μm.

To prepare a cured coating film on a printed wiring board using a dry film, the protective film is peeled off from the dry film, the exposed resin layer of the dry film is overlaid on a circuit-formed substrate, and then pasted using a laminator, etc., on the circuit-formed substrate. To form a resin layer. Subsequently, a cured coating film can be formed by exposing, developing, and heat-curing the formed resin layer. The protective film may be peeled off either before exposure or after exposure.

[Hardened cargo]

The cured product of the present invention is obtained by curing the curable resin composition of the present invention or the resin layer of the dry film of the present invention. The cured product of the present invention can be preferably used for a printed wiring board or an electronic component. Since the cured product of the present invention is excellent in flexibility, it can be particularly preferably used for a flexible printed wiring board. In addition, the cured product of the present invention is excellent in infrared shielding properties and stability over time.

[Printed wiring board]

The printed wiring board of the present invention has a cured product obtained from the curable resin composition of the present invention or a resin layer of a dry film. As a method of manufacturing a printed wiring board of the present invention, for example, the curable resin composition of the present invention is adjusted to a viscosity suitable for a coating method using the organic solvent, and a dip coating method, flow coating method, roll coating method on a substrate After applying by a method such as a method, bar coating method, screen printing method, curtain coating method, etc., the organic solvent contained in the composition is volatilized and dried (temporarily dried) for 15 to 90 minutes at a temperature of 60 to 100°C. To form a resin layer. Further, in the case of a dry film, a resin layer is formed on the substrate by attaching the resin layer to the substrate by a laminator or the like so as to contact the substrate, and then removing the carrier film.

As the substrate, in addition to a printed wiring board or a flexible printed wiring board previously formed with copper or the like, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/nonwoven cloth epoxy, glass cloth/paper epoxy, synthetic fiber epoxy, fluororesin Copper-clad laminates for high frequency circuits made of polyethylene/polyphenylene ether, polyphenylene oxide, cyanate, etc. are used, and copper-clad laminates of all grades (FR-4, etc.), other metal substrates, polyimide films , Polyethylene terephthalate film, polyethylene naphthalate (PEN) film, glass substrate, ceramic substrate, wafer plate, and the like.

The bonding of the dry film onto the substrate is preferably performed under pressure and heating using a vacuum laminator or the like. By using such a vacuum laminator, when a circuit-formed substrate is used, even if there are irregularities on the surface of the circuit board, since the dry film adheres to the circuit board, there is no mixing of air bubbles, and the hole filling property of the concave portion of the substrate surface is also improved. . The pressurizing condition is preferably about 0.1 to 2.0 MPa, and the heating condition is preferably 40 to 120°C.

Volatilization drying performed after applying the curable resin composition of the present invention on a substrate is a hot air circulation type drying furnace, an IR furnace, a hot plate, a convection oven, etc. (with a heat source of an air heating method using steam, It can be carried out using a method of making hot air in countercurrent contact and a method of spraying the support body from a nozzle). Examples of the apparatus include DF610 manufactured by Yamato Chemical Co., Ltd. as a hot air circulation drying furnace.

After the resin layer is formed on the substrate, it is selectively exposed with an active energy ray through a photomask having a predetermined pattern, and the unexposed part is a dilute alkali aqueous solution (for example, an aqueous solution of 0.3 to 3.0% by mass of soda carbonate). By developing to form a pattern of the cured product. In the case of a dry film, after exposure, the support film is peeled from the dry film and developed to form a patterned cured product on the substrate. Further, as long as the properties are not impaired, the supporting film may be peeled from the dry film before exposure, and the exposed resin layer may be exposed and developed.

As the exposure machine used for the active energy ray irradiation, a high-pressure mercury lamp lamp, an ultra-high pressure mercury lamp lamp, a metal halide lamp, a mercury short arc lamp, etc. may be mounted, and an apparatus that irradiates ultraviolet rays in the range of 350 to 450 nm may be used, and direct drawing An apparatus (for example, a laser direct imaging device that draws an image with a laser directly from CAD data from a computer) can also be used. As for the lamp light source or the laser light source of a handwriting machine, what is necessary is just to have a maximum wavelength in the range of 350-450 nm. The exposure amount for image formation varies depending on the film thickness and the like, but can generally be in the range of 10 to 1,000 mJ/cm 2, preferably 20 to 800 mJ/cm 2. As an apparatus, as an exposure apparatus equipped with a metal halide lamp, HMW-680-GW20 etc. manufactured by Oak Seisakusho Co., Ltd. are mentioned.

