JP6893073B2 - Photosensitive resin composition - Google Patents

Description

The present invention is a photosensitive resin composition that can be applied to a substrate such as a printed wiring board using a rigid substrate or a flexible substrate by an inkjet method to form a cured product having adhesion to the substrate and electrical insulation. It's about things.

Conventionally, in forming an insulating coating having high resolution and high accuracy on a substrate having a desired circuit pattern (for example, a printed wiring board), a photosensitive resin composition is conventionally used by using various coating methods such as a screen printing method. After applying the material, a negative film having a pattern other than the land of the circuit pattern that is translucent is brought into close contact with the coated photosensitive resin composition, and an active energy ray such as ultraviolet rays is irradiated from above onto the land. The corresponding non-exposed region was removed with a dilute alkaline aqueous solution, the coating film of the photosensitive resin composition was developed, and the heat treatment, which is the main curing treatment, was performed.

However, the method for forming the insulating film involves many processing steps such as development using a negative film, and the work is complicated. Further, since the method for forming the insulating coating is developed using a negative film, there is a limit to the degree of freedom in the coating design of the insulating coating. Therefore, in recent years, a photosensitive resin composition is ejected onto a substrate having a desired circuit pattern to form a coating film by using an inkjet method that does not require development using a negative film, and a laser is formed on the coating film. It is also practiced to form an insulating coating having a desired coating design by exposing an active energy ray such as ultraviolet rays or ultraviolet rays to form a cured coating film.

Examples of the curable resin composition used in the inkjet method suitable for producing a printed wiring board include a bisallyl nadiimide compound having a predetermined chemical structure, a bismaleimide compound having a predetermined chemical structure, and a diluent. A curable resin composition containing the above-mentioned compound and having a viscosity of 150 mPa · s or less at 25 ° C. has been proposed (Patent Document 1).

On the other hand, in order to coat the photosensitive resin composition on the substrate by the inkjet method to form an insulating film, it is necessary that the photosensitive resin composition has a low viscosity and has adhesion to the substrate. is there. In order to impart adhesion to the substrate to the photosensitive resin composition, an adhesive resin or a (meth) acrylate compound having a hydroxyl group may be used as the base resin.

However, if an adhesive resin is used as the base resin, the viscosity of the photosensitive resin composition increases, so that it may not be possible to apply the coating by the inkjet method. Further, when a (meth) acrylate compound having a hydroxyl group is used as the base resin, it may not be possible to obtain a cured product having electrical insulating properties.

International Publication No. 2006/075654

In view of the above circumstances, the present invention is a photosensitive resin composition capable of forming a cured product having excellent coatability by an inkjet method, adhesion between a conductor and a substrate material, and electrical insulation. The purpose is to provide.

（式中、Ｒは、炭素数１〜１０個の炭化水素基、−Ｒ^１−Ｏ−Ｒ^２、または−Ｒ^３−ＮＲ^４Ｒ^５を表し、Ｒ^１は炭素数１〜５個の炭化水素基を表し、Ｒ^２は炭素数１〜１０個の炭化水素基を表し、Ｒ^３は炭素数１〜１０個の炭化水素基を表し、Ｒ^４、Ｒ^５は、それぞれ独立に、炭素数１〜５個の炭化水素基を表す。）で表される化合物である［１］または［２］に記載の感光性樹脂組成物。
［４］前記（Ｂ）水酸基を含有しない、ＮＨ基含有（メタ）アクリルアミド化合物が、イソプロピル（メタ）アクリルアミド、ジメチルアミノプロピル（メタ）アクリルアミド、Ｎ−ブトキシメチル（メタ）アクリルアミド及びブチル（メタ）アクリルアミドからなる群から選択された少なくとも１種を含む［１］または［２］に記載の感光性樹脂組成物。
［５］前記（Ｂ）水酸基を含有しない、ＮＨ基含有（メタ）アクリルアミド化合物が、イソプロピル（メタ）アクリルアミド及びジメチルアミノプロピル（メタ）アクリルアミドからなる群から選択された少なくとも１種を含む［１］または［２］に記載の感光性樹脂組成物。
［６］前記感光性樹脂組成物中に、前記（Ａ）液状（メタ）アクリレート化合物を４０質量％以上９０質量％以下、 前記（Ｂ）水酸基を含有しない、ＮＨ基含有（メタ）アクリルアミド化合物を５．０質量％以上３０質量％以下含む［１］乃至［５］のいずれか１つに記載の感光性樹脂組成物。
［７］インクジェット用である［１］乃至［６］のいずれか１つに記載の感光性樹脂組成物。
［８］［１］乃至［７］のいずれか１つに記載の感光性樹脂組成物の硬化物。
［９］［８］に記載の硬化物を備えたプリント配線板。 The gist of the structure of the present invention is as follows.
[1] A photosensitive resin composition containing (A) a liquid (meth) acrylate compound, (B) a hydroxyl group-free NH group-containing (meth) acrylamide compound, and (C) a photopolymerization initiator.
[2] The photosensitive resin composition according to [1], wherein the (A) liquid (meth) acrylate compound contains (A1) a liquid (meth) acrylate compound having an epoxy group.
[3] The NH group-containing (meth) acrylamide compound, which does not contain the hydroxyl group (B), has the following general formula (1).

