JP2707495B2 - Photosensitive thermosetting resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] TECHNICAL FIELD The present invention relates to a novel photosensitive thermosetting
More specifically, regarding a curable resin composition, a printed wiring board
Manufacturing, precision metal processing, etching of glass and stone, plastic
Used for relief materials, printing plate materials, etc.
A new feeling useful as a solder resist for lint wiring boards
The present invention relates to a photothermosetting resin composition. [0002] 2. Description of the Related Art Solder
Resist is used when soldering components to printed wiring boards
Prevent solder adhesion to parts other than necessary and protect circuits
The purpose is to improve adhesion, electrical insulation
Resistance, solder heat resistance, solvent resistance, alkali resistance, acid resistance
And various properties such as plating resistance. Solder cash register
The initial strike was made of epoxy melamine-based hardened
Used, but solder heat resistance, chemical resistance
Printing for industrial use due to problems such as resistance and plating resistance
For use in wiring boards, for example, Japanese Patent Publication No. 51-14044
Disclosed epoxy thermoset type improved from these
It has become mainstream. Also, pudding for consumer use
For wiring boards, since productivity is important,
For example, it is disclosed in Japanese Patent Publication No. 61-48800.
The fast-curing UV-curing type is the mainstream.
You. However, the UV-curing type has a problem with the internal curability at the film thickness
And also has poor soldering heat resistance, making it an industrial print
It cannot be used for wiring boards. These are solder
-Screen printing as a method for forming resist patterns
Use of electronic devices
Higher density of printed wiring boards due to shorter size, surface of parts
For formation of solder resist pattern corresponding to mounting
Has problems with bleeding and embedding between circuits.
Can no longer function as a dark resist film
I have. [0003] To solve these problems, Drife
Film type photo solder resist and liquid photo solder
Resists are being developed. Dry film type photoso
As the rudder resist, for example, JP-A-57-5591
No. 4 discloses urethane di (meth) acrylate
Linear polymer having a glass transition temperature of
And a photosensitive resin composition for a dry film comprising:
Is disclosed. However, these dry filters
High-density printing for Lum-type photo solder resist
When used for wiring boards, solder heat resistance and adhesion are not sufficient.
No. On the other hand, as a liquid photo solder resist
States in GB-2032939A
If epoxide and ethylenically unsaturated carboxylic acid are solid
Or semi-solid reaction product, inert inorganic filler, photopolymerization
For photopolymerizable coatings containing initiators and volatile organic solvents
A composition is disclosed, in this case an ultraviolet curable component
Printed wiring because only thermosetting components are used together
Adhesion to the board, solder heat resistance, electrical insulation, etc.
There is a problem of inferiority. Considering such thermosetting properties,
For example, Japanese Patent Application Laid-Open No. 60-208377 discloses that
Unsaturated monobasic acid of phenol novolak type epoxy resin
Of cresol novolak type epoxy resin
Partial reaction product with unsaturated monobasic acid, organic solvent, photopolymerization
Solder resist containing initiator and amine curing agent
A resin composition for an ink is disclosed. In this case,
Thermosetting properties are maintained by leaving epoxy groups in the resin
I'm sorry. However, leaving epoxy groups
The amount of photosensitive groups decreases, so the curability by ultraviolet rays decreases.
Therefore, it is difficult to leave many epoxy groups,
Unable to satisfy the characteristics as solder resist
No. On the other hand, as an example of using an epoxy resin together,
JP-A-49-107333 discloses a terminal ethylene group.
An unsaturated compound having two, a polymerization initiator, and at least
Also has a compound containing two epoxy groups and a carboxyl group
A photosensitive composition comprising at least two compounds is opened.
And Japanese Patent Application Laid-Open No. 61-272 discloses
Volak type epoxy compound and unsaturated monocarboxylic acid
Reactant, diisocyanate and one hydroxyl group in one molecule
Reaction with poly (meth) acrylates having
Active energy ray-curable resin obtained by reaction
An initiator that uses an epoxy resin in combination with an organic solvent.
A key composition is disclosed. However, the latter
Characteristics as a black resist.
Although the former is the (meth) acrylic group-containing acrylic linear
It is based on a polymer compound and has solder heat resistance and solvent resistance.
Poor. Also, increase the ratio of epoxy resin
And the photocurability, the so-called sensitivity decreases, and the developer in the exposed part
Resistance tends to decrease, long-term development is not possible,
There is a problem that undeveloped portions are easily left behind in development. Ma
JP-A-61-243869 discloses a novolak.
Reaction product of epoxy type epoxy compound and unsaturated monocarboxylic acid
Obtained by reaction with a saturated or unsaturated polybasic anhydride.
Photosensitive resin, photopolymerization initiator, diluent, epoxy
A resist ink composition using a resin is disclosed.
You. In this case, since the alkaline aqueous solution is used as the developer,
Ratio of insoluble epoxy resin to aqueous lukari solution
Increasing the sensitivity also decreases the sensitivity, and
The solubility in the image liquid is apt to decrease, resulting in residual development.
Or exposed for a long time, and exposed areas
There are problems such as being done. [0006] Accordingly, an object of the present invention is to provide such a species as described above.
Excellent in developability and sensitivity without various disadvantages, and in the exposed area
With long pot life
An object of the present invention is to provide a thermosetting resin composition. further,
The object of the present invention is to provide a solder
-Adhesion, electrical insulation, and corrosion resistance required for resist
Resistance, solder heat resistance, solvent resistance, alkali resistance, acid resistance,
A cured coating film with excellent plating resistance, etc. is obtained.
Suitable for manufacturing lint wiring boards and industrial printed wiring boards
To provide a photosensitive thermosetting resin composition. [0007] According to the present invention, the eye
In order to achieve the target, (A) at least two
Of the following (a-1) to (a)
−4One) selected from the group consisting of one or more of
Two or more photosensitive prepolymers, (A-1) between an epoxy compound and an unsaturated monocarboxylic acid
Total Este of Epoxy Group Generated by Esterification Reaction
ConversionThingSecondary hydroxyl group and saturated or unsaturated polybasic anhydride
The reaction product of (A-2) Diisocyanates and one hydroxyl in one molecule
A reaction product with a (meth) acrylate having a group,
Esterification of epoxy compounds with unsaturated monocarboxylic acids
Of the epoxy group generated by the reactionTotal esterificationThingtwo
Reaction products obtained by reacting with a graded hydroxyl group, (A-3) Epoxy compound and unsaturated monocarboxylic acid
Partial S of epoxy group formed by esterification reaction
TellingThingSecondary hydroxyl group and saturated or unsaturated polybasic anhydride
Reaction product with (A-4) Diisocyanates and one hydroxyl in one molecule
A reaction product with a (meth) acrylate having a group,
Esterification of epoxy compounds with unsaturated monocarboxylic acids
Of the epoxy group generated by the reactionPartial esterificationThing
A reaction product obtained by reacting with a secondary hydroxyl group, (B) a photopolymerization initiator, (C) a photopolymerizable vinyl monomer as a diluent and / or
Or organic solvent, (D) having at least two epoxy groups in one molecule,
And an epoxy compound that is hardly soluble in the diluent used.
Heterocyclic epoxy resin and / or vixile
At least one polyfunctional epoxy resin containing a phenolic epoxy resin
Poxy compounds, (E) dicyandiamide, melamine, guanamine and the like
Derivatives, and their organic acid salts and epoxy adducts
At least one compound containing a compound selected from the group consisting of
Characterized by containing a curing agent for epoxy resin
A light thermosetting resin composition is provided. [0008] DESCRIPTION OF THE PREFERRED EMBODIMENTS Such a photosensitive thermosetting resin set
The product is placed on a printed circuit board on which a circuit is formed, for example.
Lean printing, curtain coating, roll coating
Coating by spraying, spray coating, etc.
Or a dry film of the composition
Laminate directly on the printed circuit board or use the method described above.
Apply in a more liquid state, wet or dry
Such as laminating a dry film on top
A coating film can also be formed by the above method. After that, the laser light
Contact mask or photomask with a predetermined pattern
High pressure mercury lamp, ultra high pressure mercury lamp, metal
Ride lamps, chemical lamps, xenon lamps, etc.