The developing method may be a dipping method, a shower method, a spray method, a brush method, etc., and as a developer, an alkaline aqueous solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines, etc. Can be used.

In addition, after irradiating the cured product with active energy rays, heat curing (for example, 30 to 90 minutes at a temperature of 100 to 220°C), or irradiating active energy rays after heat curing (for example, 1,000 to 2,000 mJ/ Cm2), or final curing (main curing) only by heat curing to form a cured coating film having excellent properties such as adhesion and hardness. Examples of the device include a UV conveyor using a high-pressure mercury lamp, such as QRM-2082 manufactured by Oak Seisakusho Co., Ltd.

The above is a method of forming a cured coating film using a photocurable thermosetting resin composition, and in the case of only photocuring or thermosetting, it can be prepared as follows.

In the case of photocuring alone, a cured coating film is formed by applying the curable resin composition of the present invention on a substrate by pattern printing or the like and then curing by irradiating with active energy rays (eg, 1,000 to 2,000 mJ/cm 2 ).

On the other hand, in the case of only thermal curing, the curable resin composition of the present invention is applied on a substrate by pattern printing, etc., and then heat cured (for example, 30 to 90 minutes at a temperature of 100 to 220°C) to form a cured coating film. .

[Example]

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to the following examples. In addition, what is described as "parts" and "%" below are all based on mass unless otherwise noted.

(Synthesis of resin varnish 1 of carboxyl group-containing resin)

In an autoclave equipped with a thermometer, a nitrogen introducing device and an alkylene oxide introducing device and a stirring device, a novolac cresol resin (manufactured by Aika Kogyo Co., Ltd., brand name ``Shonor CRG951'', OH equivalent: 119.4) 119.4 g, hydroxide 1.19 g of potassium and 119.4 g of toluene were put, and the inside of the system was replaced with nitrogen while stirring, and the temperature was raised by heating. Next, 63.8 g of propylene oxide was gradually added dropwise and reacted at 125 to 132°C and 0 to 4.8 kg/cm 2 for 16 hours. After that, it was cooled to room temperature, and 1.56 g of 89% phosphoric acid was added and mixed to the reaction solution to neutralize potassium hydroxide, and a propylene oxide reaction solution of a novolac-type cresol resin having a solid content of 62.1% and a hydroxyl value of 182.2 g/eq. Got it. This was an average of 1.08 mol of alkylene oxide added per equivalent of phenolic hydroxyl group. Then, 293.0 g of the alkylene oxide reaction solution of the obtained novolak-type cresol resin, 43.2 g of acrylic acid, 11.53 g of methanesulfonic acid, 0.18 g of methylhydroquinone and 252.9 g of toluene were put into a reactor equipped with a stirrer, a thermometer and an air blowing tube. , Air was blown at a rate of 10 ml/min and reacted at 110° C. for 12 hours while stirring. The water produced by the reaction was an azeotropic mixture with toluene, and 12.6 g of water flowed out. Then, it cooled to room temperature, and the obtained reaction solution was neutralized with 35.35 g of 15% sodium hydroxide aqueous solution, and then washed with water. Thereafter, toluene was distilled off while substituting 118.1 g of diethylene glycol monoethyl ether acetate in an evaporator to obtain a novolac-type acrylate resin solution. Next, 332.5 g of the obtained novolak-type acrylate resin solution and 1.22 g of triphenylphosphine were put into a reactor equipped with a stirrer, thermometer and air blowing tube, and air was blown at a rate of 10 ml/min, while stirring, 60.8 g of phthalic anhydride was gradually added and reacted at 95 to 101°C for 6 hours. Thus, resin varnish 1 of a carboxyl group-containing resin having a solid dispersion value of 88 mgKOH/g, a solid content of 71%, and a weight average molecular weight of 2,000 was obtained.