(In the formula, R represents a hydrocarbon group having 1 to 10 carbon atoms, -R ^1- O-R ² , or -R ^3- NR ⁴ R ⁵ and R ¹ is a hydrocarbon having 1 to 5 carbon atoms. R ^{2 represents a hydrocarbon group having 1 to 10 carbon atoms, R 3} represents a hydrocarbon group having 1 to 10 carbon atoms, and R ⁴ and R ⁵ have independent carbon atoms. The photosensitive resin composition according to [1] or [2], which is a compound represented by 1 to 5 hydrocarbon groups).
[4] The NH group-containing (meth) acrylamide compound containing no hydroxyl group (B) is isopropyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide and butyl (meth) acrylamide. The photosensitive resin composition according to [1] or [2], which comprises at least one selected from the group consisting of.
[5] The NH group-containing (meth) acrylamide compound containing no hydroxyl group (B) contains at least one selected from the group consisting of isopropyl (meth) acrylamide and dimethylaminopropyl (meth) acrylamide [1]. Alternatively, the photosensitive resin composition according to [2].
[6] In the photosensitive resin composition, the (A) liquid (meth) acrylate compound is 40% by mass or more and 90% by mass or less, and the (B) hydroxyl group-free NH group-containing (meth) acrylamide compound is contained. The photosensitive resin composition according to any one of [1] to [5], which contains 5.0% by mass or more and 30% by mass or less.
[7] The photosensitive resin composition according to any one of [1] to [6] for inkjet.
[8] The cured product of the photosensitive resin composition according to any one of [1] to [7].
[9] A printed wiring board provided with the cured product according to [8].

The liquid (meth) acrylate compound is a (meth) acrylate compound that is liquid at 25 ° C. (room temperature).

According to the aspect of the photosensitive resin composition of the present invention, the inkjet method is carried out by containing (A) a liquid (meth) acrylate compound and (B) an NH group-containing (meth) acrylamide compound containing no hydroxyl group. A photosensitive resin composition having excellent coatability can be obtained, and a cured product having excellent adhesion between a conductor and a substrate material and excellent electrical insulation can be formed.

According to the aspect of the photosensitive resin composition of the present invention, the (A) liquid (meth) acrylate compound contains (A1) the liquid (meth) acrylate compound having an epoxy group, so that the conductor and the substrate material are in close contact with each other. A cured product having further excellent properties and electrical insulation can be obtained.

According to the aspect of the photosensitive resin composition of the present invention, (B) the NH group-containing (meth) acrylamide compound containing no hydroxyl group is isopropyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, or N-butoxymethyl. By containing at least one selected from the group consisting of (meth) acrylamide and butyl (meth) acrylamide, the cured product can be reliably imparted with adhesion between the conductor and the substrate material and electrical insulation. Further, according to the aspect of the photosensitive resin composition of the present invention, (B) a group in which the NH group-containing (meth) acrylamide compound containing no hydroxyl group is composed of isopropyl (meth) acrylamide and dimethylaminopropyl (meth) acrylamide. By including at least one selected from the above, the adhesion to the substrate material can be further improved.

According to the aspect of the photosensitive resin composition of the present invention, the photosensitive resin composition contains 40% by mass or more and 90% by mass or less of the (A) liquid (meth) acrylate compound, and (B) an NH group containing no hydroxyl group. By containing 5.0% by mass or more and 30% by mass or less of the contained (meth) acrylamide compound, the adhesiveness between the conductor and the substrate material and the electrical insulating property can be reliably imparted to the cured product.

Next, the details of the photosensitive resin composition of the present invention will be described below. The photosensitive resin composition of the present invention contains (A) a liquid (meth) acrylate compound, (B) a hydroxyl group-free NH group-containing (meth) acrylamide compound, and (C) a photopolymerization initiator. ..