Exposure to actinic light, develop the unexposed areas with a developer
A resist pattern can be formed. After that,
Solder resist pattern by heating and curing
Is formed. A thermosetting component together with a photosensitive prepolymer
For solder resist using epoxy resin
In the case of a photothermosetting resin composition, conventionally, an organic solvent is generally used.
A soluble epoxy resin is used. like this
Preparation of photosensitive thermosetting resin composition using epoxy resin
The epoxy resin is entangled with the photosensitive prepolymer
In a state where the chain length of each resin is entangled
It is presumed that it has melted. As a result,
When unexposed parts are developed, for example,
Alkaline composition using soluble photosensitive prepolymer
Epoxy resins are generally alkaline when developed with aqueous solutions.
Insoluble in aqueous solution, and epoxy resin and photosensitive prepoly
In the unexposed area due to the
Reduces the solubility of the photosensitive prepolymer and
The reaction with the curing agent is fast because the resin is dissolved in the solvent.
In addition, the phenomenon that development residue occurs during development, so-called heat fogging
And developability deteriorates. On the other hand, used for development
Using photosensitive prepolymer soluble in organic solvent
When the product is developed with an organic solvent, the epoxy resin
Is soluble in a solvent, so the same thermal fogging is likely to occur as above.
And the developability tends to decrease. Also, in the exposure section
In the presence of an epoxy resin,
Does not increase the crosslink density and dissolves in the developer.
There is a problem that the film is easily attacked and sensitivity is deteriorated.
In any of the above cases, the preservation of the photosensitive thermosetting resin composition
The lifetime is determined by the reaction between the epoxy resin and the curing agent as described above.
Shorter for faster. Also uses water-soluble epoxy resin
However, when developed with an alkaline aqueous solution, the epoxy resin
Because it is soluble in the image liquid, the exposed part is easily attacked by the developer,
Degree worse. On the other hand, as in the present invention,
Separates epoxy compounds (resins) that are hardly soluble in diluents into fine particles.
When used in a dispersed state, the epoxy compound (fine-grained epoxy resin)
A photosensitive prepolymer wraps around the particles of
Immersed, and therefore soluble in alkaline aqueous solutions
A composition using a light-sensitive prepolymer is treated with an alkaline aqueous solution.
When developed, the epoxy compound is
It does not reduce solubility, and epoxy compounds
Hardener for epoxy resin due to poor solubility in the diluent used
With low reactivity, hardly cause fogging, and developability
Gets better. On the other hand, it is soluble in organic solvents used for development.
Using a light prepolymer, and using the organic solvent as a diluent
Use a sparingly soluble fine-grained epoxy compound
When the composition was developed with the organic solvent,
Because the compound is hardly soluble in the above organic solvents, the exposed area
It is hardly affected and does not cause a decrease in sensitivity. Also unexposed
About the developability of the epoxy compound,
Of photosensitive prepolymer due to the dispersion of particles
It does not reduce the properties and it is hard to cause fogging
Therefore, the developability is improved. In addition, in any of the above cases
Even the shelf life of the composition, as described above epoxy compound
With the photosensitive prepolymer wrapped around the particles
And the low reactivity between the epoxy compound and the curing agent
become longer. That is, the photosensitive thermosetting resin set of the present invention
The product is dispersed in finely particulate form that is hardly soluble in the diluent used.
The biggest use of oxy compounds as thermosetting components
Features. This essential component is fine (powder)
Poxy compounds are poorly soluble in the diluent used and are
Because it is used dispersed as it is,
Because it is used in the same way, it is hard to be affected by the developer.
The degree of degradation does not decrease, and the fine-grained
Since the xy compound is washed away by the developer, the developability is excellent.
Development in a short time, followed by subsequent heating
Melts and cures the epoxy compound alone, or
Is copolymerized with a photosensitive prepolymer to obtain the desired properties.
Excellent solder resist pattern for printed wiring boards
It can be formed. In addition, it is clear from the above description of the operation.
As is apparent, the term "poorly soluble" in the present invention refers to the rare
Not only those that are insoluble in excipients,
This is a concept that includes those with low solubility. Hereinafter, the photosensitive thermosetting resin composition of the present invention will be described.
Each component will be described. Less in one molecule
Photosensitive prepolymer having two ethylenically unsaturated bonds
As Rimmer (A), (A-1) between an epoxy compound and an unsaturated monocarboxylic acid
Total Este of Epoxy Group Generated by Esterification Reaction
Fluoride(Hereinafter, when referring to this compound, the abbreviation CE is used.
Used.)) With a secondary hydroxyl group and a saturated or unsaturated polybasic anhydride
Reaction product with the product, (A-2) Diisocyanates and one hydroxyl in one molecule
A reaction product with a (meth) acrylate having a group,
All the above esterified compounds (CE) To react with secondary hydroxyl groups
Reaction product obtained by (A-3) Epoxy compound and unsaturated monocarboxylic acid
Partial S of epoxy group formed by esterification reaction
Telluride(Hereinafter, when referring to this compound, the abbreviation PE
Is used.) No secondary hydroxyl group and saturated or unsaturated polybasic acid
Reaction products with water, and (A-4) Diisocyanates and one hydroxyl in one molecule
A reaction product with a (meth) acrylate having a group,
The above partial esterified product (PE) Reacts with secondary hydroxyl groups
Reaction product obtained by the reaction. The photosensitive press
When the polymer (A) is solid or semi-solid at room temperature,
Can be used for both contact and non-contact exposure methods.
In the case of a liquid, it is mainly used for a non-contact exposure system. Exposure
The reactive prepolymer (A) is used in accordance with such an exposure method.
To select at least one of the above prepolymers.
Used to be used. [0013] The photosensitive prepolymer (A) is used for the synthesis.
Epoxy compounds used include, for example, phenol,
Sol, halogenated phenol, alkyl phenol
Which phenols and formaldehyde under acidic catalyst
Novolaks obtained by the reaction and epichlorohydrin and
And / or methyl epichlorohydrin.
Novolac epoxy compounds are suitable for
YDCN-701, YDCN-704, YD
PN-638, YDPN-602; manufactured by Dow Chemical Company
DEN-431, DEN-439; manufactured by Ciba Geigy
EPN-1138, EPN-1235, EPN-129
9; N-730 and N-7 manufactured by Dainippon Ink and Chemicals, Inc.
70, N-865, N-665, N-673, N-69
5, VH-4150, VH-4240, VH-444
0; Nippon Kayaku Co., Ltd. EOCN-120, EOCN-1
04, BRRN-1020; ECN manufactured by Asahi Kasei Corporation
-265, ECN-293, ECN-285, ECN-
299 and the like. Further, the novolak-type epoxy compound
Part or all, for example, Epicoat manufactured by Yuka Shell Co., Ltd.
828, Epikote 1007, Epikote 807; Dainichi
Epicron 840, Epichrom manufactured by Hon Ink Chemical Industry Co., Ltd.
860, Epicron 3050, Epicron 830;
U-Chemical DER-330, DER-337, D
ER-361: Celloxide manufactured by Daicel Chemical Industries, Ltd.
2021, Celloxide 3000; Mitsubishi Gas Chemical Co., Ltd.
TETRAD-X, TETRAD-C; Nippon Soda
EPB-13 and EPB-27 manufactured by Toto Kasei Co., Ltd.
YD-116, YD-128, YD-013, YD-
020, YDG-414, ST-3000, ST-11
0, YDF-190, YDF-2004, YDF-20
07; GY-260, GY-25 manufactured by Ciba Geigy
5, XB-2615; DER-33 manufactured by Dow Chemical Company
2, DER-662, DER-542, etc.
Enol A type, bisphenol F type, hydrogenated bisphenol
A type, brominated bisphenol A type, containing amino group, fat
Glycidyl ester such as cyclic or polybutadiene modified
It can be replaced with an epoxy-type epoxy compound.
As a result, the adhesion and flexibility are improved.
If there is too much, the heat resistance of the cured film tends to deteriorate, so print
Phenol Novola is used as a solder resist for wiring boards.
Or cresol novolac epoxy compounds, especially
Cresol novolak type epoxy compound
preferable. Next, the photosensitive prepolymer (A)
As the unsaturated monocarboxylic acid used for the synthesis,
Acid, methacrylic acid, β-styrylacrylic acid, β-
Rufuryl acrylic acid, crotonic acid, α-cyanocinnamic acid,
Cinnamic acid, etc .; and saturated or unsaturated dibasic anhydride for 1 minute
(Meth) acrylates having one hydroxyl group in the
With half-esters of saturated or unsaturated dibasic acids
Half esters with saturated monoglycidyl compounds, e.g.
