JP2003295433A - Photosensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition capable of forming an image by UV exposure and development with a dilute aqueous alkali solution, having no tackiness and a good working property, capable of giving a pattern excellent in adhesion, electric insulating property, resistance to the heat of soldering and chemical resistance, and suitable for use as a solder resist for production of a printed wiring board. <P>SOLUTION: The photosensitive resin composition comprises a carboxylic copolymer resin synthesized from (meth)acrylic acid and a (meth)acrylic ester or a carboxylic copolymer resin (A) synthesized from (meth)acrylic acid, a (meth)acrylic ester and a styrene derivative, a photosensitive resin (B) having at least two ethylenically unsaturated bonds per molecule, a reactive diluent (C), a photopolymerization initiator (D) and a thermosetting compound (E). <P>COPYRIGHT: (C)2004,JPO

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention
An image can be formed by development with an aqueous solution of potassium
Free and good workability, furthermore adhesion, electrical insulation,
Can provide a pattern with excellent heat resistance and chemical resistance.
Can be used as a solder resist for printed wiring board manufacturing
It relates to a suitable photosensitive resin composition. 2. Description of the Related Art A printed wiring board is formed by a conductive circuit on a substrate.
Pattern is formed on the soldering land of the pattern.
Electronic components are mounted by soldering.
Sol as a permanent protective film on the circuit part except
Is covered with a dark resist film. As a result, the print distribution
When soldering electronic components to the wire plate,
Parts and prevent circuit conductors from air
To prevent corrosion due to oxidation and humidity due to direct exposure to
You. Conventionally, a thermosetting type solder resist has been used.
It is often used and printed by screen printing.
Although the method was general, in recent years the wiring of the printed wiring board
Screen printing method is limited in resolution due to high density
There is a photo solder register that forms a pattern by photographic method
Strikes are being used extensively. However, the conventional photo solder resist is
Harmful substances such as 1,1,1-trichloroethane during development
Because of the use of organic solvents, there are problems such as effects on the human body and environmental pollution.
The title is inevitable. In recent years, sodium carbonate solution
Alkaline development type that can be developed with alkaline solution has appeared
For example, in Japanese Patent Publication No. 1-54390,
Novolak type epoxy compound and unsaturated monocarboxylic acid
Is reacted with a saturated or unsaturated polybasic acid anhydride.
Using active energy ray-curable resin obtained
A hydrophilic resin composition is described. [0004] However, this feature is to be solved.
Photosensitive resin composition described in Japanese Patent Publication No. 1-54390
Also characteristics such as exposure sensitivity, resolution, chemical resistance, solvent resistance
Not only isn't enough in terms of
After applying to the printed circuit board, drying was performed to evaporate the solvent.
Even after the film has tack (stickiness), for example,
After applying the film and removing it after exposure,
Of the coating film adheres to the
Dirty film and hinders reuse
It is becoming clear that there is a problem that there is
You. The present invention has solved the above-mentioned problems, and
A first object of the present invention is to provide an exposure film for forming a pattern image.
Tack free against film, i.e.
To provide a photosensitive resin composition capable of forming a coating film
It is in. A second object of the present invention is to provide an exposure sensitivity, resolution,
Has excellent properties such as chemical resistance and solvent resistance, especially
Excellent heat resistance, adhesion, chemical resistance and tack-free
To provide a photosensitive resin composition having good workability.
You. SUMMARY OF THE INVENTION [0006] The present inventors have developed the above-mentioned object.
(Meth) acrylic as a result of diligent research to achieve
Cal synthesized from acid and (meth) acrylate
Boxyl group-containing copolymer resin or (meth) acrylic
Acids, (meth) acrylates and styrene derivatives
Carboxyl group-containing copolymers synthesized from tylene derivatives
Exposure sensitivity, resolution, chemical resistance by using resin
Excellent properties in terms of resistance and solvent resistance, especially heat resistance
Excellent in adhesiveness, adhesion, chemical resistance, tack-free,
Found that a photosensitive resin composition with good workability can be obtained
Was. Based on this finding, the present invention provides the following general formula:
1], among the monomers represented by [Chemical Formula 2] and [Chemical Formula 3]
Monomers represented by at least general formulas [Chemical Formula 1] and [Chemical Formula 2]
Carboxyl group-containing copolymer resin consisting of a copolymer of a polymer
(A) and at least two ethylenically unsaturated compounds in one molecule
Photosensitive resin (B) having a sum bond and reactive diluent
(C), photopolymerization initiator (D), and thermosetting compound
(E) a photosensitive resin composition comprising: (Where R ₁ Is a hydrogen atom or a methyl group, R ₂ Is 1 carbon
And 6 to 6 represent an aliphatic hydrocarbon group or an aromatic group. ) (Where R ₁ Represents a hydrogen atom or a methyl group. ) (Where R ₃ Is a hydrogen atom or an aliphatic carbon having 1 to 6 carbon atoms
Hydrogen group, R ₄ Is a hydrogen atom or a hydroxyl group, alkoxy
Represents a sil group. )I will provide a. In the present invention, the following general formula:
The `` monomer represented '' is not particularly limited
Not available, but alkyl (meth) acrylates,
T) Hydroxyalkyl acrylate, acrylic
Amides, alkylated acrylamides, alkylolated amines
Acrylamide, acrylonitrile and the like. What
These may be used alone or in combination of two or more.