(A) Liquid (meth) acrylate compound The chemical structure and molecular weight of the liquid (meth) acrylate compound as the component (A) are particularly limited as long as it is a (meth) acrylate compound that is liquid at 25 ° C. (room temperature). Not done. Examples of the liquid (meth) acrylate compound include monofunctional (meth) acrylates such as monofunctional (meth) acrylate monomers, bifunctional (meth) acrylates such as bifunctional (meth) acrylate monomers, and trifunctional or higher. (Meta) acrylate compounds such as trifunctional or higher functional (meth) acrylates such as (meth) acrylate monomers can be mentioned. By blending the liquid (meth) acrylate compound with the photosensitive resin composition of the present invention, a photosensitive resin composition having excellent coatability in the inkjet method can be obtained, and the photosensitive resin composition can also be obtained. It can contribute to imparting adhesion to the conductor and the substrate material and electrical insulation to the cured product. Further, since the viscosity of the photosensitive resin composition at 25 ° C. is lowered by blending the liquid (meth) acrylate compound, it is not necessary to blend a non-reactive diluent (for example, an organic solvent) for inkjet. Can be used as. In addition, in this specification, "(meth) acrylate compound" means an acrylate compound and / or a methacrylate compound.

The viscosity of the liquid (meth) acrylate compound at 25 ° C. is not particularly limited, but is preferably 1.0 mPa · s or more and 50 mPa · s or less, preferably 2.0 mPa · s or more, from the viewpoint of further improving the coatability in the inkjet method. 30 mPa · s or less is particularly preferable.

The molecular weight of the liquid (meth) acrylate compound is not particularly limited, but is preferably 500 or less, more preferably 400 or less, and particularly preferably 300 or less.

Examples of the liquid (meth) acrylate compound include benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, hydroxybutyl (meth) acrylate, phenol (meth) acrylate, and phenoxyethyl (meth) acrylate. , Diethylene glucol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylic rate, etc., monofunctional (meth) acrylate compound such as epoxy (meth) acrylate, 1,4-butanediol di (meth) Acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, dicyclopenta Bifunctional (meth) acrylate compounds such as nildi (meth) acrylate, ethylene oxide-modified di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, and isocyanurate di (meth) acrylate, trimethyl propantri (meth). Examples of trifunctional or higher functional (meth) acrylate compounds such as acrylate, ditrimethylol propanetetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. Can be done. Further, as the liquid (meth) acrylate compound, a (meth) acrylate having an epoxy group such as glycidyl (meth) acrylate, hydroxybutyl (meth) acrylate glycidyl ether, allyl glycidyl ether, pentaerythritol tri (meth) acrylate monoglycidyl ether, etc. Examples include compounds. These (meth) acrylate compounds may be used alone or in combination of two or more.

Of these, it is preferable to use (meth) acrylate compounds having different functional numbers in combination from the viewpoint of surely obtaining a cured product having excellent adhesion between the conductor and the substrate material and electrical insulation, and monofunctional (meth). It is more preferable to use the acrylate compound and the bifunctional (meth) acrylate compound in combination, and the (meth) acrylate having an epoxy group is obtained from the viewpoint of obtaining a cured product having further excellent adhesion between the conductor and the substrate material and electrical insulation. Liquid (meth) acrylate compounds containing compounds are particularly preferred. A (meth) acrylate compound having an epoxy group is particularly preferable because the epoxy group of the (meth) acrylate compound having an epoxy group is the NH group of the (meth) acrylamide compound having no hydroxyl group and having an NH group, which will be described later. It is considered that this is because a small amount of hydroxyl groups are generated in the photosensitive resin composition by reacting with the above, so that the adhesion between the conductor and the substrate material can be obtained without impairing the electrical insulating property.

The content of the liquid (meth) acrylate compound in the photosensitive resin composition is not particularly limited, but the lower limit thereof is the viscosity of the photosensitive resin composition while surely imparting the photosensitivity of the photosensitive resin composition. 40% by mass is preferable, 50% by mass is more preferable, and 60% by mass is particularly preferable, from the viewpoint of preventing an increase in the amount of the resin and reliably obtaining a photosensitive resin composition having excellent coatability by an inkjet method. On the other hand, the upper limit of the content of the liquid (meth) acrylate compound in the photosensitive resin composition is obtained by blending other components such as (B) hydroxyl group-free, NH group-containing (meth) acrylamide compound, which will be described later. Therefore, 90% by mass is preferable, 80% by mass is more preferable, and 75% by mass is particularly preferable, from the viewpoint of surely obtaining a cured product having excellent adhesion between the conductor and the substrate material and electrical insulation.

