TW201335705A - Photosensitive resin composition, photosensitive resin film produced using said composition, and electronic component produced using said composition or said film - Google Patents

Abstract

A photosensitive resin composition comprising (A) a (meth)acrylate compound and (B) a photopolymerization initiator, wherein a (meth)acrylate compound having a urethane bond is contained as the component (A). The photosensitive resin composition enables the formation of a fine pattern even when the resin composition is formed into a film having a large thickness. A photosensitive resin layer formed from the resin composition has an excellent visible light transmissivity, and also has excellent heat resistance to such an extent that the resin layer undergoes less resin discoloration even when subjected to a long-term high-temperature thermal history.

Description

Photosensitive resin composition, photosensitive resin film obtained by using the composition, and electronic parts using the same

The present invention relates to a photosensitive resin composition, a photosensitive resin film obtained by using the composition, and an electronic component obtained by sealing an upper portion of a light-emitting element using the same.

With the miniaturization and high image quality of LED (Light-Emitting Diode) displays, it is required to reduce the size and density of light-emitting elements such as LED elements. For example, LED displays used in mobile phones and the like require high definition and low power consumption. In addition, it is required to be able to withstand the heat resistance of a harsh environment as it is deployed to people's livelihood machines and vehicle-mounted applications. Therefore, in the sealing member covering the upper portion of the light-emitting element such as the LED element, not only the fine pattern is required to have excellent workability and light transmittance, but also high heat resistance is required.

For example, Patent Document 1 discloses a transparent sealing resin, but since it is sealed by resin bonding, it is disadvantageous in that it is not suitable for microfabrication.

Further, although a photosensitive resin composition having a high transmittance such as those disclosed in Patent Documents 2 and 3 is considered as a sealing resin, there is a problem that the resin may be colored due to a thermal history, and there may be a problem. The hue changes and brightness reduction of light-emitting elements such as LEDs are affected.

[Previous Technical Literature] (Patent Literature)

Patent Document 1: Japanese Laid-Open Patent Publication No. 2007-308695

Patent Document 2: Japanese Laid-Open Patent Publication No. 2010-32991

Patent Document 3: Japanese Laid-Open Patent Publication No. 2004-35821

The present invention has been made in order to solve the above problems, and an object of the invention is to provide a photosensitive resin composition, a photosensitive resin film, and an electronic component using the same, which can be formed into a thick film. A fine pattern is formed, and has excellent visible light transmittance and excellent heat resistance, which is that resin coloration is still small at a high temperature over a long period of heat history.

As a result of intensive studies, the present inventors have found that the use of a (meth) acrylate compound having an urethane bond as a photopolymerizable compound and a photopolymerization initiator can achieve the above object. invention.

In other words, the present invention provides the following [1] to [3].

[1] A photosensitive resin composition comprising (A) a (meth) acrylate compound and (B) a photopolymerization initiator, wherein (A) component contains a (meth) group having an amine ester bond Acrylate compound.

[2] A photosensitive resin film having a photosensitive resin layer, the photosensitive The photosensitive resin layer is formed by molding the photosensitive resin composition described in the above [1] into a film shape.

[3] An electronic component obtained by sealing the upper portion of the light-emitting device using the photosensitive resin composition according to the above [1] or the photosensitive resin film according to the above [2].

The photosensitive resin composition of the present invention can form a fine pattern even when formed into a thick film, and the cured product has excellent visible light transmittance and excellent heat resistance, which is high temperature over a long period of time. Resin coloration is still rare after the thermal history.

10‧‧‧Photosensitive resin film

11‧‧‧Support film

12‧‧‧Photosensitive resin layer

12a‧‧‧(Exposure part) photosensitive resin layer

50‧‧‧PCB with light-emitting components

51‧‧‧Electronic circuit board

52a, 52b‧‧‧ lines

53‧‧‧Metal wire

54‧‧‧Electrode

55‧‧‧Lighting elements

56‧‧‧ reflector

60‧‧‧Electronic parts

110‧‧‧Laminator

120‧‧‧negative mask

130‧‧‧Developing machine

1 is a cross-sectional view showing an example of a method of manufacturing an electronic component in which an upper portion of a light-emitting element is sealed by using the photosensitive resin film of the present invention.

2 is a cross-sectional view showing an example of a method of manufacturing an electronic component in which an upper portion of a light-emitting element including a reflector is sealed by using the photosensitive resin film of the present invention.

3 is a cross-sectional view showing an example of a method of manufacturing an electronic component in which an upper portion of a light-emitting element including a reflector is sealed by using the photosensitive resin film of the present invention.

[Preferred form of implementing the invention] [Photosensitive Resin Composition]

The photosensitive resin composition of the present invention comprising (A) a (meth) acrylate compound and (B) a photopolymerization initiator, wherein (A) component contains a (meth)acrylic acid having an amine ester bond Ester compound.

In the present invention, the "(meth) acrylate compound" is used in the form of an acryl compound or a methacrylate compound, and the "(meth) acrylonitrile group" is It is used in the form of a term indicating an acryloyl group or a methacryl group. In addition, other similar terms are also the same.

Since the photosensitive resin composition of the present invention contains the above-described respective components, it is possible to form a fine pattern even when formed into a thick film, and has excellent visible light transmittance and excellent heat resistance, which is high temperature. After a long period of heat history, light having a wavelength of 450 to 740 nm is excellent in light transmittance and resin coloring is small.

The reason should be as follows.

In other words, the (meth) acrylate compound which is a component (A) has high transparency and excellent visible light transmittance. In addition, since it is polymerized by light or heat to perform three-dimensional crosslinking, it exhibits excellent heat resistance. Further, since the (meth) acrylate compound of the component (A) is excellent in compatibility, it can be sufficiently compatible with the component (B).

Further, when the photopolymerization initiator of the component (A) and the component (B) are used in combination, the deep curability is good when formed into a thick film, so that a high-resolution pattern can be formed.

Further, the (meth) acrylate having an amine ester bond contained in the component (A) can suppress the coloration and yellowing of the resin even when exposed to a high temperature for a long period of time in an air atmosphere, and can improve heat resistance and maintain high. Penetration.

Hereinafter, each component contained in the photosensitive resin composition of the present invention will be described.

((A) component: (meth) acrylate compound)

In the present invention, the (meth) acrylate compound as the component (A) contains a (meth) acrylate compound having an amine ester bond.

In addition, from the viewpoint of obtaining a photosensitive resin composition having excellent resolution and excellent pattern formation, the content of the component (A) relative to the total amount of the photosensitive resin composition of the present invention is 80% by mass or more. Preferably, it is preferably 85 mass% or more, more preferably 90 mass% or more, and still more preferably 95 mass% or more.

In addition, the upper limit of the content of the component (A) is not particularly limited, and a photosensitive resin capable of forming a high-resolution pattern when a deep film is formed in a thick film while securing the content of the component (B) is obtained. From the viewpoint of the composition, the content of the component (A) relative to the total amount of the photosensitive resin composition of the present invention is preferably 99.9% by mass or less, preferably 99.5% by mass or less, more preferably 99.0% by mass or less. .

<(meth)acrylate compound having an amine ester bond>

In the present invention, the (meth) acrylate compound having an amine ester bond (hereinafter also referred to as "amine ester compound (A1)")) may be used singly or in combination of two or more.

The amine ester-based compound (A1) may, for example, be a reactant obtained from a (meth) acrylate having a hydroxyl group and an isocyanate.

As the (meth) acrylate having a hydroxyl group, a compound having one hydroxyl group and one to five (meth) acrylonitrile groups in one molecule is preferred.

Further, as the isocyanate, an isocyanate having 1 to 3 isocyanate groups in one molecule is preferred.

As a reactant obtained from a (meth) acrylate having one hydroxyl group and 1 to 5 (meth) acrylonitrile groups in one molecule and an isocyanate having 1 to 3 isocyanate groups in one molecule, for example, A compound represented by the following formula (A-1).

In the above formula (A-1), R ^a represents a monovalent organic group having 1 to 5 (meth)acrylonyl groups, and examples thereof include one hydroxyl group and 1 to 5 molecules in one molecule (A) A residue obtained by removing a hydroxyl group among (meth) acrylates of an acrylonitrile group. R ^b represents a monovalent organic group of an aliphatic, alicyclic or aromatic skeleton, and examples thereof include a residue obtained by removing one isocyanate group from an isocyanate.

The present invention is obtained from the viewpoint of maintaining the transparency of the photosensitive resin composition, maintaining good heat resistance, low hygroscopicity, and toughness, and improving the solubility of the solvent used in the developer to obtain high resolution. The amine ester compound (A1) contained in the resin composition preferably contains a (meth) acrylate compound having at least one of an aliphatic skeleton and an alicyclic skeleton and having an amine ester bond.

From the viewpoint of maintaining the transparency of the photosensitive resin composition and maintaining good heat resistance, low hygroscopicity, and toughness, and obtaining high resolution, the above is relative to the total amount of the amine ester compound (A1). The content of the (meth) acrylate compound having at least one of an aliphatic skeleton and an alicyclic skeleton and having an amine ester bond is preferably 70% by mass or more, and more preferably 80% by mass or more. More preferably 90% by mass or more.