(Synthesis of resin varnish 2 of carboxyl group-containing resin)

Put 220 g of ortho cresol novolak type epoxy resin (manufactured by DIC Corporation, EPICLON N-695, epoxy equivalent: 214, average number of functional groups 7.6) into a 4-neck flask equipped with a stirrer and reflux cooler, and diethylene glycol monoethyl ether 214 g of acetate was added and heated and dissolved. Next, 0.1 g of hydroquinone as a polymerization inhibitor and 2.0 g of dimethylbenzylamine were added as a reaction catalyst. The mixture was heated to 95 to 105°C, and 72 g of acrylic acid was gradually added dropwise to react for 16 hours. The reaction product was cooled to 80 to 90°C, 106 g of tetrahydrophthalic anhydride was added, reacted for 8 hours, cooled, and then taken out. Resin varnish 2 of the carboxyl group-containing resin thus obtained had a solid content of 65%, an acid value of a solid of 100 mgKOH/g, and a weight average molecular weight Mw of about 3,500.

(Synthesis of resin varnish 3 of carboxyl group-containing resin)

Diethylene glycol monoethyl ether acetate 650 parts by mass of ortho cresol novolak type epoxy resin (manufactured by DIC Corporation, EPICLON N-695, softening point 95°C, epoxy equivalent 214, average number of functional groups 7.6) 1070 g, acrylic acid 360 g, and hydroquinone 1.5 g was put, and heated and stirred at 100°C to dissolve uniformly. Subsequently, 4.3 parts by mass of triphenylphosphine was added, heated to 110°C and reacted for 2 hours, then 1.6 parts by mass of triphenylphosphine was further added, the temperature was raised to 120°C, and further reaction was performed for 12 hours. To the obtained reaction solution, 525 g of an aromatic hydrocarbon (manufactured by Standado Sekiyu Osaka Hatsubaisho Co., Ltd., Tisor 150) and 608 g (4.0 mol) of tetrahydrophthalic anhydride were added and reacted at 110° C. for 4 hours. Further, 142.0 g of glycidyl methacrylate was added to the obtained reaction solution, and the reaction was carried out at 115°C for 4 hours. Thus, resin varnish 3 of a carboxyl group-containing resin having a solid dispersion of 77 mgKOH/g and a solid content of 65% was obtained.

(Synthesis of resin varnish 4 of carboxyl group-containing resin)

In a flask equipped with a thermometer, stirrer, dropping funnel, and reflux condenser, 325.0 parts by mass of dipropylene glycol monomethyl ether as a solvent is heated to 110° C., and 174.0 parts by mass of methacrylic acid, ε-caprolactone-modified methacrylic acid (average molecular weight 314) 174.0 parts by mass, 77.0 parts by mass of methyl methacrylate, 222.0 parts by mass of dipropylene glycol monomethyl ether, and t-butylperoxy 2-ethylhexanoate as a polymerization catalyst (manufactured by Nichiyu Corporation, Perbutyl O) A 12.0 mass part mixture was dripped over 3 hours, stirred at 110 degreeC for 3 hours, the polymerization catalyst was deactivated, and a resin solution was obtained. After cooling this resin solution, 289.0 parts by mass of Cychroma M100 (3,4-epoxycyclohexylmethylmethacrylate) manufactured by DICER, 3.0 parts by mass of triphenylphosphine, and 1.3 parts by mass of hydroquinone monomethyl ether It added, heated up to 100 degreeC, and the ring-opening addition reaction of an epoxy group was performed by stirring, and the carboxyl group-containing resin varnish 4 was obtained. The carboxyl group-containing resin varnish 4 thus obtained had a nonvolatile content of 45.5 mass% and a solid acid value of 79.8 mgKOH/g.

(Example 1 to Example 4, Comparative Example 1 to Comparative Example 3)

(Preparation of curable resin composition)

With respect to each composition, each component was blended according to the blending shown in Table 1 below, and an organic solvent (diethylene glycol monoethyl ether acetate) was blended as needed, and premixed with a stirrer. Subsequently, all of the compositions of Formulation Examples 1 to 4 were dispersed at 70°C or less by a bead mill, kneaded and adjusted. On the other hand, all of the compositions of Formulation Examples 5 to 7 were prepared by dispersing and kneading at 70°C or less by a roll mill. In addition, although the components of the compositions of Formulation Example 1 and Formulation Example 5 are the same, the dispersion method is different, and the components of the compositions of Formulation Example 2 and Formulation Example 6 are the same, but the dispersion method is different, and Formulation Examples 3 and 4 And the components of the composition of Formulation Example 7 are the same, but the dispersion method is different.