They may be used together. Also, the following general formula [Formula 2]
Methacrylic acid, acrylic acid
Is exemplified. These may be used alone,
Two types may be used in combination. On the other hand, "General
The monomer represented by the formula [Formula 3] is not particularly limited.
Styrene, α-alkylstyrene
And ring-substituted styrene. These are simply
It may be used alone or in combination of two or more
Is also good. [0008] In the present invention, the above-mentioned formula (1)
Less of the monomers represented by [Chemical Formula 2] and [Chemical Formula 3]
Both of the monomers represented by the above general formulas [Chemical Formula 1] and [Chemical Formula 2]
Carboxyl group-containing copolymer resin composed of
“(A)” is not particularly limited.
(T) Acrylic acid-ethyl (meth) acrylate monomer
Of (meth) acrylic acid-ethyl (meth)
Illustrative examples include a copolymer of a styrene-styrene monomer.
You. The above carboxyl group-containing copolymer resin (A)
The method for synthesizing is not particularly limited.
It can be synthesized by the following method. Methacrylic
For a mixture of methyl methacrylate, methacrylic acid and styrene
The solution in which the polymerization initiator (AIBN) is dissolved is not stirred.
Carboxyl group-containing copolymer resin by heating
Can be obtained. In the present invention, the most important ones are described above.
In the described "Carboxyl group-containing copolymer resin (A)"
is there. This “carboxyl group-containing copolymer resin (A)”
The reason is not clear, but the negative film at the time of exposure
Film forming a tack-free film that can adhere
Sodium carbonate aqueous solution that has an action and is used for development
Characteristic that does not decrease the solubility of
have. In addition, this "carboxyl group-containing copolymer
Resin (A) "has an average molecular weight of 5,000 to 700,000.
Is preferred. If it is less than 5,000, the softening point of the resin decreases.
Therefore, it is difficult to form a tack-free film,
If it exceeds 0000, the solubility in a dilute alkaline solution is reduced.
Therefore, the developing property is reduced. Also, this "Carbo
The acid value of the “xyl group-containing copolymer resin (A)” is 50 to 15
0 mgKOH / g is preferred. Less than 50mgKOH / g
In this case, the solubility in dilute alkaline solution decreases,
Causes a decline in sex. Over 150mgKOH / g
And the properties of the finally obtained cured coating film deteriorate. The above one
The compound represented by the general formula [Chemical Formula 2] is
1], 20 in the compounds represented by [Chemical Formula 2] and [Chemical Formula 3].
Preferably, it accounts for at least mol%. Less than 20 mol%
Is less soluble in dilute alkaline solutions,
Causes decline. This carboxyl group-containing copolymer tree
Fat (A) ”is 1 to 40 with respect to“ photosensitive resin (B) ”.
%. In the present invention, "%"
Means "% by mass". If less than 1%, tack
It is difficult to form a coating film of
The properties of the effect coating finally obtained are reduced. [0011] Next, "At least two molecules in one molecule
The photosensitive resin (B) having a lenic unsaturated bond is exposed
Is necessary to form an image. Departure
In the light, "at least two ethylenic in one molecule
Examples of the “photosensitive resin having an unsaturated bond (B)” include
Multifunctional epoxy having two or more epoxy groups in the molecule
Acrylic acid or methyl
Radical polymerizable unsaturated monocarboxylic acids such as tacrylic acid
After the reaction, polybasic anhydride reacts with the generated hydroxyl group.
And the like. The polyfunctional epoxy resin includes two
Any type of epoxy resin can be used.