Talic acid, tetrahydrophthalic acid, hexahydrophthalic
Acid, maleic acid, succinic acid, itaconic acid, chlorend
Acid, methyl hexahydrophthalic acid, methyl endomethyl
Tetrahydrophthalic acid, methyltetrahydrophthalic acid
A saturated or unsaturated dibasic acid anhydride such as
Tyl acrylate, hydroxypropyl acrylate,
Hydroxybutyl acrylate, polyethylene glycol
Lumonoacrylate, glycerin diacrylate, tri
Methylol propane diacrylate, pentaerythritol
Triacrylate, dipentaerythritol penta
Acrylate, triglycidyl isocyanurate dia
Acrylate or meta corresponding to the above acrylate
Acrylates or the saturated or unsaturated dibasic
Acid and glycidyl (meth) acrylate
Half ester obtained by reacting at a
These may be used alone or in combination of two or more.
From the viewpoint of curability, acrylic acid and methacrylic acid, especially
Lylic acid is preferred. Next, the photosensitive prepolymer (A)Horse
(A-1) and (a-3)Used in the synthesis of
Or unsaturated polybasic acid anhydrides such as phthalic acid,
Hydrophthalic acid, hexahydrophthalic acid, maleic acid,
Succinic acid, itaconic acid, chlorendic acid, methyl hexahi
Drophthalic acid, methyl endmethylene tetrahydrophthalate
Luic acid, methyltetrahydrophthalic acid, trimellitic acid,
Pyromellitic acid, benzophenonetetracarboxylic acid, etc.
Is used, especially tetrahydrophthalic anhydride or
Is preferably hexahydrophthalic anhydride. Next, the photosensitive prepolymer (A)Horse
(A-2) and (a-4)Used in the synthesis of
As the cyanates, tolylene diisocyanate,
Xylylene diisocyanate, hydrogenated xylylene diisocyanate
Anate, hexamethylene diisocyanate, isophoro
Diisocyanate, diphenylmethane diisocyanate
G, toluidine diisocyanate, lysine diisocyanate
And the like, especially tolylene diisocyanate or
Is preferably isophorone diisocyanate. Next,
(Meth) acrylates having one hydroxyl group in the molecule
As hydroxyethyl acrylate, hydroxy
Propyl acrylate, hydroxybutyl acrylate
G, polyethylene glycol monoacrylate, glycer
Phosphorus diacrylate, trimethylolpropane diacrylate
Rate, pentaerythritol triacrylate, dipe
Antaerythritol pentaacrylate, tris (hydr
Roxyethyl) isocyanurate diacrylate
Or a methacrylate corresponding to the above acrylate
Used, especially hydroxyethyl acrylate or pen
Taerythritol triacrylate is preferred. The epoxy compound and unsaturated monocarboxylic acid
All esterified products of epoxy group with acid (CE) And parts
Esterified (PE) Is the equivalent number of epoxy groups / carbo
The equivalent number of the xyl group is 0.8 to 3.3, preferably
Telluride (CE) For 0.9-1.1, partial esterification
Stuff(PE) In the range of 1.1 to 2.5
Is performed. If the equivalent number ratio is less than 0.8, the free acid
By remaining, solder heat resistance decreases, while
When the ratio exceeds 3.3, the photosensitivity decreases, so that it is preferable.
Absent. For example, the novolak type epoxy compound is
Solve acetate, carbitol acetate, methyl ether
Dissolved in organic solvents such as tyl ketone, hydroquinone,
Thermal polymerization inhibitors and catalysts such as catechol and pyrogallol
As benzyldimethylamine, triethylamine, etc.
Tertiary amines or benzyltrimethylammonium
Muchloride, benzyltriethylammonium bromer
Quaternary ammonium salts such as
Nocarboxylic acid is mixed and heated and stirred at 70-140 ° C.
It is obtained by reacting. Next, total esterification of the epoxy compound
Stuff(CE) And partially esterified compounds (PE) Esterification
Secondary hydroxyl group generated by the reaction and the polybasic anhydride
Of the esterified compound (CEas well asP
E)), The equivalent of acid anhydride to the number of equivalents of secondary hydroxyl groups
The number is preferably 0.3 or more, and the range of the acid value of the formed resin is 3
0 to 160 mgKOH / g, preferably 45 to 120 m
gKOH / g. The reaction product (a-1And a-
3) Is used as a photosensitive prepolymer.
Development with a developer is possible. Acid value is 30mgKOH / g
If it is less than 10, the solubility in an alkali developing solution is deteriorated.
Over 160mgKOH / g, alkali resistance of cured film
Various characteristics as solder resist such as properties and electrical characteristics
It becomes a factor to lower. In this case, the esterified compound (CE
as well asPE) Is saturated or unsaturated when the residual epoxy group is large.
Because it is easy to gel when reacting with a polybasic acid anhydride,
The residual ratio of the epoxy group is suitably 20% or less, preferably 1%.
5% or less. For example, the esterified compound (CEas well as
PE), Wherein the polybasic anhydride is selected from the group consisting of:
At least one kind is selected and mixed, and 70-
It is obtained by reacting under heating and stirring at 120 ° C. Next, total esterification of the epoxy compound
Stuff(CE) And partially esterified compounds (PE) Esterification
Secondary hydroxyl group generated by the reaction and the diisocyanate
(Meth) having one hydroxyl group in one molecule via
Addition reaction product with acrylates (a-2) And (a-
4First, the synthesis of the diisocyanates
(Meth) acryle having one hydroxyl group in one molecule
Equimolar ratio of cellosolve acetate, carbitol
Organic solvents such as toluene acetate and methyl ethyl ketone
In the presence or absence of tributyltin dilaurate
Any organotin compound or benzyldimethylamine,
Using tertiary amines such as triethylamine as a catalyst,
Reaction at 30-100 ° C with heating and stirring for 2-12 hours
Then, a semi-urethane (meth) acrylate is synthesized. This
In the case of (1), one molecule has one hydroxyl group in the molecule ((meth))
Acrylate and diisocyanate are preferably in equimolar ratio
However, the excess of the (meth) acrylates
It may be used as it is as an excipient. Then the obtained half
Cool urethane (meth) acrylate to 25-35 ° C
And the esterified compound (CEas well asPEAt least than)
One selected and the esterified product (CEas well asPE) Has
Semi-urethane (meth) acryle for equivalent number of secondary hydroxyl groups
The equivalent number of isocyanate of the salt is 0.1 or more, preferably
Is from 0.1 to 1.0, most preferably from 0.2 to 0.9
After mixing so as to obtain a working ratio, 2-30 at 30-100 ° C.
It is obtained by reacting under heating and stirring for hours. Equivalent in this case
When the ratio is less than 0.1, the effect of enhancing curability by actinic rays is obtained.
Can not be obtained. As the photosensitive prepolymer (A),
Are those that can be alkali developed from the viewpoint of environmental pollution.
Preferably, from the viewpoint of the stability of the photosensitive prepolymer,
All esters with saturated monocarboxylic acidsSynthesized from
ThingsAre preferable, and from the viewpoint of photocurability,
Unsaturated mono using lylic acid (and / or methacrylic acid)
Esters with carboxylic acids are preferred. Therefore, feeling
Novolak-type epoxy resin is used as the optical prepolymer (A).
More in all esters of acrylic acid with acrylic acid
The reaction product obtained by reacting a basic acid anhydride (a-
1Is particularly preferred. Next, representative examples of the photopolymerization initiator (B)
Benzoin, benzyl, benzoin methyl
Benzo, such as ether and benzoin isopropyl ether
Ins and zonzoin alkyl ethers; acetophen
Non, 2,2-dimethoxy-2-phenylacetopheno
, 2,2-diethoxy-2-phenylacetopheno
1,1-dichloroacetophenone, 1-hydroxy
Cyclohexyl phenyl ketone, 2-methyl-1- [4
-(Methylthio) phenyl] -2-morpholino-pro
Pan-1-one, 2-benzyl-2-dimethylamino-
1- (4-morpholinophenyl) -butanone-1,
Acetophone such as N, N-dimethylaminoacetophenone
Enones: 2-methylanthraquinone, 2-ethylan
Traquinone, 2-tert-butylanthraquinone, 1
-Chloroanthraquinone, 2-amylanthraquinone,
Anthraquinones such as 2-aminoanthraquinone;
2,4-dimethylthioxanthone, 2,4-diethylthio
Oxanthon, 2-chlorothioxanthone, 2,4-di
Thioxanthones such as isopropylthioxanthone;
Acetophenone dimethyl ketal, benzyl dimethyl ke
Ketals such as tar; benzophenone, methylben
Zophenone, 4,4'-dichlorobenzophenone, 4,
Benzo such as 4'-bisdiethylaminobenzophenone
Phenones; and xanthones, alone or
Two or more can be used in combination. further,
The photopolymerization initiator (B) is ethyl-4-dimethylamido.
