KR20200000834A - Photosensitive film, photosensitive film laminate and cured product formed by using same - Google Patents

Abstract

The present invention relates to a photosensitive film which is excellent in adhesiveness with a die attach material, and can improve a yield in the external appearance inspection of a cured film. The photosensitive film comprises a surface having a concave portion on a surface thereof and is formed of a photosensitive resin composition, wherein the number of concave portions per a unit area of 1 mm^2 of the surface is not less than 3.0 × 10^2.

Description

Photosensitive film, photosensitive film laminated body, and hardened | cured material formed using them {PHOTOSENSITIVE FILM, PHOTOSENSITIVE FILM LAMINATE AND CURED PRODUCT FORMED BY USING SAME}

This invention relates to the photosensitive film, the photosensitive film laminated body, and the hardened | cured material formed using these.

In general, in a printed wiring board used for an electronic device or the like, when mounting an electronic component on a printed wiring board, in order to prevent solder from adhering to an unnecessary portion, a solder resist layer is provided in an area excluding a connection hole on a substrate on which a circuit pattern is formed. Is formed.

With high precision and high density of printed wiring boards due to light and short size reduction of electronic devices in recent years, the solder resist layer is currently patterned resin after applying a photosensitive resin composition to a substrate, and forming a pattern by exposure and development. What is formed by the so-called photo solder resist which hardens this by heating or light irradiation is mainstream.

Moreover, it is also proposed to form a soldering resist layer using what is called a photosensitive film laminated body provided with a photosensitive film, without using the liquid photosensitive resin composition as mentioned above. By using the photosensitive film laminated body, the drying process after application | coating can be unnecessary compared with the case of wet coating. Moreover, surface smoothness and surface hardness are also excellent.

The board | substrate with which the soldering resist was formed advances to a semiconductor mounting process. Especially, the soldering resist used for the wire bonding specification is a semiconductor mounted by die attach material, and is connected by wire bonding. Here, as the solder resist, surface smoothness and adhesion with the die attach material are very important factors. In recent years, with the thinning of a board | substrate, the improvement of the very high specification precision is calculated | required in the various materials used. In view of this, the solder resist is also the film laminate as described above, and surface uniformity is required. Similarly, the die attach material on which the semiconductor is mounted is required to have a uniform film thickness and a thin film. For example, Japanese Unexamined Patent Application Publication No. 2016-069625 discloses a dry film laminate corresponding to a thin film substrate. However, the improvement of the above-mentioned specification precision and the adhesiveness of a soldering resist and a die attach material were very difficult.

On the other hand, since a soldering resist is used for the outermost layer of a board | substrate and is formed in the last stage of a board | substrate manufacturing process, a scratch may arise at the time of use of apparatuses, conveyance tools, etc. during a board | substrate manufacturing process (for example, Japanese Patent Laid-Open No. 2015-206992. This flaw becomes NG determination by the external inspection before a semiconductor mounting process, and production yield may deteriorate. In particular, in recent years, even a small scratch which does not have a quality problem causes a loss of productivity, which is one of important requirements and a new improvement method is required.

Therefore, the objective of this invention is providing the photosensitive film which is excellent in adhesiveness with a die attach material, and can improve a yield also in the external inspection of a cured film. Moreover, another object of this invention is to provide the photosensitive film laminated body provided with the photosensitive film, and the hardened | cured material formed using the same.

MEANS TO SOLVE THE PROBLEM In the case where the layer formed using the photosensitive film laminated body and the soldering resist layer were formed especially in this, especially when it is applied to the board | substrate for IC packages, this invention solder-resist in the die attach material formation process after IC chip mounting. It was found that the cause of the poor adhesion with the layer lies in the surface form of the solder resist layer. And the present inventors can provide a suitable recessed part to the surface of a soldering resist layer by using the photosensitive film provided with the surface which has a specific recessed part in the surface, As a result, adhesiveness with a die attach material can be improved. Gained knowledge. Furthermore, the inventors of the present invention find that the solder resist layer formed by using a photosensitive film having a surface having a specific recess as described above makes it difficult to visually recognize a scratch even when the surface is scratched, thereby improving the yield in appearance inspection. I got the knowledge that I could. This invention is based on this knowledge.

[1] The photosensitive film according to the first embodiment of the present invention includes a surface having a concave portion on its surface and is formed of a photosensitive resin composition, wherein the number of the concave portions per unit area of 1 mm ² of the surface. Is 3.0 × 10 ² or more.

[2] The photosensitive film according to the second embodiment of the present invention is the photosensitive film of [1], wherein the number of recesses per unit area of 1 mm ² of the surface is 2.0 × 10 ⁴ or less.

[3] The photosensitive film according to the third embodiment of the present invention is the photosensitive film of [1] or [2], in which arithmetic mean surface roughness Ra of the surface is 0.05 µm or more.

[4] The photosensitive film according to the fourth embodiment of the present invention is the photosensitive film according to any one of [1] to [3], in which the photosensitive resin composition contains a filler and a crosslinking component.

[5] The photosensitive film laminate according to the fifth embodiment of the present invention is characterized in that the supporting film is laminated on the photosensitive film of any one of [1] to [4].

[6] The photosensitive film laminate according to the sixth embodiment of the present invention has a surface having a recess on its surface and is formed by a photosensitive resin composition, and is supported on the surface side having the recess on the surface. It is a photosensitive film laminated body of [6] by which film is laminated | stacked.

[7] The cured product according to the seventh embodiment of the present invention is formed by using the photosensitive film of any of [1] to [4] or the photosensitive film laminate of [5] or [6]. It is.

According to this invention, the photosensitive film which is excellent in adhesiveness with a die attach material and which can improve a yield also in the external appearance inspection of a cured film can be implement | achieved. Moreover, according to the preferable aspect of this invention, the photosensitive film excellent in formation of the photosensitive pattern, especially suppression of the furrow collapse of a pattern can be implement | achieved. It is especially effective when the photosensitive film is used for formation of a soldering resist layer.

The photosensitive film by this invention is demonstrated. The photosensitive film is made into the film form of the photosensitive resin composition, and says that the other layer, such as a support film and a protective film, is not laminated | stacked. In addition, in this invention, in consideration of the workability and the ease at the time of forming the surface of the photosensitive film later in the predetermined form, the support film may be provided in one surface of the photosensitive film, and it is dusty on the surface of the photosensitive film A protective film may be further provided in the surface opposite to a support film in consideration of preventing adhesion, etc., and the handleability of the photosensitive film laminated body. Hereinafter, the photosensitive film and other layers arbitrarily provided by this invention are demonstrated.

<Photosensitive film>

The photosensitive film which concerns on this invention is provided with the surface which has a recessed part in the surface, and is formed of the photosensitive resin composition, The number of recessed parts per unit area 1mm <^2> of the said surface is 3.0 * 10 <^2> or more, It is characterized by the above-mentioned. . The number of recesses per unit area of 1 mm ² is measured three-dimensionally by measuring the unevenness of the surface of the photosensitive film as a target with the z-axis in the height direction to obtain the maximum value and the minimum value of the aggregate of z values obtained, and are calculated from the maximum value and the minimum value. The value calculated by counting the number of recessed areas existing in a unit area of 1 mm ² is assumed to be a recessed area, with a Zs value 0.2 µm lower than the average value as the threshold value. For example, in the three-dimensional measurement which measures height z using the surface of the photosensitive film as an xy-axis surface, when the maximum value and minimum value of the aggregate of z values obtained are 3.00 micrometer and 1.00 micrometer, respectively, the average value will be 2.00 micrometer 1.80 micrometers which is 0.2 micrometers lower than this turns into a Zs value, ie, a "threshold value." The number of recesses can be determined by counting the number of recessed regions interspersed in the measurement surface with the set on the xy-axis surface continuous to a value lower than the threshold value of 1.80 µm. More detailed measurement procedures will be described later.

In this invention, adhesiveness with a die attach material can be improved by using the photosensitive film provided with the surface whose number of recesses per unit area 1mm <^2> computed as mentioned above is 3.0 * 10 <^2> or more. Moreover, when a soldering resist layer etc. are formed using the photosensitive film which has such a specific surface form, a yield can be improved in the external inspection which examines the presence or absence of the surface flaw of a soldering resist layer. The reason why such an unexpected effect is exerted is not necessarily clear, but by forming a recess on the surface of the photosensitive film and setting the recess to an appropriate number, a suitable continuous surface is formed on the surface of the photosensitive film, and the continuous surface and the recess are mixed. Even if minute scratches are formed in the region, it is inferred that the reflections of the scratches are alleviated by the recesses, making it difficult to see the scratches. On the other hand, it is inferred that the adhesive force with a die attach material is remarkably improved by the anchor effect by a recessed part. However, it is an area of speculation to the last, but it is not necessarily so.

It is preferable that it is 4.0 * 10 <^2> or more, and, as for the number of recessed parts per unit area 1mm <^2> of the photosensitive film surface, 5.0 * 10 <^2> or more is more preferable. The number of recesses per unit area of 1 mm ² is not particularly limited as long as such a surface can be formed. However, by setting the number of concave portions to 2.0 × 10 ⁴ or less, the adhesiveness with the die attach material is excellent, and the yield is also obtained in the appearance inspection of the cured coating film. In addition to being able to improve, it is also possible to obtain an excellent effect of suppressing the formation of the photosensitive pattern of the solder resist layer, in particular, the collapse of the pattern. The number of recesses per unit area of 1 mm ² is more preferably 1.5 × 10 ⁴ or less, and still more preferably 1.0 × 10 ⁴ or less. Here, in the case where the furrow collapse of the pattern is, for example, when forming an SRO (solder resist opening) using a photosensitive film, the resin powder contained in the photosensitive film on the groove of the opening collapses after exposure and development, and the inside of the opening is collapsed. It means the phenomenon of being pushed out. In this invention, it turned out that the sulcus collapse of a pattern can be suppressed unexpectedly by making it into the photosensitive film which has a specific surface form as mentioned above.

Moreover, it is preferable that arithmetic mean surface roughness Ra of the surface which has a recessed part in the surface of the photosensitive film is 0.05 micrometer or more, and it is 0.06 micrometer or more from a viewpoint of the balance of the adhesiveness with a die attach material, and the yield improvement in an external appearance test. It is preferable and it is more preferable that it is 0.07 micrometer or more. Moreover, when setting an upper limit, it is preferable that it is 5.0 micrometers or less, It is more preferable that it is 3.0 micrometers or less, It is further more preferable that it is 1.0 micrometer or less.

Moreover, although the recessed part of the photosensitive film surface may be uniform or nonuniform, it is preferable from a viewpoint of the balance of the adhesiveness with a die attach material, and the yield improvement in an external appearance test. Moreover, it is preferable that the depth of a recessed part is 0.2 micrometer or more.

Moreover, it is preferable that arithmetic mean surface roughness Ra of the surface which has predetermined recessed part of the photosensitive film is 0.05 micrometer or more from a viewpoint of the above-mentioned balance, It is more preferable that it is 0.06 micrometer or more, It is still more preferable that it is 0.07 micrometer or more. Moreover, when setting an upper limit, it is preferable that it is 5.0 micrometers or less, It is more preferable that it is 3.0 micrometers or less, It is further more preferable that it is 1.0 micrometer or less.

In this invention, said "number of recessed parts per unit area 1mm <^2>" and "arithmetic mean surface roughness Ra" mean the value measured by the measuring apparatus based on JISB0601-1994. Hereinafter, the specific measuring method is demonstrated. The number and the arithmetic mean surface roughness Ra of a recessed part per unit area 1mm <^2> can be measured using a shape measuring laser microscope (for example, VK-X100 by Keyence Co., Ltd.). After starting a shape measurement laser microscope (VK-X100) main body (control part) and a VK observation application (VK-H1VX by Keyence Co., Ltd.), the sample to measure is mounted on an xy stage. The objective lens with a magnification of 10 times is selected by turning the lens revolver of the microscope section (VK-X110 manufactured by Keyence Co., Ltd.), and in the image observation mode of the VK observation application (the same VK-H1VX), approximately the focus and brightness are adjusted. By operating the xy stage, the center of the screen is adjusted to the center of the sample surface. The objective lens of 10 times magnification is changed to 100 times magnification, and the focus is set on the surface of the sample by the autofocus function of the image observation mode of VK observation application (the same VK-H1VX). By selecting the simple mode of the shape measurement tab of the VK observation application (the same VK-H1VX), pressing the measurement start button, the surface shape of the sample can be measured to obtain a surface image file. After starting a VK analysis application (VK-H1XA manufactured by Keyence Co., Ltd.) and displaying the obtained surface image file, the tilt correction is performed.