Although there is no particular limitation on the epoxy equivalent, it is usually 1,000
Hereinafter, those having 100 to 500 are preferably used. example
For example, bisphenol A type, bisphenol F type, bisphenol
Bisphenol type epoxy resin such as Nord AD type, o-
Novolac type epoxy tree such as cresol novolak type
Fat, bisphenol A novolak epoxy resin, cyclic
Aliphatic polyfunctional epoxy resin, glycidyl ester type
Epoxy resin, glycidylamine type polyfunctional epoxy resin
Fat, heterocyclic polyfunctional epoxy resin, bisphenol modified
Novolak type epoxy resin, polyfunctional modified novolak type d
Poxy resins, having phenols and phenolic hydroxyl groups
Epoxy resin and other condensate with aromatic aldehyde
Can be In addition, Br, Cl, etc.
Those into which a halogen atom has been introduced are also exemplified. these
Considering heat resistance, novolak epoxy resin
Fats are preferred. These epoxy resins can be used alone
Or two or more of them may be used in combination. [0013] These epoxy resins are not radically polymerizable.
The saturated monocarboxylic acid is reacted. Epoxy group and carbo
The epoxy group is cleaved by the reaction of the xyl group, and the hydroxyl group and
Tell bonds are formed. Radical polymerizable unsaturated monomer used
The carboxylic acid is not particularly limited.
Lulic acid, methacrylic acid, crotonic acid, cinnamic acid, etc.
However, at least one of acrylic acid and methacrylic acid is preferred.
Acrylic acid is particularly preferred. Epoxy resin and la
Especially for the reaction method with dical polymerizable unsaturated monocarboxylic acid
There is no restriction, for example, epoxy resin and acrylic acid
The reaction can be performed by heating in a diluent. As diluent
For example, methyl ethyl ketone, cyclohexanone
Ketones and aromatic hydrocarbons such as toluene and xylene
, Methanol, isopropanol, cyclohexanol
Alcohols such as cyclohexane, methylcycl
Alicyclic hydrocarbons such as rohexane, petroleum ether, petroleum
Petroleum solvents such as naphtha, cellosolve, butyl cellosol
And other cellosolves, carbitol, butyl carbitol
Such as carbitols, ethyl acetate, butyl acetate, cello
Solve acetate, butyl cellosolve acetate, cal
Bitol acetate, butyl carbitol acetate, etc.
And the like. Also with catalyst
For example, triethylamine, tributylamine
Amines such as triphenylphosphine, triphenylene
Phosphorus compounds such as ruphosphate
Wear. In the present invention, "reactive diluent (C)"
Is necessary for improving the photosensitivity. This "reactive rare
The excipient (C) is composed of “at least two ethylenes per molecule”.
Photosensitive resin having an unsaturated bond (B) "
Used in the range of 40%. If this content is less than 2%
Insufficient photo-curing and fully demonstrates the acid resistance of the cured coating
If it exceeds 40%, the tack becomes severe and the exposure
Of the artwork film on the substrate at the time
It becomes difficult to obtain a desired cured coating film. Photocurable, hard
Physical properties of oxidized coating film and prevention of adhesion of artwork fill to substrate
More preferable content of this reactive diluent in terms of properties and the like
Amounts range from 4 to 30%. As the above-mentioned “reactive diluent (C)”,
1,4 butanediol di (meth) acrylate, 1,
6-hexanediol di (meth) acrylate, neope
Ethylene glycol di (meth) acrylate, polyethylene
Glycol di (meth) acrylate, neopentyl
Recall adipate di (meth) acrylate, hydroxy
Neopentyl glycol di (meth) acrypivalate
, Dicyclopentanyl di (meth) acrylate,
Caprolactone-modified dicyclopentenyl di (meth) ac
Relate, EO-modified phosphoric di (meth) acrylate, Ali
Cycloihexyl di (meth) acrylate, iso
Cyanurate di (meth) acrylate, trimethylol
Propane tri (meth) acrylate, dipentaerythri
Tall tri (meth) acrylate, propionic acid-modified di
Pentaerythritol tri (meth) acrylate, pen
Taerythritol tri (meth) acrylate, PO modified
Trimethylolpropane tri (meth) acrylate,
Lis (acryloxyethyl) isocyanurate, propyl
On-acid-modified dipentaerythritol penta (meth) ac
Relate, dipentaerythritol hexa (meth) ac
Relate, caprolactone-modified dipentaerythritol
Examples include reactive diluents such as hexa (meth) acrylate
It is. These diluents may be used alone or in combination of two or more.
The above may be used in combination. In the present invention, "photopolymerization initiator (D)"
Means that the active energy rays used for photopolymerization are ultraviolet
Line, visible light is necessary.
Photosensitivity having at least two ethylenically unsaturated bonds
Resin (B) ”is used in the range of 0.2 to 30%.
be able to. If the amount is less than 0.2%, the photosensitive
The photo-curing of the resin is difficult to progress, and if it exceeds 30%,
The effect has not been improved for the amount of
This is disadvantageous and may reduce the mechanical properties of the cured coating film.
