JPS62160440A - Liquid photosensitive resin composition - Google Patents

Abstract

PURPOSE:To obtain superior alkali developability by using specified amounts of a linear acrylic polymer and/or a linear methacrylic polymer, a liq. monomer, a monomer and/or an oligomer and a photopolymn. initiator and/or a photosensitizer as essential components. CONSTITUTION:This liq. photosensitive resin composition contains 3-20wt% linear acrylic polymer and/or linear methacrylic polymer (A) contg. carboxylic groups in the molecule and having 60-180 acid value and >=20,000 number average mol.wt., 10-60wt% liq. acrylic monomer and/or liq. methacrylic monomer (B) contg. one or more ethereal oxygen atoms which do not take part in an ester bond in the molecule and having 4/1-9/1 ratio of the total number of carbon atoms in the molecule to the total number of oxygen atoms which do not take part in an ester bond and/or an amido bond in the molecule, 20-60wt% acrylic monomer and/or methacrylic monomer which does not dissolve the component A and/or oligomer thereof (C) and 0.05-20wt% photopolymn. initiator and/or photosensitizer (D) as essential components. A cross-linkable monomer and/or a cross-linkable oligomer is used as part of the component B and/or the component C by 10-80wt% of the total amount of the composition.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a liquid photosensitive resin composition, and more particularly to a pattern-forming liquid photosensitive resin composition that can be used for solder resists (solder masks) for manufacturing printed wiring boards. The present invention relates to a synthetic resin composition.

[Conventional technology]

Conventionally, solder resists (solder masks) have been widely used in the printed wiring board manufacturing industry as permanent protective coatings for printed wiring boards. Solder resist is used for the purposes of preventing solder bridges during soldering, preventing corrosion of conductor parts during use, and maintaining electrical insulation. As is clear from the purpose of use, solder resists are used under harsh conditions, and therefore, unlike etching resists, etc., they are required to have the following performance.

(a) Retention of adhesion during solder immersion (240 to 280°C) (port 1) Permanent adhesion retention V→ Excellent resistance to solvents, chemicals, etc. (-J High electrical insulation under high humidity conditions) In order to meet these requirements, a method of forming solder resist by screen printing thermosetting ink or photocurable ink has been widely used.However, in recent years, the density of printed wiring has increased. As a result, thick film and highly accurate solder resists are required1, and the current situation is that the screen printing method for forming solder resists is no longer able to meet this demand due to problems with accuracy and thickness.

A method for forming a solder resist using a development method has been proposed as a method to cope with this increase in density. The development method involves coating a printed wiring board with a liquid made of a photosensitive resin composition or laminating a photosensitive film, and then hardening the necessary parts with actinic rays through the artwork, etc., and then removing the uncured parts. This is a method of forming a pattern by washing it away at a temperature using a developing solution, and by using this method, it is possible to form a thick solder resist pattern with high precision.

Solder resists for development methods are considered to be of dry film type, solvent volatilization type, or solvent-free liquid type, depending on the method of forming the coating before curing. Among these, for example, the dry film type proposed in JP-A No. 54-1018 requires the use of JP-A No. 52-1018 in order to adhere tightly to the uneven surface on which wiring has already been formed.
As proposed in Publication No. 52703, it requires a special process such as heat-compression bonding under reduced pressure, and furthermore, even if such a process is used, complete adhesion cannot be guaranteed. . On the other hand, although the solvent volatilization type proposed in JP-A-51-15733 has excellent adhesion to uneven surfaces on which wiring is formed,
This method has a problem in that it requires a step of volatilizing the solvent using an explosion-proof dryer after coating the liquid photosensitive resin. Therefore, it is strongly desired to develop a solvent-free liquid type photosensitive resin composition for solder resists.

On the other hand, when liquid photosensitive resins are classified according to the type of developer, there are two types: a type that uses an organic solvent such as 1,1.1-)lichloroethane, and a type that uses a dilute alkaline aqueous solution.