Nobenzoate, 2- (dimethylamino) ethylbenzo
Benzoic acid esters such as ethate, or triethyl
Tertiary amines such as amines and triethanolamine
In combination with one or more known and commonly used photosensitizers
Can be used. Photopolymerization initiator as described above
The preferred range of the amount of (B) used is that of the photosensitive prepolymer.
-0.2 to 30 parts by weight, preferably 100 parts by weight of (A)
The preferred amount is 2 to 20 parts by weight. Next, as the diluent (C), photopolymerization
Vinylic monomers and / or organic solvents can be used.
Representative photopolymerizable vinyl monomers include 2
-Hydroxyethyl acrylate, 2-hydroxybuty
Hydroxyalkyl acrylates such as acrylate
Class: ethylene glycol, methoxytetraethylene glycol
Coal, polyethylene glycol, propylene glycol
Mono- or diacrylates of glycols such as
N-dimethyl acrylamide, N-methyl acryl
Acrylamides such as amides; N, N-dimethylamido
Amino alkyl acrylates such as ethyl acrylate
G; hexanediol, trimethylolpropane, pe
Antaerythritol, dipentaerythritol, tris
Polyhydric alcohols such as -hydroxyethyl isocyanurate
Or their ethylene oxide or propylene
Acrylates of oxide adducts; phenoxy
Acrylate, bisphenol A diacrylate, and
These phenols are ethylene oxide or
Acrylates such as propylene oxide adducts;
Serine diglycidyl ether, trimethylolpropane
Triglycidyl ether, triglycidyl isocyanurate
Acrylates of glycidyl ethers such as salts; and
Melamine acrylate and / or the above acrylates
And methacrylates corresponding to On the other hand, as the organic solvent, methyl ethyl ketone is used.
And ketones such as cyclohexanone; toluene,
Aromatic hydrocarbons such as silene and tetramethylbenzene
: Methyl cellosolve, butyl cellosolve, methyl carb
Bitol, butyl carbitol, propylene glycol
Monomethyl ether, dipropylene glycol monoethyl
Ruether, triethylene glycol monoethyl ether
Glycol ethers such as ethyl acetate;
Acetic acid ester of the above glycol ethers
Esters such as ethanol, propanol, and ethyl
Alcohols such as ethylene glycol and propylene glycol
Classes; aliphatic hydrocarbons such as octane and decane;
Ter, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha
Such as petroleum-based solvents, such as the photosensitive prepolymer
(A) good compatibility with the finely divided epoxy compound
Those which do not dissolve (D) are preferred. The diluent (C) as described above may be used alone or
Used as a mixture of two or more, suitable range
Is based on 100 parts by weight of the photosensitive prepolymer (A).
20 to 300 parts by weight, preferably 30 to 200 parts by weight
It is. The purpose of use of the above diluents is
In the case of nomers, dilute the photosensitive prepolymer and apply
A material that enhances photopolymerizability while making it easy to cloth
In the case of an organic solvent, the photosensitive prepolymer is dissolved.
And then apply it as a liquid, then
This is to form a film by drying. Obedience
Depending on the diluent used, a photomask is
Touch or non-contact exposure
A method is used. Next, at least two enes in one molecule are used.
The epoxy compound (D) having a oxy group is the one molecule
Having at least two ethylenically unsaturated bonds therein
It is necessary to disperse finely in the optical prepolymer (A).
Must be solid or semi-solid at room temperature
At the time of kneading, and the photosensitive prepolymer (A)
Insoluble in diluent (C) used and / or photosensitive
Soluble in a range that does not adversely affect the developability and developability
It is. It is preferable to satisfy these conditions
Is TEPIC (triglycidyliso) manufactured by Nissan Chemical Industries, Ltd.
Ciba Geigy, a registered trademark of Cyanurate)
Heterocyclic D such as Araldite PT810
Poxy resin and Yuka Shell Co., Ltd. YX-4000 etc.
It is a bixylenol type epoxy resin. These epoki
Resin has a high melting point (for example, the melting point of TEPIC is 90
~ 125 ° C, about 105 ° C for YX-4000)
Does not dissolve even at the heating temperature during drying (usually 60 to 85 ° C)
It is preferred. In addition, Blemmer D manufactured by NOF Corporation
Diglycidyl phthalate resin such as GT or oiled shell
Biphenol type epoxy such as YL-6056 manufactured by Co., Ltd.
Resin, Tetrag such as ZX-1063 manufactured by Toto Kasei Co., Ltd.
Ricidyl xylenoyl ethane resin etc.CombinedThat
Although it is preferable, the heterocyclic
It is a epoxy resin. The epoxy compound (D) is prepared by a conventional method.
By grinding the epoxy compound and / or
Is a component of another composition such as the photosensitive prepolymer (A).
And disperse and disperse with a kneader such as a roll mill.
Granular, used alone or as a mixture of two or more
Can be. The preferred range of the amount used is the photosensitive
The mixing ratio of the repolymer (A) and the epoxy compound (D) is
50 to 95: 50 to 5 (parts by weight) (photosensitive prepoly
About 5-100 parts by weight per 100 parts by weight of
This), more preferably 60-90: 40-10.
You. If it exceeds 50:50, it is not exposed to light and a developer.
Part is less soluble, while if less than 95: 5, heat resistance is poor.
Various characteristics as a solder resist cannot be obtained. Ma
The particle size (the particle size of the particles dispersed in the composition 2) is 50.
μm or less is suitable, and preferably 30 μm or less. Particle size
Exceeds 50 μm, the coating by screen printing
Cloth impairs the passage of the screen and causes
Holes are likely to occur, and the coating surface
It is not preferable because roughness is easily generated on the surface. The above hardly soluble epoxy compound (D)
Replaced partially, bisphenol A type epoxy resin,
The diluent such as bisphenol F type epoxy resin
(C) contains two or more epoxy groups per molecule
Epoxy compound having photosensitivity and non-exposure with developer
Use within a range that does not cause practical problems in the solubility of
Can be Use of this soluble epoxy compound (S)
The preferred range of the dose is the above-mentioned poorly soluble epoxy compound (D).
D: S = 40-100: 60-0, preferably 6
0 to 100: 40 to 0, more preferably 70 to 10
0:30 to 0, and the photosensitive prepolymer
The compounding ratio to (A) is 75:25 or less, more preferably
More preferably, it is 80:20 or less. Over 75:25
And in the case of an alkali developing type,
Solubility is reduced, and development residue tends to occur.
In the case of the developer development type, the coating film is damaged by the developer,
Crevice is likely to occur and it is difficult to use practically.
The combined use of a soluble epoxy compound allows
Some of the characteristics as a distant, for example, improved plating resistance
The effect is obtained. As the soluble epoxy compound (S),
Is, for example, Epicoat 1009 manufactured by Yuka Shell Co., Ltd.
1031, Epicron N manufactured by Dainippon Ink and Chemicals, Inc.
-3050, N-7050, N-9050, Asahi Kasei Corporation
AER-664, AER-667, AER-6 manufactured by Co., Ltd.
69, YD-012, YD-017, manufactured by Toto Kasei Co., Ltd.
YD-014, YD-020, YD-002, Chiba
IACY XAC-5005, GT-7004, 648
4T, 6099, DER-642 manufactured by Dow Chemical Company
U, DER-673MF, Asahi Denka Kogyo Co., Ltd. EP-5
Bisphenol A type epo such as 400, EP-5900
Xyresin; ST-2004, ST-2 manufactured by Toto Kasei Co., Ltd.