There is. Photocurability, economical efficiency, mechanical properties of cured coating
From any aspect, the more preferable content of this photopolymerization initiator is
It is in the range of 1 to 15%. The above "photopolymerization initiator (D)" is
Zonzoin, benzoin methyl ether, benzoin ethyl
Ether, benzoin isopropyl ether, benzo
N-butyl ether, benzoin isobutyl ether
, Acetophenone, dimethylaminoacetophenone,
2,2 dimethoxy-2-phenylacetophenone,
2,2 dimethoxy-2-phenylacetophenone, 2
-Hydroxy-2-methyl-1-phenylpropane-1
-One, 1-hydroxycyclohexylphenyl keto
2-Methyl-1- [4- (methylthio) phenyl]
-2-morpholino propane-1-one, benzophene
Non, 2-methylanthraquinone, 2-ethylanthra
Quinone, 2-tert-butyl anthraquinone, 2-
Aminoanthraquinone, 2-methylthioxanthone, 2
-Ethylthioxanthone, 2-chlorothioxanthone,
2,4-dimethylthioxanthone, 2,4-diethylthio
Oxantone, benzyl dimethyl ketal, acetophen
Non-dimethyl ketal, p-dimethylaminobenzoic acid
Butyl esters and the like. These are used alone
Or two or more of them may be used in combination. In the present invention, the term "thermosetting compound"
(E) "means film strength, heat resistance, durability, chemical resistance,
In order to improve the performance such as environmental performance, "
Photosensitive resin having at least two ethylenically unsaturated bonds
(B) ”in the range of 5 to 100%.
You. If this content is less than 5%, it is
As a result, a coating film having the desired physical properties cannot be obtained.
%, The photocurability may decrease. Pos
Thermosetting from the viewpoint of physical properties and photo-curing properties after coating
The more preferable content of the chemical compound is in the range of 10 to 70%.
It is. The “thermosetting compound (E)” includes:
"At least one epoxy group per molecule, preferably
A known epoxy resin having two or more epoxy groups (d)
Including oxy oligomers) "
Absent. Examples of this known epoxy resin include Glycidi
Epoxy resin such as bisphenol A and epichrom
A resin obtained by reacting ruhydrin with alkali
Sphenol A epoxy resin, bisphenol A and e
Epoxidation of resin obtained by condensation reaction of rumarin
Products, in these resins, instead of bisphenol A
Using brominated bisphenol A, novolak
React epichlorohydrin with the resin to give glycidyl
-Novolak type epoxy resin (phenol
Volak type, o-cresol novolak type, pt-bu
Butylphenol novolak type), bisphenol F
Of bisphenol S and epichlorohydrin
The obtained bisphenol F type and bisphenol S type epo
Xy resin, etc., and cyclohexeneoxy
Group, tricyclodecane oxide group, cyclopentene
Cycloaliphatic epoxy resin having an oxide group, phthalate
Acid diglycidyl ester, tetrahydrophthalic acid diglyceride
Sidyl ester, diglycidyl hexahexaphthalate
Stele, diglycidyl p-oxybenzoic acid, dimer
Glycidyl ester resins such as acid glycidyl ester,
Tetraglycidyldiaminodiphenylmethane, trigly
Glycidylamines such as sidyl p-aminophenol
Resin, triglycidyl isocyanate having triazine ring
Rates and the like. The photosensitive resin composition of the present invention contains
In addition to the components (A) to (E), improved physical properties and improved workability
Above, if necessary for the purpose of improving storage stability, etc.
Each of the components (F) to (I) can be used. Pigment
(F) includes silica, alumina, talc, calcium carbonate
Inorganic pigments such as calcium and barium sulfate, phthalocyanine
And azo-based organic pigments. Latent heat hardening
Boron trifluoride-amine complex
Plex, dicyandiamide (DICY) and its
Derivatives, organic acid hydrazide, diaminomaleonitrile
(DAMN) and its derivatives, melamine and its derivatives,
Anamin and its derivatives, amine imide (AI), polyamine
Min salts and azoles. As organic solvent (H)
Is methyl ethyl ketone, cyclohexanone, toluene,
Xylene, cellosolve, butyl cellosolve, carbitol
Butyl carbitol, ethyl acetate, butyl acetate,
Rosolve acetate, butyl cellosolve acetate,
Rubitol acetate, butyl carbitol acetate
And the like. As other additives (I)
Are, for example, paint additives such as antifoaming agents, leveling agents,
Examples include a silane coupling agent. The above (A) to (E) and, if necessary,
(F) to (I) are mixed, and if necessary, three rolls,
Kneading means such as ball mill and sand mill, or super
-By stirring means such as a mixer, a planetary mixer, etc.