However, the type that uses an organic solvent has problems in the working environment and treatment of waste liquid, and development using a dilute alkaline aqueous solution is strongly desired.

[Problem that the invention seeks to solve]

An object of the present invention is to provide a liquid photosensitive resin composition that has excellent alkaline developability and excellent electrical insulation properties under high humidity conditions after curing.

[Means for solving problems]

The gist of the present invention is (g) having a carboxyl group in the molecule and having an acid value of 60 to 18.
0, 3 to 20% by weight of an acrylic and/or methacrylic linear polymer with a number average molecular weight of 2,000 or more, (Bl having one or more etheric oxygen atoms that do not participate in ester bonds in the molecule, and The ratio (n,
/,! 10 to 60% by weight of an acrylic and/or methacrylic liquid monomer having a ratio of ') of '/1 to 9/1; (C) an acrylic and/or methacrylic liquid monomer that does not substantially dissolve the linear polymer (A) component; /or methacrylic monomer and/or oligomer 20 to 60% by weight, and (Dl photoinitiator and/or photosensitizer 0.05 to 20% by weight)
% by weight as an essential component, and the above (Bl component and/or (C1
Among the components, a liquid photosensitive resin composition is characterized in that a crosslinking monomer and/or oligomer is contained in an amount of 10 to 80% by weight based on the total weight of the composition.

The liquid photosensitive resin composition of the present invention is an acrylic and/or methacrylic linear polymer (AJ3 to
Contains 20% by weight.

By having a carboxyl group, this polymer matrix imparts alkaline developability to the composition, improves the adhesion of the cured coating film to metal surfaces, and further improves the adhesion of the cured coating film to metal surfaces. It can impart toughness.

The amount of carboxyl groups in the linear polymer and the Sunawachi acid value are important in constructing the desired composition. If the amount of carboxyl groups is too small, the developability of the composition will deteriorate and at the same time the adhesion to metal surfaces will decrease. On the other hand, if the amount of carboxyl groups is too large, it becomes difficult to uniformly dissolve the acrylic and/or methacrylic monomer mixture of the (Bl component and (C1 component), and furthermore, the hygroscopicity of the cured coating film becomes poor. In view of the above, it is necessary that the carboxyl group-containing linear polymer has an acid value of 60 to 180, and a preferable acid value range is 80 to 180. It is 165.

The linear polymer) plays the role of imparting toughness to the cured coating. For this reason, when a polymer with a low molecular weight is used, sufficient toughness cannot be imparted to the cured coating film. Therefore, the linear polymer needs to have a number average molecular weight of 2,000 or more, and a preferable number average molecular weight is 5,000 or more.

Further, as the linear polymer (A), it is necessary to use an acrylic and/or methacrylic linear polymer from the viewpoint of compatibility with the monomers used together.

Specific examples of the linear polymer include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, Benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-
Alkyl (such as hydroxypropyl/L/(meth)acrylate, tetrahydrofurfuryl (meth)acrylate,
A monomer unit (a) consisting of meth)acrylate and its derivatives, (meth)acrylamide and its derivatives, etc.
), (meth)acrylic acid, itaconic acid, cinnamic acid, maleic acid, maleic acid monoester, fumaric acid, fumaric acid monoester, etc. ethylenically unsaturated carboxylic acid units (bl
l, optionally a linear polymer (up to 50% by weight of other vinyl monomer units in N, such as styrene, α-
Examples include copolymers consisting of monomer units (c) such as aromatic vinyl monomers such as methylstyrene; vinyl cyanide monomers such as acrylonitrile; and vinyl esters such as vinyl acetate.

In the present invention, (meth)acrylate refers to acrylate and/or methacrylate, and for example, methyl (meth)acrylate refers to methyl acrylate and/or methyl methacrylate.