In order to introduce an aliphatic skeleton or an alicyclic skeleton into the structure of the amine ester compound (A1), as the raw material compound of the amine ester compound (A1), it is preferred to use the above-mentioned aliphatic skeleton or alicyclic skeleton. Isocyanate; a diol compound having an aliphatic skeleton or an alicyclic skeleton.

When a diol compound is used as a raw material compound of the amine ester-based compound (A1), the amine ester-based compound (A1) is obtained by a (meth) acrylate compound having a hydroxyl group and a diol compound and a diisocyanate. It is preferred that the terminal isocyanate group of the addition polymer is reacted to obtain a reactant, and the reactant is preferably a compound represented by the following formula (A-2).

In the above formula (A-2), R ¹¹ each independently represents a monovalent organic group having 1 to 5 (meth)acryl fluorenyl groups, and may, for example, have one hydroxyl group and 1 to 5 from one molecule. A residue obtained by removing a hydroxyl group among (meth)acryloyl (meth)acrylates.

R ¹² represents a divalent organic group of an aliphatic, alicyclic or aromatic skeleton, and examples thereof include a residue obtained by removing two isocyanato groups from a diisocyanate.

R ¹³ represents an organic group having 2 to 30 carbon atoms, preferably a saturated hydrocarbon group having 2 to 20 carbon atoms, and examples thereof include a linear alkyl group, a branched alkyl group, an alicyclic alkyl group, or an alicyclic ring. A combination of an alkyl group and a linear alkyl group and/or a branched alkyl group. n is an integer from 5 to 20.

Further, the amine ester-based compound (A1) may, for example, be a (meth) acrylate having a hydroxyl group and a isocyanuric acid type triisocyanate such as a compound represented by the following formula (A-3). The reaction product obtained by the reaction, the isocyanuric acid type triisocyanate is a terpolymer of a diisocyanate.

In the above formula (A-3), R ¹¹ , R ¹² , R ¹³ and n are the same as those in the above formula (A-2).

Further, * in the structure of the group A of the formula (A-3) represents a portion bonded to a nitrogen atom in the above-described structure.

Examples of the compound having one hydroxyl group and one to five (meth)acrylonium groups in one molecule include 2-hydroxyethyl (meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol. A (meth) acrylate having a hydroxyl group at a β-position such as a (meth) acrylate, a hydroxypropylated trimethylolpropane triacrylate, or a propylene glycol di(meth)acrylate. These compounds may be used singly or in combination of two or more.

Among these, pentaerythritol tri(meth)acrylate and dipentaerythritol penta(meth)acrylate are preferred.

As an isocyanate having 1 to 3 isocyanato groups in one molecule, For example, monoisocyanate such as phenyl isocyanate; diisocyanate having an alicyclic skeleton such as isophorone diisocyanate, hydrogenated xylene diisocyanate or norbornene diisocyanate; phenyl diisocyanate, toluene diisocyanate, xylene diisocyanate, a diisocyanate having an aromatic skeleton such as naphthalene diisocyanate; trimethylhexamethylene diisocyanate such as hexamethylene diisocyanate or 2,4,4-trimethylhexamethylene diisocyanate having an aliphatic skeleton; A diisocyanate; a compound obtained by preparing these diisocyanates into a trimer, and when it is a terpolymer, can be used as an isocyanuric acid type triisocyanate.

In the present invention, the isocyanate may be a compound derived from such an isocyanate, such as an isocyanate itself or an addition polymer obtained from the isocyanate and the diol compound.

The diol compound used in the present invention may, for example, be a diol compound represented by the following formula (A-4).

HO-R-OH (A-4)

In the above formula (A-4), R represents a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. The hydrocarbon group has a carbon number of 1 to 20, preferably 1 to 15, more preferably 1 to 12.

As the hydrocarbon group, a saturated hydrocarbon group is preferred, and a linear alkyl group which may have a substituent, a branched alkyl group which may have a substituent, and an alicyclic alkyl group which may have a substituent are preferable. Further, an alicyclic alkyl group which may have a substituent may be used in combination with a linear alkyl group and/or a branched alkyl group which may have a substituent.

The substituent may, for example, be an alkyl group, an alkoxy group, an aryl group, an aralkyloxy group, an aryloxy group, an aryloxyalkoxy group, an alkylthio group, an aralkylthio group, an arylthio group or an arylthio group. An alkylthio group, a halogen atom or the like.

The diol compound having a linear alkyl group is preferably a diol compound represented by the following formula (A-5).

HO-(CH ₂ ) _m -OH(m=2~12) (A-5)

Examples of the diol compound represented by the above formula (A-5) include ethylene glycol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, and 1,12. - dodecanediol and the like.

m is an integer of 1 to 20, preferably an integer of 1 to 15, and preferably an integer of 1 to 12.

Further, examples of the diol compound having a branched alkyl group include octadecanediol, propylene glycol, 1,3-butylene glycol, and isoprene glycol.

From the viewpoint of improving the glass transition temperature (Tg) of the polymer after polymerization to improve the transparency and the effect of increasing the water resistance by adding a chain alkyl group, among these, octadecanediol is used. good.

From the above viewpoint, as the octadecanediol, 1,2-octadecanediol represented by the following formula (A-5a), and 1,4-tenth represented by the following formula (A-5b) The octanediol, 1,10-octadecanediol represented by the following formula (A-5c), and 1,12-octadecanediol represented by the following formula (A-5d) are preferred.

From the viewpoint of improving the glass transition temperature (Tg) of the polymer after polymerization and improving the transparency and the moist heat resistance, the diol compound having an alicyclic alkyl group is represented by the following formula (A-6a). 1,4-cyclohexanedimethanol, 1,4-cyclohexanediol represented by the following formula (A-6b), and 1,3-cyclohexane represented by the following formula (A-6c) The alkanediol and the hydrogenated bisphenol A represented by the following formula (3-24) are preferred.

Increased robustness by adding polyfunctional groups to make rigidity even more From the viewpoint of the improvement of the viewpoint and the improvement of the heat resistance, as the diol compound other than the above, a compound such as an epoxy (meth) acrylate having two hydroxyl groups and two (meth) acrylonitrile groups is used. Specifically, for example, a compound represented by the following formula (A-7) can be mentioned.

In the above formula (A-7), R ^{21 is} each independently a hydrogen atom or a methyl group.

R ²² represents a divalent organic group which has a linear alkyl or branched alkyl group having 1 to 15 carbon atoms which may have a substituent, and an alicyclic ring having 1 to 20 carbon atoms which may have a substituent Alkyl is preferred. Further, an alicyclic alkyl group which may have a substituent may be used in combination with a linear alkyl group and/or a branched alkyl group which may have a substituent.

Further, examples of the substituent include an alkyl group, an alkoxy group, an aryl group, an aralkyloxy group, an aryloxy group, an aryloxyalkoxy group, an alkylthio group, an aralkylthio group, and an arylthio group. An arylthioalkylthio group, a halogen atom or the like.

In the diol compound represented by the formula (A-7), the diol compound represented by the following formula (A-7a) is preferred from the viewpoint of the improvement of the rigidity and the heat resistance.

Furthermore, in the present invention, these diol compounds may be used singly or in combination of two or more.

The amine ester compound (A1) obtained by using the above-mentioned raw material compound is preferably a compound represented by the following formula (A-8), from the viewpoint of suppressing the coloring property at the time of heating and the adhesion. The compound represented by the formula (A-8) is a compound synthesized using the diol compound represented by the above formula (A-7).

In the above formula (A-8), R ₁ and R ₂ each independently represent a divalent organic group which has a linear alkyl group or a branched alkyl group having 1 to 15 carbon atoms which may have a substituent. An alicyclic alkylene group having 1 to 20 carbon atoms which may have a substituent is preferred. Further, an alicyclic alkyl group which may have a substituent may be used in combination with a linear alkyl group and/or a branched alkyl group which may have a substituent. The substituent may, for example, be a group exemplified as a substituent which R ²² in the formula (A-7) may have. p is an integer of 1 or more, preferably an integer of 1 to 5, and preferably an integer of 1 to 3.

In the compound represented by the above formula (A-8), R ₂ in the formula (A-8) is a divalent group represented by the following structure, from the viewpoints of transparency, water resistance, and moisture resistance. good.

In addition, the amine ester type compound (A1) obtained by using the above-mentioned raw material compound may, for example, be a compound represented by the following formulas (A-9) to (A-13).

[Further, in the above formula (A-9), n represents an integer of 5 to 20].

The commercial product of the compound represented by the above formula (A-9) may, for example, be UN-952 (trade name, Gensei Industrial Co., Ltd., functional group number: 10, Mw: 6500 to 11000, having an amine ester bond) Acrylate compound) and the like.

Further, in the above formula (A-10), n represents an integer of 5 to 20, and ** in the structure of the group A represents a moiety bonded to a carbon atom in the above-described structure].

[Further, in the above formula (A-11), n represents an integer of 5 to 20].

[Further, in the above formula (A-12), n represents an integer of 5 to 20, and *, **, and *** represent a bonding portion].