In the measurement of "the number of recesses per unit area 1mm <^2> , the observation measurement range (area) in the measurement of the surface shape of a sample shall be 15073 micrometer <^2> . For example, an analysis application (VK-H1XA) can be used. Select [Volume and Area] from the measurement analysis menu on the display screen to display the [Volume and Area] window. After selecting [Height] from the [Display image] box in the [Volume / area] window, press the [Threshold] button to display the [Threshold area setting dialog] box. The value of the displayed upper limit box and the lower limit box were added to calculate the value Ave. (µm) divided by 2, and the portion below the Zs value (µm) obtained by subtracting 0.2 µm from the Ave. Concave portion ”. Without changing the value of the [Lower limit] box, enter the Zs value (µm) in the [Upper limit] box, and after pressing the OK button, the number of places C (colors) changed to the ROI drawing color in the image display area. It is set as the value which computed the number D (piece / mm <^2> ) (D = C * 66.34) per unit area of 1 mm <^2> from this number C (piece). In addition, what is broken in the boundary part of an image display area and cannot be recognized as one among the places which turned into the color of the said ROI drawing color is counted as 0.5 piece.

In addition, in the measurement of "arithmetic mean surface roughness Ra", the objective lens is switched 50 times, and the observation measurement range (width) in the measurement of the surface shape of a sample is 270 micrometers. Display the line roughness window, select JIS B0601-1994 in the parameter setting area, select the horizontal line from the measurement line button, display the horizontal line anywhere in the surface image, and press the OK button to Obtain the value of roughness Ra ₁ . In addition, horizontal lines are displayed in four different places in the surface image to obtain numerical values of the arithmetic mean surface roughness Ra ₁ . Average value of the obtained five values Ra _ave. Is calculated and this value is used as the arithmetic mean surface roughness Ra value of the sample surface. In addition, when measuring the photosensitive film in the photosensitive film laminated body, after peeling a support film and exposing the photosensitive film surface, the measurement of "the number of recessed parts per unit area 1mm <^2>and" arithmetic mean surface roughness Ra "within 5 minutes. Shall be performed.

In order to make the surface shape of the photosensitive film into the range of the specific number of recesses and the specific arithmetic mean surface roughness Ra per unit area of 1 mm ² described above, a known and conventional method can be applied, but in particular, the surface shape of the photosensitive film It is preferable to form a photosensitive film using the support film mentioned later from a viewpoint of the ease of thing. That is, in the case of the photosensitive film laminated body by which a support film is laminated | stacked on the photosensitive film of this invention, the surface of the photosensitive film which has the surface which has the above-mentioned specific number of recessed parts, and also has a specific arithmetic mean surface roughness Ra if desired is a support film. It is preferable that it is a surface which contacts. Moreover, it is preferable that the photosensitive film is for soldering resist layer formation.

A photosensitive film having a surface having a concave portion number of 3.0 × 10 ² or more per unit area of 1 mm ^{2 as described} above, and in a more preferred embodiment, the photosensitive film having arithmetic mean surface roughness Ra of the surface of 0.05 µm or more is exposed and developed. It becomes patterned by this and becomes the hardened film provided on the circuit board. As a hardened film, it is preferable that it is a soldering resist layer. Such a photosensitive film can be formed using a photosensitive resin composition, and the photosensitive resin composition can use a conventionally well-known solder resist ink etc. without limitation, Hereinafter, the photosensitive resin composition which can be preferably used for the photosensitive film by this invention. An example will be described.

In this invention, it is preferable that the photosensitive resin composition contains a crosslinking component and a filler. Moreover, it is more preferable to contain a photoinitiator. A carboxyl group-containing photosensitive resin and a photosensitive monomer are preferable, and when a crosslinking component heats further, it is preferable to include the component bridge | crosslinked by heat. Hereinafter, each component is demonstrated.

[Crosslinking Ingredients]

The crosslinking component is not particularly limited as long as it is a component to be crosslinked, and known conventional ones can be used. In particular, a carboxyl group-containing photosensitive resin or a photosensitive monomer is preferable, and when further heated, it is preferable to include a component (hereinafter, thermally crosslinked component) crosslinked by heat.

The carboxyl group-containing photosensitive resin is a component which is polymerized or crosslinked and cured by light irradiation, and can be made alkali developable by containing a carboxyl group. In addition, it is preferable to have an ethylenically unsaturated bond in a molecule other than a carboxyl group from a viewpoint of photocurability and developability. As ethylenically unsaturated double bond, the thing derived from acrylic acid or methacrylic acid, or derivatives thereof is preferable.

Moreover, as carboxyl group-containing photosensitive resin, it is preferable to use carboxyl group-containing photosensitive resin which did not use an epoxy resin as a starting material. The carboxyl group-containing photosensitive resin which does not use an epoxy resin as a starting material has very low halide ion content, and can suppress deterioration of insulation reliability. As a specific example of carboxyl group-containing photosensitive resin, the compound (any of an oligomer or a polymer) enumerated below is mentioned.

(1) (meth) acrylic acid is made to react with bifunctional or more than polyfunctional (solid) epoxy resin, and bibasic acid anhydrides, such as phthalic anhydride, tetrahydro phthalic anhydride, hexahydro phthalic anhydride, are added to the hydroxyl group which exists in a side chain. Carboxyl group-containing photosensitive resin

(2) Containing the carboxyl group in which the hydroxyl group of the bifunctional (solid) epoxy resin was further epoxidized with epichlorohydrin, (meth) acrylic acid was reacted to add the dibasic anhydride to the generated hydroxyl group. Photosensitive resin,

(3) A compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, and an unsaturated group-containing monocarboxylic acid such as (meth) acrylic acid is reacted with an epoxy compound having two or more epoxy groups in one molecule. The carboxyl group-containing photosensitive resin obtained by making polybasic acid anhydrides, such as maleic anhydride, tetrahydro phthalic anhydride, trimellitic anhydride, a pyromellitic anhydride, adipic acid, react with the alcoholic hydroxyl group of the obtained reaction product,

(4) In one molecule such as bisphenol A, bisphenol F, bisphenol S, novolac phenol resin, poly-p-hydroxystyrene, a condensate of naphthol and aldehydes, and a condensate of dihydroxynaphthalene and aldehydes To a reaction product obtained by reacting a compound having two or more phenolic hydroxyl groups with an alkylene oxide such as ethylene oxide and propylene oxide, and an unsaturated group-containing monocarboxylic acid such as (meth) acrylic acid Carboxyl group-containing photosensitive resin obtained by making polybasic acid anhydride react,

(5) Polybasic acid to the reaction product obtained by making unsaturated group containing monocarboxylic acid react with the reaction product obtained by making the compound which has two or more phenolic hydroxyl groups in 1 molecule, and cyclic carbonate compounds, such as ethylene carbonate and a propylene carbonate, react. Carboxyl group-containing photosensitive resin obtained by making anhydride react,

(6) diisocyanate compounds such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate and aromatic diisocyanate, polycarbonate polyol, polyether polyol, polyester polyol, polyolefin polyol, acrylic polyol, bisphenol Terminal carboxyl group-containing urethane resin which makes acid anhydride react with the terminal of the urethane resin by polyaddition reaction of diol compounds, such as A type alkylene oxide adduct diol, a compound which has a phenolic hydroxyl group, and alcoholic hydroxyl group,

(7) During synthesis of carboxyl group-containing urethane resin by polyaddition reaction of diisocyanate, carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutyric acid and diol compound, such as hydroxyalkyl (meth) acrylate The carboxyl group-containing urethane resin which added the compound which has one hydroxyl group and one or more (meth) acryloyl groups in a molecule | numerator, and terminal (meth) acrylated,

(8) During synthesis of the carboxyl group-containing urethane resin by the polyaddition reaction of a diisocyanate, a carboxyl group-containing dialcohol compound, and a diol compound, 1 in a molecule | numerator, such as equimolar reactants of isophorone diisocyanate and pentaerythritol triacrylate Carboxyl group-containing urethane resin which added the compound which has one isocyanate group and 1 or more (meth) acryloyl group, and was terminal (meth) acrylated,

(9) To carboxyl group-containing polyester resin which made dibasic acid, such as adipic acid, phthalic acid, and hexahydrophthalic acid, react with polyfunctional oxetane resin, and added dibasic acid anhydride to the produced | generated primary hydroxyl group, Carboxyl group-containing photosensitive property which adds the compound which has one epoxy group and one or more (meth) acryloyl groups in 1 molecule, such as glycidyl (meth) acrylate and (alpha) -methyl glycidyl (meth) acrylate, Suzy,

(10) The carboxyl group-containing photosensitive resin which added the compound which has a cyclic ether group and a (meth) acryloyl group in 1 molecule to carboxyl group-containing photosensitive resin in any one of (1)-(9) mentioned above,

(11) About carboxyl group-containing resin obtained by copolymerization of unsaturated carboxylic acids, such as (meth) acrylic acid, and unsaturated group containing compounds, such as styrene, (alpha) -methylstyrene, lower alkyl (meth) acrylate, and isobutylene, Carboxyl group containing photosensitive resin etc. which made the compound which has a cyclic ether group and a (meth) acryloyl group react in 1 molecule, such as 3, 4- epoxycyclohexyl methacrylate, are mentioned. In addition, the term (meth) acrylate here is generic terms for acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions below.

Among the carboxyl group-containing photosensitive resins described above, carboxyl group-containing photosensitive resins obtained by synthesizing resins other than carboxyl group-containing photosensitive resins and epoxy resins which do not use epoxy resins as starting materials can be suitably used. Therefore, in the specific example of the carboxyl group-containing photosensitive resin mentioned above, any 1 or more types of carboxyl group-containing photosensitive resin in (4)-(8) and (11) can be used suitably, and it is illustrated in (4)-(8). Resin can be used especially suitably. It may have characteristics required for solder resists for semiconductor packages, that is, PCT resistance, HAST resistance, and cold shock resistance.

Thus, by not using an epoxy resin as a starting material, the amount of chlorine ion impurities can be suppressed very little to 100 ppm or less, for example. Chlorine ion impurity content of the carboxyl group-containing photosensitive resin used suitably in this invention is 0-100 ppm, More preferably, it is 0-50 ppm, More preferably, it is 0-30 ppm.

In addition, by not using an epoxy resin as a starting material, resin which does not contain a hydroxyl group (or the quantity of hydroxyl group was reduced) can be obtained easily. In general, the presence of a hydroxyl group also has excellent characteristics such as improvement in adhesion due to hydrogen bonding, but it is known to significantly lower moisture resistance, and it is possible to improve moisture resistance by using a carboxyl group-containing photosensitive resin containing no hydroxyl group. Become.

Moreover, the carboxyl group-containing urethane resin which is synthesize | combined from the isocyanate compound which does not use phosgene as a starting material, and the raw material which does not use epihalohydrin, and the amount of chlorine ion impurities is 0-30 ppm is also used suitably. In such a urethane resin, the resin which does not contain a hydroxyl group can be synthesize | combined easily by matching the equivalent of a hydroxyl group and an isocyanate group.

In addition, an epoxy acrylate modified raw material can also be used as a diol compound at the time of the synthesis | combination of a urethane resin. Although chlorine ion impurity enters, it can be used from the point which can control the amount of chlorine ion impurity.

Since the said carboxyl group-containing photosensitive resin has many carboxyl groups in the side chain of a backbone polymer, image development by aqueous alkali solution is possible.

It is preferable that the acid value of carboxyl group-containing photosensitive resin is 40-150 mgKOH / g. Alkali image development becomes favorable by making the acid value of carboxyl group-containing photosensitive resin into 40 mgKOH / g or more. In addition, by setting the acid value to 150 mgKOH / g or less, it is possible to easily draw a normal resist pattern. More preferably, it is 50-130 mgKOH / g.

Although the weight average molecular weight of carboxyl group-containing photosensitive resin changes with resin skeleton, it is preferable that it is generally 2,000-150,000. By setting the weight average molecular weight to 2,000 or more, the touch drying performance and the resolution can be improved. Moreover, developability and storage stability can be improved by making a weight average molecular weight 150,000 or less. More preferably, it is 5,000-100,000.

It is preferable that the compounding quantity of carboxyl group-containing photosensitive resin is 20-60 mass% in total composition in solid content conversion. By setting it as 20 mass% or more, coating film strength can be improved. Moreover, when it is 60 mass% or less, viscosity becomes moderate and workability improves. More preferably, it is 30-50 mass%.