The blending amount of the linear polymer (A) in the resin composition of the present invention is:
3 to 20% by weight from the viewpoint of developability, adhesion, electrical insulation, etc., and from the viewpoint of making the photosensitive resin composition of the present invention liquid at room temperature.
, preferably 5 to 15% by weight. If the amount of the linear polymer (linear polymer) is less than 3% by weight, the developability and adhesion will be poor, and if the amount exceeds 20% by weight, the electrical insulation will be deteriorated. The composition may not become liquid.

The liquid photosensitive resin composition of the present invention has one or more etheric oxygen atoms that do not participate in ester bonds in the molecule,
and the ratio (''/,, ) of the total number of carbon atoms in the molecule (n2) to the total number of oxygen atoms not involved in ester bonds and/or amide bonds in the molecule (n2) is 4/l-9/ Acrylic and/or methacrylic liquid monomer (Bl
It is necessary to contain 10 to 60% by weight.

The liquid monomer (B) must have appropriate polarity from the viewpoint of compatibility with the linear polymer (linear polymer) and electrical insulation of the coating film after curing of the resin composition of the present invention. Therefore, a monomer that does not have an ether oxygen atom that does not participate in an ester bond in its molecule is not preferred because it cannot uniformly dissolve the linear polymer.

Further, the ratio (n1/n2) of the total number of carbon atoms in the molecule (n2) to the total number of oxygen atoms (n2) not involved in ester bonds and/or amide bonds in the molecule is 4/, ~9/ If it deviates from the range 1, it is not preferable because the linear polymer (linear polymer) cannot be uniformly dissolved and the cured coating film cannot have excellent electrical insulation properties under high humidity conditions. Furthermore, (meth)acrylic monomers are preferred from the viewpoint of compatibility within the linear polymer and curability with actinic rays.

In addition, from the viewpoint of compatibility with the linear polymer, a Brookfield viscometer (spindle #7, 0 r
The viscosity of the liquid monomer (B) measured in pm) is 1000
It is preferably at most cps, more preferably at most 300 cps.

As a specific example of the liquid monomer (B), Tetrahuman 07A
/7lyl acrylate (''/n, = 8/1), tetrahydrofurfuryl methacrylate-F (ns/1.=
:9//1), methylcarpitol acrylate) (”
t/H*=4/l), methylcarpitol methacrylate (''*/nl = 4.5/l), ethylcarpitol acrylate (s/n, = 4-5/1), ethylcarpitol methacrylate ( ”/n* = 5/1
), methoxycyfropylene glycol acrylate (
n1/n! = 5/X), methoxydipropylene-glyco-1V) tafrylate (n1/n! = 5.5/1), phenoxydiethylene glycol acrylate (n1/n
! = 6.5/1), phenoxydiethylene glycol methacrylate (n1/n! = 7/l), 2-hydroxy-3-phenokidib tetraviral acrylate (nㅅ, = 6/l),
1), 2-hydroxy-3-phenokidipropyl methacrylate (H,/n, ==5.5/1), methoxymethylacrylamide (s/n, =5/1), methoxymethylmethacrylamide (n1 /n!=6/l)
, butoxymethylacrylamide (n weight/n!=871
), butoxymethyl methacrylamide (n1/n!=9
Monofunctional monomer having one polymerizable double bond such as /1); triethylene glycol diacrylate (n1/n!
= 5 /
Tetraethylene glycol dimethacrylate (n1/n
! == 5.3/l) 2) Lipropylene glycol diacrylate (n1/n!=7.5/1), tripropylene glycol dimethacrylate (nl/n!=8・
5/1), heptapropylene glycol diacrylate (nt/n, = 4.Vl), heptapropylene glycol dimethacrylate ("1/nt = 4-9/l)
), which may be used singly or in combination of two or more.