Hydrogenated bisphenol A type epoxy resin such as 007;
YDF-2004 and YDF-2007 manufactured by Tokyo Kasei Co., Ltd.
Which bisphenol F type epoxy resin; Sakamoto Pharmaceutical
SR-BBS, SR-TBA-400, Asahi Denka
Industrial Co., Ltd. EP-62, EP-66, Asahi Kasei Corporation
AER-755, AER-765, Toto Kasei
Bromination of YDB-600, YDB-715, etc. manufactured by Co., Ltd.
Bisphenol A type epoxy resin; E manufactured by Nippon Kayaku Co., Ltd.
PPN-201, EOCN-103, EOCN-102
0, EOCN-1025, BREN, Asahi Kasei Corporation
ECN-278, ECN-292, ECN-299,
ECN-1273, ECN-129 manufactured by Ciba Geigy
9. YDCN-220L, YDCN- manufactured by Toto Kasei Co., Ltd.
220HH, YDCN-702, YDCN-704, Y
DPN-601, YDPN-602, Dainippon Ink and Chemicals
Industrial Co., Ltd. Epicron-673, N-680, N-6
Novolak type epo such as 95, N-770, N-775
Xylene resin; EPX-8001, EP manufactured by Asahi Denka Kogyo Co., Ltd.
X-8002, EPPX-8060, EPPX-806
1. Epicron N-88 manufactured by Dainippon Ink and Chemicals, Inc.
Novolak type epoxy tree of bisphenol A such as 0
Fat; EPX-49-60, EPX- manufactured by Asahi Denka Kogyo Co., Ltd.
Chelate type epoxy resin such as 49-30; Toto Kasei
Glyoxal type epoki such as YDG-414 manufactured by Co., Ltd.
Resin; YH-1402, ST-11 manufactured by Toto Kasei Co., Ltd.
0, YL-931 and YL-933 manufactured by Yuka Shell Co., Ltd.
Which amino group-containing epoxy resin; Dainippon Ink and Chemicals
Epicron TSR-601 manufactured by Asahi Denka Kogyo Co., Ltd.
Rubber modification of EPX-84-2, EPX-4061, etc.
Epoxy resin: DCE-400 manufactured by Sanyo Kokusaku Pulp Co., Ltd.
Dicyclopentadiene phenolic epoxy tree
Fat; silicone such as X-1359 manufactured by Asahi Denka Kogyo Co., Ltd.
Modified epoxy resin; Praxe manufactured by Daicel Chemical Industries, Ltd.
Ε-caprolactone modification such as G-402, G-710
Epoxy resin and the like. In addition, these
By (meth) acrylic acid of oxy compounds (D and S)
Partially esterified compounds can also be used. The photosensitive thermosetting resin composition thus obtained
The product contains hydroxyl groups and / or hydroxyl groups in the photosensitive prepolymer (A).
Or a photosensitive prepolymer containing a carboxyl group
The hydroxyl group and / or carboxyl group in (A) is epoxy
Since it works as a hardener for resin, it is harder for epoxy resin.
Sufficient as a solder resist without using an agent
To work. In addition, as the photopolymerization initiator (B),
Amino group-containing photopolymerization initiator used to improve the
When an initiator and a photosensitizer are included, a photopolymerization initiator and a photosensitizer
Due to the effect of amino groups in the agent, the epoxy compound
The curing of (D) is further promoted. However, close contact
Properties such as resistance, chemical resistance, heat resistance, and electroless plating resistance
For the purpose of further raising, the following epoxy tree
It is preferable to use a curing agent for fat (E) in combination. Such a curing agent for epoxy resin or
As the curing accelerator (E), for example, dicyandiamine
De, melamine, acetoguanamine, benzoguanami
3,9-bis [2- (3,5-diamino-2,4,
6-triazaphenyl) ethyl] 2,4,8,10 tet
Guanamines such as laoxaspiro [5,5] undecane and the like
And their derivatives, and their organic acid salts and epoxy adducts
And the like can be suitably used. These compounds
Has been known to have adhesion to copper and rust prevention.
Not only works as a curing agent for epoxy resin
And contribute to the prevention of discoloration of copper on printed wiring boards.
Wear. In addition, 2MZ, 2E4M manufactured by Shikoku Chemical Industry Co., Ltd.
Z, C₁₁Z, C₁₇Z, 2PZ, 1B2MZ, 2MZ-C
N, 2E4MZ-CN, C₁₁Z-CN, 2PZ-CN,
2PHZ-CN, 2MZ-CNS, 2E4MZ-CN
S, 2PZ-CNS, 2MZ-AZINE, 2E4MZ
-AZINE, C₁₁Z-AZINE, 2MA-OK, 2
Imidazo such as P4MHZ, 2PHZ, 2P4BHZ
Derivative; diaminodiphenylmethane, m-phenylene
Diamine, diaminodiphenyl sulfone, cyclohex
Silamine, m-xylylenediamine, 4,4'-dia
Mino-3,3'-diethyldiphenylmethane, diethyl
Triamine, tetraethylenepentamine, N-amino
Ethyl piperazine, isophorone diamine, urea, urea derivative
Conductors, polyamines such as polybasic hydrazides, etc.
Organic acid salts and / or epoxy adducts; boron trifluoride
Amine complex; trimethylamine, triethanolamine
, N, N-dimethyloctylamine, N, N-dimethyl
Luaniline, N-benzyldimethylamine, pyridine,
N-methylpyridine, N-methylmorpholine, hexame
Toximethylmelamine, 2,4,6-tris (dimethyl
Aminophenol), N-cyclohexyldimethylami
, Tetramethylguanidine, m-aminophenol
Any tertiary amines; polyvinylphenol, polyvinyl
Phenol bromide, phenol novolak, alkyl
Polyphenols such as phenol novolak; Trib
Tylphosphine, triphenylphosphine, tris-2
Organic phosphines such as cyanoethylphosphine;
L-n-butyl (2,5-dihydroxyphenyl) phos
Honium bromide, hexadecyltributylphosphoni
Phosphonium salts such as um chloride; benzyltri
Methyl ammonium chloride, phenyl tributyl butyl
Ammonium chloride, benzyltrimethylammonium
Quaternary ammonium salts such as mubromide; the above polybasic acids
Anhydride; diphenyliodonium tetrafluorovolley
G, triphenylsulfonium hexafluoroantimo
Nate, 2,4,6-triphenylthiopyrylium hex
Safluorophosphate, Irgaki manufactured by Ciba Geigy
Photopolymerization catalyst such as urea 261; styrene-male
For example, a known and commonly used curing is used.
Agents and curing accelerators with one or more of the above compounds
They can be used in combination. Hardness for these epoxy resins
The amount of the agent (E) to be used in the usual quantitative ratio is sufficient.
For example, for the photosensitive thermosetting resin composition according to the present invention
The content is preferably from 0.1% by weight to 10% by weight. The above-mentioned thermosetting component is prepared in advance.
Although it may be mixed with the photosensitive resin composition, a circuit board
Since it tends to thicken before application to ink, follow normal usage.
In use, it is desirable to use a mixture of the two.
That is, curing mainly using the epoxy compound (D)
Agent solution and the photosensitive prepolymer (A) as a main component,
A main composition obtained by mixing the curing agent for epoxy resin (E) and the like with this.
Composition into a two-part formulation, and mix these before use.
It is preferable to use them. In addition, the above-mentioned photopolymerizable material
Mer and fillers, coloring pigments and the like as the thermosetting component
Mixing with epoxy solvent (D) in organic solvent
it can. Further, the photosensitive thermosetting resin composition of the present invention
In order to improve properties such as adhesion and hardness,
According to barium sulfate, barium titanate, silicon oxide
Powder, finely divided silicon oxide, amorphous silica, talc,
ー, magnesium carbonate, calcium carbonate, aluminum oxide
, Aluminum hydroxide, mica powder, etc.
Filler can be compounded, and the compounding ratio is
0 to 60% by weight of the fat composition, preferably 5 to 40%
% By weight. If necessary, add phthalocyanine
Lou, Phthalocyanine Green, Iosin Glee
, Disazo yellow, crystal violet, oxidation
Titanium, carbon black, naphthalene black, etc.