As a compound used as a photosensitive monomer, the conventionally well-known polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, and epoxy (meth) acrylate Etc. can be mentioned. Specifically, hydroxyalkyl acrylates, such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; Diacrylates of glycols such as ethylene glycol, methoxy tetraethylene glycol, polyethylene glycol and propylene glycol; Acrylamides such as N, N-dimethylacrylamide, N-methylolacrylamide and N, N-dimethylaminopropylacrylamide; Aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate and N, N-dimethylaminopropyl acrylate; Polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate or ethylene oxide adducts thereof, propylene oxide adducts, ε-caprolactone adducts and the like Polyhydric acrylates; Polyhydric acrylates, such as phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide adduct or propylene oxide adduct of these phenols; Polyhydric acrylates of glycidyl ethers such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether and triglycidyl isocyanurate; Not limited to the above, acrylates and melamine acrylates in which polyols such as polyether polyol, polycarbonate diol, hydroxyl terminal polybutadiene and polyester polyol are directly acrylated or urethane acrylated through diisocyanate, and It can select suitably from at least 1 sort (s) of each methacrylate corresponding to the said acrylate, and can use.

Hydroxyacrylates, such as pentaerythritol triacrylate, and isophorone to the epoxy acrylate resin which made acrylic acid react with polyfunctional epoxy resins, such as a cresol novolak-type epoxy resin, and the hydroxyl group of this epoxy acrylate resin further You may use the epoxyurethane acrylate compound which made the half urethane compound of diisocyanate, such as diisocyanate react, as a photosensitive monomer. Such epoxy acrylate-based resin can improve photocurability without deteriorating the touch dryness.

The compounding quantity of the compound which has an ethylenically unsaturated group in the molecule | numerator used as a photosensitive monomer, when containing carboxyl group-containing resin in a composition, it is 5-100 mass parts with respect to 100 mass parts of carboxyl group-containing resin in solid content conversion, Preferably it is more preferable. Preferably it is the ratio of 5-70 mass parts. By setting the compounding quantity of the compound which has an ethylenically unsaturated group into 5 mass parts or more, the photocurability of a photocurable resin composition improves. Moreover, coating film hardness can be improved by making compounding quantity 100 mass parts or less. The carboxyl group-containing resin as used herein includes any of carboxyl group-containing photosensitive resin and carboxyl group non-photosensitive resin. That is, when either is mix | blended individually in a composition, when it mix | blends individually, it says the sum total (it is the same in the following paragraph).

The photosensitive monomer, in particular, when using a carboxyl group-containing non-photosensitive resin having no ethylenically unsaturated double bond, it is necessary to use a compound (photosensitive monomer) having at least one ethylenically unsaturated group in the molecule in order to make the composition photocurable. Because of that, it is valid.

Thermosetting resin etc. are mentioned as a thermal crosslinking component. Examples of the thermosetting resin include known isocyanate compounds, blocked isocyanate compounds, amino resins, maleimide compounds, benzoxazine resins, carbodiimide resins, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, episulfide resins, and the like. Ordinary ones can be used. Among these, a preferable thermal crosslinking component is a thermal crosslinking component which has at least any 1 type (hereinafter abbreviated as cyclic (thio) ether group) of some cyclic ether group and cyclic thioether group in 1 molecule. There exist many types of thermosetting components which have these cyclic (thio) ether groups, and can provide various characteristics according to the structure.

The thermosetting component which has a some cyclic (thio) ether group in a molecule | numerator is a compound which has one or two types of groups of 3, 4 or 5 membered cyclic ether group or cyclic thioether group in a molecule | numerator, for example in a molecule | numerator A compound having a plurality of epoxy groups, 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, etc. Can be mentioned.

Examples of the polyfunctional epoxy compound include jER828, jER834, jER1001, jER1004, and DIC Corp., Inc. Epiclo 840, Epiclone 840-S, Epiclone 850, Epiclone 1050, and Epiclone. 2055, Efototo YD-011, YD-013, YD-127, YD-128, DER317, DER331, DER661, DER664 manufactured by Shinnitetsu Sumikin Corporation Of Sumier epoxy ESA-011, ESA-014, ELA-115, ELA-128, ASA330, AER331, AER661, AER664 manufactured by Asahi Kasei Kogyo Co., Ltd. Bisphenol A epoxy resin; JERYL903 manufactured by Mitsubishi Chemical Corporation, Epiclone 152, Epiclone 165, manufactured by DIC Corporation, Inc., Efototo YDB-400, YDB-500, manufactured by Shinnitetsu Sumikin Corporation, DER542, manufactured by Dow Chemical Co., Ltd. Brominated epoxy resins such as Sumitomo Kagaku Kogyo Co., Ltd. (Sumiepoxy ESB-400, ESB-700, Asahi Kasei Kogyo Co., Ltd.) AER711, AER714 (all brand names); JER152, jER154 manufactured by Mitsubishi Chemical Corporation, DEN431, DEN438 manufactured by Dow Chemical Corporation, Epiclone N-730, Epiclone N-770, Epiclone N-865, Shinnitetsu Smykin manufactured by DIC Corporation Efototo YDCN-701, YDCN-704, Nippon Kayaku Co., Ltd. EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, NC-3000H, Sumitomo Novolak-type epoxy resins, such as Sumerepoxy ESCN-195X, ESCN-220, and Asahi Kasei Kogyo Co., Ltd. AERECN-235 and ECN-299 (all brand names) by Kagaku Kogyo Co., Ltd .; Bisphenol F type of epiclon 830 made by DIC Corporation, Mitsubishi Chemical Corporation, jER807, Shinnitetsu Sumikin Corporation, Efototo YDF-170, YDF-175, YDF-2004, etc. (all brand names) Epoxy resins; Hydrogenated bisphenol A type epoxy resins such as Efototo ST-2004, ST-2007, and ST-3000 (trade name) manufactured by Shinnitetsu Sumikin Corporation; Glycidyl amines such as jER604 manufactured by Mitsubishi Chemical Corporation, Efototo YH-434 manufactured by Shinnitetsu Sumikin Corporation, Inc., Sumitomo Chemical Co., Ltd., Sumiepoxy ELM-120 manufactured by Sumitomo Chemical Co., Ltd. (all brand names) Type epoxy resins; Alicyclic epoxy resins such as Celoxide 2021 (trade name) manufactured by Daicel Corporation; Trihydroxyphenylmethane type epoxy resins, such as Mitsubishi Chemical Corporation YL-933 (made by Mitsubishi Chemical Corporation), T.E.N., EPPN-501, and EPPN-502 (all brand names) by Dow Chemical Company; Bixylenol type or biphenol type epoxy resins such as YL-6056, YX-4000, and YL-6121 (all trade names) manufactured by Mitsubishi Chemical Corporation; or mixtures thereof; Bisphenol S type epoxy resins, such as Nippon Kayaku Co., Ltd. EBPS-200, Asahi Denka Kogyo Co., Ltd. EPX-30, and DIC Corporation EXA-1514 (brand name); Bisphenol A novolak-type epoxy resins, such as Mitsubishi Chemical Corporation jER157S (brand name); Tetraphenylolethane type epoxy resins such as jERYL-931 (trade name) manufactured by Mitsubishi Chemical Corporation; Heterocyclic epoxy resins such as TEPIC manufactured by Nissan Chemical Industries, Ltd. (trade name); Diglycidyl phthalate resins such as Blemmer DGT manufactured by Nihon Yushi Co., Ltd .; Tetraglycidyl xylenoyl ethane resins such as Zintetsu Sumikin Chemical Co., Ltd. ZX-1063; Naphthalene group-containing epoxy resins such as ESN-190, ESN-360 manufactured by Shinnitetsu Chemical Co., Ltd., ESN-360 manufactured by DIC Corporation, and HP-4032, EXA-4750, EXA-4700; Epoxy resin which has dicyclopentadiene frame | skeleton, such as DIC Corporation HP-7200 and HP-7200H, and flexible steel of EXA-4816, EXA-4822, EXA-4850 series; Glycidyl methacrylate copolymer epoxy resins such as CP-50S and CP-50M manufactured by Nihon Yushi Co., Ltd .; Moreover, although the copolymerization epoxy resin of cyclohexyl maleimide and glycidyl methacrylate etc. are mentioned, It is not limited to these. These epoxy resins can be used individually or in combination of 2 or more types.

Examples of the polyfunctional oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether and 1,4-bis [( 3-methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methylacrylic Latex, (3-ethyl-3-oxetanyl) methylacrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate or their In addition to polyfunctional oxetanes such as oligomers or copolymers, oxetane alcohols and novolac resins, poly (p-hydroxystyrenes), cardo type bisphenols, calixarylenes, calyx resorcinarylenes or silsesquioxanes And etherates with resins having hydroxyl groups such as these. In addition, the copolymer etc. of the unsaturated monomer which has an oxetane ring, and an alkyl (meth) acrylate are mentioned.

As episulfide resin, Mitsubishi Chemical Co., Ltd. product YL7000 (bisphenol-A episulfide resin) etc. are mentioned, for example. Moreover, the episulfide resin etc. which substituted the oxygen atom of the epoxy group of the novolak-type epoxy resin by the sulfur atom can also be used using the same synthesis method.

When the compounding quantity of the thermosetting component which has a some cyclic (thio) ether group in a molecule | numerator contains the thermosetting component which has a some cyclic (thio) ether group in a molecule | numerator in a composition, with respect to 1 equivalent of the carboxyl group of carboxyl group-containing resin in solid content conversion Preferably it is 0.3-2.5 equivalent, More preferably, it is the range which becomes 0.5-2.0 equivalent. By making the compounding quantity of the thermosetting component which has a some cyclic (thio) ether group in a molecule into 0.3 equivalent or more, a carboxyl group does not remain in a hardened film, and heat resistance, alkali resistance, electrical insulation, etc. improve. Moreover, by setting it as 2.5 equivalent or less, the low molecular weight cyclic (thio) ether group does not remain in a dry coating film, but the intensity | strength of a cured film, etc. improve.

When using the thermosetting component which has a some cyclic (thio) ether group in a molecule | numerator, it is preferable to mix | blend a thermosetting catalyst. As such 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, N-dimethylbenzylamine Hydrazine compounds such as compounds, adipic dihydrazide and sebacic acid dihydrazide; Phosphorus compounds, such as a triphenylphosphine, etc. are mentioned. Moreover, as what is marketed, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all are brand names of an imidazole type compound) by Shikoku Kasei Kogyo Co., Ltd., and San Afro Corporation are manufactured, for example. U-CAT (registered trademark) 3503N, U-CAT3502T (both trade names of block isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (both bicyclic amidine compounds and salts thereof) and the like. . In particular, it is not limited to these, What is necessary is just to accelerate reaction of the thermosetting catalyst of an epoxy resin or an oxetane compound, or an epoxy group and / or an oxetanyl group, and a carboxyl group, and may be used individually or in mixture of 2 or more types none. Also, 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 S-triazine derivatives, such as an adduct, can also be used, Preferably, the compound which functions also as these adhesive imparting agents is used together with a thermosetting catalyst.

When the compounding quantity of a thermosetting catalyst contains the thermosetting component which has several cyclic (thio) ether group in a molecule | numerator in a composition, it is solid content conversion with respect to 100 mass parts of thermosetting components which have several cyclic (thio) ether group in a molecule | numerator. Preferably it is 0.1-20 mass parts, More preferably, it is 0.5-15.0 mass parts.

As amino resin, amino resins, such as a melamine derivative and a benzoguanamine derivative, are mentioned. For example, a methylol melamine compound, a methylol benzoguanamine compound, a methylol glycoluril compound, a methylol urea compound, etc. are mentioned. Moreover, the alkoxy methylation melamine compound, the alkoxy methylation benzoguanamine compound, the alkoxy methylation glycoluril compound, and the alkoxy methylation urea compound are each methylol melamine compound, methylol benzoguanamine compound, methylol glycoluril compound, and methylol urea compound. It is obtained by converting the methylol group of to an alkoxy methyl group. It does not specifically limit about the kind of this alkoxy methyl group, For example, it can be set as a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, butoxymethyl group. Particularly preferred are melamine derivatives having a formalin concentration of 0.2% or less that is friendly to humans and the environment.

As a commercial item of an amino resin, Cymel 300, copper 301, copper 303, copper 370, copper 325, copper 327, copper 701, copper 266, copper 267, copper 238, copper 1141, copper 272, copper 202, copper 1156, copper 1158, copper 1123, copper 1170, copper 1174, copper UFR65, copper 300 (above, Mitsui Cycamide Co., Ltd.), Nikalak Mx-750, copper Mx-032, copper Mx-270, copper Mx -280, Mx-290, Mx-706, Mx-708, Mx-40, Mx-31, Ms-11, Mw-30, Mw-30HM, Mw-390, Mw -100LM, the copper Mw-750LM (above, Sanwa Chemical Co., Ltd.), etc. are mentioned.