(B) Hydroxyl group-free, NH group-containing (meth) acrylamide compound The (B) component, hydroxyl group-free, NH group-containing (meth) acrylamide compound has no hydroxyl group and has an NH group (meth). ) If it is an acrylamide compound, its chemical structure and molecular weight are not particularly limited. Examples of the NH group-containing (meth) acrylamide compound containing no hydroxyl group include a hydroxyl group-free NH group-containing (meth) acrylamide monomer. The number of NH groups in one molecule may be one or two or more. By blending the photosensitive resin composition of the present invention with an NH group-containing (meth) acrylamide compound that does not contain a hydroxyl group, the cured product of the photosensitive resin composition is imparted with adhesion to the conductor and the substrate material. At the same time, electrical insulation can be imparted. In addition, in this specification, "(meth) acrylamide compound" means an acrylamide compound and / or a methacrylamide compound.

（式中、Ｒは、炭素数１〜１０個の炭化水素基、−Ｒ^１−Ｏ−Ｒ^２、または−Ｒ^３−ＮＲ^４Ｒ^５を表し、Ｒ^１は炭素数１〜５個の炭化水素基を表し、Ｒ^２は炭素数１〜１０個の炭化水素基を表し、Ｒ^３は炭素数１〜１０個の炭化水素基を表し、Ｒ^４、Ｒ^５は、それぞれ独立に、炭素数１〜５個の炭化水素基を表す。）で表される化合物を挙げることができる。このうち、Ｒとしては、炭素数１〜１０個の炭化水素基、−Ｒ^３−ＮＲ^４Ｒ^５が好ましい。また、炭素数１〜１０個の炭化水素基としては、炭素数２〜１０個の鎖状炭化水素基が好ましく、炭素数３〜５個の鎖状炭化水素基がより好ましく、分岐鎖を有する炭素数３〜５個の鎖状炭化水素基が特に好ましい。また、Ｒ^１としては、炭素数１〜４個の炭化水素基が好ましく、炭素数１〜３個の炭化水素基が特に好ましい。また、Ｒ^２としては、炭素数２〜８個の鎖状炭化水素基が好ましく、炭素数３〜５個の鎖状炭化水素基が特に好ましい。また、Ｒ^３としては、炭素数２〜１０個の鎖状炭化水素基が好ましく、炭素数３〜５個の鎖状炭化水素基が特に好ましい。また、Ｒ^４、Ｒ^５としては、炭素数１〜４個の炭化水素基が好ましく、炭素数１〜３個の炭化水素基が特に好ましい。 Examples of the NH group-containing (meth) acrylamide compound containing no hydroxyl group include the following general formula (1).

(In the formula, R represents a hydrocarbon group having 1 to 10 carbon atoms, -R ^1- O-R ² , or -R ^3- NR ⁴ R ⁵ and R ¹ is a hydrocarbon having 1 to 5 carbon atoms. R ^{2 represents a hydrocarbon group having 1 to 10 carbon atoms, R 3} represents a hydrocarbon group having 1 to 10 carbon atoms, and R ⁴ and R ⁵ each independently represent a hydrocarbon group having 1 to 10 carbon atoms. A compound represented by 1 to 5 hydrocarbon groups) can be mentioned. Among them, as the R, the number 1 to 10 hydrocarbon group having a ^carbon is -R 3 ^-NR 4 ^{R 5} preferably. Further, as the hydrocarbon group having 1 to 10 carbon atoms, a chain hydrocarbon group having 2 to 10 carbon atoms is preferable, a chain hydrocarbon group having 3 to 5 carbon atoms is more preferable, and the hydrocarbon group has a branched chain. A chain hydrocarbon group having 3 to 5 carbon atoms is particularly preferable. Further, as R ¹ , a hydrocarbon group having 1 to 4 carbon atoms is preferable, and a hydrocarbon group having 1 to 3 carbon atoms is particularly preferable. Further, as R ² , a chain hydrocarbon group having 2 to 8 carbon atoms is preferable, and a chain hydrocarbon group having 3 to 5 carbon atoms is particularly preferable. As the R ^3, preferably 2 to 10 chain hydrocarbon group having a carbon number, particularly preferably the number 3 to 5 chain hydrocarbon group having a carbon. Further, as R ⁴ and R ⁵ , a hydrocarbon group having 1 to 4 carbon atoms is preferable, and a hydrocarbon group having 1 to 3 carbon atoms is particularly preferable.