The dispersion by the bead mill was carried out under the following conditions. Each composition of Formulation Examples 1 to 3 and 5 to 7 in which the viscosity was adjusted to 100 dPa·s with an organic solvent (diethylene glycol monoethyl ether acetate) was prepared as zirconia beads having a particle diameter of φ 1.0 mm. The composition of Example 4 was subjected to dispersion treatment so that the average particle diameter (D ₅₀ ) shown in Table 2 could be obtained by using a horizontal wet grinder (manufactured by Burr Co., Ltd.) using zirconia beads having a particle diameter of 0.65 mm. The filling rate of the zirconia beads was 85%, and the rotation speed of the rotor was 1000 rpm. In addition, the viscosity is 50°C, 100 rpm, 30 seconds, according to the method of measuring viscosity using a 10-conical-plate rotational viscometer of JIS Z 8803:2011, and a cone plate viscometer using 3°×R9.7 as a cone rotor. It measured with (TVEE-33H Tokisankyo Corporation make).

In addition, for dispersion by the roll mill described above, each composition was subjected to dispersion treatment so that the average particle diameter (D ₅₀ ) shown in Table 2 was obtained using a 3-roll mill manufactured by Inoue Seisakusho Co., Ltd.

The blending amount in Table 1 represents parts by mass.

Details of each component in Table 1 are as follows.

※ 1: The carboxyl group-containing resin varnish synthesized above 1, the blending amount is the value in terms of solid content

※ 2: The carboxyl group-containing resin varnish 2 synthesized above, the blending amount is the value in terms of solid content

※ 3: The carboxyl group-containing resin varnish 3 synthesized above, the blending amount is the value in terms of solid content

※ 4: The carboxyl group-containing resin varnish synthesized above 4, the blending amount is the value in terms of solid content

※ 5: Photopolymerizable monomer (dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.))

※ 6: 2-[4-(methylthio)benzoyl]-2-(4-morpholinyl)propane (manufactured by IGM Resins, Omnirad 907)

※ 7: Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (BASF Japan Co., Ltd., Irgacure OXE02 )

※ 8: Bis-(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (manufactured by IGM Resins, Omnirad 819)

※ 9: 2,4-diethyl thioxanthone (KAYACURE DETX-S, manufactured by Nippon Kayaku Co., Ltd.)

※ 10: Blue colorant (C.I.Pigment Blue 15:3)

※ 11: Yellow colorant (C.I.Pigment Yellow 147)

※ 12: Red colorant (Paliogen Red K3580, manufactured by BASF Japan Co., Ltd.)

※ 13: Bisphenol A type epoxy resin (DIC Corporation, EPICLON 840-S)

※ 14: Phenol novolak type epoxy resin (manufactured by DIC Corporation, EPICLON N-770)

※ 15: Biphenyl type epoxy resin (manufactured by Mitsubishi Chemical Corporation, YX-4000)

※ 16: 1,3,5-tris(2,3-epoxypropyl)-1,3,5-triazine-2,4,6(1H, 3H, 5H)-trion (high melting point type, Nissan Kaga Co., Ltd., TEPIC-HP)

※ 17: Melamine

※ 18: Barium sulfate (average particle diameter 0.3 µm (measured in the state before kneading as a curable resin composition) (manufactured by Sakai Chemical Industry Co., Ltd., B-34)

※ 19: Amorphous silica (average particle diameter of 6.3 μm (measured in the state before kneading as a curable resin composition), oil absorption: 260 ml/100 g) (manufactured by Evonik Degusa Japan, ACE MATT OK 500)

(Measurement of average particle diameter (D ₅₀ ) and specific surface area (CS))

About each curable resin composition of each Example and each comparative example, the average particle diameter (D ₅₀ ) (micrometer) and specific surface area (CS) (m2/ml) were measured as follows.