The liquid monomer (B) is used in an amount of 10 to 60% by weight based on the total weight of the liquid photosensitive resin composition. That is, if an amount of less than 10% by weight is used, there is a problem in uniformly dissolving the linear polymer, and conversely, if an amount of more than 60% by weight is used, the hydrophilicity of the composition as a whole becomes poor. Therefore, there is a problem in maintaining high electrical insulation properties of the cured coating film under high humidity conditions. Furthermore, the liquid monomer (B
l is a linear polymer (
It is preferable to use 1.5 to 20 times the weight of A1.

The liquid photosensitive resin composition of the present invention contains 20 to 60% by weight of acrylic and/or methacrylic monomers and/or oligomers (C) that are not substantially dissolved in the linear polymer.
It is necessary to contain The monomer and/or oligomer (C) participates in curing by actinic rays together with the liquid monomer (B), has the role of maintaining high electrical insulation of the cured coating film, and also has the role of a curing agent and/or It also has the role of improving physical properties after curing. This monomer and/or
Alternatively, it is necessary to use an acrylic and/or methacrylic oligomer (C1) from the viewpoint of curability with actinic rays.

In addition, the monomer and/or oligomer (C) has polymerizable 2! Based on the number of bonds, there are two types: monofunctional monomers and/or oligomers and polyfunctional crosslinking monomers and/or oligomers.

Monofunctional monomers and/or oligomers have one monomerizable double bond in their molecules, and are used to improve electrical insulation, adjust viscosity before curing, or improve the coating film after curing. It is used for the purpose of imparting flexibility, and examples thereof include 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, benzyl (meth)acrylate, and cyclohexyl (meth)acrylate.

On the other hand, crosslinking monomers and/or oligomers have two or more polymerizable double bonds in their molecules, and they improve electrical insulation, curing speed, and the coating film after curing. It is used for the purpose of improving the solvent resistance of, for example, hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, hydroxypivalic acid neopentyl glycol ester diacrylate, trimethylolpropane tri(meth)acrylate,
Pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, oligoester(meth)acrylate (e.g. succinic acid/trimethylolethane/acrylic acid (molar ratio 1/2/4) '
) or Aronix [F] M6200°M7100. manufactured by Toagosei Kagaku Kogyo Co., Ltd. M8100 etc.)
, epoxy (meth)acrylate (e.g. Showa Polymer (
Co., Ltd., Lipoxy ■5P4010, Tobu Kasei Co., Ltd.,
Thorad ■3700, etc.), urethane (meth)acrylate (for example, manufactured by Osaka Organic Chemical Industry Co., Ltd., Viscoat ■
$812. $813. $823. $851, etc.).

In the present invention, monomer and/or oligomer (C)
may be any acrylic and/or methacrylic monomer and/or oligomer that does not substantially dissolve Al, but from the viewpoint of electrical insulation under high humidity conditions, More preferred are those that do not contain hydrophilic groups such as hydroxyl groups and carboxyl groups.

These monomers and/or oligomers (C1 are used alone or in combination of two or more types).

The monomer and/or oligomer (C1) is used in an amount of 20 to 60% by weight based on the total weight of the composition in terms of uniform solubility, alkali developability, and electrical insulation. That is,
If the monomer and oligomer (C) content is less than 20% by weight, the electrical insulation properties under high humidity conditions will decrease, and if it exceeds 60% by weight, the homogeneity of the solution will be lost. Or, the alkali developability may deteriorate.

A more preferred amount range of the monomer and/or oligomer (C1) is 25 to 50% by weight.

The liquid photosensitive resin composition of the present invention contains a crosslinking monomer and/or oligomer in a range of 10 to 80% by weight based on the total weight of the composition (Bl component and/or (C) component). It is characterized by being

When a liquid photosensitive resin composition is used as a solder resist, the cured coating film is required to have excellent mechanical strength and chemical resistance. For this reason, the coating film after curing needs to be crosslinked with a crosslinking component and kept at 10°C. The present inventors conducted extensive studies on the proportion of crosslinking components, and as a result,
By using crosslinking monomers and/or oligomers in an amount of 10 to 80% by weight based on the total weight of the composition, various performances as a solder resist, such as mechanical strength, chemical resistance, electrical insulation, flexibility, It has been found that a liquid photosensitive resin composition with excellent adhesion to metal surfaces can be obtained.