As an isocyanate compound, the polyisocyanate compound which has several isocyanate group in a molecule | numerator can be used. As a polyisocyanate compound, aromatic polyisocyanate, aliphatic polyisocyanate, or alicyclic polyisocyanate is used, for example. Specific examples of the aromatic polyisocyanate include 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate and 2,4-tolylene dimer are mentioned. Specific examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate) and isophorone diisocyanate. Specific examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate. And adducts, biurets and isocyanurates of the isocyanate compounds exemplified above.

The blocked isocyanate group contained in the blocked isocyanate compound is a group in which an isocyanate group is protected by a reaction with a blocking agent and is temporarily inactivated. When heated to a predetermined temperature, the blocking agent dissociates to form an isocyanate group.

As a block isocyanate compound, the addition reaction product of an isocyanate compound and an isocyanate blocking agent is used. As an isocyanate compound which can react with a blocking agent, an isocyanurate type, a biuret type, an adduct type, etc. are mentioned. As an isocyanate compound used for synthesize | combining a block isocyanate compound, aromatic polyisocyanate, aliphatic polyisocyanate, or alicyclic polyisocyanate is mentioned, for example. Specific examples of the aromatic polyisocyanate, aliphatic polyisocyanate and alicyclic polyisocyanate include the compounds exemplified above.

As an isocyanate blocking agent, For example, phenol type blocking agents, such as phenol, cresol, xylenol, chlorophenol, and ethyl phenol; lactam block agents such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propiolactam; Active methylene blockers such as ethyl acetoacetate and acetylacetone; Methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl ether, methyl glycolate, glycol Alcohol blocking agents such as butyl acid, diacetone alcohol, methyl lactate and ethyl lactate; Oxime block agents, such as formaldehyde doxime, acetaldehyde, acetoxime, methyl ethyl ketoxime, diacetyl monooxime and cyclohexane oxime; Mercaptan-based blocking agents such as butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, methylthiophenol and ethylthiophenol; Acid amide block agents such as acetic amide and benzamide; Imide block agents such as succinic acid imide and maleic acid imide; Amine blocking agents such as xyldine, aniline, butylamine and dibutylamine; Imidazole blockers such as imidazole and 2-ethylimidazole; And imine-based blocking agents such as methyleneimine and propyleneimine.

A block isocyanate compound may be commercially available, for example, smidule BL-3175, BL-4165, BL-1100, BL-1265, death module TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117, death Moss 2170, Des Moss 2265 (above, Sumitomo Bayer urethane Co., Ltd. make, brand name), coronate 2512, coronate 2513, coronate 2520 (above, Tosoh Co., Ltd., brand name), B-830, B-815 , B-846, B-870, B-874, B-882 (above, Mitsui Chemical Co., Ltd., brand name), TPA-B80E, 17B-60PX, E402-B80T (above, Asahi Kasei Chemicals Co., Ltd. Shigisa Co., Ltd. brand name) etc. are mentioned. In addition, the smead BL-3175 and BL-4265 are obtained using methyl ethyl oxime as a blocking agent.

You may mix | blend a urethanization catalyst with the photosensitive resin composition in order to accelerate hardening reaction of a hydroxyl group, a carboxyl group, and an isocyanate group. As the urethane-forming catalyst, it is preferable to use a urethane-forming catalyst selected from at least one of tin-based catalysts, metal chlorides, metal acetylacetonate salts, metal sulfates, amine compounds and amine salts.

As a tin type catalyst, organic tin compounds, such as a stannous octoate and dibutyltin dilaurate, an inorganic tin compound, etc. are mentioned, for example. Moreover, as a metal chloride, it is a metal chloride selected from the group which consists of Cr, Mn, Co, Ni, Fe, Cu, and Al, For example, a cobalt chloride, a nickel nickel chloride, ferric chloride, etc. are mentioned. have. In addition, the metal acetylacetonate salt is an acetylacetonate salt of a metal selected from the group consisting of Cr, Mn, Co, Ni, Fe, Cu, and Al. For example, cobaltacetylacetonate, nickel acetylacetonate, iron Acetylacetonate, and the like. Moreover, as a metal sulfate, it is a sulfate of the metal chosen from the group which consists of Cr, Mn, Co, Ni, Fe, Cu, and Al, for example, copper sulfate etc. are mentioned.

Examples of the amine compound include conventionally known triethylenediamine, N, N, N ', N'-tetramethyl-1,6-hexanediamine, bis (2-dimethylaminoethyl) ether, N, N, N' , N ", N" -pentamethyldiethylenetriamine, N-methylmorpholine, N-ethylmorpholine, N, N-dimethylethanolamine, dimorpholino diethyl ether, N-methylimidazole, dimethylamino Pyridine, triazine, N '-(2-hydroxyethyl) -N, N, N'-trimethylbis (2-aminoethyl) ether, N, N-dimethylhexanamine, N, N-dimethylaminoethoxy Ethanol, N, N, N'-trimethyl-N '-(2-hydroxyethyl) ethylenediamine, N- (2-hydroxyethyl) -N, N', N ", N" -tetramethyldiethylenetri Amine, N- (2-hydroxypropyl) -N, N ', N ", N" -tetramethyldiethylenetriamine, N, N, N'-trimethyl-N'-(2-hydroxyethyl) propane Diamine, N-methyl-N '-(2-hydroxyethyl) piperazine, bis (N, N-dimethylaminopropyl) amine, bis (N, N-dimethylaminopropyl) isopropanol Min, 2-aminoquinuclidin, 3-aminoquinuclidin, 4-aminoquinuclidin, 2-quinuclidinol, 3-quinuclidinol, 4-quinuclidinol, 1- (2'-hydroxypropyl ) Imidazole, 1- (2'-hydroxypropyl) -2-methylimidazole, 1- (2'-hydroxyethyl) imidazole, 1- (2'-hydroxyethyl) -2-methyl Midazole, 1- (2'-hydroxypropyl) -2-methylimidazole, 1- (3'-aminopropyl) imidazole, 1- (3'-aminopropyl) -2-methylimidazole, 1- (3'-hydroxypropyl) imidazole, 1- (3'-hydroxypropyl) -2-methylimidazole, N, N-dimethylaminopropyl-N '-(2-hydroxyethyl) amine , N, N-dimethylaminopropyl-N ', N'-bis (2-hydroxyethyl) amine, N, N-dimethylaminopropyl-N', N'-bis (2-hydroxypropyl) amine, N , N-dimethylaminoethyl-N ', N'-bis (2-hydroxyethyl) amine, N, N-dimethylaminoethyl-N', N'-bis (2-hydroxypropyl) amine, melamine and benzo At least one kind of guanamine, etc. can be mentioned have.

As an amine salt, organic acid salt amine salts, such as DBU (1,8- diaza-bicyclo [5.4.0] undecene-7), etc. are mentioned, for example.

[filler]

As the filler, known conventional inorganic or organic fillers can be used, but barium sulfate, spherical silica, titanium oxide, Neuburg silica particles and talc are particularly preferably used. Moreover, aluminum hydroxide, magnesium hydroxide, boehmite, etc. can also be used for the purpose of providing flame retardance. Further, NANOCRYL (trade name) manufactured by Hanse-Chemie, Inc., in which nanosilica is dispersed in a compound having one or more ethylenically unsaturated groups or the polyfunctional epoxy resin, XP 0396, XP 0596, XP 0733, XP 0746, XP 0765, XP 0768 , XP 0953, XP 0954, XP 1045 (all product grade names), or NANOPOX (brand name) XP 0516, XP 0525, XP 0314 (all product grade names) manufactured by Hanse-Chemie. These may be used alone or in combination of two or more thereof. By including a filler, the physical strength etc. of the hardened | cured material obtained can be raised.

When the compounding quantity of a filler contains carboxyl group-containing resin in a composition, it is 500 mass parts or less with respect to 100 mass parts of carboxyl group-containing resin in solid content conversion, More preferably, it is 0.1-300 mass parts, Especially preferably, it is 0.1 150 mass parts. When the compounding quantity of a filler is 500 mass parts or less, the viscosity of a photocurable thermosetting resin composition does not become high too much, printability is good and hardened | cured material is hard to embrittle.

[Photopolymerization Initiator]

In this invention, although a well-known thing can be used as a photoinitiator used for photopolymerizing the said carboxyl group-containing photosensitive resin, The oxime ester type photoinitiator which has an oxime ester group, the (alpha)-amino acetophenone type photoinitiator, Acylphosphine oxide type photoinitiators are preferable. A photoinitiator may be used individually by 1 type, and may be used in combination of 2 or more type.

As an oxime ester-type photoinitiator, it is a commercial item, CGI-325 by the BASF Japan company, Irgacure (registered trademark) OXE01, Irgacure OXE02, Adeka Corporation N-1919, Adeka Ackles (registered trademark). NCI-831 and the like.

Moreover, the photoinitiator which has two oxime ester groups in a molecule | numerator can also be used suitably, Specifically, the oxime ester compound which has a carbazole structure represented by following General formula (I) is mentioned.

(In formula, X <_1> is a hydrogen atom, a C1-C17 alkyl group, a C1-C8 alkoxy group, a phenyl group, a phenyl group (C1-C17 alkyl group, a C1-C8 alkoxy group, an amino group, C1-C1-C1). Substituted with an alkylamino or dialkylamino group having an alkyl group of 8), a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms or di Y ₁ , Z each represent a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a halogen group, a phenyl group, a phenyl group (an alkyl group having 1 to 17 carbon atoms, Substituted by an alkylamino group having 1 to 8 carbon atoms, an amino group, an alkylamino group having 1 to 8 carbon atoms or a dialkylamino group), a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group) Or an alkylamino group having an alkyl group of 1 to 8 carbon atoms or di Substituted with a chelamino group), an anthryl group, a pyridyl group, a benzofuryl group, a benzothienyl group, and Ar represents an alkylene, vinylene, phenylene, biphenylene, pyridylene, Naphthylene, thiophene, anthylene, thienylene, furylene, 2,5-pyrrole-diyl, 4,4'-stilbene-diyl, 4,2'-styrene-diyl, n is 0 or 1 Is an integer of)

In particular, an oxime ester photoinitiator wherein X ₁ , Y ₁ are each a methyl group or an ethyl group, Z is methyl or phenyl, n is 0, and Ar is phenylene, naphthylene, thiophene or thienylene. Is preferred.

As a preferable carbazole oxime ester compound, the compound which can be represented by the following general formula (II) is also mentioned.

(In formula, R <_3> represents the phenyl group which may be substituted by the C1-C4 alkyl group, or a nitro group, a halogen atom, or a C1-C4 alkyl group.

R <_4> represents the phenyl group which may be substituted by the C1-C4 alkyl group, the C1-C4 alkoxy group, or the C1-C4 alkyl group or the alkoxy group.

R <_5> represents the benzyl group which may be connected by the oxygen atom or the sulfur atom, and may be substituted by the C1-C20 alkyl group and the C1-C4 alkoxy group which may be substituted by the phenyl group.

R ₆ represents a nitro group or an acyl group represented by X ₂ -C (═O)-.

X ₂ represents a structure represented by an aryl group, thienyl group, morpholino group, thiophenyl group, or the following formula (III), which may be substituted with an alkyl group having 1 to 4 carbon atoms.)

In addition, Japanese Patent Laid-Open No. 2004-359639, Japanese Patent Laid-Open No. 2005-097141, Japanese Patent Laid-Open No. 2005-220097, Japanese Patent Laid-Open No. 2006-160634, and Japanese Patent Laid-Open No. 2008-094770 The carbazole oxime ester compound etc. which were described in Unexamined-Japanese-Patent No. 2008-509967, Unexamined-Japanese-Patent No. 2009-040762, and Unexamined-Japanese-Patent No. 2011-80036 are mentioned.

When the compounding quantity in the case of using an oxime ester system photoinitiator contains carboxyl group-containing resin in a composition, it is preferable to set it as 0.01-5 mass parts with respect to 100 mass parts of carboxyl group-containing resin in solid content conversion. By setting it as 0.01 mass part or more, photocurability on copper becomes more certain, and coating-film characteristics, such as chemical-resistance, improve. Moreover, when it is 5 mass parts or less, there exists a tendency for the light absorption in the coating film surface to be suppressed and the hardenability of a core part improves. More preferably, it is 0.5-3 mass parts with respect to 100 mass parts of carboxyl group-containing resin.

Specific examples of the α-aminoacetophenone-based photopolymerization initiator include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1,2-benzyl-2-dimethylamino-1 -(4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1 -Butanone, N, N-dimethylaminoacetophenone, etc. are mentioned. Examples of commercially available products include Omnirad 907, Omnirad 369, Omnirad 379, and the like, manufactured by IGM Resins.