[In the above formula (A-13), n represents an integer of 5 to 20].

Further, the amine ester compound (A1) contained in the photosensitive resin composition of the present invention may be an amine ester di(methyl) modified with ethylene oxide (EO) or propylene oxide (PO). An amine ester (meth) acrylate having an alkylene oxide skeleton such as acrylate is preferable from the viewpoint of preventing a decrease in heat resistance, and an amine ester (meth) acrylate having an alkylene oxide skeleton is not preferred.

In the component (A), the content of the amine ester (meth) acrylate having an alkylene oxide skeleton is preferably 5% by mass or less, more preferably 1% by mass or less, even more preferably 0.1% by mass or less, and substantially It is 0% by mass and even better.

Further, from the viewpoint of preventing the decrease in compatibility, the amine ester compound (A1) is preferably an amine ester (meth) acrylate which does not contain a polyester system.

In the component (A), the content of the amine ester (meth) acrylate having a polyester structure is preferably 5% by mass or less, preferably 1% by mass or less, more preferably 0.1% by mass or less, and substantially Above is 0% by mass and even better.

Further, depending on the temperature at the time of synthesis and the selected catalyst, the amine ester-based compound (A1) used may have initial coloration, but from the viewpoint of transparency, it does not contain initial coloration. The amine ester (meth) acrylate is preferred.

The amine ester (meth) acrylate which has an initial coloring, for example, UA-21 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.), TMCH-5R (trade name, manufactured by Hitachi Chemical Co., Ltd.), JTX -0309N (trade name, manufactured by Hitachi Chemical Co., Ltd.).

In the component (A), the content of the amine ester (meth) acrylate having an initial coloration is preferably 5% by mass or less, more preferably 1% by mass or less, even more preferably 0.1% by mass or less, and substantially 0. The quality % is even better.

In addition, from the viewpoint of determining a resin structure capable of coexisting heat resistance, rigidity, and high adhesion, the number of functional groups ((meth)acryl fluorenyl group) of the (meth) acrylate compound having an amine ester bond and The weight average molecular weight is preferably optimized. Containing such a (meth) acrylate compound having an amine ester bond, Since the selection range of the material having a low viscosity is widened, it is easy to arbitrarily adjust the viscosity of the photosensitive resin composition applied to the substrate at the time of forming the LED sealing portion. The low viscosity of the applied photosensitive resin composition can also be carried out using a solvent, but when at least the compound is used, the solvent which adversely affects the characteristics and reliability of the cured resin composition can be reduced. the amount.

The number of functional groups ((meth) acrylonitrile group) of the (meth) acrylate compound having an amine ester bond, in terms of heat resistance, adhesion, paintability, and pattern formability, in one molecule It is preferably from 2 to 15 and from 2 to 12, more preferably from 2 to 10, from the viewpoint of stabilizing the physical properties and characteristics of the obtained cured product.

When the number of the functional groups is two or more, the heat resistance can be improved, and the rigidity of the cured product at a high temperature can be improved.

On the other hand, when the number of the functional groups is 15 or less, it is possible to prevent the cured product from becoming brittle and to maintain good adhesion. Further, since the weight average molecular weight of the compound is not excessively large, a resin composition having an appropriate viscosity can be produced, and the paintability is good. In addition, when the brushed resin composition is irradiated, it is possible to suppress the phenomenon that the surface portion is easily photocured and the photo hardening is not sufficiently performed inside, and the excellent resolution can be exhibited to form the pattern formability. good. Further, since a large amount of unreacted (meth) acrylonitrile group remains after photohardening and/or thermal curing, the problem that the physical properties and characteristics of the obtained cured product are likely to be easily changed can be suppressed.

Further, the weight average molecular weight (Mw) of the (meth) acrylate compound having an amine ester bond is preferably 950 to 25,000, and is preferably 950 to 15,000 from the viewpoint of coatability and resolution. Developability and compatibility Point to see, 950~11000 is better. Further, in the present invention, the value of the weight average molecular weight (Mw) means a value measured by gel permeation chromatography (GPC) using a developing solvent such as tetrahydrofuran or toluene.

When the weight average molecular weight is 950 or more, the viscosity of the obtained resin composition is not too low, and the composition applied when applied to a substrate does not relax. Further, it is also possible to suppress the problem that it is difficult to form a thick film or hardening shrinkage causes an increase in stress of the resin and a decrease in reliability.

On the other hand, when the weight average molecular weight is 25,000 or less, the viscosity of the obtained resin composition is not excessively high, and the coating property can be improved, and a thick film can be formed. Further, since the solubility in the developer is also good, excellent resolution can be exhibited. Further, it is possible to suppress the coloring of the resin, that is, the resin, as the molecular weight increases, and it is possible to obtain a cured product having excellent transmittance required as a transparent material.

As a commercially available product of a (meth) acrylate compound having an amine ester bond, an acrylate compound having an amine ester bond (a compound having an acryl oxime group), for example, UN-904 (functional number: 10, Mw: 4900), UN-952 (functional group number: 10, Mw: 6500~11000), UN-333 (functional group number: 2, Mw: 5000), UN-1255 (functional group number: 2, Mw: 8000), UN-2600 (Function number: 2, Mw: 2500), UN-6200 (functional number: 2, Mw: 6500), UN-3320HA (functional number: 6, Mw: 1500), UN-3320HC (functional number: 6, Mw: 1500), UN-9000PEP (functional number: 2, Mw: 5000), UN-9200A (functional number: 2, Mw: 15000), UN-3320HS (functional number: 15, Mw: 4900), UN-6301 (functional) Base: 2, Mw: 33000) (all of the above are trade names, manufactured by Gensei Industrial Co., Ltd.); TMCH-5R (commodities) Name, manufactured by Hitachi Chemical Co., Ltd.; KRM 8452 (functional group number = 10, Mw = 1200), EBECRYL 8405 (amine ester acrylate / 1,6-hexanediol diacrylate = 80/20 addition reaction, The number of functional groups = 4, Mw = 2700) (all of the above are trade names, manufactured by DAICEL CYTEC Co., Ltd.) and the like.

The methacrylate compound (compound having a methacryl oxime group) having an amine ester bond, for example, UN-6060PTM (functional group number: 2, Mw: 6000, trade name, manufactured by Gensei Industrial Co., Ltd.), JTX-0309 (trade name, manufactured by Hitachi Chemical Co., Ltd.), UA-21 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.), etc.

From the viewpoint of low initial coloration and high initial transparency, it is preferable to use an amine ester (meth) acrylate having no aromatic skeleton such as UN-904 or UN-952 in such commercial products. The amine ester (meth) acrylate is a reactant obtained from an epoxy (meth) acrylate having two hydroxyl groups in one molecule and having no aromatic skeleton, and a bifunctional isocyanate. Further, by using the amine ester (meth) acrylate such as UN-904 or UN-952, moisture resistance, hydrophobicity, and chemical resistance (acid resistance and alkali resistance) can be improved, so that in the cutting step of the LED element. It is possible to sufficiently suppress moisture absorption by the cutting water, and it is possible to sufficiently suppress the erosion of the electrode pad cleaning liquid in the wire bonding step after the substrate assembly.

From the viewpoint of improving the heat resistance, the content of the (meth) acrylate having an amine ester bond is preferably 10% by mass or more, and more preferably 30% by mass or more, based on the total amount of the component (A). More preferably, it is 50% by mass or more, and more preferably 55 mass% or more, and more preferably 65% by mass or more. When the content is 10% by mass or more, even if various properties and characteristics required for the coating property, the formability, and the cured product of the resin composition are maintained, When exposed to a high temperature for a long period of time in an air environment, it is possible to suppress coloration and yellowing of the resin, and it is possible to improve heat resistance and maintain high penetration.

In addition, from the viewpoint of selectively adjusting other (meth) acrylate compounds to be described later, in consideration of the paintability, pattern formability, and physical properties and characteristics required for the cured product of the resin composition The upper limit of the content of the (meth) acrylate having an amine ester bond is preferably 95% by mass or less, preferably 90% by mass or less, more preferably 85% by mass or less, and still more preferably 80% by mass. The following is better, and it is more preferable to further reduce the amount to 75% by mass or less.

The (meth) acrylate having an amine ester bond, that is, the (meth) acrylate which is contained in the component (A) other than the amine ester compound (A1), is preferably one selected from the following compounds. The above compound (hereinafter also referred to as "compound (A2)"): a (meth) acrylate compound having a guanamine bond; a compound obtained by reacting an α,β-unsaturated carboxylic acid with a polyhydric alcohol; bisphenol A-based (meth) acrylate compound; a compound obtained by reacting an α,β-unsaturated carboxylic acid with a glycidyl-containing compound; and introducing an ethylenicity into a copolymer of an alkyl (meth) acrylate A compound of a saturated group.

These can be used alone or in combination of two or more.