First, prepare the following equipment and equipment.

Particle size distribution meter: Nikkiso Corporation Microtrack MT3300EX

・Circulation device: ASVR manufactured by Nikkiso Co., Ltd.

Next, the measurement conditions are input in the following procedure. Start up the software ("Particle size distribution measurement") attached to Microtrack, proceed from the SET UP screen, and set the time from the option of setting the measurement conditions. Set zero time is 30sec., measurement is 30sec., and number of times is measured twice. Next, enter the analysis conditions. In the analysis information, the particle refractive index is 1.81 (fixed value: the average value of the refractive index of all inorganic substances), the transmittance is transmitted through the characteristics of the particles, and the shape is made non-spherical. In addition, PMA (propylene glycol monomethyl ether acetate) is selected from the solvent information, and the solvent refractive index is set to 1.4. Next, input the scale setting. In the particle diameter range, the minimum particle diameter is set to 0.021 μm and the maximum particle diameter is set to 704 μm. Next, input the sampling system. Set ASVR cleaning times 4 times, flow rate 50%, ultrasonic output 40W, ultrasonic time 300sec. When all measurement conditions are entered, click Save to close the setting of measurement conditions.

Next, the sample is adjusted in the following procedure. 0.3 g of a sample (curable resin composition) is weighed into a screw bottle, and 30 g of propylene glycol monomethyl ether acetate is added little by little using a dropper, and the sample is dissolved by shaking the screw bottle to prepare an adjustment sample. Adjustment samples do not undergo external dispersion or pre-dispersion. Next, the adjustment sample is measured. Click the particle size distribution measurement in the software supplied with MicroTrack to open the sample loading screen. A few drops of the adjusted sample are added dropwise to the sample inlet of the main body using a dropper. When a red indicator bar is displayed on the sample loading screen, an adjusted sample is dropped into the sample inlet until it falls within the range from red to green. Once within the green range, the measurement button is pressed to start measurement. From the adjustment of the sample to the measurement of the adjusted sample, it is carried out within 5 minutes. The values of the cumulative average diameter 50% and the area average diameter (MA), which are displayed as the measurement result, are read, respectively. The value of the cumulative average diameter of 50% is taken as the value of the average particle diameter (D ₅₀ ) measured by the microtrack. In addition, CS=6/MA is calculated. The calculated CS value is taken as the value of the specific surface area measured by Microtrack.

(Measurement of average spacing of irregularities (Sm) (㎛) and maximum height (Ry) (㎛))

Screen printing of each curable resin composition of each example and each comparative example on the surface of a clean glass substrate (76 mm × 26 mm × 1.1 mmt) using a 180 mesh polyester plate (with bias) so that it becomes 12 μm after drying It printed with solid, and dried for 15 minutes at 90 degreeC, and formed a dry coating film. For the obtained "dry coating film" (hereinafter, a sample), using a shape-measurement laser microscope (VK-X100 manufactured by Keyence Corporation), the average interval (Sm) (µm) of the irregularities and the maximum height are as follows. (Ry) (µm) was measured in accordance with JIS B0601-1994, respectively. In addition, the measurement was carried out after drying at 90°C for 15 minutes and then leaving to stand at room temperature for 30 minutes.

After starting the shape measurement laser microscope (copper VK-X100) body (control unit) and the VK observation application (VK-H1VX manufactured by Keyence Corporation), the sample to be measured was placed on the x-y stage. By rotating the lens revolver of the microscope unit (VK-X110 manufactured by Keyence Corporation), an objective lens with a magnification of 10 times was selected, and in the image observation mode of the VK observation application (VK-H1VX), the focus and brightness were approximately adjusted. . The x-y stage was operated to adjust the part of the sample surface to be measured so that it was in the center of the screen. The objective lens with a magnification of 10 times was changed to a magnification of 50 times, and the object was focused on the surface of the sample with the autofocus function of the image observation mode of the VK observation application (VK-H1VX). The simple mode of the shape measurement tab of the VK observation application (VK-H1VX) was selected, the measurement start button was pressed, the surface shape of the sample was measured, and a surface image file was obtained. After the VK analysis application (VK-H1XA manufactured by Keyence Corporation) was started and the obtained surface image file was displayed, tilt correction was performed.