Among these compounds of the general formula (1), isopropyl (meth) acrylamide and dimethylaminopropyl (meth) can be surely imparted to the cured product with adhesion between the conductor and the substrate material and electrical insulation. Acrylamide, N-butoxymethyl (meth) acrylamide, and butyl (meth) acrylamide are preferable, and isopropyl (meth) acrylamide and dimethylaminopropyl (meth) acrylamide are particularly preferable from the viewpoint of further improving the adhesion to the substrate material. In addition, isopropylmethacrylamide is preferable because it can reliably impart adhesion between the conductor and the substrate material and electrical insulation to the cured product. These (meth) acrylamide compounds may be used alone or in combination of two or more.

The content of the NH group-containing (meth) acrylamide compound, which does not contain a hydroxyl group, in the photosensitive resin composition is not particularly limited, but the lower limit thereof is the adhesion between the conductor and the substrate material and the electrical insulation of the cured product. From the viewpoint of reliably imparting properties, 5.0% by mass is preferable, 10 parts by mass is more preferable, and 12 parts by mass is particularly preferable. On the other hand, the upper limit of the content of the NH group-containing (meth) acrylamide compound, which does not contain a hydroxyl group, ensures excellent electrical insulation while reliably preventing deterioration of the coatability of the photosensitive resin composition. From the point of view, 30% by mass is preferable, 25% by mass is more preferable, and 18% by mass is particularly preferable.

(C) Photopolymerization Initiator The photopolymerization initiator as the component (C) is not particularly limited as long as it is generally used, and any of them can be used. Specifically, for example, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1. Α-Aminoalkylphenone-based photopolymerization initiator such as -one, 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone 1- [9-ethyl-6 -(2-Methylbenzoyl) -9H-carbazole-3-yl] -1- (0-acetyloxime), 2- (acetyloxyiminomethyl) thioxanthene-9-one, 1,8-octanedione, 1, 8-bis [9-ethyl-6-nitro-9H-carbazole-3-yl]-, 1,8-bis (O-acetyloxime), 1,8-octanedione, 1,8-bis [9-( 2-Ethylhexyl) -6-nitro-9H-carbazole-3-yl]-, 1,8-bis (O-acetyloxime), (
Z)-(9-Ethyl-6-nitro-9H-carbazole-3-yl) (4-((1-methoxypropan-2-yl) oxy) -2-methylphenyl) Oxime such as metanone O-acetyloxime An ester-based photopolymerization initiator can be mentioned.

Examples of photopolymerization initiators other than the above-mentioned α-aminoalkylphenone-based photopolymerization initiator and oxime ester-based photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin-n. -Butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1- On, 1-Hydroxycyclohexylphenyl ketone, 4- (2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2 -Methylanthraquinone, 2-ethylanthraquinone, 2-tershary butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, Butyldimethylketal, acetophenonedimethylketal, P-dimethylaminobenzoic acid ethyl ester, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,6-- Dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, (2,4,6-trimethylbenzoyl) ethoxyphenylphosphine oxide and the like can be mentioned. These photopolymerization initiators may be used alone or in combination of two or more.

The content of the photopolymerization initiator in the photosensitive resin composition is not particularly limited, but is preferably 1.0% by mass or more and 20% by mass or less, and particularly preferably 2.0% by mass or more and 10% by mass or less.

In the photosensitive resin composition of the present invention, in addition to the above-mentioned components (A) to (C), various components such as a colorant, a flame retardant, various additives, and a non-reactive diluent are required. Etc. can be blended.

The colorant is not particularly limited, such as a pigment and a pigment. The colorant may be a white colorant, a blue colorant, a green colorant, a yellow colorant, a purple colorant, a black colorant, or the like, depending on the desired color to be applied to the cured product of the photosensitive resin composition. Colors are also available. Examples of the colorant include inorganic colorants such as titanium oxide which is a white colorant and carbon black which is a black colorant, phthalocyanine green which is a green colorant, and phthalocyanine blue and lionol blue which are blue colorants. Phthalocyanine-based colorants such as phthalocyanine, chromophthal-based yellow colorant such as chromophthal yellow, and organic colorants such as anthraquinone-based.