Kneaded or mixed, the photosensitive resin composition of the present invention is obtained
You. The obtained photosensitive resin composition was formed with a copper circuit.
With a coating thickness of approximately 5 to 100 μm on the printed wiring board
Coated. As a means of coating, currently screen printing
Generally, full-scale printing by the method is widely used.
What kind of coating means can be applied uniformly including
Means may be used. For example, spray coater, hot
Tmelt coater, bar coater, applicator, breaker
Do coater, knife coater, air knife coater, curtain
Flow coater, roll coater, gravure coater, offset
Printing, dip coating, brush coating, and other ordinary
The law can all be used. After coating, if necessary, hot air stove or far-red
Prebaking, that is, temporary drying, is performed in an external furnace, etc.
To the tack-free state. The pre-bake temperature is
About 50 to 100 ° C. is preferred. Next, the active energy
Active energy using a negative mask that is
Exposure with energy rays is performed. As a negative mask
When the active energy ray is ultraviolet light, a negative film
Metallic mask for electron beam, leady for X-ray
A mask is used for each, but a simple negative film
Active energy in printed wiring board manufacturing because it can be used
Ultraviolet rays are often used as rays. The amount of UV irradiation
Generally 10 to 1000 mJ / cm ² It is. After exposure,
Use a weak alkaline solution such as a dilute aqueous solution of sodium carbonate as the developer.
And then developed by means such as spraying or dipping, and
The components are removed by actions such as dissolution, swelling, and peeling. Next, heat
Heating in a wind oven or far-infrared oven, or UV irradiation
And post-cure to achieve the objective
A photo solder resist film can be formed. This
Printed pattern covered with solder resist film
A wire plate is obtained, and the electronic components are jet-soldered.
Or soldered by reflow soldering
Connected, fixed and mounted by one electronic circuit
A unit is formed. It should be noted that the claims of the present invention are as follows.
Can be as street. (1) Tables represented by the following general formulas [Chemical Formula 1], [Chemical Formula 2] and [Chemical Formula 3]
At least one of the monomers represented by the general formula [Formula 1] and
A carbohydrate comprising a copolymer of monomers represented by the following formula
Xyl group-containing copolymer resin (A) and at least
Resin having two ethylenically unsaturated bonds
(B), a reactive diluent (C), and a photopolymerization initiator (D)
And a thermosetting compound (E).
A photosensitive resin composition, (Where R ₁ Is a hydrogen atom or a methyl group, R ₂ Is 1 carbon
And 6 to 6 represent an aliphatic hydrocarbon group or an aromatic group. ) (Where R ₁ Represents a hydrogen atom or a methyl group. ) (Where R ₃ Is a hydrogen atom or an aliphatic carbon having 1 to 6 carbon atoms
Hydrogen group, R ₄ Is a hydrogen atom or a hydroxyl group, alkoxy
Represents a sil group. (2) Average of the above carboxyl group-containing copolymer resin (A)
The above-mentioned (1), wherein the molecular weight is 5,000 to 70,000.
Photosensitive resin composition, (3) Carboxyl group-containing copolymer
The acid value of the synthetic resin (A) is 50 to 150 mgKOH / g.
The photosensitive resin composition according to the above (1) or (2),
(4) A compound represented by the general formula (Chemical Formula 2)
1) 20 mol% in the compound represented by (Chemical Formula 2) or (Chemical Formula 3)
The photosensitive resin according to any one of (1) to (3) above.
Composition, (5) the above-mentioned carboxyl group-containing copolymer resin
The content of (A) is at least two in one molecule.
1 to the photosensitive resin (B) having a lenic unsaturated bond
The photosensitive tree according to any one of (1) to (4), which is 40%.
Fat composition, (6) the reactive diluent (C) is a photopolymerizable
And at least two ethylenes in one molecule.
Resin (B) having a photosensitive unsaturated bond
The above (1) to (5), which are used at a ratio of 2 to 40%.
(7) the photopolymerization initiator (D)
Is at least two ethylenically unsaturated bonds in one molecule.
0.2 to 30% based on photosensitive resin (B)
The photosensitive tree according to any one of the above (1) to (6), which is used at a ratio of
Fat composition, (8) the thermosetting compound (E) is added for 1 minute
Having at least two ethylenically unsaturated bonds in the
Used at a ratio of 5 to 100% based on the photosensitive resin (B)
The photosensitive resin composition according to any one of the above (1) to (7). DESCRIPTION OF THE PREFERRED EMBODIMENTS Next, the present invention will be described in more detail by way of examples.