In systems where the amount of crosslinking monomer and/or oligomer is less than 10% by weight based on the total weight of the composition,
This is undesirable because the mechanical strength and chemical resistance of the cured coating film deteriorates, and the electrical insulation properties under high humidity conditions decrease. Conversely, the amount of crosslinking monomer and/or oligomer is
If the amount exceeds 80% by weight based on the total amount of the composition, the cured coating will lose its flexibility and its adhesion to metal surfaces will deteriorate, which is not preferable.

A more preferable amount of the crosslinking monomer and/or oligomer to be used is 20 to 70% of the total weight of the composition from the viewpoint of the balance of various physical properties. It is in the range of t%.

The photosensitive resin composition of the present invention contains 0.05 to 20% by weight of a photoinitiator and/or a photosensitizer.

Any photoinitiator and/or photosensitizer may be used as long as it can generate radicals and cause a polymerization reaction when exposed to actinic rays such as ultraviolet rays or visible light. Photoinitiators and/or photosensitizers that can be used include, for example, 2-ethylanthraquinone, 1,4-naphthoquinone, benzoin ethyl ether, penzoin globyl ether, benzophenone, 4,4'-bisdialkylaminobenzophenone, Benzyl dimethyl ketal, 4'-
Representative examples include isopropyl-2-hydroxy-2-methylglobiophenone, 2-hydroxy-2-methylglopiofenone, 2-methyl(A-M'F-ruthio)phenyl-2-morpholino-1-propane, etc. An example is ℃.

These photoinitiators and/or photosensitizers can be used alone or in combination of two or more. It is necessary to add the photoinitiator and/or photosensitizer in an amount of 0.05 to 20% by weight based on the total weight of the composition, and from the viewpoint of curing speed and physical properties of the cured coating film, it is necessary to add the photoinitiator and/or photosensitizer in an amount of 0.1 to 10% by weight based on the total weight of the composition.
It is more preferable to use it within a range of % by weight.

Depending on the purpose, the liquid photosensitive resin composition of the present invention may contain various conventional additives such as thermal polymerization inhibitors, inorganic fillers, thickeners, coloring pigments or dyes, and antifoaming agents. can do.

Thermal polymerization inhibitors are added for the purpose of preventing the photosensitive resin composition from being cured by heat at a stage before photocuring, and include, for example, p-methoxyphenol, human tetraquinone, p-benzoquinone, and t-benzoquinone. -Butylcatechol, pyrogallol, naphthylamine, phenothiazine, etc. can be used. The thermal polymerization inhibitor is preferably used in an amount of 3% by weight or less, more preferably 1% by weight or less based on the weight of the composition, in view of its influence on photocurability.

Inorganic fillers are used for the purpose of improving the adhesion of the coating film after curing. The liquid photosensitive resin composition of the present invention exhibits good adhesion even when no inorganic filler is added, but by adding an inorganic filler, it is possible to further improve the adhesion. As the inorganic filler, those used in general paints or printing inks can be used, and typical examples include talc, mica, calcium carbonate, and the like.

The inorganic filler is preferably used in an amount of 35% by weight or less based on the total amount of the composition from the viewpoint of developability and the like.

Thickeners are used to improve the viscosity, thixotropy, and coating properties of liquid photosensitive resin compositions. Specific examples of the thickener include A@rosLl 4#200.
Examples include silica-based materials such as (manufactured by Nippon Aerosil Co., Ltd.), and modified bentonite-based materials such as Benton* 500 (manufactured by National Red Industry Co., Ltd.). The thickener is used within a range with an upper limit of 20% in view of the physical properties of the cured coating film.