The (meth) acrylate having an amine ester bond, that is, the mass ratio of the amine ester compound (A1) to the compound (A2) [(A1)/(A2)], preferably 10/90 to 95/5, Preferably, it is 30/70~90/10, more preferably 50/50~85/15, and even more preferably 55/45~80/20, and more preferably 60/40~75/25, the compound ( A2) is one or more selected from the group consisting of a (meth) acrylate compound having a guanamine bond; a compound obtained by reacting an α,β-unsaturated carboxylic acid with a polyol; bisphenol A a (meth) acrylate compound; an α,β-unsaturated carboxy group A compound obtained by reacting an acid with a glycidyl group-containing compound; and a compound having an ethylenically unsaturated group introduced into a copolymer of an alkyl (meth)acrylate.

<(meth)acrylate compound having a guanamine bond>

From the viewpoint of the resolution and the adhesion, the (meth) acrylate compound having a guanamine bond is preferably a compound represented by the following formula (1).

In the above formula (1), R ₃₁ , R ₃₂ and R ₃₃ each independently represent a divalent organic group, R ₃₄ represents a hydrogen atom or a methyl group, and R ₃₅ and R ₃₆ each independently represent a hydrogen atom and have a carbon number of 1 to 4; Alkyl or phenyl.

The divalent organic group may, for example, be a phenyl group which may have a substituent, a pyridine group which may have a substituent, a branchable alkyl group having a carbon number of 1 to 10, or a carbon number of 1 to 10. An alicyclic structure-containing group or the like of a substituent.

The polymerizable compound represented by the above formula (1) is preferably a di(meth)acrylate having a guanamine bond, and the di(meth)acrylate having a guanamine bond is contained. An oxazoline-based compound is obtained by reacting a carboxyl group-containing compound and/or a phenol-containing hydroxy compound. By using this compound, it is easy to obtain a cured resin of high elasticity and high heat resistance.

The polymerizable compound represented by the above formula (1) can be obtained by, for example, a double represented by the following formula (2) The oxazoline reacts with (meth)acrylic acid with a compound having two phenolic hydroxyl groups in one molecule.

In the formula (2), Y ⁴ represents a divalent organic group, a phenyl group which may have a substituent, a pyridyl group which may have a substituent, or a branched alkyl group having a carbon number of 1 to 10, carbon The alicyclic structure-containing group having a substituent of 1 to 10 is preferred. Further, R ⁴⁵ and R ⁴⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group.

As the double shown in the general formula (2) An oxazoline, for example, 2,2'-(1,3-phenylene)bis-2- Oxazoline, 2,6-bis(4-isopropyl-2- Oxazolin-2-yl)pyridine, 2-2'-isopropylidene bis(4-phenyl-2- Oxazoline), 2-2'-isopropylidene bis(4-tert-butyl-2- Oxazoline) and the like. These can be used individually or in combination of 2 or more types.

Examples of the compound having two phenolic hydroxyl groups in one molecule include biphenol, tetramethylbiphenol, dihydroxynaphthalene, dihydroxymethylnaphthalene, dihydroxydimethylnaphthalene, and bis(4-hydroxyphenyl). Ketone, bis(4-hydroxy-3,5-dimethylphenyl) ketone, bis(4-hydroxy-3,5-dichlorophenyl) ketone, bis(4-hydroxyphenyl)anthracene (bis) 4-hydroxyphenyl)sulfone), bis(4-hydroxy-3,5-dimethylphenyl)anthracene, bis(4-hydroxy-3,5-dichlorophenyl)anthracene, bis(4-hydroxyphenyl) Hexafluoropropane, bis(4-hydroxy-3,5-dimethylphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dichlorophenyl)hexafluoropropane, bis(4-hydroxyphenyl) ) dimethyl decane, bis(4-hydroxy-3,5-dimethylphenyl)dimethyl decane, bis(4-hydroxy-3,5-dichlorophenyl)dimethyl decane, bis (4) -hydroxyphenyl)methane, bis(4-hydroxy-3,5-dichlorophenyl)methane, bis(4-hydroxy-3,5-dibromophenyl)methane, 2,2-bis(4-hydroxyl Phenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl) Propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, bis(4-hydroxyphenyl)ether, double (4-hydroxy-3,5-dimethylphenyl)ether, bis(4-hydroxy-3,5-dichlorophenyl)ether, 9,9-bis(4-hydroxyphenyl)anthracene, 9, 9-bis(4-hydroxy-3-methylphenyl)anthracene, 9,9-bis(4-hydroxy-3-chlorophenyl)anthracene, 9,9-bis(4-hydroxy-3-bromophenyl) ), 9,9-bis(4-hydroxy-3-fluorophenyl)fluorene, 9,9-bis(4-hydroxy-3-methoxyphenyl)fluorene, 9,9-bis(4-hydroxyl) -3,5-dimethylphenyl)anthracene, 9,9-bis(4-hydroxy-3,5-dichlorophenyl)anthracene, 9,9-bis(4-hydroxy-3,5-dibromo Phenyl) oxime and the like.

Among these, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane is preferred. These can be used individually or in combination of 2 or more types.

Contain The reaction of the oxazoline group compound with the carboxyl group-containing compound and/or the phenol-containing hydroxy compound is preferably carried out at a reaction temperature of 50 to 200 °C. When the reaction temperature is 50° C. or higher, the reaction can be efficiently carried out, and when the reaction temperature is 200° C. or lower, the side reaction can be sufficiently suppressed. Further, the reaction can be carried out in a polar organic solvent such as dimethylformamide, dimethylacetamide or dimethyl sulfoxide as needed.

<Compound obtained by reacting an α,β-unsaturated carboxylic acid with a polyhydric alcohol>

The compound obtained by reacting an α,β-unsaturated carboxylic acid with a polyhydric alcohol may, for example, be a polyethylene glycol di(meth)acrylate having an ethyl group number of 2 to 14 and a stretching number of 2 to 2. 14 polypropylene glycol di(meth) acrylate, polyethylene glycol-polypropylene glycol di(meth) acrylate, trimethylolpropane di (ethylene glycol) having an ethyl group number of 2 to 14 and a propyl group number of 2 to 14. Methyl) acrylate, trimethylolpropane tri(meth) acrylate, ethylene oxide (EO) modified trimethylolpropane tri(methyl) propyl Ethyl ester, propylene oxide (PO) modified trimethylolpropane tri(meth) acrylate, EO and PO modified trimethylolpropane tri(meth) acrylate, tetramethylol methane three ( Methyl) acrylate, tetramethylol methane tetra(meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like. These can be used alone or in combination of two or more.

<Bisphenol A-based (meth) acrylate compound>

Examples of the bisphenol A-based (meth) acrylate compound include 2,2-bis(4-((meth)propenyloxypolyethoxy)phenyl)propane, 2,2-bis ( 4-((meth)acryloxypolypropoxy)phenyl)propane, 2,2-bis(4-((meth)propenyloxypolybutoxy)phenyl)propane, 2,2 - bis(4-((meth)acryloxypolyethoxypolypropyloxy)phenyl)propane or the like. These can be used alone or in combination of two or more.

<Compound obtained by reacting an α,β-unsaturated carboxylic acid with a glycidyl group-containing compound>

The compound obtained by reacting an α,β-unsaturated carboxylic acid and a glycidyl group-containing compound may, for example, be an epoxy acrylate compound obtained by reacting an epoxy resin with (meth)acrylic acid. The epoxy resin is a novolak type epoxy resin, a bisphenol type epoxy resin, a salicylaldehyde type epoxy resin, or the like.

Further, an acid-modified epoxy acrylate compound obtained by reacting an acid anhydride such as tetrahydrophthalic anhydride with an OH group of the above epoxy acrylate compound can also be used. For the acid-modified epoxy acrylate compound, for example, EA-6340 (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name) represented by the following formula (3) can be obtained commercially.

[wherein, the ratio of m to n is 100/0 to 0/100].

<Compound in which an ethylenically unsaturated group is introduced into a copolymer of an alkyl (meth) acrylate>

The compound having an ethylenically unsaturated group introduced into the copolymer of the alkyl (meth)acrylate may, for example, be methyl (meth)acrylate, ethyl (meth)acrylate or butyl (meth)acrylate. A compound in which an ethylenically unsaturated group is introduced into a copolymer of an ester or 2-ethylhexyl (meth)acrylate. These can be used alone or in combination of two or more.

From the viewpoint of improving heat resistance and adhesion, the (meth) acrylate contained in the above (A) component is preferably a (meth) acrylate containing a carbon-nitrogen bond, and has a decylamine. The (meth) acrylate compound of the bond and/or the (meth) acrylate compound having an amine ester bond is preferred.

In addition, from the viewpoint of improving the adhesion density and improving the adhesion, and the balance between transparency, resolution, and heat resistance, a (meth) acrylate compound having a guanamine bond and an amine are contained. The (meth) acrylate compound of the ester bond is preferred as the component (A).

When the above compound is used in combination, the ratio of the (meth) acrylate compound having an amine ester bond to the (meth) acrylate compound having a guanamine bond [having an amine The (meth) acrylate compound of the ester bond / the (meth) acrylate compound having a guanamine bond is preferably 40/60 to 90/10, preferably 50/50 to 85/15, and 60/ 40~80/20 is better.

(Component (B): Photopolymerization initiator)

The (B) photopolymerization initiator used in the present invention is not particularly limited as long as it generates free radicals due to active light.