As an acyl phosphine oxide type photoinitiator, 2,4,6- trimethyl benzoyl diphenyl phosphine oxide, bis (2,4,6- trimethyl benzoyl) -phenyl phosphine oxide, bis (2, 6- dimeth) specifically, Oxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, and the like. Examples of commercially available products include Omnirad TPO, Omnirad 819, etc. manufactured by IGM Resins.

As the photopolymerization initiator, Yueyang Kimoutain Sci-tech Co., Ltd. JMT-784 of manufacture can also be used suitably.

When using a photoinitiator other than an oxime ester system photoinitiator, when containing carboxyl group-containing resin in a composition, it is preferable that it is 0.01-15 mass parts with respect to 100 mass parts of carboxyl group-containing resin in solid content conversion. By setting it as 0.01 mass part or more, photocurability on copper becomes more certain, and coating-film characteristics, such as chemical-resistance, improve. Moreover, by setting it as 15 mass parts or less, the effect of reducing sufficient outgas is acquired, the light absorption in the surface of a cured film is suppressed, and the sclerosis | hardenability of a core part also improves. More preferably, it is 0.5-10 mass parts with respect to 100 mass parts of carboxyl group-containing resin.

You may use photoinitiator or a sensitizer in combination with said photoinitiator. As a photoinitiation adjuvant or a sensitizer, a benzoin compound, an acetophenone compound, an anthraquinone compound, a thioxanthone compound, a ketal compound, a benzophenone compound, a tertiary amine compound, a xanthone compound, etc. are mentioned. Although these compounds can be used as a photoinitiator, it is preferable to use together with a photoinitiator. In addition, a photoinitiation adjuvant or a sensitizer may be used individually by 1 type, and may use 2 or more types together.

As a benzoin compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, etc. are mentioned, for example. Moreover, as an acetophenone compound, acetophenone, 2, 2- dimethoxy- 2-phenylacetophenone, 2, 2- diethoxy 2-phenyl acetophenone, 1, 1- dichloro acetophenone, etc. are mentioned, for example. have. Moreover, as an anthraquinone compound, 2-methyl anthraquinone, 2-ethyl anthraquinone, 2-t- butyl anthraquinone, 1-chloro anthraquinone, etc. are mentioned, for example. Moreover, as a thioxanthone compound, 2, 4- dimethyl thioxanthone, 2, 4- diethyl thioxanthone, 2-chloro thioxanthone, 2, 4- diisopropyl thioxanthone, etc. are mentioned, for example. Can be. Moreover, as a ketal compound, acetophenone dimethyl ketal, benzyl dimethyl ketal, etc. are mentioned, for example. Moreover, as a benzophenone compound, for example, benzophenone, 4-benzoyl diphenyl sulfide, 4-benzoyl-4'-methyldiphenyl sulfide, 4-benzoyl-4'-ethyldiphenyl sulfide, 4-benzoyl -4'- propyl diphenyl sulfide etc. are mentioned.

As the tertiary amine compound, for example, an ethanolamine compound or a compound having a dialkylaminobenzene structure, for example, a commercially available product, 4,4'-dimethylaminobenzophenone (Nisso Soda Co., Ltd. Dialkylaminobenzophenone, 7- (diethylamino) -4-methyl-2H-1-, such as MABP) and 4,4'-diethylaminobenzophenone (EAB made by Hodogaya Chemical Co., Ltd.). Dialkylamino group-containing coumarin compounds, such as benzopyran-2-one (7- (diethylamino) -4-methylcoumarin), and 4-dimethylaminobenzoate ethyl (Kayakyue Co., Ltd. make Kayacure (registered trademark) EPA ), Ethyl 2-dimethylaminobenzoate (Quantacure DMB manufactured by International Bio-Synthetics Co., Ltd.), 4-dimethylaminobenzoic acid (n-butoxy) ethyl (Quantacure BEA manufactured by International Bio-Synthetics Co., Ltd.), p-dimethylaminobenzoic acid Soy Mil Ethyl Ester (Nipbon Kayaku Kabuki Kaisha) Manufactured Kayacure DMBI), 4-dimethylaminobenzoic acid 2-ethylhexyl (Esolol 507 by Van Dyk), etc. are mentioned. As the tertiary amine compound, a compound having a dialkylaminobenzene structure is preferable, and in particular, a dialkylaminobenzophenone compound, a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 450 nm, and ketocoumarins are particularly preferred. desirable.

As the dialkylaminobenzophenone compound, 4,4'-diethylaminobenzophenone is preferable because of low toxicity. Since the dialkylamino group-containing coumarin compound has a maximum absorption wavelength in the ultraviolet region at 350 to 410 nm, there is little coloration, and a colored photosensitive film reflecting the color of the colored pigment itself using a color pigment as well as a colorless transparent photosensitive resin composition. It becomes possible to obtain. In particular, since 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one shows the outstanding sensitizing effect with respect to the laser beam of wavelength 400-410 nm, it is preferable.

Among these, thioxanthone compounds and tertiary amine compounds are preferable. In particular, by including a thioxanthone compound, deep-hardening property can be improved.

When the total amount of a photoinitiator, a photoinitiation adjuvant, and a sensitizer contains carboxyl group-containing resin in a composition, it is preferable that it is 35 mass parts or less with respect to 100 mass parts of carboxyl group-containing resin in solid content conversion. By setting it as 35 mass parts or less, these light absorption is suppressed and the sclerosis | hardenability of a core part improves.

Moreover, since these photoinitiators, photoinitiation adjuvant, and a sensitizer absorb a specific wavelength, in some cases, a sensitivity becomes low and may function as an ultraviolet absorber. However, they are not used only for the purpose of improving the sensitivity of the composition. By absorbing light of a specific wavelength as needed, it improves the photoreactivity of the surface, changes the line shape and opening of the resist into vertical, tapered and inverse tapered shape, and improves the processing accuracy of the line width and the opening diameter. Can be.

The photosensitive resin composition used for the photosensitive film which concerns on this invention may contain other components, such as a block copolymer, a coloring agent, an elastomer, and a thermoplastic resin, in addition to the above-mentioned component. Hereinafter, these components are also demonstrated.

A block copolymer can be mix | blended suitably to said photosensitive resin composition. The block copolymer refers to a copolymer having a molecular structure in which two or more kinds of polymers having different properties are covalently linked to form a long chain. It is preferable that it is solid in the range of 20 degreeC-30 degreeC. Solid may be sufficient in this range, and solid may be sufficient even at the temperature outside this range. By being solid in the said temperature range, it is excellent in the adhesiveness at the time of making it into a photosensitive film, or apply | coating to a support film and making it temporarily dry.

As a block copolymer, XYX or XYX 'type block copolymer is preferable. Among the XYX or XYX 'type block copolymers, the central Y is a soft block, the glass transition point Tg is low, preferably less than 0 ° C, and both outer X to X' are hard blocks, and the Tg is high, preferably It is preferable that it is comprised by the polymer unit which is 0 degreeC or more. The glass transition point Tg is measured by differential scanning calorimetry (DSC).

Moreover, the block copolymer which contains the polymer unit whose Tg of X-X 'is 50 degreeC or more among the XYX or XYX' type block copolymer, and contains the polymer unit whose Tg of Y is -20 degrees C or less is more preferable. Moreover, in XYX or XYX 'type block copolymer, it is preferable that X-X' has high compatibility with carboxyl group-containing resin, and it is preferable that Y has low compatibility with carboxyl group-containing resin. Thus, it is thought that the block copolymer of both ends is compatible with a matrix, and the center block becomes a block copolymer incompatible with a matrix, and it becomes easy to show a specific structure in a matrix.

The block copolymer can be used without particular limitation as long as it has at least one hard block and soft block component as well as the XYX or XYX 'type.

As the X to X 'component, polymethyl methacrylate (PMMA), polystyrene (PS) and the like are preferable, and as the Y component, polyn-butyl acrylate (PBA), polybutadiene (PB) and the like are preferable. In addition, a hydrophilic unit excellent in compatibility with the carboxyl group-containing resin represented by a styrene unit, a hydroxyl group-containing unit, a carboxyl group-containing unit, an epoxy-containing unit, an N-substituted acrylamide unit, or the like is introduced into a part of the X to X 'component. It becomes possible to improve compatibility. The inventors have found that the block copolymer obtained in this way has particularly good compatibility with the carboxyl group-containing resin, and surprisingly improves the cold shock resistance, and even more surprisingly, the water to which the elastomer is added is glass. While the transition temperature (Tg) tends to decrease, it has been found that the material to which the block copolymer is added tends not to lower Tg.

As a manufacturing method of a block copolymer, the method of Unexamined-Japanese-Patent Application 2005-515281 and Unexamined-Japanese-Patent Application 2007-516326 is mentioned, for example. As a commercial item of a block copolymer, the acryl-type triblock copolymer manufactured using living polymerization by Arkema company is mentioned. SBM type represented by polystyrene-polybutadiene-polymethylmethacrylate, MAM type represented by polymethylmethacrylate-polybutylacrylate-polymethylmethacrylate, and MAM N treated with carboxylic acid modification or hydrophilic group modification Type or MAM A type. Examples of the SBM type include E41, E40, E21, and E20. Examples of the MAM type include M51, M52, M53, and M22. Examples of the MAM N type include 52N, 22N, and MAM A type, SM4032XM10. . In addition, Kuraray made by Kuraray Co., Ltd. is also a block copolymer derived from methyl methacrylate and butyl acrylate.

As the block copolymer, a block copolymer of three or more members is preferable, and a block copolymer in which the molecular structure synthesized by the living polymerization method is precisely controlled is more preferable for obtaining the effect of the present invention. This is considered to be because the block copolymer synthesized by the living polymerization method has a narrow molecular weight distribution, and the characteristics of each unit become clear. 2.5 or less are preferable and, as for the molecular weight distribution of the block copolymer to be used, More preferably, it is 2.0 or less.

It is preferable that the weight average molecular weight of a block copolymer generally exists in the range of 20,000-400,000, Furthermore, 30,000-300,000. If the weight average molecular weight is less than 20,000, the desired effects of toughness and flexibility are not obtained, and the adhesiveness is also poor. On the other hand, when a weight average molecular weight exceeds 400,000, the viscosity of a photocurable resin composition will become high and printability and developability will remarkably worsen.

When the compounding quantity of a block copolymer contains carboxyl group-containing resin in a composition, 1-50 mass parts is preferable with respect to 100 mass parts of carboxyl group-containing resin in solid content conversion, More preferably, it is 5-35 mass parts. The effect can be expected at 1 mass part or more, and developability and applicability | paintability become favorable as a photocurable resin composition at 50 mass parts or less.

The coloring agent may be contained in the photosensitive resin composition. As a coloring agent, well-known coloring agents, such as red, blue, green, and sulfur, can be used, and any of a pigment, dye, and a pigment may be sufficient. However, it is preferable not to contain a halogen from a viewpoint of environmental load reduction and an influence on a human body.

Examples of the red colorant include monoazo, disazo, azolake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, quinacridone, and the like. The same color index (CI; issued by The Society of Dyers and Colourists) number is given.

As a mono azo red coloring agent, 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. Moreover, Pigment Red 37, 38, 41 etc. are mentioned as a disazo red coloring agent. Moreover, as a monoazo lake type red coloring agent, 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. Moreover, Pigment Red 171, 175, 176, 185, 208 etc. are mentioned as a benzimidazolone type red coloring agent. Examples of the perylene-based red colorant include Solvent Red 135, 179, Pigment Red 123, 149, 166, 178, 179, 190, 194, and 224. Moreover, Pigment Red 254, 255, 264, 270, 272 etc. are mentioned as a diketopyrrolopyrrole red coloring agent. Moreover, Pigment Red 220, 144, 166, 214, 220, 221, 242 etc. are mentioned as a condensation azo red coloring agent. Moreover, as an anthraquinone type red coloring agent, Pigment Red 168, 177, 216, Solvent Red 149, 150, 52, 207 etc. are mentioned. Examples of the quinacridone-based red colorant include Pigment Red 122, 202, 206, 207, and 209.

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

Examples of the yellow colorant include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, anthraquinone, and the like. Examples of the anthraquinone yellow colorant include Solvent Yellow 163 and 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 coloring agent. Examples of the condensed azo yellow colorant include Pigment Yellow 93, 94, 95, 128, 155, 166, 180 and the like. Pigment Yellow 120, 151, 154, 156, 175, 181 etc. are mentioned as a benzimidazolone type yellow coloring agent. Moreover, as a monoazo yellow coloring agent, 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 and the like. In addition, as a disazo yellow colorant, Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198, etc. Can be mentioned.

In addition, you may add coloring agents, such as purple, orange, brown, black, white. 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, Pigment Brown 23, 25, titanium oxide And carbon black.