Explain, but they limit the scope of the present invention.
Not something. In the examples, parts are parts by weight and% is quality.
% Shall be expressed. [Synthesis Example 1] Carbitol acetate 19
0 g, styrene 104 g, methacrylic acid 86 g, azo
Dissolve 4 g of isobutyronitrile (AIBN) and heat
Under the conditions described above, and a carboxyl group-containing polymer having a solid content of 50%.
A limmer (a1) was obtained. The average molecular weight of the polymer (G
PC method, hereinafter the same) is 20,000 and the acid value is 147.
Met. [Synthesis Example 2] Carbitol acetate 19
4 g, 62.4 g of styrene, 86 g of methacrylic acid,
45.6 g of tyl methacrylate, azoisobutyronitrile
(AIBN) 4 g is dissolved and reacted under heating conditions.
Carboxyl group-containing polymer (a2) having a solid content of 50%
Obtained. Average molecular weight of the polymer (GPC method, hereinafter the same)
) Was 25,000 and the acid value was 144. [Synthesis Example 3] Carbitol acetate 22
5 g, 62.4 g of styrene, 72 g of acrylic acid,
Methacrylate 91.2 g, azoisobutyronitrile
(AIBN) 4 g was dissolved and reacted under heating conditions to solidify.
50% carboxyl group-containing polymer (a3)
Was. Average molecular weight of the polymer (GPC method, hereinafter the same)
Was 24,000 and the acid value was 125. [Synthesis Example 4] Carbitol acetate 20
6 g, 4-hydroxystyrene 120 g, methacryl
86 g of acid and 4 g of azoisobutyronitrile (AIBN)
Dissolve and react under heating conditions to obtain a 50% solids carb
A xyl group-containing polymer (a4) was obtained. Of that polymer
The average molecular weight (GPC method, hereinafter the same) is 30,000
The acid value was 136. [Synthesis example 5] Carbitol acetate 20
4 g, 4-hydroxystyrene 72 g, methacrylic acid
86 g, ethyl methacrylate 45.6 g, azoisobu
Dissolve 4 g of thyronitrile (AIBN) and heat
Carboxyl group-containing polymer with 50% solid content by reaction
(A5) was obtained. Average molecular weight of the polymer (GPC
Method, the same applies hereinafter) is 28,000, and the acid value is 137.
Was. [Production Example 1 of Photosensitive Resin (B)] Carbitol
To 380 parts by weight of luacetate, add bisphenol A type epoxy
Xy resin [made by Yuka Shell, Epicoat 1001, Epoki
Equivalent weight 480] 480 parts by weight and acrylic acid 72 parts by weight
Is dissolved and reacted under reflux to obtain bisphenol A-type epoxy resin.
Xyacrylate was obtained. Then, this epoxy acrylic
154 parts by weight of hexahydrophthalic anhydride
Reaction under reflux until the acid value reaches the theoretical value.
A photosensitive resin (b1) having a content of 65% was obtained. [Production Example 2 of Photosensitive Resin (B)] Carbitol
Add cresol novolak type epo to 392 g of luacetate
Epoxy resin "Nippon Kayaku, EOCN104S, epoxy
215 g) and 430 g of acrylic acid are dissolved,
Reaction under reflux to produce cresol novolak epoxy
Got a acrylate. Then the epoxy acrylate
154 g of hexahydrophthalic anhydride was added to the mixture, and the acid value was adjusted.
The reaction was carried out under reflux until the theoretical value was reached.