The (B) photopolymerization initiator may, for example, be a mercaptophosphine oxide, an oxime ester, an aromatic ketone, an anthracene, a benzoin ether compound, a benzyl derivative or a 2,4,5-triarylimidazole. Dimer, acridine derivative, coumarin compound, N-phenylglycine, N-phenylglycine derivative, and the like. Further, the photopolymerization initiator (B) used in the present invention can be synthesized by a conventional method, and a commercially available product can also be obtained.

From the viewpoint of improving photocurability, high sensitivity, and transparency of the cured film, among these, a mercaptophosphine oxide or an oxime ester is preferred.

Further, the (B) photopolymerization initiator may be used singly or in combination of two or more.

<Mercaptophosphine oxide>

Examples of the mercaptophosphine oxide include bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide (commercial product: "IRGACURE-819 (manufactured by BASF Corporation)"), 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide (commercial product: "LUCIRIN TPO (manufactured by BASF Corporation)").

<肟 esters>

Examples of the oxime esters include 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzopyridinyl) represented by the following formula (4). ) (commercially available: "IRGACURE-OXE01 (manufactured by BASF Corporation)"), 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]ethanone-1-(O- Ethyl acetate (commercial product: "IRGACURE-OXE02 (manufactured by BASF)"), 1-phenyl-1,2-propanedione-2-[O-(ethoxycarbonyl)anthracene] (commercially available) ("Quantacure-PDO (manufactured by Nippon Kayaku Co., Ltd.)").

<aromatic ketone>

The aromatic ketone may, for example, be benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N, N'- Tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2,2-dimethoxy-1,2-di Phenylethyl-1-one (commercial product: "IRGACURE-651 (manufactured by BASF)"), 2-benzyl-2-dimethylamino-1-(4-(N-morpholinyl) Phenyl)butan-1-one (commercial product: "IRGACURE-369 (manufactured by BASF)"), 2-methyl-1-[4-(methylthio)phenyl]-2-(N-? Polinyl)propan-1-one (commercial product: "IRGACURE-907 (manufactured by BASF Corporation)").

<醌>

Examples of the hydrazines include 2-ethyl hydrazine, phenanthrenequinone, 2-tributyl sulfonium, octamethyl hydrazine, 1,2-benzopyrene, and 2,3-benzopyrene. , 2-phenylindole, 2,3-diphenylanthracene, 1-chloroindole, 2-methylindole, 1,4-naphthoquinone, 9,10-phenanthrenequinone, 2-methyl- 1,4-naphthoquinone, 2,3-dimethylhydrazine, and the like.

<benzoin ether compound>

Examples of the benzoin ether compound include benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether.

<Benzylmethyl derivative>

Examples of the benzyl derivative include benzoin compounds such as benzoin, methylbenzoin, and ethyl benzoin; and benzyl dimethyl ketal.

<2,4,5-triaryl imidazole dimer>

As the 2,4,5-triaryl imidazole dimer, for example, 2-(2-chlorophenyl)-1-[2-(2-chlorophenyl)-4,5-diphenyl-1 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer such as 3-oxazol-2-yl]-4,5-diphenylimidazole; 2-(o-chlorophenyl)- 4,5-bis(methoxyphenyl)imidazole dimer; 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer; 2-(o-methoxyphenyl)-4 , 5-diphenylimidazole dimer; 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, and the like.

<Acridine derivative>

The acridine derivative may, for example, be 9-phenylacridine or 1,7-bis(9,9'-acridinyl)heptane.

<Coumarin Compound>

Examples of the coumarin-based compound include 7-amino-4-methylcoumarin, 7-dimethylamino-4-methylcoumarin, and 7-diethylamino-4-methyl. Coumarin, 7-methylamino-4-methylcoumarin, 7-ethylamino-4-methylcoumarin, 7-dimethylaminocyclopenta[c]coumarin, 7- Aminocyclopenta[c]coumarin, 7-diethylaminocyclopenta[c]coumarin, 4,6-dimethyl-7-ethylaminocoumarin, 4,6-di Ethyl-7-ethylaminocoumarin, 4,6-dimethyl-7-diethylaminocoumarin, 4,6-dimethyl-7-dimethylaminocoumarin, 4, 6-Diethyl-7-ethylaminocoumarin, 4,6-diethyl-7-dimethylaminocoumarin, 2,3,6,7,10,11-hexanehydrogen-1H ,5H-cyclopenta[3,4][1]benzopyrano[6,7,8-ij]quina 12(9H)-ketone, 7-diethylamino-5',7'-dimethoxy-3,3'-carbonyl dicoumarin, 3,3'-carbonyl bis[7-(diethylamine) Keto), 7-diethylamino-3-thienyloxycoumarin, and the like.

The amount of the photopolymerization initiator (B) to be added is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, even more preferably 0.75 to 5 parts by mass, per 100 parts by mass of the component (A). When the amount is adjusted to the above range, the sensitivity and photocurability of the photosensitive resin composition can be improved, and the shape of the resist can be prevented from being deteriorated, and the shape of the pattern can be improved.

((C) component: antioxidant)

In the resin composition of the present invention, (C) an antioxidant may be further formulated.

The (C) antioxidant to be formulated is not particularly limited, and a compound having a hindered phenol-based structure (hereinafter also referred to as a "hindered phenol-based compound") is preferably added.

In addition, the "hindered phenol type compound" used in the present invention may, for example, be a compound having at least one group (hindered phenol group) represented by the following formula (5) in one molecule.

In the above formula (5), R ⁵² and R ⁵³ each independently represent a hydrogen atom, a linear alkyl group or a branched alkyl group. Further, examples of the linear alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the branched alkyl group include an isopropyl group, an isobutyl group, and a tertiary butyl group. When a plurality of groups represented by the formula (5) are present in one molecule, R ⁵² and R ⁵³ may be the same or different in a plurality of groups. Further, the aromatic ring in the formula (5) may have a group such as a lower alkyl group in addition to the phenol group, R ⁵² and R ⁵³ .

The hindered phenol-based compound (C) used in the present invention is preferably a compound wherein R ⁵² and/or R ⁵³ in the above formula (5) is a branched alkyl group, and at least one of R ⁵² and R ⁵³ is used. The compound which is a tertiary butyl group is more preferable, and the compound in which R ⁵² and R ⁵³ are each a tertiary butyl group is more preferable.

Further, such a hindered phenol compound (C) can be synthesized by a conventional method, and a commercially available product can also be obtained.

The hindered phenol-based compound (C) used in the present invention may, for example, be barium pentaerythritol [3-(3,5-di(tri-butyl)-4-hydroxyphenyl)propionate] (commercially available) "IRGANOX 1010 (manufactured by BASF)"), bis(3-tert-butyl-4-hydroxy-5-methylphenylpropionic acid)-extended ethyl bis(oxyethyl) ester (commercial product: "IRGANOX 245 (manufactured by BASF Corporation)"), 4-[[4,6-bis(octylthio)-1,3,5-three -2-yl]amino]-2,6-di(tributyl)phenol (commercial product: "IRGANOX 565 (manufactured by BASF)"), 3-(3,5-di(tributyl) Octadecyl 4-hydroxyphenyl)propionate (commercial product: "IRGANOX 1076 (manufactured by BASF)"), N,N'-(1,6-hexanediyl) bis [3,5- Bis(1,1-dimethylethyl)-4-hydroxybenzamide] (commercial product: "IRGANOX 1098 (manufactured by BASF)"), ginseng (4-tertiary butyl-3-hydroxy-) 2,6-Dimethylbenzyl)isocyanurate (commercial product: "CYANOX 1790 (manufactured by American Cyanamid)"), 6-tertiary butyl-4-[3-[(2,4) ,8,10-tetrakis(tributyl)dibenzo[d,f][1,3,2]dioxaphosphin-6-yloxy]propyl]-2-methyl Phenol (commercial product: "Sumilizer GP (manufactured by Sumitomo Chemical Co., Ltd.)"), 3,9-bis[1,1-dimethyl-2-{β-(3-tert-butyl-4-hydroxy-5) -Methylphenyl)propenyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane (commercial product: "ADEKA STAB AO80 (made by ADEKA)" ), 2,2'-methylenebis(4-ethyl-6-tributylphenol) (commercial product: "YOSHINOX 425 (manufactured by API Corporation)").

Particularly, from the viewpoints of molecular weight and solubility, among these, pentaerythritol 肆 [3-(3,5-di(tri-butyl)-4-hydroxyphenyl)propionate] (commercially available: IRGANOX 1010) is preferred.

In addition, these (C) components can be used individually or in combination of 2 or more types.

The compounding amount of the component (C) is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, even more preferably 0.75 to 5 parts by mass, per 100 parts by mass of the component (A). By setting the blending amount to the above range, it is possible to prevent the film property of the photosensitive resin composition from being embrittled and the pattern shape from being deteriorated, and it is possible to suppress coloration of the resin at a high temperature.

((D) component: light stabilizer)

Further, the photosensitive resin composition of the present invention may be further formulated with a (D) light stabilizer.

Examples of the (D) light stabilizer to be blended include hindered amine compounds such as TINUVIN 144, TINUVIN 765, and TINUVIN 744DF (all trade names, manufactured by BASF Corporation).