Although the compounding quantity of a coloring agent does not have a restriction | limiting in particular, When a carboxyl group-containing resin is included in a composition, it is 10 mass parts or less with respect to 100 mass parts of carboxyl group-containing resin in solid content conversion, Preferably it is 0.1-7 mass parts. However, the compounding quantity of white coloring agents, such as titanium oxide, is 0.1-200 mass parts with respect to 100 mass parts of carboxyl group-containing resin in solid content conversion, More preferably, it is 1-100 mass parts, More preferably, it is 3-80 It is a mass part.

Moreover, an elastomer can be mix | blended with the photosensitive resin composition for the purpose of providing the softness | flexibility with respect to the hardened | cured material obtained, improvement of the brittleness of hardened | cured material, etc. Examples of the elastomer include polyester elastomers, polyurethane elastomers, polyester urethane elastomers, polyamide elastomers, polyesteramide elastomers, acrylic elastomers, and olefin elastomers. Moreover, the resin etc. which modified | denatured some or all the epoxy groups of the epoxy resin which has various skeletons with both terminal carboxylic acid modified butadiene- acrylonitrile rubber can also be used. Furthermore, epoxy-containing polybutadiene-based elastomers, acrylic-containing polybutadiene-based elastomers, hydroxyl-containing polybutadiene-based elastomers, hydroxyl-containing isoprene-based elastomers, and the like can also be used. Elastomer may be used individually by 1 type, and may be used as two or more types of mixtures.

Moreover, a conventionally well-known binder polymer can be used for the purpose of the improvement of the flexibility of a hardened | cured material obtained, and a touch-drying property. As a binder polymer, a cellulose type, a polyester type, and a phenoxy resin type polymer are preferable. Examples of the cellulose polymer include cellulose acetate butyrate (CAB) and cellulose acetate propionate (CAP) manufactured by Eastman Co., Ltd .; and the Byron series manufactured by Toyobo Corp. Phenoxy resins of bisphenol F and their hydrogenated compounds are preferred.

When the compounding quantity of a binder polymer contains carboxyl group-containing resin in a composition, it is 50 mass parts or less with respect to 100 mass parts of carboxyl group-containing resin in solid content conversion, More preferably, it is 1-30 mass parts, Especially preferably, It is 5-30 mass parts. When the compounding quantity of a binder polymer is 50 mass parts or less, alkali developability of the photosensitive resin composition is more excellent, and the pot life which can be developed becomes long.

Moreover, components, such as an adhesion promoter, antioxidant, and a ultraviolet absorber, can be mix | blended with the photosensitive resin composition further as needed. These can use water well-known in the field of an electronic material. In addition, at least one of known conventional thickeners such as finely divided silica, hydrotalcite, organic bentonite and montmorillonite, antifoaming agents and leveling agents such as silicone, fluorine and polymers, and silanes such as imidazole, thiazole and triazole At least any one of known conventional additives such as coupling agents, rust inhibitors, fluorescent brighteners and the like can be blended.

The photosensitive film can apply | coat the above-mentioned photosensitive resin composition to one surface of a support film, and can dry and form it. In consideration of the applicability of the photosensitive resin composition, the photosensitive resin composition is diluted with an organic solvent and adjusted to an appropriate viscosity, and a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater, gravure coater, It is apply | coated to one side of a support film by a spray coater etc. with uniform thickness, and it normally dries at the temperature of 50-130 degreeC for 1 to 30 minutes, and volatilizes an organic solvent, and can obtain a dry touch coating film. There is no restriction | limiting in particular about coating film thickness, Generally, it is a film thickness after drying, and is selected suitably in the range of 5-150 micrometers, Preferably it is 10-60 micrometers.

Although there is no restriction | limiting in particular as an organic solvent which can be used, For example, ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, ester, alcohol, aliphatic hydrocarbon, petroleum solvent, etc. are mentioned. More specifically, Ketones, such as methyl ethyl ketone and cyclohexanone; Aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; Cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether Glycol ethers such as these; Esters such as ethyl acetate, butyl acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, and propylene glycol butyl ether acetate; Alcohols such as ethanol, propanol, ethylene glycol and propylene glycol; Aliphatic hydrocarbons such as octane and decane; Petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. These organic solvents may be used individually by 1 type, and may be used as 2 or more types of mixtures.

The volatilization drying of the organic solvent is a hot air circulation drying furnace, an IR plate, a hot plate, a convection oven, or the like. Spraying method).

[Photosensitive Film Laminate]

The photosensitive film laminated body which is another embodiment of this invention says that the support film is laminated | stacked on said any photosensitive film. Moreover, it is preferable that the protective film is further laminated | stacked in the photosensitive film laminated body of this invention. The details will be described below.

[Support film]

A support film supports said photosensitive film (namely, the layer containing a photosensitive resin composition, hereafter abbreviated as "photosensitive resin layer"), and at the time of exposure and image development of a photosensitive film, a photosensitive film It has a role of shaping a predetermined surface shape on the surface of the side in contact with the supporting film. In this invention, it is preferable to use the support film whose number of protrusions per unit area 1mm <^2> of the surface of the surface side which contact | connects a photosensitive film is 3.0 * 10 <^2> or more. Moreover, it is more preferable to use the support film whose arithmetic mean surface roughness Ra 'of the surface of the surface side which contact | connects a photosensitive film is 0.05 micrometer or more. By using the support film which has such a surface form, it becomes easy to form the photosensitive film whose number of recessed parts per unit area 1mm <^2> of 3.0 * 10 <^2> or more, and further has a photosensitive film which has an arithmetic mean surface roughness Ra of 0.05 micrometer or more. It becomes easy to form. That is, the predetermined surface form of the support film is shaped on the surface of the photosensitive film, whereby the adhesion between the cured film formed later and the die attach material can be improved, and furthermore, the photosensitive film can be improved in appearance inspection. It is effective at the point which becomes easy to form. The number of the support protrusions of the unit area of 1mm ² of the film surface is more preferably not less than 4.0 × 10 ² pieces, and 5.0 and more preferably ² × 10 pieces or more. Moreover, when an upper limit is set, 2.0 * 10 <^4> or less is preferable, 1.5 * 10 <^4> or less is more preferable, 1.0 * 10 <^4> or less is more preferable. Moreover, although the protrusion part of the support film surface may be uniform or nonuniform, it is preferable that it is nonuniform.

Moreover, it is more preferable that the range of arithmetic mean surface roughness Ra 'of a support film is 0.06 micrometer or more, and it is especially preferable that it is 0.07 micrometer or more. Moreover, when setting an upper limit, it is preferable that it is 5.0 micrometers or less, It is more preferable that it is 3.0 micrometers or less, It is further more preferable that it is 1.0 micrometer or less. Here, the number of protrusions per unit area of 1 mm ² of the surface of the supporting film is a three-dimensional measurement of the surface unevenness of the target supporting film with the z-axis as the height direction to obtain the maximum value and the minimum value of the aggregate of z values obtained, and the maximum value thereof. The value calculated by counting the number of protrusion areas existing in the unit area of 1 mm ² and using the Zs' value 0.2 µm higher than the average value calculated from the minimum value as the threshold value, and the area having the z value equal to or more than that threshold value as the protrusion area. I say it. In addition, arithmetic mean surface roughness Ra 'means what was demonstrated by the above-mentioned [photosensitive film]. The specific measuring method is as described above. In addition, the number of protrusions per unit area of 1 mm ² of the support film surface and the number of recesses per unit area of 1 mm ² of the photosensitive film surface do not necessarily coincide with each other, and the arithmetic surface roughness Ra ′ and the photosensitive film of the support film surface are the same. Although the arithmetic surface roughness Ra of the surface does not necessarily coincide, by appropriately adjusting the surface shape of the support film, the number of recesses and the arithmetic surface roughness Ra per unit area of 1 mm ^{2 of the} surface of the photosensitive film can be made within a specific range as described above. Can be.

As a support film, if it has the above-mentioned surface form, it can use without a restriction | limiting especially, For example, polyester films, such as a polyethylene terephthalate and a polyethylene naphthalate, a polyimide film, a polyamideimide film, a polypropylene film, a polystyrene film Although the film containing thermoplastic resins, such as these, can be used conveniently, Among these, a polyester film can be used suitably from a viewpoint of heat resistance, mechanical strength, handleability, etc. A single layer may be sufficient as a support film, and 2 or more layers may be laminated | stacked.

In addition, it is preferable to use the film extended | stretched to the uniaxial direction or the biaxial direction for the thermoplastic resin film as mentioned above in order to improve intensity | strength.

When the number of protrusions per unit area 1 mm ² of the surface as described above is 3.0 × 10 ² or more, and the arithmetic mean surface roughness Ra 'is 0.05 μm or more, when a thermoplastic resin film is used, a film is formed. The surface is prepared by adding a filler (kneading treatment), matte coating (coating treatment), blast treatment such as sand blast treatment, or hairline treatment, chemical etching, or the like in the resin at the time. It can be made in the same predetermined form. For example, when adding a filler in resin, the number of protrusions and arithmetic mean surface roughness Ra 'per unit area of 1 mm <^2> can be controlled by adjusting the particle size and addition amount of a filler. In addition, when coating the surface of a support film, the number and arithmetic mean surface roughness Ra 'of a protrusion per unit area 1mm <^2> can be controlled by adjusting the kind and quantity of a coating agent. In the case of blasting, the number of protrusions and the arithmetic mean surface roughness Ra 'per unit area of 1 mm ² can be controlled by adjusting processing conditions such as blasting material and blast pressure. As a thermoplastic resin film which has such a surface roughness, a commercially available thing may be used, for example, Unitica Kabushiki Kaisha CM-25, Kikimoto G50, etc. are mentioned, It is not limited to these.

The mold release process may be given to the surface in which the photosensitive resin layer of a support film is provided. For example, coating methods prepared by dissolving or dispersing release agents such as waxes, silicone waxes, alkyd resins, urethane resins, melamine resins, and silicone resins in a suitable solvent may be coated by a roll coating method or a spray coating method. A mold release process can be performed by apply | coating and drying to a support film surface by well-known means, such as the gravure printing method and the screen printing method.

Although the thickness in particular of a support film is not restrict | limited, It selects suitably according to a use in the range of about 10-150 micrometers.

Moreover, in the photosensitive film laminated body which concerns on this invention by which the support film is laminated | stacked on the surface side which has a recessed part in the surface of any one said photosensitive film, it is excellent in adhesiveness with a die attach material, and improves a yield in an external inspection. It is preferable at the point which becomes easy to exhibit the effect of this invention.

[Protective film]

The photosensitive film laminate according to the present invention has a protective film on the opposite side to the support film of the photosensitive resin layer for the purpose of preventing dust and the like from adhering to the surface of the photosensitive resin layer and improving the handleability. It may be installed.

As a protective film, a polyester film, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, the surface-treated paper etc. can be used, for example, The adhesive force of a protective film and the photosensitive resin layer has a support film and photosensitive It is preferable to select the material which becomes smaller than the adhesive force with a resin layer. In addition, when using a photosensitive film laminated body, in order to make it easy to peel a protective film, you may perform the mold release process as mentioned above to the surface which contact | connects the photosensitive resin layer of a protective film.

Although the thickness in particular of a protective film is not restrict | limited, It selects suitably according to a use in the range of about 10-150 micrometers.

<Method of manufacturing hardened and printed wiring board>

Hardened | cured material is formed using the photosensitive film or photosensitive film laminated body of this invention. The formation method of such hardened | cured material and the method of manufacturing the printed wiring board provided with the said hardened | cured material (hardened film) on the board | substrate with which the circuit pattern was formed are demonstrated. As an example, the method to manufacture a printed wiring board using the photosensitive film laminated body provided with a protective film is demonstrated. First, i) peeling a protective film from said photosensitive film laminated body, exposing a photosensitive film, ii) bonding the photosensitive film of the said photosensitive film laminated body on the board | substrate with the said circuit pattern, iii) said photosensitive Exposing from the support film of the film laminate, and iv) peeling the support film from the photosensitive film laminate and performing development to form a patterned photosensitive film on the substrate, and v) forming the patterned photosensitive film. A printed wiring board is formed by hardening by light irradiation or a heat and forming a hardened film. In addition, when using the photosensitive film laminated body in which a protective film is not provided, of course, the peeling process (i process) of a protective film is unnecessary. Hereinafter, each process is demonstrated.

First, a protective film is peeled from a photosensitive film laminated body, a photosensitive resin layer is exposed, and the photosensitive resin layer of the photosensitive film laminated body is bonded on the board | substrate with a circuit pattern. As a board | substrate with a circuit pattern, in addition to the printed wiring board and flexible printed wiring board which were formed beforehand, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / nonwoven fabric epoxy, glass cloth / paper epoxy, synthetic fiber epoxy, fluororesin Copper clad laminates for high frequency circuits using polyethylene, polyphenylene ether, polyphenylene oxide, cyanate ester, etc. are used, and copper clad laminates of all grades (FR-4, etc.), other polyimide films, PET films, A glass substrate, a ceramic substrate, a wafer board, etc. are mentioned.