In addition, the observation measurement range (horizontal) in the measurement of the surface shape of the sample was set to 270 µm. Display the line roughness window, select JIS B0601-1994 in the parameter setting area, select a horizontal line from the measurement line button, display a horizontal line in an arbitrary place in the surface image, and press the OK button to The values of the average spacing (Sm) (µm) and the maximum height (Ry) (µm) were obtained. Further, horizontal lines were displayed at four other locations in the surface image, and values of the average spacing (Sm) (µm) and maximum height (Ry) (µm) of the respective uneven surfaces were obtained. The average value of the obtained five numerical values was calculated, and it was set as the average spacing (Sm) value and the maximum height (Ry) value of the uneven surface of the sample surface. Table 2 shows the measurement results.

(Measurement of glossiness)

After curing on a 35 μm-thick 300 mm × 150 mm copper foil substrate with a buff roll polished surface, solid-state printing is performed by screen printing so that the film thickness becomes 12 μm, and hot air circulation drying furnace (Yamato Chemical Co., Ltd.) It cured at 150° C. for 60 minutes using DF610 manufactured by Geisha, and a cured coating film was formed on the copper foil substrate, and allowed to stand for 30 minutes at room temperature under a yellow lamp to prepare an evaluation substrate.

All of the cured coating films formed on the copper foil substrate were placed on a waste containing isopropyl alcohol (IPA) on the surface of the cured coating film under an environment of 25°C and 50% RH, and a weight of 500 g was placed thereon and allowed to stand for 1 minute. Later, the waste was removed, and it was confirmed that all or part of the resin layer was not adhered to the surface of the waste that was in contact with the cured coating film. In addition, the glossiness is measured using a cured coating film formed by heat curing without performing a development step after exposure.

Thereafter, Gs (60°) of the surface of each cured coating film was measured using a digital variable angle gloss meter (Micro-Tri-Gloss, manufactured by BYK Gardener). The measurement results are shown in Table 2 below.

(Difference of coating film before drying when thin film)

As a method of simply checking the deviation of the coating film before drying during the thin film, a method of checking the deviation of the powder in the curable resin composition was adopted, and the degree of dispersion was measured for the curable resin composition.

Specifically, for the curable resin composition of each Example and Comparative Example, according to JIS K5101-5-2: 2004 and JIS K5600-2-5: 1999, a particle size gauge having a width of 90 mm, a length of 240 mm, and a maximum depth of 25 μm. By using (manufactured by Daiichi Sokuhan Seisakusho Co., Ltd.), the degree of dispersion was measured and evaluated based on the following evaluation criteria. In addition, the degree of dispersion observes that noticeable spots begin to appear on the gauge. In particular, it was observed that 5 to 10 particles were included in a width of 3 mm along the groove of the gauge, and this point was referred to as a dispersion degree. In front of the point at which the prominent spot starts to appear, the spot that appears sparsely is ignored. Calculate the average value of the three measurements. Table 2 shows the evaluation results.

(Circle): The dispersion degree (average value of three measurements) was 20 micrometers or less.

×: The degree of dispersion (average value of three measurements) was more than 20 μm.

(Variation of dry coating film when thin film)

A printability test was performed as a method of simply checking the variation of the dry coating film upon thin film. Specifically, on a beta glass substrate, beta printing is performed by screen printing using a 180 mesh polyester plate (bias oil) so that the film thickness after drying becomes 12 μm, and a hot air circulation drying furnace (Yamato Chemical Co., Ltd.) DF610 manufactured by Geisha) was used to dry at 90°C for 15 minutes, and then cooled and allowed to stand for 30 minutes at room temperature under a yellow lamp. Further, after leaving to stand, it was confirmed that the curable resin composition did not adhere to the finger when the coated surface was touched with a finger. After leaving to stand, using a surface roughness measuring machine (Kosaka Genkyusho Co., Ltd.: Surfcoder SE600), the dry coating and the uncoated portion were measured in 4 places at random, and the step difference analysis by a 3-point designation type was performed. Carried out. Details will be described with reference to the cross section of the dried coating film shown in FIG. 1. In the step analysis by the 3-point designation type, two reference points 3 of the surface of the dry coating film 2 on the substrate 1 are input, and the evaluation point 5 of the uncoated portion 4 of the substrate 1 is 1 By inputting a point, the reference line 6 is obtained. Next, the step P between the reference line 6 and the evaluation point 5 is measured. The film thickness and the standard deviation of the film thickness were respectively calculated from the measured steps P, and evaluated based on the following evaluation criteria. In addition, as the measurement conditions, the measurement magnification was 2,000 times, the feed rate was 0.5 mm/s, and the trace length was 6.0 mm. Table 2 shows the evaluation results.