The blending amount of the component (D) is preferably 0.1 to 30 parts by mass, more preferably 0.2 to 20 parts by mass, even more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the component (A).

((E) component: UV absorber)

Further, the photosensitive resin composition of the present invention may be further formulated with (E) a UV absorber.

Examples of the (E) UV absorber to be blended include benzotriazole-based compounds such as TINUVIN P, TINUVIN 234, TINUVIN 326, TINUVIN 328, TINUVIN 213, and TINUVIN 571 (all trade names, manufactured by BASF Corporation). .

The amount of the component (E) is preferably 0.1 to 30 parts by mass, more preferably 0.2 to 20 parts by mass, even more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the component (A).

((F) component: thermal radical generator)

Further, the photosensitive resin composition of the present invention may further contain (F) a thermal radical generating agent.

As the (F) thermal radical generating agent to be formulated, for example, t-butylcumyl peroxide (commercial product: "PERBUTYL C (trade name, Nippon Oil Co., Ltd.) is mentioned. )))), n-butyl 4,4-di(tertiary butylperoxy)pentanoate (commercial product: "PERHEXA V (trade name, manufactured by Nippon Oil Co., Ltd.)"), dicumyl Peroxide (commercially available as a peroxide such as "PERCUMYL D (trade name, manufactured by Nippon Oil Co., Ltd.)").

The amount of the component (F) is preferably 0.1 to 30 parts by mass, more preferably 0.2 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the component (A).

(other ingredients)

Further, in the photosensitive resin composition, in order to make the photosensitive resin The adhesion between the object and the substrate is improved, and an adhesion aid is added as needed. Examples of the adhesion aid include a decane coupling agent such as γ-glycidoxydecane, amino decane or γ-ureido decane.

The amount of the adhesion aid is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass, more preferably 0.5 to 2 parts by mass, per 100 parts by mass of the component (A).

In addition, when applied to a film or a support substrate, the photosensitive resin composition of the present invention is preferably in the form of a solution obtained by dissolving the above components by adding a solvent from the viewpoint of workability.

The solvent to be used is not particularly limited, and examples thereof include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, and propylene glycol. A polar solvent such as methyl ether acetate or the like; a solvent such as γ-butyrolactone. These solvents may be used singly or in combination of two or more.

When it is in the form of a solution, the solid content concentration of the photosensitive resin composition solution is preferably from 20 to 85% by mass, more preferably from 30 to 80% by mass.

[Photosensitive Resin Film]

The photosensitive resin film of the present invention has a photosensitive resin layer obtained by molding the photosensitive resin composition of the present invention into a film shape.

The photosensitive resin film of the present invention may be a single layer composed only of the above-mentioned photosensitive resin layer, or may be a plurality of layers having a photosensitive resin layer on the support film.

The photosensitive resin film of the present invention can be obtained by dissolving the photosensitive resin composition of the present invention in the above solvent, by various methods known in the art. It is applied to a support film such as an organic film such as polyethylene terephthalate, and after forming a coating film, it is dried to remove the solvent contained in the coating film, thereby forming photosensitivity on the support film. The resin layer was obtained in the form of two layers of photosensitive resin film (dry film photoresist).

Further, a protective film such as polyethylene terephthalate, a polyethylene film, or a polypropylene film may be laminated on the photosensitive resin layer to form a three-layer photosensitive resin film.

In addition, as long as the photosensitive resin layer composed of the photosensitive resin composition of the present invention has self-supporting property, the support film can be peeled off, and the single-layer photosensitive film composed only of the photosensitive resin layer can be used as the unsupported film. Resin film.

When a photosensitive resin film is produced, the thickness of the support sheet such as the photosensitive resin layer or the support film and the thickness of the protective film can be appropriately set depending on the application.

For example, the thickness of the photosensitive resin layer is preferably from 1 to 500 μm, and the thickness of the support sheet is preferably from 10 μm to 3 mm, and the thickness of the protective film is preferably from 10 to 200 μm.

In addition, when the photosensitive resin film of the present invention is used for sealing a light-emitting element such as an LED element such as a wiring board with an electronic component having irregularities, from the viewpoint of the unevenness of the landfill and the formation of a flat surface The thickness of the photosensitive resin layer is preferably 10 to 500 μm, more preferably 20 to 450 μm, and still more preferably 30 to 400 μm.

In addition, when the photosensitive resin film of the present invention is used for the above-mentioned use, it is supported from the viewpoint of suppressing generation of wrinkles in the photosensitive resin layer at the time of sealing. The thickness of the sheet is preferably 18 to 100 μm, preferably 25 to 75 μm.

The photosensitive resin layer having a film thickness of 30 μm in the photosensitive resin film preferably has a light transmittance of light of 450 nm or more, preferably 85% or more, more preferably 87% or more, more preferably 89% or more.

The photosensitive resin layer having a film thickness of 30 μm preferably has a light transmittance of light of 365 nm or more, preferably 65% or more, more preferably 70% or more, and still more preferably 75% or more.

The photosensitive resin layer having a film thickness of 30 μm preferably has a light transmittance of 80% or more of light having a wavelength of 740 nm, preferably 85% or more, more preferably 88% or more.

Furthermore, the value of the light transmittance of light of such wavelengths means the value measured by the method described in the examples.

The photosensitive resin layer which is a cured product of the photosensitive resin composition of the present invention has excellent heat resistance, and the heat resistance is such that the resin coloration is still small at a high temperature over a long period of heat history.

After a heat history of 500 hours at 130 ° C, the photosensitive resin layer having a film thickness of 30 μm has a light transmittance of light of 450 nm or more, preferably 80% or more, more preferably 83% or more, and 85%. The above is better.

After a heat history of 500 hours at 130 ° C, the photosensitive resin layer having a film thickness of 30 μm preferably has a light transmittance of light of 365 nm or more, preferably 55% or more, more preferably 60% or more, and 65%. The above is better.

After a heat history of 500 hours at 130 ° C, the photosensitive resin layer having a film thickness of 30 μm has a light transmittance of light of 740 nm, preferably 85% or more, more preferably 87% or more, and 89%. The above is better.

In addition, the conditions of each of the above thermal history and the value of the light transmittance are described in the examples.

[Pattern forming method]

The photosensitive resin composition and the photosensitive resin film of the present invention can form a desired pattern by the following method. The pattern forming method can form a desired pattern by a laminating step of laminating a photosensitive resin layer (photosensitive resin film) formed using the photosensitive resin composition or the photosensitive resin film on a substrate; and an exposure step And irradiating the predetermined portion of the photosensitive resin layer with a mask to photo-curing the exposed portion, and removing the step of removing the portion of the photosensitive resin layer other than the exposed portion by using a developing solution; In the hardening step, the exposed portion of the photosensitive resin layer is thermally cured to form a cured resin.

(layering step)

In the present lamination step, the photosensitive resin film can be formed by applying the photosensitive resin composition or the photosensitive resin film onto a support substrate, drying it, or laminating it on a support substrate.

Examples of the support substrate include a glass substrate, a semiconductor, a metal oxide insulator (for example, TiO ₂ or SiO ₂ ), a tantalum nitride, a ceramic piezoelectric substrate, and the like.

When the photosensitive resin composition is applied, it is preferably a form in which it is dissolved in the above solvent to form a solution. In addition, the coating method of the photosensitive resin composition is not particularly limited, and examples thereof include spin coating, spray coating, dip coating, and roll coating using a spinner. Further, when a photosensitive resin film is used, it can be laminated using a laminator or the like.

The coating film thickness of the photosensitive resin composition differs depending on the coating means, the solid content concentration and the viscosity of the photosensitive resin composition, and the film thickness of the film (photosensitive resin layer) after drying is usually 1 to 500. Μm method of coating, 1 to 300 μm is preferred, and 1 to 250 μm is preferred.

In particular, when the film thickness of the obtained film is 300 μm or less, the resolution is good. When a photosensitive resin film is used, it can be formed in advance so that the film thickness of the photosensitive resin layer becomes the film thickness mentioned above.

Further, in order to set the film thickness of the film after drying to the above range, it is preferred to dissolve the photosensitive resin composition in the solvent to form a solution, but the viscosity of the solution is 0.5 to 20 Pa. s is better, with 1~10 Pa. s is preferred.

Then, by heating and drying in a temperature range of 60 to 120 ° C for 1 minute to 1 hour using a hot plate, an oven, or the like, a photosensitive resin film can be formed on the support substrate.

(exposure step)

In the exposure step, the photosensitive resin film which is a film on the support substrate is irradiated with a reactive light to a predetermined portion via a negative mask having a desired pattern, and the exposed portion is photocured.

Here, examples of the active light used for the exposure include ultraviolet rays, visible light, electron beams, and X-rays. Among them, ultraviolet light and visible light are particularly preferable.

In the present invention, when the exposure step is performed, the temperature of the film (photosensitive resin layer) composed of the photosensitive resin composition on the support substrate can be increased to perform exposure.