In order to bond the photosensitive film of the photosensitive film laminated body on a circuit board, it is preferable to bond together under pressure and heating using a vacuum laminator etc. By using such a vacuum laminator, even if there is an unevenness | corrugation on the circuit board surface, since the photosensitive resin composition layer sticks to a circuit board | substrate, there is no mixing of foam | bubble, and the hole filling property of the recessed part of a board | substrate surface also improves. It is preferable that pressurization conditions are about 0.1-2.0 Mpa, and it is preferable that heating conditions are 40-120 degreeC.

Next, exposure (irradiation of an active energy ray) is performed from the support film image of a photosensitive film laminated body. By this process, only the exposed photosensitive resin layer is cured. The exposure step is not particularly limited and, for example, may be selectively exposed by an active energy ray through a photomask in which a desired pattern is formed by contact (or non-contact method), but the desired pattern may be directly exposed by a drawing device. You may expose with an active energy ray.

As an exposure machine used for active energy ray irradiation, it is sufficient to mount a high pressure mercury lamp lamp, an ultra high pressure mercury lamp lamp, a metal halide lamp, etc., and irradiate ultraviolet rays in the range of 350 to 450 nm, and also directly draw a device (for example, from a computer). Can also be used. As the laser light source of the weaving machine, any of a gas laser and a solid laser may be used as long as the laser light having a maximum wavelength in the range of 350 to 410 nm is used. Although the exposure amount for image formation changes with film thickness etc., it is generally 20-800mJ / cm <^2> , Preferably it can be in the range of 20-600mJ / cm <^2> .

After exposure, the patterned photosensitive film is formed on a board | substrate by peeling a support film from a photosensitive film laminated body and developing. When peeling a support film, the form of a support film surface is shape | molded to the surface of the photosensitive film which was exposed and hardened | cured. Moreover, as long as it is a range which does not impair a characteristic, you may peel a support film from the photosensitive film laminated body before exposure, and may expose and develop the exposed photosensitive film.

The image development process is not specifically limited, A dipping method, a shower method, a spray method, the brush method, etc. can be used. Moreover, as a developing solution, aqueous alkali solution, such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines, can be used.

Next, the patterned photosensitive film is cured by active energy ray (light) irradiation or heat to form a cured product (cured film). This step is called main curing or further curing, promotes polymerization of unreacted monomers in the photosensitive film, and further thermosets the carboxyl group-containing photosensitive resin and epoxy resin to reduce the amount of remaining carboxyl groups. Although active energy ray irradiation can be performed similarly to above-mentioned exposure, it is preferable to carry out on conditions stronger than irradiation energy at the time of exposure. For example, it can be set as 500-3000mJ / cm <^2> . In addition, thermosetting can be performed at the heating conditions of about 20 to 90 minutes at 100-200 degreeC. Moreover, it is preferable to perform thermosetting after this hardening by photocuring. By performing photocuring first, the flow of resin is also suppressed at the time of heat curing, and the shaped surface may be maintained.

As described above, an appropriate uneven state can be given to the surface of the cured product. As a result, while adhesiveness with a die attach material improves, the yield in an external appearance test also improves. The die attach material can use a well-known conventional thing, and is not specifically limited. Therefore, the photosensitive film laminated body which concerns on this invention can be used suitably for a printed wiring board, can be used more suitably for formation of a soldering resist layer, and especially can be used for formation of the soldering resist layer for IC packages. have.

Example

Next, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these Examples.

<Preparation of carboxyl group-containing photosensitive resin>

In an autoclave equipped with a thermometer, a nitrogen introducing device, an alkylene oxide introducing device, and a stirring device, 119.4 g of novolac-type cresol resin (Shonol CRG951 manufactured by Showa Denko Co., Ltd., OH equivalent: 119.4) and 1.19 g of potassium hydroxide 119.4 g of toluene and toluene were added, the inside of the system was replaced with nitrogen while stirring, and the temperature was increased by heating. Next, 63.8 g of propylene oxide was slowly added dropwise and reacted at 125 to 132 ° C and 0 to 4.8 kg / cm ² for 16 hours. Thereafter, the mixture was cooled to room temperature, and 1.56 g of 89% phosphoric acid was added to the reaction solution to neutralize potassium hydroxide. The propylene oxide reaction of a novolak-type cresol resin having a nonvolatile content of 62.1% and a hydroxyl value of 182.2 g / eq. A solution was obtained. In the obtained novolak-type cresol resin, an average of 1.08 mol of alkylene oxide was added per equivalent of phenolic hydroxyl group.

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 introduced into a reactor equipped with a stirrer, a thermometer, and an air suction tube. And it was made to react at 110 degreeC for 12 hours, blowing air and blowing at a rate of 10 ml / min. The water produced by the reaction was an azeotropic mixture with toluene, and 12.6 g of water flowed out. Thereafter, the mixture was cooled to room temperature, and the obtained reaction solution was neutralized with 35.35 g of an aqueous 15% sodium hydroxide solution, followed by washing with water. Thereafter, toluene was distilled off while replacing toluene with 118.1 g of diethylene glycol monoethyl ether acetate in an evaporator to obtain a novolak-type acrylate resin solution. Subsequently, 332.5 g of the obtained novolak-type acrylate resin solution and 1.22 g of triphenylphosphine were introduced into a reactor equipped with a stirrer, a thermometer, and an air intake tube, and the air was blown at a rate of 10 ml / min, followed by stirring. 62.3 g of phthalic anhydride was added gradually, and it was made to react at 95-101 degreeC for 6 hours, and the carboxyl group-containing photosensitive resin varnish 1 was obtained as 71% of non volatile matters of 88 mgKOH / g of acid value.

<Preparation of the photosensitive resin composition>

As carboxyl group-containing photosensitive resin varnish 1 obtained as mentioned above, dipentaerythritol hexaacrylate (KAYARAD DPHA by Nippon Kayaku Co., Ltd.) which is a photosensitive monomer as an acrylate compound, and an epoxy resin which is a thermosetting component, bisphenol A type Epoxy resin (EPICLON840-S manufactured by DIC Corporation) and biphenol novolac type epoxy resin (NC-3000H, manufactured by Nippon Kayaku Co., Ltd.), and Omnirad (Omniard) TPO or BASF Japan manufactured by IGM Resins, Inc. as a photopolymerization initiator. IRGACURE OXE02 by the company, barium sulfate (B-30 manufactured by Kakaku Kogyo Co., Ltd.) and / or spherical silica (Admafine SO-E2 by Admatex Co., Ltd.) and a thermosetting catalyst as a filler As melamine and colorant, Mitsubishi Chemical Co., Ltd. carbon black M-50, dioxazine violet CI Pigment Violet 23, C.I. Pigment Yellow 147, C.I. Pigment Blue 15: 3 and C.I. Each component selected from Pigment Red 177 and diethylene glycol monoethyl ether acetate as an organic solvent were blended in the ratio (mass part) shown in Table 1 below, premixed with a stirrer, and kneaded with three roll mills to form a photosensitive resin. Compositions 1 and 2 were prepared.

<Production of Photosensitive Film Laminate>

Example 1

Sandblasting was performed on the single side | surface of the polyethylene terephthalate film (Dysfoil R310 by Mitsubishi Chemical Corporation), and the support film of thickness 16micrometer which provided the nonuniform protrusion part on the film surface was prepared. As a result of measuring the number of protrusions per unit area 1 mm ² of the surface of the obtained support film and the arithmetic mean surface roughness Ra 'as follows, the number of protrusions per unit area 1 mm ^{2 of the} surface was 8.0 × 10 ² , Arithmetic mean surface roughness Ra 'was 0.13 micrometer.

A shape measuring laser microscope (VK-X100, manufactured by Keyence, Inc.) was used for the measurement of the number of protrusions and the arithmetic mean surface roughness Ra 'per unit area of 1 mm ² . After activating the shape measurement laser microscope (VK-X100) main body (control unit) and the VK observation application (VK-H1VX manufactured by Keyence Co., Ltd.), a sample (support film) to be measured on the xy stage of the support film was The surface with the protrusions was placed on top. The objective lens of 10x magnification was selected by rotating the lens revolver of the microscope part (VK-X110 by Kyens Co., Ltd.), and about the focus and brightness were adjusted in the image observation mode of VK observation application (the same VK-H1VX). The xy stage was operated to adjust the center of the screen to be almost the center of the sample surface. The objective lens of 10 times magnification was changed to 100 times magnification, and the focus was made to the surface of a sample by the autofocus function of the image observation mode of VK observation application (the same 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, and the surface shape of the sample was measured to obtain a surface image file. After starting the VK analysis application (VK-H1XA manufactured by Keyence Co., Ltd.) and displaying the obtained surface image file, tilt correction was performed.

In the measurement of "the number of protrusions per unit area 1mm <^2> , the observation measurement range (area) in the measurement of the surface shape of a sample was 15073 micrometer <^2> . An analysis application (VK-H1XA manufactured by Keyence Co., Ltd.) was used. Select [Volume / Area] from the Measurement Analysis menu on the display screen, display the [Volume / Area] window, select [Height] from the [Display image] box in the [Volume / Area] window, and then select [Threshold]. By pressing the button, the [Threshold area setting dialog] box was displayed. The value of the [upper limit] box and the value of the [lower limit] box were added to calculate the value Ave. (µm) divided by 2, and the portion equal to or greater than the Zs' value (µm) obtained by adding 0.2 µm to the Ave. Was made. Do not change the value of the [Lower limit] box, enter the Zs' value (µm) in the [Upper limit] box, press the OK button, and then change the number of points C (colors) in the image display area to the color of the ROI drawing color. ), And the number D (piece / mm ² ) (D = C × 66.34) per unit area 1 mm ² was calculated from the number C (piece). In addition, about the part which changed to the color of the said ROI drawing color, it cut in the image display area | region, and was not recognized as one, it counted as 0.5 piece.

In addition, in the measurement of "arithmetic mean surface roughness Ra '," the objective lens was switched 50 times and the observation measurement range (width) in the measurement of the surface shape of the sample was 270 m. 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 at any place in the surface image, and press the OK button to perform the arithmetic of the surface. The numerical value of average surface roughness Ra 'was obtained. In addition, horizontal lines were displayed in four other places in the surface image, and a numerical value of the arithmetic mean surface roughness Ra 'was obtained. The average value of five obtained numerical values was computed, and it was set as the arithmetic mean surface roughness Ra 'value of a sample surface.

Subsequently, 300 g of methyl ethyl ketone was added and diluted to the photosensitive resin composition 1 obtained as mentioned above, and it stirred for 15 minutes with the stirrer, and obtained the coating liquid. The coating solution was applied to the surface of the support film subjected to sand blasting, dried at a temperature of 80 ° C. for 15 minutes to form a photosensitive film having a thickness of 20 μm. Subsequently, a polypropylene film (OPP-FOA manufactured by Futamura Chemical Co., Ltd.) having a thickness of 18 µm was bonded on the photosensitive film to prepare a photosensitive film laminate including three layers.

<Production of Test Board>

The surface of the circuit-formed substrate (500 mm x 600 mm x 0.4 mmt) was chemically polished by CZ8101 manufactured by Mack Corporation, and the polypropylene film was peeled off from the photosensitive film laminate obtained as described above on the chemically polished surface of the substrate. The exposed surface of the exposed photosensitive film was bonded and subsequently heated using a vacuum laminator (MVLP-500 manufactured by MEI Seiki Co., Ltd.) under a pressure of 0.8 Mpa, 70 ° C., 1 minute, and a vacuum degree of 133.3 Pa. It laminated and stuck the board | substrate and the photosensitive film.

Subsequently, using a parallel light exposure apparatus equipped with a short arc type high pressure mercury lamp, a solid exposure was applied to the visibility of the scratches and the adhesion to the die attach material from the polyethylene terephthalate film contacting the photosensitive film through an exposure mask. About the furrow collapse, after exposing using the negative pattern designed so that it might become SRO 80 micrometers, the polyethylene terephthalate film was peeled off and the photosensitive film was exposed. In addition, exposure amount was made into the exposure amount which becomes 7 steps, when it exposes using 41 steps of Stouffers on the polyethylene terephthalate film which contact | connects the photosensitive film. Thereafter, the exposed surface of the exposed photosensitive film was developed for 60 seconds under conditions of 30 ° C. and a spray pressure of 2 kg / cm ² using a 1% by weight Na ₂ CO ₃ aqueous solution, and then patterned. Subsequently, after irradiating the photosensitive film patterned at the exposure amount of 1 J / cm <^2> in the UV conveyor furnace equipped with a high pressure mercury lamp, it heated at 160 degreeC for 60 minutes, and further hardened | cured to form a hardened film, and the test in which the hardened film was formed on the board | substrate. Substrate 1 was produced.