The flame retardant is for imparting flame retardancy to the cured product of the photosensitive resin composition of the present invention. Since electronic components having a large calorific value may be mounted on the printed wiring board or the like, the safety of the printed wiring board is improved by imparting flame retardancy to the cured product. Examples of the flame retardant include a phosphorus-based flame retardant. Examples of phosphorus-based flame retardants include tris (chloroethyl) phosphate, tris (2,3-dichloropropyl) phosphate, tris (2-chloropropyl) phosphate, tris (2,3-bromopropyl) phosphate, and tris (bromo). Halogen-containing phosphoric acids such as chloropropyl) phosphate, 2,3-dibromopropyl-2,3-chloropropyl phosphate, tris (tribromophenyl) phosphate, tris (dibromophenyl) phosphate, and tris (tribromoneopentyl) phosphate. Esters; non-halogen aliphatic phosphates such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate; triphenyl phosphate, cresil diphenyl phosphate, dicredyl phenyl phosphate, tricresyl phosphate, trixylate Nylphosphate, xylenyldiphenyl phosphate, tris (isopropylphenyl) phosphate, isopropylphenyldiphenyl phosphate, diisopropylphenylphenyl phosphate, tris (trimethylphenyl) phosphate, tris (t-butylphenyl) phosphate, hydroxyphenyldiphenyl phosphate, octyldiphenyl phosphate Non-halogen aromatic phosphate esters such as: aluminum trisdiphenylphosphinate, aluminum trismethylethylphosphinate, aluminum trisdiphenylphosphinate, zinc bisdiphenylphosphinate, zinc bismethylethylphosphinate, zinc bisdiphenylphosphinate, bisdiethyl Metal salts of phosphinic acids such as titanyl phosphinate, titanium tetrakisdiphenylphosphinate, titanyl bismethylethylphosphinate, titanium tetrakismethylethylphosphinate, titanyl bisdiphenylphosphinate, titanium tetrakisdiphenylphosphinate, 9,10-dihydro-9 Examples thereof include phosphine oxide compounds such as -oxa-10-phosphaphenanthrene-10-oxide, diphenylvinylphosphine oxide, triphenylphosphine oxide, trialkylphosphine oxide, and tris (hydroxyalkyl) phosphine oxide. These may be used alone or in combination of two or more.

Various additives include, for example, defoaming agents such as silicone-based, hydrocarbon-based and acrylic-based, inorganic fillers such as talc, barium sulfate, alumina, aluminum hydroxide, mica and silica, powdered urethane resin, and (meth) acrylic. Examples thereof include polymers, vinyl-based polymers, modified carboxyl group-containing polymers, and organic fillers such as carboxylic acid esters.

The non-reactive diluent is for adjusting the viscosity and drying property of the photosensitive resin composition. Examples of the non-reactive diluent include organic solvents. Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexane, aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol, isopropanol and cyclohexanol, and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane. Cellosolves such as cellosolve and butylcellosolve, carbitols such as carbitol and butylcarbitol, ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether Examples thereof include esters such as acetate.

The method for producing the photosensitive resin composition of the present invention is not limited to a specific method. For example, after blending each of the above components in a predetermined ratio, at room temperature (for example, 25 ° C.), a three-roll, ball mill, or bead mill. , Sand mill or the like, or kneading or mixing by a stirring means such as a super mixer or a planetary mixer. Further, prior to the kneading or mixing, pre-kneading or pre-mixing may be performed at room temperature (for example, 25 ° C.), if necessary.

Next, an example of how to use the photosensitive resin composition of the present invention will be described. The photosensitive resin composition of the present invention is used, for example, to form an insulating coating (for example, a solder resist film) on a substrate (for example, a printed wiring board having a predetermined circuit pattern) by using an inkjet printing method. be able to. First, the photosensitive resin composition of the present invention is coated on a printed wiring board in a desired pattern by an inkjet method (for example, an inkjet method using a jet dispenser). After coating, the coated coating film is photocured by laser direct drawing using LDI (Laser Direct Imaging) or active energy rays such as ultraviolet rays (exposure treatment). When the photocuring treatment is performed with active energy rays such as ultraviolet rays, the amount of irradiation light is, for example, in the range of ^{100 to 2000 mJ / cm 2.} After the photocuring treatment of the coating film, a solder resist film having a desired pattern is printed and wired by performing post-cure (thermosetting treatment) for 20 to 80 minutes in a hot air circulation type dryer or the like at 130 to 170 ° C. It can be formed on a board.

Next, examples of the present invention will be described, but the present invention is not limited to these examples as long as the gist of the present invention is not exceeded.