The temperature of the film (photosensitive resin layer) may be a temperature that can suppress the change in the physical properties of the film, and can be set to 100 ° C or lower in accordance with the heating method or the heating device. At this time, the temperature adjustment can increase the temperature of the support substrate having the film. In addition, a method of heating from a temperature above the film by warm air or the like, or increasing the temperature of the entire exposure environment may be used. According to the present invention, since the hardening of the light-irradiating portion by the polymerization reaction is further performed as compared with the case where the photo-radical generating agent is not contained, the pattern is prevented from collapsing or cracking in the developing step described later. In addition, pattern formation and resolution can be improved.

(removal step)

In the removal step, a portion other than the exposed portion of the photosensitive resin layer (unexposed portion) is removed by using a developing solution of an organic solvent or an alkaline aqueous solution to form a pattern, and then the photosensitive resin layer is formed. The exposed portion is thermally cured to form a pattern composed of a cured resin.

As the developer, an organic solvent or an alkaline aqueous solution can be used.

The organic solvent may, for example, be N-methylpyrrolidone, ethanol, cyclohexanone, cyclopentanone or propylene glycol methyl ether acetate.

The alkaline aqueous solution may, for example, be an aqueous solution of sodium hydroxide, potassium hydroxide, sodium citrate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine or tetramethylammonium hydroxide.

From the viewpoint of the development speed, among these, propylene glycol methyl ether acetate is preferably used.

Further, after the removal step, it is preferred to wash (flush) with the following liquids as needed: water; alcohols such as methanol, ethanol, isopropanol; n-butyl acetate, propylene glycol monomethyl ether acetate Ester, diethylene glycol dimethyl ether acetate, and the like.

It is preferable to further perform a thermal curing step of thermally curing the exposed portion of the photosensitive resin layer to form a resin hardening step. Things. It is preferable to carry out heat hardening (cooking) after development for 1 to 2 hours while gradually increasing the temperature while selecting the temperature. The temperature in the thermal hardening step is preferably 120 to 240 ° C. When the temperature is raised stepwise, it is preferred to heat treatment at about 120 ° C and about 160 ° C for 10 to 50 minutes (20 to 40 minutes is preferred) After that, heat treatment is carried out at about 220 ° C for 30 to 100 minutes (preferably 50 to 70 minutes).

The photosensitive resin composition of the present invention can form a fine pattern even when formed into a thick film, and has excellent visible light transmittance and excellent heat resistance, which is after a long heat history at a high temperature. Resin coloring is still rare. Therefore, the photosensitive resin composition or the photosensitive resin film of the present invention is suitable as a sealing member for a light-emitting element such as an LED element, and the light-emitting element is required to be small-sized, high-density mounted, and used for a long period of time in a high-temperature environment. In other words, the electronic component obtained by sealing the upper portion of the light-emitting element such as an LED element using the photosensitive resin composition or the photosensitive resin film of the present invention can be used as a camera illumination and LED display for use in a mobile phone or the like. Parts.

Hereinafter, a case where the photosensitive resin film of the present invention is used as a sealing member of a light-emitting element such as an LED element will be described using the first to third drawings.

1 is a cross-sectional view showing an example of a method of manufacturing an electronic component in which an upper portion of a light-emitting element is sealed using the photosensitive resin film of the present invention.

The wiring board 50 with a light-emitting element shown in Fig. 1(a) has an electronic circuit board 51, and a light-emitting element 55 such as an LED element, which is provided on the wiring board 50. The electronic circuit board 51 is formed with a line 52a through which electric power is passed, and is connected to a line 52b formed on the surface of the wiring board 50. And this line 52b is electrically connected to the electrode 54 provided on the light-emitting element 55 via the metal wire 53.

The sealing of the light-emitting element 55 can be performed by laminating the photosensitive resin film 10 from the surface of the wiring board 50 with the light-emitting element provided with the light-emitting element 55 as shown in Fig. 1(b).

In addition, in the first drawing (b), the photosensitive resin film 10 is used for sealing. However, a solution of a varnish-like photosensitive resin composition may be applied to a substrate by a spin coating method or the like to be sealed. . However, it is preferable to use a photosensitive resin film for sealing from the viewpoint of surface smoothness and uneven landfill.

Further, as shown in Fig. 1(b), the photosensitive resin film 10 to be used is preferably formed by peeling off the protective film in advance and attaching the supporting sheet 11 such as a support film. The layer of the resin layer 12 is laminated on the side of the light-emitting element 55 by using the laminator 110.

The conditions for the lamination are preferably carried out under the following conditions, for example, a temperature of 40 to 100 ° C, a pressure of 0.05 to 2 MPa, and a speed of 0.1 to 3.0 m/min. By laminating under these conditions, there is an effect that the unevenness and the like are excellent, and the adhesion to the substrate is excellent.

In addition, when the photosensitive resin film 10 to be used has the support sheet 11, the support sheet 11 is preferably removed by being peeled off from the photosensitive resin layer 12 after lamination.

After sealing with a photosensitive resin film, it is preferable to individually pattern each of the light-emitting elements by an exposure step and a removal step.

In the exposure step, preferably, as shown in FIG. 1(c), the photosensitive resin layer is subjected to a predetermined exposure amount (100 to 1000) via a negative mask 120 having a desired pattern. Preferably, mJ/cm ^{2 is applied} to the predetermined portion to irradiate the active light to cause the exposed portion to be photocured.

Further, the conditions of the exposure step are the same as those of the exposure step in the pattern forming method described above.

In the developing step, preferably, as shown in FIG. 1(d), the developing machine 130 is used to eject a developing solution of an organic solvent system such as propylene glycol methyl ether acetate or an alkaline aqueous solution to expose the film. A portion (unexposed portion) other than the photosensitive resin layer 12a is dissolved and removed, and each of the light-emitting elements 55 is individually patterned, and the photosensitive resin layer 12a of the exposed portion is thermally cured.

Further, the conditions of the developing step are the same as those of the developing step in the pattern forming method described above, and it is preferred to carry out development using an organic solvent.

Then, each of the light-emitting elements 55 is individually divided by the dicing step, and an electronic component 60 such as that shown in FIG. 1(e) can be obtained, and the electronic component 60 is a light-emitting element 55 with the photosensitive resin layer 12a. The upper part is sealed.

Further, as shown in FIGS. 2 and 3, the wiring board 50 with the light-emitting element of the reflector 56 is formed around the light-emitting element 55, and the light-emitting element 55 is sealed using the photosensitive resin film of the present invention.

Further, the reflector 56 can be formed by forming the reflector 56 before the electronic circuit board 51 as in the second drawing (a) to (b), and then connecting the line 52b of the electronic circuit board 51 with the metal wire 53. The electrode 54 of the light-emitting element 55 is connected, and the line 52b of the electronic circuit board 51 and the electrode 54 of the light-emitting element 55 may be connected by a metal wire 53 as shown in Figs. 3(a) to 3(b).

The sealing side of the circuit board 50 with the light-emitting elements of the reflector 56 is formed The method can be carried out in the same manner as described above, as shown in FIGS. 2 and 3 (c) to (f), to manufacture an electronic component 60 which emits light by the photosensitive resin layer 12a. Element 55 is sealed.

[Examples]

The present invention will be more specifically described below based on examples and comparative examples, but the present invention is not limited by the following examples.

[Manufacturing Example 1] [Synthesis of Amine Ester Acrylate]

In a reaction vessel equipped with a thermometer and a stirring device, 12.0 g of 1,4-cyclohexanedimethanol, 222.2 g of isophorone diisocyanate, and 380 g of cyclohexanone were added, and stirred under a nitrogen gas stream. The mixture was heated to 90 ° C to 100 ° C for one hour. Then, 306.0 g of pentaerythritol triacrylate was added, and the reaction was carried out until the absorption of the isocyanate disappeared in the infrared spectroscopic analysis, and a solution of the amine ester acrylate represented by the following formula (6) was obtained. The solid content of the obtained solution was 60% by mass.

[Manufacturing Example 2] [Synthesis of guanamine methacrylate]

Adding 1,3-phenylene double in a 1 L reaction vessel equipped with a thermometer and a stirring device Oxazoline 380.0 g (2.0 mol) and bisphenol A 228.0 g (1.0 mol) were stirred at 150 ° C for 10 hours. Then, 500 ppm of p-methoxyphenol and 172.0 g (2.0 mol) of methacrylic acid were added, and after stirring at 100 ° C for 6 hours, 190 g of dimethylacetamide was added dropwise, and the mixture was further stirred at 100 ° C for 6 hours. When the acid value became 1.1 mgKOH/g, the stirring was stopped, and a solution of the guanamine methacrylate represented by the following formula (7) was obtained. The solid content of the obtained solution was 80% by mass.

[Examples 1 to 10, Comparative Examples 1 to 3]

The components (A) and (B) and the decane coupling agent were mixed in the blending ratio (parts by mass and solid fraction) shown in Table 1, and the photosensitivity of Examples 1 to 10 and Comparative Examples 1 to 3 were obtained. A solution of a resin composition.

Further, the weight average molecular weight (Mw) of the amine ester acrylate to be used and the amine ester acrylate shown below is measured by a GPC method using tetrahydrofuran (THF) as a solution. The standard polystyrene was obtained by conversion, and the details of the GPC method are as follows.