Example 2

In Example 1, the test board 2 was produced like Example 1 except having used the photosensitive resin composition 2 instead of the photosensitive resin composition 1.

Example 3

In Example 1, polyethylene tere instead of the support film of thickness 16micrometer which has the surface where the number of protrusions per unit area 1mm <^2> of surfaces is 8.0x10 <^2> , and whose arithmetic mean surface roughness Ra 'is 0.13micrometer on one side. The test board | substrate was carried out similarly to Example 1 except having used the 125-micrometer-thick support film (G-50 by Kikimoto Co., Ltd.) which coated the single side | surface of a phthalate film, and formed the nonuniform protrusion part on the film surface. 3 was produced. As a result of measuring the number of protrusions per unit area 1mm ² and the arithmetic mean surface roughness Ra 'of the surface subjected to coating of the supporting film in the same manner as described above, the number of protrusions per unit area 1mm ^{2 of the} surface was 1.3 × 10. ^{It was three} pieces and the arithmetic mean surface roughness Ra 'was 0.19 micrometer.

Example 4

In Example 3, the test board 4 was produced like Example 3 except having used the photosensitive resin composition 2 instead of the photosensitive resin composition 1.

Example 5

In Example 1, polyethylene tere instead of the support film of thickness 16micrometer which has the surface where the number of protrusions per unit area 1mm <^2> of surfaces is 8.0x10 <^2> , and whose arithmetic mean surface roughness Ra 'is 0.13micrometer on one side. The test board | substrate was carried out similarly to Example 1 except having used the 25-micrometer-thick support film (CM-25 by Unitika Co., Ltd.) which formed the coating process on the single side | surface of a phthalate film, and formed the nonuniform protrusion part on the film surface. 5 was produced. As a result of measuring the number of protrusions per unit area 1mm ² and the arithmetic mean surface roughness Ra 'of the surface subjected to coating of the support film in the same manner as described above, the number of protrusions per unit area 1mm ^{2 of the} surface was 4.5 × 10. ^{It was three} pieces and the arithmetic mean surface roughness Ra 'was 0.48 micrometer.

Example 6

In Example 5, the test board 6 was produced like Example 5 except having used the photosensitive resin composition 2 instead of the photosensitive resin composition 1.

Example 7

In Example 1, polyethylene tere instead of the support film of thickness 16micrometer which has the surface where the number of protrusions per unit area 1mm <^2> of surfaces is 8.0x10 <^2> , and whose arithmetic mean surface roughness Ra 'is 0.13micrometer on one side. The test substrate 7 was carried out in the same manner as in Example 1, except that sand blasting was performed on one surface of the phthalate film (E5041 manufactured by Toyobo Co., Ltd.) and a support film having a thickness of 25 μm in which uneven protrusions were formed on the film surface was used. Was produced. The number of protrusions per unit area 1 mm ² of the surface subjected to sand blasting of the support film and the measurement of arithmetic mean surface roughness Ra 'were measured in the same manner as above, and as a result, the number of protrusions per unit area 1 mm ^{2 of the} surface was 1.7 ×. It was 10 ⁴ pieces, and the arithmetic mean surface roughness Ra 'was 5.00 micrometers.

Example 8

In Example 7, the test board 8 was produced like Example 7 except having used the photosensitive resin composition 2 instead of the photosensitive resin composition 1.

Comparative Example 1

In Example 1, the thickness 25 instead of the support film of thickness 16micrometer which has the surface where the number of protrusions per unit area 1mm <^2> of surfaces is 8.0x10 <^2> , and whose arithmetic mean surface roughness Ra 'is 0.13micrometer on one side. A test substrate 9 was produced in the same manner as in Example 1 except that a micrometer polyethylene terephthalate film (Toyobo Corporation E5041) was used as the support film. The number of protrusions per surface unit area 1 mm ² of the support film and the measurement of arithmetic mean surface roughness Ra 'were measured in the same manner as described above. As a result, the number of protrusions per unit area 1 mm ^{2 of the} surface was 0, and the arithmetic mean surface roughness was 0. Ra 'was 0.02 micrometer.

Comparative Example 2

In the comparative example 1, the test board 10 was produced like the comparative example 1 except having used the photosensitive resin composition 2 instead of the photosensitive resin composition 1.

<Evaluation of visibility of scratches>

In the state which applied the pencil core of hardness 2H, angle 45 degrees, and load 4.9 N were applied to the surface of the cured film in the exposure area | region of each test board | substrate of Examples 1-8 and Comparative Examples 1-2 produced as mentioned above. It pressed, it moved 1 cm by the speed | rate of 1 mm in 1 second, and changed place and performed it three times in total. The visibility of the scratches on the surface of the cured film was visually evaluated. Evaluation criteria were as follows.

(Double-circle): A scratch is not recognized all three times on the surface of the cured film in an exposure area.

(Circle): Scratches are confirmed 1-2 times on the surface of the cured film in an exposure area.

X: All the scratches are confirmed 3 times on the surface of the cured film in an exposure area.

In addition, test and evaluation were performed based on the said content within 5 minutes after each test board | substrate was produced. The evaluation results were as shown in Table 2 below.

<Production of die attach materials>

80 parts of trishydroxyphenylmethane type epoxy resins (EPPN-502H manufactured by Nippon Kayaku Co., Ltd.), 15 parts of bisphenol F type epoxy resin (RE-303S-L manufactured by Nippon Kayaku Co., Ltd.), 50 parts of methyl ethyl ketones were added to 5 parts of flexible epoxy resins (YX7105 by Mitsubishi Chemical Corporation), and it heated and melted and obtained resin varnish A. 3 parts of imidazole compounds (2E4MZ by Shikoku Kasei Kogyo Co., Ltd.) as a hardening catalyst with respect to 150 parts of obtained resin varnish A, 150 parts of fused silica (FB-3SDX by Tenka Corporation), a silane coupling agent as a filler (1 part of Shin-Etsu Chemical Co., Ltd. KBE-402) was added, it pre-mixed with the stirrer, and it knead | mixed in three roll mills and obtained resin varnish B. Obtained resin varnish B was apply | coated to the base film, it dried at the temperature of 80 degreeC for 15 minutes, and the die attach material of thickness 45micrometer was produced.

<Evaluation of adhesion with die attach material>

The die attach material produced as described above was cut into a predetermined size (5 mm × 5 mm × 0.045 mm in thickness), and attached to a silicon chip (5 mm × 5 mm × 0.725 mm in thickness, oxide film coating) at 70 ° C. Using the thermal compression tester, the surfaces of the cured films of the test substrates of Examples 1 to 8 and Comparative Examples 1 and 2 were pressed in the order of silicon chips, die attach materials, and cured films (compression conditions: 260 ° C). , For 10 seconds, 1.0 MPa). Subsequently, the die attach material was completely cured by heating at 175 ° C. for 120 minutes. Subsequently, it was left to stand in a constant temperature / humidity device (PR-2KP made by EPSP Co., Ltd.) of 85 degreeC and a relative humidity of 85% for 72 hours, and after taking out, the adhesion force measuring device (Nordson Advanced Technology Co., Ltd. product, universal type) Using the bond tester 4000Plus), the temperature of the stage for setting the sample was 260 ° C, and the adhesive force was measured under the conditions of a tool height of 0.05 mm and a tool speed of 0.05 mm / second from the substrate. Ten test pieces were produced, and evaluation criteria were as follows.

(Circle): Adhesive force is 3 MPa or more in all 10 test pieces.

X: 1 or more test pieces whose adhesive force is less than 3 Mpa generate | occur | produced among 10 test pieces

In addition, test and evaluation were performed based on the said content within 5 minutes after each test board | substrate was produced. The measurement results are as shown in Table 2 below.

<Measurement of number of recesses and arithmetic mean surface roughness Ra per 1 mm ² of surface unit area of photosensitive film>

The surface of the circuit-formed board | substrate (150 mm x 95 mm x 0.8 mmt) was chemically polished by CZ8101 manufactured by Mack Industries, Ltd., and each photosensitive material used in Examples 1 to 8 and Comparative Examples 1 to 2 on the chemically polished surface of the substrate. The polypropylene film was peeled from the film laminate, and the exposed surface of the exposed photosensitive film (140 mm x 90 mm) was bonded to each other, and the pressure was then 0.8 Mpa using a vacuum laminator (MVLP-500 manufactured by MEI Seisakusho). , 70 ° C, 1 minute, and vacuum lamination under the conditions of 133.3 Pa to adhere the substrate and the photosensitive film. Thereafter, the polyethylene terephthalate film was peeled off at 90 ° to the substrate to expose the photosensitive film. Within 5 minutes after the exposure, the number of recesses and the arithmetic mean surface roughness Ra of the unit area of 1 mm ² of the surface of the photosensitive film were measured as follows.

The number of recesses per unit area 1 mm ² of the photosensitive film surface is the same as that for measuring the number of protrusions per unit area 1 mm ² of the support film surface, and the substrate is bonded to the exposed photosensitive film instead of the support film. Measurement was performed similarly to the above except having made photosensitive film surface into the upper part). In the measurement of "the number of recesses per unit area 1mm <^2> of the photosensitive film surface, the observation measurement range (area) in the measurement of the surface shape of a sample was 15073 micrometer <^2> . An analysis application (VK-H1XA) was used. Select [Volume / Area] from the Measurement Analysis menu on the display screen to display the [Volume / Area] window, select [Height] from the [Display image] box in the [Volume / Area] window, and then select [Threshold]. By pressing the button, the [Threshold area setting dialog] box was displayed. The value of the [Upper limit] box and the value of the [Lower limit] box are added to calculate the value Ave. (µm) divided by 2, and the portion equal to or smaller than the value Zs (µm) obtained by subtracting 0.2 µm from the Ave. Wealth ”. Do not change the value of the [Lower limit] box, enter the value of Zs (µm) in the [Upper limit] box, press the OK button, and then change the number C of the areas that changed to the color of the ROI drawing color at the boundary of the image display area. (dogs) for counting, was calculated from the number C (one), the number of unit area of 1mm ² D (dog / mm ²⁾ per (D = C × 66.34). In addition, about the part which turned into the color of the said ROI drawing color, it cut | disconnected in the image display area and was not able to recognize it as one, and it counted as 0.5 piece. In addition, "arithmetic mean surface roughness Ra" of the photosensitive film surface was measured similarly to the above except having made into the board | substrate (photosensitive film surface being upper part) which bonded the sample to the exposed photosensitive film instead of the support film, and measured it. It was done. The "number of recesses per unit area 1mm <^2>and" arithmetic mean surface roughness Ra "of each measured photosensitive film surface were as showing in Table 2. Moreover, also in any of the Example, the confirmed recessed part was nonuniform.

<Furrow collapse of pattern>

Using each test substrate produced as described above, the furrows of the ten openings were observed by a 1000-time scanning electron microscope (SEM). Evaluation criteria were made in this way.

(Double-circle): A groove formation is favorable for all ten opening parts.

(Circle): Although an opening part becomes a taper shape, the push of the resin powder contained in a photosensitive film in the upper part of a furrow is not observed in any of ten opening parts.

X: Extrusion of the resin powder contained in the photosensitive film in the upper part of a furrow is observed in one or more opening parts.

The evaluation results are as shown in Table 2 below.

Claims (7)

In the photosensitive film provided with the surface which has a recessed part in the surface, and is formed of the photosensitive resin composition, the number of recessed parts per unit area 1mm <^2> of the said surface is 3.0 * 10 <^2> or more,
The said photosensitive resin composition contains the component which has at least any one of a some cyclic ether group and a some cyclic thioether group in 1 molecule as a thermal crosslinking component. The photosensitive film of Claim 1 whose number of recesses per unit area 1mm <^2> of the said surface is 2.0 * 10 <^4> or less. The photosensitive film of Claim 1 or 2 whose arithmetic mean surface roughness Ra of the said surface is 0.05 micrometer or more. The photosensitive film of Claim 1 or 2 in which the said photosensitive resin composition contains a filler. The support film is laminated | stacked on the photosensitive film of Claim 1, The photosensitive film laminated body characterized by the above-mentioned. The photosensitive film laminated body of Claim 5 provided with the surface which has a recessed part in the surface, and is formed by the photosensitive resin composition, and the support film is laminated | stacked on the surface side which has a recessed part in the said surface. The hardened | cured material formed using the photosensitive film laminated body by which the support film is laminated | stacked on the photosensitive film of Claim 1, or the said photosensitive film.