Examples 1-8, Comparative Examples 1-4
Each component shown in Table 1 below was blended in the blending ratio shown in Table 1 below, mixed and dispersed at room temperature (about 25 ° C.) using a bead mill, and in Examples 1 to 8 and Comparative Examples 1 to 4. The photosensitive resin composition to be used was prepared. Unless otherwise specified, the blending amount of each component shown in Table 1 below is shown in parts by mass. In addition, the blank part of the compounding amount in Table 1 below means that there is no compounding.

The details of each component in Table 1 below are as follows.
(A) Liquid (meth) acrylate compound ・ EBECRYL3907: Daicel Cytec Co., Ltd. ・ R-684: Nippon Kayaku Co., Ltd. ・ IBXXA: Osaka Organic Chemical Industry Co., Ltd. ・ Light Ester IB-X: Kyoeisha Chemical Co., Ltd. ・ 4HBA: Osaka Organic Chemical Industry Co., Ltd. (A1) Liquid (meth) acrylate compound having an epoxy group ・ 4HBAGE: Mitsubishi Chemical Co., Ltd. ・ Light ester G: Kyoeisha Chemical Co., Ltd.

(B) NH group-containing (meth) acrylamide compound that does not contain hydroxyl groups ・ NIPAM: KJ Chemicals Co., Ltd. ・ DMAPAA: KJ Chemicals Co., Ltd. ・ Nn-butoxymethylacrylamide: Tokyo Kasei Kogyo Co., Ltd. ・ N-isobutoxymethyl Acrylamide: Tokyo Kasei Kogyo Co., Ltd. ・ tert-Butylacrylamide: Tokyo Kasei Kogyo Co., Ltd.

(C) Photopolymerization Initiator, IRGACURE907: BASF Japan Ltd., LUCIRIN TPO: BASF Japan Ltd., Chemcure DETX: Chembridge International Inc.

Colorant ・ Lionol Blue FG-7351: Toyo Color Co., Ltd. ・ Chromophthal Yellow AGR: Ciba Specialty Chemicals Co., Ltd. Flame Retardant ・ V-4: Katayama Chemical Industry Co., Ltd. Additive ・ BYK-361N: Big Chemie Japan Co., Ltd.

Hydroxy group-containing acrylamide compound ・ HEAA: KJ Chemicals Co., Ltd. NH group-free acrylamide compound ・ ACMO: KJ Chemicals Co., Ltd.

Specimen manufacturing process Substrate: Copper-clad laminate (thickness 1.6 mm)
Surface treatment: Buff scrub polishing Printing method: Inkjet printing (inkjet equipment: "MJP2013F1-DU", Microcraft)
DRY film thickness: 20-23 μm
^{Exposure: 1000mJ / cm 2} on the coating film, Eye Graphics Co., Ltd. "UB093-5AM"
Post-cure (main curing, thermosetting): BOX type drying oven 150 ° C, 60 minutes

Evaluation items (1) Adhesion to copper (Cu) Adhesion of the test piece prepared in the above test piece preparation step to copper was evaluated according to JIS K 5400, and the number of grids remaining was as follows. Was evaluated on a 4-point scale.
⊚: 100/100
◯: 70/100 to 99/100
Δ: 10/100 to 69/100
X: 0/100 to 9/100
(2) Adhesion to the substrate A polyimide substrate (thickness 25 μm) was used instead of the copper-clad laminate, and both sides of the polyimide substrate were coated with a DRY film thickness of 20 μm in the same manner as in the above test specimen manufacturing step. , A test piece was prepared, the adhesion to the substrate was evaluated according to JIS K 5400, and the evaluation was made in four stages as described below according to the remaining number of grids.
⊚: 100/100
◯: 70/100 to 99/100
Δ: 10/100 to 69/100
X: 0/100 to 9/100

(3) Electrical insulation A cured coating film is formed according to the above-mentioned test piece manufacturing process, except that the substrate is changed from a copper-clad laminate to a comb-shaped test pattern (line width 100 μm, line spacing 100 μm), and a highly accelerated life is achieved. Using a test device (HAST device), apply 50 V of DC in an atmosphere of temperature 130 ° C. and humidity 85%, leave it for 200 hours, take out the test piece out of the tank, measure the insulation resistance value, and perform the following three steps. Evaluated in.
◯: 1.0 × 10 ⁷ Ω or more Δ: 1.0 × 10 ⁶ Ω or more and 1.0 × 10 ⁷ Ω or less ×: 1.0 × 10 less than ^{6 Ω}

The evaluation results are shown in Table 1 below.