●Device name: HLC-8220GPC (product name, Tosoh Co., Ltd.)

●Pipe column: Gelpack R-420, R-430, R-440 (product name, manufactured by Hitachi Chemical Co., Ltd.)

●Detector: RI detector

● Column temperature: 40 ° C

●Solution solution: tetrahydrofuran (THF)

● Flow rate: 1 mL / minute

●Standard material: polystyrene

The components in the first table are as follows.

<(A) component>

Amine ester acrylate (the compound represented by the above formula (6) obtained in the above Production Example 1)

●UN-904 (trade name, acrylate compound with amine ester bond, functional group number = 10, Mw = 4900, manufactured by Gensei Industrial Co., Ltd.)

●UN-952 (trade name, acrylate compound with amine ester bond, functional group number = 10, Mw = 6500 ~ 11000, manufactured by Gensei Industrial Co., Ltd.)

●UN-2600 (trade name, acrylate compound with amine ester bond, functional group number = 2, Mw = 2500, manufactured by Gensei Industrial Co., Ltd.)

●UN-6200 (trade name, acrylate compound with amine ester bond, functional group number = 2, Mw = 6500, manufactured by Gensei Industrial Co., Ltd.)

●UN-9200A (trade name, acrylate compound with amine ester bond, functional group number = 2, Mw = 15000, manufactured by Gensei Industrial Co., Ltd.)

●EBECRYL 8405 (trade name, amine ester acrylate / 1,6-hexanediol diacrylate = 80/20 addition reactant, functional group number = 4, Mw = 2700, manufactured by DAICEL CYTEC Co., Ltd.)

●KRM 8452 (trade name, acrylate compound having an amine ester bond, functional group number = 10, Mw = 1,200, manufactured by DAICEL CYTEC Co., Ltd.)

• guanamine methacrylate (the compound represented by the above formula (7) obtained in the above Production Example 2)

●EA-6340 (trade name, tetrahydrophthalic anhydride modified vinyl-containing phenolic epoxy resin, manufactured by Nakamura Chemical Co., Ltd.)

●BPE-100 (trade name, ethoxylated bisphenol A dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.)

●A-BPEF (trade name, diacrylate containing anthracene skeleton, manufactured by Shin-Nakamura Chemical Co., Ltd.)

●A-DPH (trade name, dipentaerythritol hexaacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.)

<(B) component>

●IRGACURE-OXE-01 (trade name, 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzhydrylhydrazine, manufactured by BASF)

●IRGACURE-819 (trade name, bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, manufactured by BASF)

<Other ingredients>

● decane coupling agent: AY43-031 (trade name, manufactured by TORAY Dow Corning)

<Evaluation of resolution>

A solution of the photosensitive resin composition obtained in the examples and the comparative examples was uniformly applied onto a ruthenium substrate using a spin coater, and dried using a hot plate at 90 ° C for 5 minutes to form a film thickness after drying. It is a photosensitive resin layer of 30 μm. The substrate on which the photosensitive resin layer is formed is provided with a hole diameter of 60 μm. The negative-type mask of the opening pattern was exposed to a photosensitive resin layer at a exposure amount of 100 mJ/cm ² using a proximity exposure machine (trade name: UX-1000SM, manufactured by USHIO Electric Co., Ltd.). After the exposure, the test substrate was immersed in an organic solvent-based developer, that is, propylene glycol monomethyl ether acetate, for 3 minutes to carry out development. The developed photoresist pattern was washed with n-butyl acetate, dried, and observed, and the resolution (fine pattern formation property) was evaluated in accordance with the following criteria. The result is as shown in the second table.

A: formed with a hole diameter of 60 μm The opening is rectangular.

B: Although the hole diameter is 60 μm The opening, but the opening is tapered.

C: No hole diameter 60 μm was formed The opening is filled and the through hole is filled.

<Measurement of initial light transmittance>

A solution of the photosensitive resin composition obtained in the examples and the comparative examples was uniformly applied onto a thin glass substrate using a spin coater, and dried using a hot plate at 90 ° C for 5 minutes to form a dried film. A photosensitive resin layer having a thickness of 30 μm. The test substrate on which the photosensitive resin layer was formed was exposed to a photosensitive resin layer at a exposure amount of 100 mJ/cm ² using a proximity exposure machine (trade name: UX-1000SM, manufactured by USHIO Electric Co., Ltd.). Perform photohardening. Then, the photosensitive resin layer was heated at 150 ° C for 60 minutes and heated at 200 ° C for 60 minutes to be completely cured, thereby obtaining a test substrate having a photosensitive resin layer having a film thickness of 30 μm.

For the transmittance of the resin-attached glass, the transmittance of the glass monomer was used as a reference, and an ultraviolet-visible spectrophotometer "U-3310 Spectrophotometer (manufactured by Hitachi High-Technologies)" was used to measure a wavelength of 345 nm and 450. Light transmittance of light at nm and 740 nm. The result is as shown in the second table.

<Measurement of light transmittance after <130 ° C / 500 hours>

In the air environment, the test substrate used for the measurement of the initial light transmittance was allowed to stand in an environment of 130 ° C for 500 hours, and then the wavelength of 345 nm and 450 was measured by the same measurement method as the initial light transmittance. Light transmittance of light at nm and 740 nm. The result is as shown in the second table.

<Evaluation of adhesion>

A solution of the photosensitive resin compositions of the examples and the comparative examples was uniformly applied onto a crucible substrate on which an SiO ₂ film was formed, and dried using a hot plate at 90 ° C for 5 minutes using a spin coater. A photosensitive resin layer having a film thickness of 30 μm after drying. The test substrate on which the photosensitive resin layer was formed was exposed to a photosensitive resin layer at a exposure amount of 100 mJ/cm ² using a proximity exposure machine (trade name: UX-1000SM, manufactured by USHIO Electric Co., Ltd.). Perform photohardening.

Then, the test substrate was heated at 150 ° C for 60 minutes and heated at 200 ° C for 60 minutes to be hardened. Then, the test substrate was allowed to stand in an environment of 121 ° C, 100% RH (relative humidity), and 2 atm for 100 hours, and the adhesion was evaluated by a checkerboard test. The evaluation criteria are as follows.

A: No peeling was observed.

B: A little peeling can be observed.

As a result of the results shown in the second table, the photosensitive resin composition of the present invention of Examples 1 to 10 can form a fine pattern even when formed into a thick film, and has excellent visible light transmittance and excellent Heat resistance, This heat resistance is that resin coloration is still small after a long period of heat history at a high temperature. Moreover, the adhesion is also good.

On the other hand, Comparative Examples 1 to 3 are compositions containing no (meth) acrylate compound having an amine ester bond, and as a result, the light transmittance after the heat history is lowered and the heat resistance is poor.

[Industrial availability]

The photosensitive resin composition of the present invention can form a fine pattern even when formed into a thick film, and has excellent visible light transmittance and excellent heat resistance, which is after a long heat history at a high temperature. Resin coloring is still rare. Therefore, it is suitable as a sealing member of a light-emitting element such as an LED element, which is required to be miniaturized, high-density mounting, and used for a long time in a high-temperature environment.

Claims (10)

A photosensitive resin composition comprising (A) a (meth) acrylate compound and (B) a photopolymerization initiator, wherein (A) component comprises a (meth) acrylate compound having an amine ester bond . The photosensitive resin composition according to claim 1, wherein the (meth) acrylate compound having an amine ester bond comprises at least one of an aliphatic skeleton and an alicyclic skeleton and has an amine ester bond. (Meth) acrylate compound. The photosensitive resin composition according to claim 1, wherein the (meth) acrylate compound having an amine ester bond is a compound represented by the following formula (A-8): In the formula (A-8), R ₁ and R ₂ each independently represent a divalent organic group, and p is an integer of 1 or more]. The photosensitive resin composition according to claim 1, wherein the (A) component further contains a (meth) acrylate compound having a guanamine bond. The photosensitive resin composition according to claim 4, wherein the (meth) acrylate compound having a guanamine bond is a compound represented by the following formula (1): [In the formula (1), R ₃₁ , R ₃₂ and R ₃₃ each independently represent a divalent organic group, R ₃₄ represents a hydrogen atom or a methyl group, and R ₃₅ and R ₃₆ each independently represent a hydrogen atom and have a carbon number of 1 to 4; Alkyl or phenyl]. A photosensitive resin film having a photosensitive resin layer formed by molding the photosensitive resin composition according to any one of claims 1 to 5 into a film shape. The photosensitive resin film according to claim 6, wherein the photosensitive resin layer having a thickness of 30 μm has a light transmittance of light of a wavelength of 450 nm of 85% or more. The photosensitive resin film according to claim 6 or 7, wherein the photosensitive resin layer having a film thickness of 30 μm has a light transmittance of light having a wavelength of 450 nm after a heat history of 500 hours at 130 °C. More than 80%. An electronic component which is obtained by sealing the upper portion of the light-emitting element with the photosensitive resin composition according to any one of claims 1 to 5, or the photosensitive resin film according to any one of claims 6 to 8. . The electronic component of claim 9, wherein the light emitting component is an LED component.