Known and common coloring agents, hydroquinone, hydroquinone
Nomethyl ether, tert-butyl catechol, pyro
Known and common thermal polymerization such as gallol and phenothiazine is prohibited
Agent, asbestos, orben (organo bentonite),
Benton, known and conventional thickeners such as montmorillonite,
Defoamers such as silicone-based, fluorine-based, and polymer-based defoamers and / or
Or leveling agents, imidazoles, thiazoles,
Providing adhesion of lyazole, silane coupling agent, etc.
Known and commonly used additives such as
You. Another object is to improve the impact resistance of the cured coating film.
With ethylenically unsaturated compounds such as acrylates
And polyhydric alcohols with saturated or unsaturated
Polyester resins synthesized from saturated polybasic acid compounds
Known and commonly used binder resins such as, and polyhydric alcohols
And saturated or unsaturated polybasic acid compounds and glycidyl
Polyester synthesized from (meth) acrylate
TA) Acrylates, polyhydric alcohols and diisocyanates
Synthesized from nates and hydroxyl group-containing (meth) acrylates
Known and commonly used urethane (meth) acrylates
Of various photosensitive oligomers as solder masks
It can be used within a range that does not affect the operation. However, above
Of the above components, ethylenically unsaturated
Publicly available copolymers of saturated compounds and polyester resins
For the commonly used binder resin, the photosensitive thermosetting
Use epoxy resin soluble in organic solvent in conductive resin composition
As in the case where the
A commonly used binder resin is a photosensitive prepolymer (A).
It is presumed that it melts in a entangled state, and the amount used is large
Causes problems such as poor developability and sensitivity.
The amount is 10% by weight or less based on the photosensitive prepolymer (A).
(Less than about 5% by weight of the total composition). The photosensitive thermosetting resin composition is prepared by photo
Solder resist pattern after exposure through mask
As a developer for forming, a photosensitive prepolymer
Depending on the choice of (A), organic solvents include
Rohexanone, xylene, tetramethylbenzene, butyric
Lucerosolve, butyl carbitol, propylene glyco
Monomethyl ether, cellosolve acetate, pro
Panol, propylene glycol, trichloroethane,
Trichlorethylene, modified trichloroethane (Asahi Kasei Corporation
IR Co., Ltd., Toa Gosei Chemical Industry Co., Ltd.
Re-one EX-R, Kanto Denka Kogyo Co., Ltd.
Ethan SR-A, Resisolve V-5 manufactured by Asahi Glass Co., Ltd.
Any organic solvent and / or potassium hydroxide, sodium hydroxide
Lium, sodium carbonate, potassium carbonate, sodium phosphate
, Sodium silicate, ammonia, amines, etc.
Uses alkaline aqueous solution and / or surfactant aqueous solution
it can. [0036] The present invention will be described below with reference to production examples, examples and comparative examples.
The present invention will be specifically described.
Needless to say, the present invention is not limited to this. In addition,
In the following, “parts” and “%” refer to
All are by weight unless otherwise noted. Production Example-1 Cresol novolak type epoxy with an epoxy equivalent of 218
Resin (YDCN-702 manufactured by Toto Kasei Co., Ltd.) 1090
Part into a three-necked flask with stirrer and condenser,
Heat and melt at 90-100 ° C and stir. Then acrylic
396 parts of acid, 0.6 part of hydroquinone and benzyl dimethyl
7.0 parts of ruamine were added. Then the mixture is
Raise the temperature to 5 ° C, stir and react for 12 hours.
After being taken out and cooled to room temperature, the acid value was 4.5 mgK.
For OH / g novolak type epoxy compound acrylic acid
All esterified compounds (CE)was gotten. The product is semi-solid
It was of a shape. Production Example-2 Except that acrylic acid was 250 parts and the reaction time was 7 hours
Was reacted in the same manner as in Production Example 1 to obtain an acid.
Novolak type epoxy compound having a value of 0.5 mg KOH / g
Esterified product of acrylic acid with acrylic acid (PE) Got
Was. The product was solid. Production Example-3 Total esterified product obtained in Production Example-1 (CE) 450 copies
125 parts of cellosolve acetate and 125 parts of ipso
# 150 (a petroleum solvent mainly composed of tetramethylbenzene:
Idemitsu Petrochemical Co., Ltd.) and the same reactor as in Production Example-1
And heat to 70-80 ° C to dissolve. Then phthalic acid
120 parts of anhydride were mixed, and the temperature was raised to 95 to 100 ° C.
Stir and react for hours, remove from reactor, cool to room temperature
When the solid component had an acid value of 85 mgKOH / g,
Total Esthetic Treatment of Volak Epoxy Compounds with Acrylic Acid
An acid anhydride adduct of a chloride (a-1) Organic solvent solution
Was done. Production Example-4 87 parts of tolylene diisocyanate (2, 4-position 65%,
35% mixture of 2,6 positions) and 50 parts of carbitol acetate
Tate and 50 parts of Ipsol # 150 as in Production Example-1
And stirred under heating at 25 ° C. Then 65
Parts of 2-hydroxyethyl acrylate and 50 parts of cello
Solve acetate and 50 parts of ipsol # 150 and 0.1 part.
05 parts of phenothiazine and 0.2 parts of dibutyltindi
Adjust the laurate mixture not to exceed 35 ° C.
Add dropwise over 2 hours. Next, raise the temperature to 50 ° C, 4 o'clock
The mixture is stirred and reacted for a half urethane compound with terminal acrylic group
I got Next, the partial ester compound obtained in Production Example-2
(PE) 250 parts was mixed, the temperature was raised to 80 ° C, and the mixture was stirred for 6 hours.
After stirring and reacting, cool to room temperature and remove from the reactor
And the novolak-type epoxy compound
Urethane acrylate adduct of a partially esterified product (a-
4) Was obtained in an organic solvent solution. In addition, the above Production Example-3
The products prepared in steps 4 and 4 were all converted to organic solvent solutions.
Obtained when the organic solvent is removed by drying.
Becomes solid. Embodiment-1   The resin obtained in Production Example-3 (a-1) 45.0 parts   "Daiso Dup" (manufactured by Osaka Soda Co., Ltd.   5.0 parts of diallyl phthalate prepolymer   Cellosolve Acetate 5.0 parts   Trimethylolpropane triacrylate 4.0 parts   Diethylene glycol diacrylate 3.0 parts   2-methyl-1- [4- (methylthio) phenyl]       -2-morpholino-propan-1-one 3.0 parts   2,4-diisopropylthioxanthone 2.5 parts   Clay 11.0 parts   5.0 parts of fine talc   Phthalocyanine green 0.5 parts   "Modaflow" (Leveling agent manufactured by Monsanto) 1.0 part   Fine YY-4000 (manufactured by Yuka Shell Co., Ltd.)       (Bixylenol type epoxy resin) 12.0 parts   Dicyandiamide 2.0 parts   "2E4MZ-CNS" (Curing agent manufactured by Shikoku Chemical Industry Co., Ltd.) 1.0 part   Total 100.0 copies After pre-mixing the above ingredients, kneading twice with a three-roll mill
Then, a photosensitive thermosetting resin composition was prepared. Next, Toyosei
The particle size was measured with a grind meter manufactured by Koki Co., Ltd.
It was 5 μm or less. This photosensitive thermosetting resin composition is
Copper through hole printed wiring board by screen printing method
And put it in a hot air circulation furnace at 70 ° C for 20 minutes
After drying, it was cooled to room temperature to obtain a dried coating film. Next,
Bring the photomask with the turn into contact with the coating surface and
Exposure using an ultra-high pressure mercury lamp exposure system manufactured by RK Manufacturing Co., Ltd.
did. Next, a 1% aqueous solution of sodium carbonate is used as a developer,
2.0kg / cm^Two Develop with spray pressure, wash and dry
Was. Next, it is placed in a hot air circulation furnace heated to 150 ° C for 30 minutes.