(Circle): The standard deviation was within 1.0 micrometer.

X: The standard deviation was more than 1.0 µm.

(Confirmation of copper reflection phenomenon)

On a 35 μm-thick 300 mm × 150 mm copper foil substrate with surface buff roll polished, a 180-mesh polyester plate (with bias) so that the film thickness after curing becomes 12 μm is used for beta printing by screen printing and hot air. It was cured at 150°C for 60 minutes using a circulation drying furnace (DF610, Yamato Chemical Co., Ltd.), cooled and left to stand at room temperature for 30 minutes under a yellow lamp to prepare an evaluation substrate. All of the produced evaluation substrates were placed on the surface of the cured coating film in an environment of 25°C and 50% RH, and a waste containing isopropyl alcohol (IPA) was placed on it, and a weight of 500 g was placed thereon and allowed to stand for 1 minute, and then the waste was removed. , It was confirmed that all or part of the resin layer was not adhered to the surface in contact with the cured coating film of the waste.

After that, the part in which the copper of the base was visible within the range of 70 mm x 70 mm was confirmed with an optical microscope (x 50). Table 2 shows the evaluation results.

(Double-circle): The part in which copper was seen was not confirmed at all.

(Circle): The part where copper was seen was confirmed slightly, but it was a level without a problem.

X: A lot of parts where copper was seen were confirmed.

As found in Table 2, it can be seen that the curable resin composition of the example has a small variation in the pre-drying coating film or the dry coating film in the case of a thin film, and does not cause copper penetration.

1: substrate 2: dry coating
3: Reference point 4: Unapplied part
5: Score 6: Baseline
P: Step X: Measurement direction in a surface roughness measuring instrument

Claims (13)

As a curable resin composition containing a curable resin and an extender pigment,
The glossiness of 60° in the cured coating film having a film thickness of 12 μm after curing of the curable resin composition is in the range of 0.5 to 40.0,
0.3 g of the curable resin composition is mixed with 30 g of propylene glycol monomethyl ether acetate, and the average particle diameter (D ₅₀ ) as measured using a microtrack is 0.1 μm or more and 1.0 μm or less, and the specific surface area (CS) is 10.0 m 2 /ml or more, curable resin composition. The method of claim 1,
The curable resin composition, wherein the average spacing (Sm) of the irregularities of the coating film thickness after drying of the curable resin composition is in a range of more than 0 µm and not more than 12.0 µm. The method according to claim 1 or 2,
The curable resin composition, wherein the maximum height (Ry) of the coating film thickness after drying of the curable resin composition is in a range of more than 0 µm and not more than 8.0 µm. The method according to claim 1 or 2,
The curable resin composition, wherein the extender pigment is at least any one of silica and barium sulfate. The method of claim 4,
The extender pigment further comprises an oil absorption amount of 180 ~ 350 ml / 100g amorphous silica, curable resin composition. The method according to claim 1 or 2,
The curable resin composition, wherein the curable resin contains a carboxyl group-containing resin. The method according to claim 1 or 2,
The curable resin composition, wherein the curable resin contains two or more carboxyl group-containing resins. The method of claim 7,
At least one of the two or more types of carboxyl group-containing resins is a carboxyl group-containing copolymer resin. A dry film comprising a support film and a resin layer comprising a dry coating film of the curable resin composition according to claim 1 or 2 formed on the support film. A cured product obtained by curing the curable resin composition according to claim 1 or 2. A printed wiring board comprising the cured product according to claim 10. A cured product obtained by curing the resin layer of the dry film according to claim 9. A printed wiring board comprising the cured product according to claim 12.

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