The present invention relates to a liquid composition, and it may have any viscosity as long as it has substantially fluidity at room temperature, but from the viewpoint of handling properties, especially coating properties, Viscosity measured with a field viscometer is 1.000 to 100.000 cp
It is preferable that it is s, more preferably 2,000~
The viscosity range is 80.000 cps.

The liquid photosensitive resin composition of the present invention can be used using various known methods. Most commonly, a cured coating film is formed using a coating, exposure, and alkaline imaging process.

Various known methods can be used as the coating method. For example, applying a liquid photosensitive resin composition using an applicator (e.g. Baker's set applicator, bar coater, etc.),
The "direct coating method" involves applying the liquid photosensitive resin composition directly onto the printed wiring board through a silk screen. "Indirect coating method" in which the liquid photosensitive resin composition is laminated, "double-sided coating method" in which the liquid photosensitive resin composition is applied to both sides of the printed circuit board, transparent film, sheet or artwork, and then the liquid photosensitive resin composition layers are superimposed, etc. Either method can be used.

Various known methods can be used as the exposure method, and for example, the exposure can be carried out using active light such as visible light or ultraviolet light through a photomask.

In this case, the liquid photosensitive resin layer and the photomask may be in direct contact, may be in indirect contact through a transparent film or sheet, or may be separated by a thin gas layer.

Regarding development, various already known methods can be used as a developing method for an alkaline development type photosensitive resin composition.

Furthermore, for the purpose of making the cured coating film more complete, it is also possible to carry out post-treatment using actinic rays and/or heat after alkaline development.

The present invention will be explained in more detail below using Examples.

Evaluation means used in Examples and Comparative Examples are as follows.

■ Adjustment of hardening coating Copper-clad laminate (ELG470 manufactured by Bakelite Co., Ltd.)
8) After cutting into 10aa x 15mm pieces, pretreatment is performed by polishing, washing, and removing moisture. The pretreated copper-clad laminate is coated with a liquid photosensitive resin composition adjusted under various conditions to a thickness of 100 μm using an applicator set of paper sheets. A polyester film having a thickness of 25 μm is coated thereon to obtain a hardening coating.

(Hereinafter, in the present invention, the term "cured coating film" refers to a coating film prepared as described above and covered with a polyester film.) ■Optimum - Measurement of next exposure conditions and developability■-1- Negative film 5TO with a thickness of 120μ is applied on the coating film for subsequent exposure and curing.
OFF'ERRe5solution Guide #
1-T (5TOFFERGraphic Art+
s Equipment Co.

), and then a three-thick Pyrex [F] glass plate. Next, exposure is performed from above using a 100 W high-pressure mercury lamp (Ushio Inc. UH-100). The exposure time is in the range of 10 seconds to 180 seconds.

In addition, the magnitude of the irradiation energy is U manufactured by Tokyo Kogaku Kikai Co., Ltd.
Measured using VR-365.

(2) Development A 25μ polyester film was peeled off from the coating film after the primary exposure, and spray development was carried out under the following conditions.

Developing solution 1% sodium carbonate aqueous solution (A0℃) Nozzle JUPO3 manufactured by Ikeuchi Co., Ltd. (1.5 atm, 2.61/win) 'Distance from nozzle 15α Time 30 seconds After that, wash with running water, remove water with air, 70
Dry at ℃ for 5 minutes.

(2)-3 Post-curing The coated film after development is cured by light and heat under the following conditions, and then allowed to cool to room temperature.

[Curing by light]

5KW high pressure mercury lamp (Mitsubishi Electric Co., Ltd. H-500UVA) Distance: 20cm Passing speed: 0.9m 1 minute [Curing by heat] (after curing by light) 160'CX1
Measurement of 0 min - 4 Optimum - Missing exposure energy = Comparing the coating films carried out by changing the missing exposure time,
The irradiation energy required to obtain a coating that best reproduces the pattern of 5olut1on Gulde is determined.