Post cure to form a solder resist pattern
Was. Example 2   Resin obtained in Production Example-4 (a-4) 35.0 parts   Carbitol acetate 10.0 parts   Dipentaerythritol hexaacrylate 3.0 parts   Diethylene glycol diacrylate 3.0 parts   Benzyl dimethyl ketal 3.0 parts   N, N-dimethylaminoacetophenone 1.5 parts   Barium sulfate 10.0 parts   Amorphous silica 15.0 parts   Phthalocyanine green 0.5 parts   "AC-300" (Kyoeisha Yushi Co., Ltd. antifoaming agent) 1.5 parts   "EPPN-201" (Novolak type manufactured by Nippon Kayaku Co., Ltd.)       Epoxy resin) 75% cellosolve acetate solution 3.0 parts   Fine-grained “Araldite PT810” (Ciba-Geigy)       Heterocyclic epoxy resin) 12.0 parts   Dicyandiamide 2.0 parts   "2P4MHZ" (Shikoku Chemicals Co., Ltd. curing agent) 0.5 part   Total 100.0 copies After pre-mixing the above ingredients, knead three times with a three-roll mill
Then, a photosensitive thermosetting resin composition was prepared. Next, Toyosei
The particle size was measured with a grind meter manufactured by Koki Co., Ltd.
It was 0 μm or less. This photosensitive thermosetting resin composition is
Copper sulfo with a roll coater manufactured by Pilot Seiko Co., Ltd.
To the entire surface of the printed circuit board and into a hot air circulating furnace.
After drying at 80 ° C for 20 minutes, cool to room temperature
I got Next, apply the photomask with the pattern
Contact with an ultra-high pressure mercury lamp exposure device manufactured by Oak Manufacturing Co., Ltd.
Exposure was performed using a device. Next, modified trichloroethane (Asahi Ka
2.0 k (eterna IR, manufactured by Seiko Kogyo Co., Ltd.)
g / cm^Two And then heated to 150 ° C
Into a hot air circulating furnace, and post-cure for 50 minutes.
A black resist pattern was formed. Embodiment 3   The resin obtained in Production Example-3 (a-1) 35.0 parts   Carbitol acetate 10.0 parts   Pentaerythritol tetraacrylate 7.0 parts   3.0 parts of 2-ethylanthraquinone   "Aerosil # 200" (manufactured by Nippon Aerosil Co., Ltd.)       1.5 parts of finely divided silicon oxide   3.0 parts of fine talc   Silicon oxide powder 20.0 parts   Phthalocyanine green 0.5 parts   "Modaflow" 1.5 parts   "Epicoat 1009" (Bisphenol manufactured by Yuka Shell Co., Ltd.)       A type epoxy resin) 75% cellosolve acetate solution 5.0 parts   Fine-grained “TEPIC” (Heterocyclic manufactured by Nissan Chemical Co., Ltd.)       Epoxy resin) 10.0 parts   "Resin M" (polyvinyl phenol manufactured by Cosmo Oil Co., Ltd.) 2.0 parts   Melamine 0.5 parts   "2PHZ" (Curing agent manufactured by Shikoku Chemical Industry Co., Ltd.) 1.0 part   Total 100.0 copies Photosensitive thermosetting of the above ingredients in the same manner as in Example-2
When a resin composition was prepared and the particle size was measured,
m or less. Using this photosensitive thermosetting resin composition
In the same manner as in Example-1.
Formed. Comparative Example-1   Resin obtained in Production Example-1 (CE40.0 parts   Cellosolve acetate 22.0 parts   Pentaerythritol tetraacrylate 7.0 parts   2.0 parts of 2-ethylanthraquinone   1-chlorothioxanthone 2.5 parts   Fine talc 10.0 parts   Barium sulfate 15.0 parts   Phthalocyanine green 0.5 parts   "AC-300" 1.0 parts   Total 100.0 copies Except that the above components were changed as a comparative composition
Prepares a photosensitive resin composition in the same manner as in Example-1
Performed except that post-cure by heating was not performed
A solder resist pattern was formed in the same manner as in Example-2.
Formed. Comparative Example-2   The resin obtained in Production Example-3 (a-142.0 copies   Trimethylolpropane triacrylate 6.0 parts   Butyl cellosolve 4.0 parts   3.5 parts of benzyldimethyl ketal   1.5 parts of 2-ethylanthraquinone   Barium sulfate 12.0 parts   8.0 parts of fine talc   Phthalocyanine green 0.5 parts   "Modaflow" 1.5 parts   "YDCN-702" (Novolak type manufactured by Toto Kasei Co., Ltd.)       18.0 parts of a 75% butyl cellosolve solution of an epoxy resin)   Dicyandiamide 2.0 parts   "2PZ-CNS" (curing agent manufactured by Shikoku Chemical Industry Co., Ltd.) 1.0 part   Total 100.0 copies Except that the above components were changed as a comparative composition
Is a photosensitive thermosetting resin prepared by the same method as in Example-1.
A curable resin composition was prepared. This photosensitive thermosetting resin set
Copper is rolled using a roll coater manufactured by Pilot Seiko Co., Ltd.
Apply to the entire surface of through-hole printed wiring board and circulate hot air
Place in oven, dry at 70 ° C for 20 minutes, then cool to room temperature
Then, a dried coating film was obtained. Then, the same method as in Example-1
To form a solder resist pattern. Comparative Example-3   Resin obtained in Production Example-4 (a-440.0 parts   Cellosolve Acetate 5.0 parts   Dipentaerythritol hexaacrylate 4.0 parts   Diethylene glycol diacrylate 3.0 parts   Benzyl dimethyl ketal 3.0 parts   2- (dimethylamino) ethyl benzoate 2.0 parts   Fine talc 11.0 parts   Clay 12.0 parts   Phthalocyanine green 0.5 parts   "Modaflow" 1.5 parts   "Epicoat 1007" (Bisphenol manufactured by Yuka Shell Co., Ltd.)       15.0 parts of a 75% cellosolve acetate solution of type A epoxy resin)   Diaminodiphenyl sulfone 2.0 parts   "2MZ-AZIN" (Curing agent manufactured by Shikoku Chemicals Co., Ltd.) 1.0 part   Total 100.0 copies Except that the above components were changed as a comparative composition
Is a photosensitive thermosetting resin prepared by the same method as in Example-1.
A curable resin composition is prepared, and the photosensitive thermosetting resin composition is prepared.
Using the same method as in Example-2.
A strike pattern was formed. In the above Examples 1-3 and Comparative Examples 1-3
Resist resin composition and solder obtained by heating
Table 1 shows the results of testing various characteristics of the resist pattern.
Shown in In addition, the test method of each performance and the evaluation
The settings are as follows. 1) Photosensitivity test Oak Manufacturing Co., Ltd.
500 mJ / cm using an integrating photometer manufactured by^Two , 75
0mJ / cm^Two Or 1000 mJ / cm^Two Irradiate it
2 kg / cm with each developer^Two 60 seconds at a spray pressure of
The state of the coating film after the development was visually judged. ：: No change is observed ：: slightly changed surface Δ: The surface is significantly changed ×: The coating film has fallen off 2) Developability test UV light of 365nm wavelength through each photomask
Using an integrated light meter manufactured by Oak Manufacturing Co., Ltd.
750mJ / cm^Two The irradiated thing is used as a test piece,
2 kg / cm for each developer^Two 20 spray pressure
Removal of unexposed areas after developing for 40 seconds, 40 seconds or 60 seconds
The removed state was visually determined. ：: Completely developed ：: The surface has a part that is not developed thinly Δ: Residual development remains ×: hardly developed 3) Adhesion test Irradiation of ultraviolet light with a photomask wavelength of 365 nm
The light amount was measured using an integrating light meter manufactured by Oak Manufacturing Co., Ltd.
mJ / cm^Two Irradiate each developer with 2k
g / cm^Two After developing for 60 seconds at a spray pressure of
What was post-cured under various conditions was used as a test piece,
In a grid pattern according to the test method of JIS D0202.
Put the loss cut, then peel with cellophane tape
The state of peeling after the aging test was visually determined. ◎: 100/100 with no peeling ：: The cross-cut part was slightly peeled off at 100/100 Δ: 50/100 to 90/100 ×: 0/100 to 50 to 100 4) Pencil hardness test The same test pieces as in the adhesion test were used in accordance with JIS K
  Measure hardness with 1kg load according to 5400 test method
Specified. 5) Acid resistance test 10% by volume of the same test pieces as in the adhesion test
After immersion in a sulfuric acid aqueous solution at 20 ° C for 30 minutes, take out and apply
The state and the adhesion were comprehensively evaluated. ：: No change is observed ○: only slightly changed △: markedly changed ×: The coating film has blisters or swelling and falling off 6) Alkali resistance test 10% by volume sulfuric acid aqueous solution to 10% by weight sodium hydroxide aqueous solution
The test was evaluated in the same manner as in the acid resistance test except that the solution was changed. 7) Solvent resistance test Acid resistance except that 10% by volume sulfuric acid aqueous solution was changed to acetone
The test was evaluated in the same manner as the sex test. 8) Plating resistance test The same test pieces as in the adhesion test
Next CI "(gold plating solution manufactured by Celllex, USA)
1A / dm at a liquid temperature of 30 ° C^Two 9 minutes depending on the current density of
After depositing gold with a thickness of 1.5 μm by plating
Was evaluated in the same manner as in the acid resistance test. 9) Solder resistance test The same test pieces as in the adhesion test were used according to JIS C
  According to the test method of No. 6481, the solder bath at 260 ° C.