The light resin (b2) was obtained. Example 1 Carboxy obtained in Synthesis Example 1
20 g of silyl group-containing polymer (a1), photosensitive resin
(B) Photosensitive resin (b1) 100 obtained in Production Example 1
g, 2-methyl-1- [4- (methylthio) phenyl]
8.0 g of 2-morpholino-1-propanone,
8.0 g of methylolpropane triacrylate,
Glycidyl tris (2-hydroxyethyl) isocyanu
Rate 30g, phthalocyanine green 0.5g
And talc at a ratio of 8.0 g and mixed with 3 rolls
This was dispersed to prepare a solution of the photosensitive resin composition. This group
The coating performance of the product is shown in Table 1. Example 2 Carboxy obtained in Synthesis Example 1
20 g of silyl group-containing polymer (a1), photosensitive resin
(B) Photosensitive resin (b2) 100 obtained in Production Example 2
g, 2-methyl-1- [4- (methylthio) phenyl]
8.0 g of 2-morpholino-1-propanone,
8.0 g of methylolpropane triacrylate,
Glycidyl tris (2-hydroxyethyl) isocyanu
Rate 30g, phthalocyanine green 0.5g
And talc at a ratio of 8.0 g and mixed with 3 rolls
This was dispersed to prepare a solution of the photosensitive resin composition. This group
The coating performance of the product is shown in Table 1. Example 3 Carboxy obtained in Synthesis Example 2
For 20 g of the silyl-containing polymer (a2), a photosensitive resin
(B) Photosensitive resin (b2) 100 obtained in Production Example 2
g, 2-methyl-1- [4- (methylthio) phenyl]
8.0 g of 2-morpholino-1-propanone,
8.0 g of methylolpropane triacrylate,
Glycidyl tris (2-hydroxyethyl) isocyanu
Rate 30g, phthalocyanine green 0.5g
And talc at a ratio of 8.0 g and mixed with 3 rolls
This was dispersed to prepare a solution of the photosensitive resin composition. This group
The coating performance of the product is shown in Table 1. Example 4 Carboxy obtained in Synthesis Example 3
20 g of sil group-containing polymer (a3) is added to photosensitive resin
(B) Photosensitive resin (b2) 100 obtained in Production Example 2
g, 2-methyl-1- [4- (methylthio) phenyl]
8.0 g of 2-morpholino-1-propanone,
8.0 g of methylolpropane triacrylate,
Glycidyl tris (2-hydroxyethyl) isocyanu
Rate 30g, phthalocyanine green 0.5g
And talc at a ratio of 8.0 g and mixed with 3 rolls
This was dispersed to prepare a solution of the photosensitive resin composition. This group
The coating performance of the product is shown in Table 1. Example 5 Carboxy obtained in Synthesis Example 4
20 g of sil group-containing polymer (a4) is added to photosensitive resin
(B) Photosensitive resin (b2) 100 obtained in Production Example 2
g, 2-methyl-1- [4- (methylthio) phenyl]
8.0 g of 2-morpholino-1-propanone,
8.0 g of methylolpropane triacrylate,
Glycidyl tris (2-hydroxyethyl) isocyanu
Rate 30g, phthalocyanine green 0.5g
And talc at a ratio of 8.0 g and mixed with 3 rolls
This was dispersed to prepare a solution of the photosensitive resin composition. This group
The coating performance of the product is shown in Table 1. Example 6 Carboxy obtained in Synthesis Example 5
For 20 g of the sil group-containing polymer (a5), a photosensitive resin
(B) Photosensitive resin (b2) 100 obtained in Production Example 2
g, 2-methyl-1- [4- (methylthio) phenyl]
8.0 g of 2-morpholino-1-propanone,
8.0 g of methylolpropane triacrylate,
Glycidyl tris (2-hydroxyethyl) isocyanu
Rate 30g, phthalocyanine green 0.5g
And talc at a ratio of 8.0 g and mixed with 3 rolls
This was dispersed to prepare a solution of the photosensitive resin composition. This group
The coating performance of the product is shown in Table 1. Comparative Example 1 Photosensitive resin (B)
100 g of the obtained photosensitive resin (b1), 2-methyl-1
-[4- (methylthio) phenyl] -2-morpholino
8.0 g of 1-propanone, trimethylolpropane
8.0 g of triacrylate, triglycidyl tris
30 g of (2-hydroxyethyl) isocyanurate,
0.5 g of phthalocyanine green and 8.0 of talc
g, mix and disperse with 3 rolls,
A solution of the resin composition was prepared. The coating performance of this composition
It is shown in Table 1. Comparative Example 2 In the photosensitive resin (B) production example 2,
100 g of the obtained photosensitive resin (b2), 2-methyl-1
-[4- (methylthio) phenyl] -2-morpholino
8.0 g of 1-propanone, trimethylolpropane
8.0 g of triacrylate, triglycidyl tris
30 g of (2-hydroxyethyl) isocyanurate,
0.5 g of phthalocyanine green and 8.0 of talc
g, mix and disperse with 3 rolls,
A solution of the resin composition was prepared. The coating performance of this composition
It is shown in Table 1. The performance of the cured coating film was evaluated by the following method. (1) A tack photosensitive resin composition was entirely coated on a patterned copper foil substrate.
The surface was coated and dried at 80 ° C. for 20 minutes. Then, this group
The negative film adheres to the plate, and after exposure, the negative film
The state after sticking was evaluated. ◎: No film sticking marks on the coating film surface ○: Slight film sticking marks on the coating film surface △: Film sticking marks on the entire surface ×: Coating film transferred to film [0042] (2) A step tablet with a sensitivity of 21 steps is applied to the test board,
mJ / cm ² UV exposure with the irradiation amount of
After the image was evaluated, the maximum number of steps where the coating film was completely left was evaluated.