As shown in Table 1 above, in Examples 1 to 8 containing (A) a liquid (meth) acrylate compound and (B) a hydroxyl group-free, NH group-containing (meth) acrylamide compound, the conductor (copper) and the substrate were used. It was possible to form a cured product having excellent adhesion to the material (polyimide) and electrical insulation. Further, in Examples 1 to 8, a photosensitive resin composition having excellent coatability by the inkjet method could be obtained. In particular, in Examples 1 to 3 and 5 to 8 in which the (A) liquid (meth) acrylate compound contains the (A1) liquid (meth) acrylate compound having an epoxy group, the adhesion to the conductor (copper) and the electrical insulating property Has improved further.

Further, the (A) liquid (meth) acrylate compound contains (A1) a liquid (meth) acrylate compound having an epoxy group, and (B) does not contain a hydroxyl group, as an NH group-containing (meth) acrylamide compound, isopropylacrylamide. In Examples 1 to 3 containing dimethylaminopropylacrylamide as an NH group-containing (meth) acrylamide compound containing (B) a hydroxyl group, in Example 5 containing (B) a hydroxyl group and containing an NH group (meth). ) Substrate (polyhydroxy) as compared with Example 6 containing Nn-butoxymethylacrylamide as an acrylamide compound, Example 7 containing N-isobutoxymethylacrylamide, and Example 8 containing Nt-butylacrylamide. Adhesion to is further improved.

On the other hand, Comparative Example 1 which does not contain (B) a hydroxyl group and does not contain an NH group-containing (meth) acrylamide compound, and (B) a hydroxyl group-containing acrylamide compound instead of the hydroxyl group-free and NH group-containing (meth) acrylamide compound. In Comparative Example 2 in which the above was blended, and in Comparative Example 4 in which the acrylamide compound containing no NH group was blended in place of the NH group-containing (meth) acrylamide compound containing no hydroxyl group (B), electrical insulation was obtained. I couldn't. Further, (B) a hydroxyl group-free (meth) acrylamide compound, a hydroxyl group-containing acrylamide compound, and an NH group-free acrylamide compound are not contained, and (A1) a liquid (meth) acrylate compound having an epoxy group. In Comparative Example 3 in which the above was blended, adhesion to the conductor (copper) and the substrate material (polyimide) could not be obtained.

The photosensitive resin composition of the present invention is excellent in coatability by using an inkjet method, and can form a cured product having excellent adhesion between a conductor and a substrate material and excellent electrical insulation, for example. It is highly useful in the field of forming an insulating coating on a printed wiring board having a desired circuit pattern.

Claims (8)

And (A) liquid (meth) acrylate compounds, not containing (B) a hydroxyl group, seen containing a NH group-containing (meth) acrylamide compound, and a photopolymerization initiator (C),
A photosensitive resin composition in which the liquid (meth) acrylate compound (A) contains hydroxybutyl (meth) acrylate glycidyl ether. The NH group-containing (meth) acrylamide compound containing no hydroxyl group (B) has the following general formula (1).

(In the formula, R represents a hydrocarbon group having 1 to 10 carbon atoms, -R ^1- O-R ² , or -R ^3- NR ⁴ R ⁵ and R ¹ is a hydrocarbon having 1 to 5 carbon atoms. R ^{2 represents a hydrocarbon group having 1 to 10 carbon atoms, R 3} represents a hydrocarbon group having 1 to 10 carbon atoms, and R ⁴ and R ⁵ have independent carbon atoms. The photosensitive resin composition according to claim 1, which is a compound represented by 1 to 5 hydrocarbon groups). The group in which the NH group-containing (meth) acrylamide compound containing no (B) hydroxyl group comprises isopropyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide and butyl (meth) acrylamide. The photosensitive resin composition according to claim 1, which comprises at least one selected from. Wherein (B) not containing a hydroxyl group, NH group-containing (meth) acrylamide compound, isopropyl (meth) according to claim 1 comprising at least one selected from the group consisting of acrylamide and dimethylaminopropyl (meth) acrylamide Photosensitive resin composition. In the photosensitive resin composition, 5.0 of the (A) liquid (meth) acrylate compound is 40% by mass or more and 90% by mass or less, and the (B) hydroxyl group-free NH group-containing (meth) acrylamide compound is 5.0. The photosensitive resin composition according to any one of claims 1 to 4 , which comprises mass% or more and 30% by mass or less. The photosensitive resin composition according to any one of claims 1 to 5, which is for inkjet use. The cured product of the photosensitive resin composition according to any one of claims 1 to 6. A printed wiring board provided with the cured product according to claim 7.