State of the coating film after immersion once, three or five times for 10 seconds
The condition was evaluated in the same manner as in the acid resistance test. 10) Insulation resistance Using the comb test pattern B of IPC-B-25,
Create test pieces under the same conditions as the adhesion test
And according to the test method of IPC-SM-840B,
Resistance and temperature cycle of 25-65 ° C, relative humidity
90%, 100V DC applied, 7 days insulation
The resistance was measured. 11) Pot life When stored at 20 ° C, the viscosity value immediately after production doubles
The number of days until was measured. [0059] [Table 1]As is clear from the results shown in Table 1 above, each example of the present invention
The photosensitive thermosetting resin composition obtained in the examples was
Excellent light and developability, and obtained solder resist
The pattern has adhesion, hardness, acid resistance, alkali resistance, and melting resistance
Excellent properties such as chemical properties and gold plating resistance. Against this
Therefore, unlike the comparative example 1, the thermosetting component was not blended.
If post cure is not performed, adhesion and chemical resistance
Required as solder resist, such as resistance and plating resistance
Poor properties. In addition, epoxy as a thermosetting component
Even when post-curing is performed by mixing resin, comparative example
Use only solvent-soluble epoxy resin like 2 and 3
Is poor in the case of alkali development (Comparative Example
2) In the case of solvent development, poor photosensitivity was obtained.
(Comparative Example 3). [0060] As described above, the photosensitive thermosetting resin according to the present invention is
The curable resin composition contains a hardly soluble epoxy compound in a diluent.
By using it dispersed in fine particles, it has excellent developability,
In addition, it has resistance to the developer in the exposed area and
It has a long tri-life, and has excellent photosensitivity and high sensitivity. Obedience
Thus, using such a photosensitive thermosetting resin composition,
Exposure, development and post cure
, Adhesion, electrical insulation, corrosion resistance, solder heat resistance,
Solvent resistance, alkali resistance, acid resistance and electrolytic gold, electroless gold,
Excellent resistance to plating such as electroless copper
A rudder resist pattern can be formed.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location G03F 7/032 501 G03F 7/032 501 (72) Inventor Morio Suzuki Ooyama, Arashiyama-cho, Hiki-gun, Saitama 388 Otani Taiyo Ink Manufacturing Co., Ltd.Arashiyama Plant (72) Inventor Shoji Inagaki 388 Otani Okura, Arashiyama-cho, Hiki-gun, Saitama Prefecture Taiyo Ink Manufacturing Co., Ltd.Arashiyama Plant (56) References JP 63-289014 (JP, A) JP-A-61-243869 (JP, A)

Claims (1)

(57) [Claims] (A) having at least two ethylenically unsaturated bonds in one molecule, and one of the following (a-1) to (a- 4 )
Or more of one or more of the photosensitive prepolymer selected from the group, (a-1) second epoxy compound and the total esterification of epoxy groups formed by the esterification reaction of an unsaturated monocarboxylic acid (A- 2 ) a reaction product of a dihydroxy isocyanate and a (meth) acrylate having one hydroxyl group in one molecule,
Esterification of epoxy compounds with unsaturated monocarboxylic acids
The reaction product obtained by reacting a secondary hydroxyl group of the total esterification of epoxy groups formed by the reaction of epoxy groups by esterification reaction with (a- 3) an epoxy compound and an unsaturated monocarboxylic acid reaction products of secondary hydroxyl group of the partially esterified product with a saturated or unsaturated polybasic acid anhydride, and (a- 4) of the diisocyanates and one having a hydroxyl group (meth) acrylates in a molecule A reaction product;
Esterification of epoxy compounds with unsaturated monocarboxylic acids
The reaction product obtained by reacting a <br/> secondary hydroxyl group of the partially esterified product of the epoxy group produced by the reaction, (B) a photopolymerization initiator, (C) a photopolymerizable vinyl type as a diluent Monomer and / or
Or an organic solvent; (D) having at least two epoxy groups in one molecule,
And (E) dicyandiamide, melamine, guanamine and derivatives thereof, including a heterocyclic epoxy resin and / or a bixylenol type epoxy resin which are hardly soluble in the diluent to be used. A photosensitive thermosetting resin composition comprising at least one type of epoxy resin curing agent containing a compound selected from the group consisting of these organic acid salts and epoxy adducts. 2. The composition according to claim 1, wherein the epoxy compound used for synthesizing the photosensitive prepolymer (A) is a novolak type epoxy compound. 3. The epoxy compound used for the synthesis of the photosensitive prepolymer (A) is a novolak type epoxy compound, a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a hydrogenated bisphenol A type epoxy compound, a brominated bisphenol A type epoxy compound. The composition according to claim 1, wherein the composition is a mixture with at least one epoxy compound selected from the group consisting of an amino group-containing epoxy compound, an alicyclic epoxy compound and a glycidyl ether type epoxy compound. 4. 4. The composition according to claim 2, wherein the novolak epoxy compound is a cresol novolak epoxy compound or a phenol novolak epoxy compound. 5. Used for the synthesis of the photosensitive prepolymer (A)
Those wherein the total esterification product or partially esterified compound is, for an epoxy compound and an unsaturated monocarboxylic acid, the number of equivalents of equivalent number / carboxyl group of the epoxy groups is reacted at a ratio of 0.8 to 3.3 The composition according to any one of claims 1 to 4, which is: 6. Used for the synthesis of the photosensitive prepolymer (A)
The total esterified product is obtained by reacting an epoxy compound with an unsaturated monocarboxylic acid at a ratio of the number of equivalents of epoxy group / the number of equivalents of carboxyl group of 0.9 to 1.1. A composition according to any one of the preceding claims. 7. (A -1) of the photosensitive prepolymer (A ) or
(A-3) is the total esterification product or partially esterified
Product and the saturated or unsaturated polybasic acid anhydride, the equivalent number of the acid anhydride to the equivalent number of the secondary hydroxyl group of the total esterified product or partial esterified product is reacted at a ratio of 0.3 or more. The resulting resin has an acid value of 30 to 160 mgK
The composition according to any one of claims 1 to 6, wherein the composition is in the range of OH / g and the residual ratio of epoxy groups is 20% or less. 8. (A -2) of the photosensitive prepolymer (A ) or
(A-4) is a diisocyanate compound and the total esterification was one having a hydroxyl group and (meth) acrylates are reacted in approximately equimolar ratio with half urethane (meth) acrylate obtained in the molecule also ones in which the partial esterification product,該全esterified or partially esterified equivalent number of half-urethane (meth) acrylate isocyanate to the number of equivalents of secondary hydroxyl groups in product is obtained by reacting at a ratio of more than 0.1 The composition according to any one of claims 1 to 6, wherein 9. The photosensitive prepolymer (A) reacts a novolak-type epoxy compound with acrylic acid and / or methacrylic acid at a ratio of the number of equivalents of epoxy group / the number of equivalents of carboxyl group of 0.9 to 1.1. The obtained total esterified product is further obtained by reacting a saturated or unsaturated polybasic acid anhydride with a ratio of the equivalent number of the acid anhydride to the equivalent number of the secondary hydroxyl group of the total esterified product of 0.3 or more. The composition according to any one of claims 1 to 6, which is a reaction product obtained. 10. The mixing ratio of the photopolymerization initiator (B) is 0.2 to 30 per 100 parts by weight of the photosensitive prepolymer (A).
Parts by weight, the mixing ratio of the diluent (C) is 20 to 300 parts by weight, and the mixing ratio of the epoxy compound (D) is 5 to 10 parts.
The composition according to any one of claims 1 to 9, wherein 0 parts by weight and a mixing ratio of the curing agent (E) for an epoxy resin are 10 parts by weight or less.