Was. The larger the number of steps, the better the photosensitive characteristics
Is shown. (3) Coating performance The photosensitive resin composition was entirely coated on a patterned copper foil substrate.
The surface was coated and dried at 80 ° C. for 20 minutes. Then, this group
Adhere the negative film to the plate, and after exposure, 1% sodium carbonate
A pattern was formed by developing with an aqueous solution of aluminum. next,
This substrate is thermally cured at 150 ° C. for 60 minutes to form a cured coating film.
An evaluation substrate was prepared and the coating film performance was evaluated. (A) Hardness Measured according to JIS K-5400 6.14. (B) Adhesion Measured by a grid test according to JIS D0202.
did. (C) An evaluation substrate having a solder heat-resistant cured coating film was tested according to JIS C6481.
After immersion in a solder bath at 260 ° C for 30 seconds,
One cycle of the peeling test using the Hantape
Observe the state of the coating film after 1 to 3 cycles, heat resistance
Was evaluated. ◎: No change in the coating film after 3 cycles. ：: Slight change after 3 cycles. △: Change after 2 cycles. X: Peeling occurred after 1 cycle. D) An evaluation substrate having an acid-resistant cured coating film was washed with a 10% sulfuric acid aqueous solution
After immersion in water for 30 minutes, wash with water and then use cellophane adhesive tape
A peeling test using the
The color was observed and the acid resistance was evaluated. ◎: No change observed ○: Slight change Δ: Notable change ×: Film swelled and peeled (E) Solvent-resistant cured film Evaluate the substrate in methylene chloride at room temperature for 30
After soaking for a minute, wash with water and use cellophane adhesive tape
Perform a peeling test to check for peeling and discoloration of the resist layer.
And observed to evaluate the solvent resistance. ◎: No change was observed ○: Slight change Δ: Notable change ×: Coating swelled and peeled (F) Gold plating resistant cured coating After gold plating on the evaluation board
Perform a peeling test with an adhesive tape,
Peeling and discoloration were observed to evaluate gold plating properties. ◎: No change observed ○: Very slight change Δ: Notable change ×: Coating swelled and peeled (G) Electrical properties IPC SM-840B B -25 comb type electrode B cooler
Using a pom, an evaluation substrate was prepared under the above conditions,
Applying DC 100 V in a constant temperature and humidity chamber of 90% RH,
Measure the insulation resistance after 0 hour and observe discoloration
Then, the electrical characteristics were evaluated. ◎: No change observed at all ○: Very slight change Δ: Notable change ×: Black scorch [Table 1] As can be seen from Table 1, the photosensitive resin of the present invention
Tack-free, sensitivity and adhesion by using the composition
Excellent in heat resistance, solder heat resistance, acid resistance and gold plating resistance
It is clear that a rudder resist film can be formed.
You. According to the present invention, ultraviolet exposure and rare
An image can be formed by development with an aqueous solution of potassium
Free and good workability, furthermore adhesion, electrical insulation,
Can provide a pattern with excellent heat resistance and chemical resistance.
Can be used as a solder resist for printed wiring board manufacturing
A suitable photosensitive resin composition can be provided.

   ────────────────────────────────────────────────── ─── Continuation of front page    F term (reference) 2H025 AA06 AA07 AA08 AA10 AA14                       AA15 AA20 AB15 AC01 AD01                       BC13 BC42 BC82 CA00 CB13                       CB14 CB16 CB43 CB45 CC17                       FA17                 5E314 AA27 AA33 BB06 CC01 DD07                       EE09 FF01 GG03 GG10 GG11                       GG24 GG26

Claims (1)

[Claim 1] At least one of the monomers represented by the following general formulas [Chemical formula 1], [Chemical formula 2] and [Chemical formula 3] represented by the general formulas [Chemical formula 1] and [Chemical formula 2] Carboxyl group-containing copolymer resin (A) comprising a copolymer of the following monomers, a photosensitive resin (B) having at least two ethylenically unsaturated bonds in one molecule, and a reactive diluent (C) And a photopolymerization initiator (D) and a thermosetting compound (E). Embedded image (Wherein, R ₁ is a hydrogen atom or a methyl group, R ₂ is a carbon atom 1
And 6 to 6 represent an aliphatic hydrocarbon group or an aromatic group. ) (In the formula, R ₁ represents a hydrogen atom or a methyl group.) (In the formula, R ₃ represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 6 carbon atoms, and R ₄ represents a hydrogen atom, a hydroxyl group, or an alkoxyl group.)