The unit is mJ/am.

(2)-5 Optimum evaluation of developability - Evaluation is performed by observing the sample surface using a 30x microscope using a non-exposure energy.

○・・・Uncleaned resin components are present in the recesses. Does not remain.

×・・・Uncleaned resin components are present in the recesses. remain.

■ Evaluation of physical properties of cured coating ■-1- A 120μ thick polyester film was placed on the coating for curing with missing exposure, and a 3n thick Pyr@J' glass plate was then exposed to a 100W high-pressure mercury lamp (Ushio Inc.) from above. Exposure was carried out using UH-100 (manufactured by Co., Ltd.) for a time corresponding to the optimum exposure energy determined in step (1)-4.

■-2 Development ■-2 Follow the same procedure as ■-3 Post-curing ■-4 Follow the same procedure as-3 ■-4 After evaluation of heat resistance The coated film after curing is placed in 260"C solder with the board for 20 minutes. Dip for a second, observe the condition after taking it out, and evaluate the temperature.

○... No change ×... Blistering, peeling, cracking, etc. ■-5 After evaluation of adhesion For the coating film after curing, the test method described in JIS-D-0202 was applied. Adhesion is evaluated by a method based on Type 1.

(The size of the stitch is 2 angles) O...The area of the missing part is less than 10% of the total square area ×...The area of the missing part is 10% or more of the total square area ■- 6. After evaluation of solvent resistance The coated film after curing was immersed together with the substrate in trichloroethane at 25° C. for 15 minutes, and then taken out and the state of the coated film was observed and evaluated.

○...No change After storing for 100 hours at 90% condition, 5M-
The volume resistance value of the coating film is measured using a 10E type supermeter.

(soov, value 1 minute after application) [Example 1] Copolymer of methyl methacrylate/methyl acrylate/methacrylic acid (55/20/25 weight ratio) [Sun value 15
39KOH/mu number average molecular weight 52000] 100P,
Tetrahydrofurfuryl acrylate) (”s/II,
= 8/1) After completely dissolving in SOOP, succinic acid/trimethylolethane/acrylic acid (1/2
/4 molar ratio) oligoester acrylate 400p obtained by cocondensation of benzyl dimethyl ketal 407
p-methoxyphenol IP
7 talocyanine green 1t
Talc 30
0 J' (LMSlooo manufactured by Fuji Talc Industries Co., Ltd.) Amorphous silica 60P (
A*ros11 manufactured by Nippon Aerosil Co., Ltd. $200)
were added and mixed and kneaded using three rolls to prepare a liquid photosensitive resin composition Exl. The results of the test according to the method described above are shown in Table 1.

[Example 2] Copolymer of methyl methacrylate/methyl acrylate/methacrylic acid (50/13/17 weight ratio) [acid value 11
01R9KOHh, number average molecular weight 25000] 70P, 2-hydroxy-3-phenoxyprobyl acrylate (n1/n!=672) 400. After completely dissolving in a mixture of P and methoxymethylacrylamide 100P,
Hydroxypivalic acid neopentyl glycol ester diacrylate) 350P dipentaerythritol pentaacrylate 50F benzyl dimethyl ketal 40Pp-methoxyphenol 0.5P phthalocyanine green IP talc 300P
(LMSloo, manufactured by Fuji Talc Industries Co., Ltd.) Amorphous silica 100P (Aerosil $200, manufactured by Nippon Aerosil Co., Ltd.) was added and mixed, and kneaded using three rolls to prepare a liquid photosensitive resin composition Ex2. Table 1 shows the results of the test according to the method described above.

[Example 3] Instead of the linear polymer of Example 10, methyl methacrylate/l-butyl acrylate/acrylic acid (60/30
/10 weight ratio) copolymer [acid value 73 m9KOH/7
．． A liquid photosensitive resin composition EX3 was prepared in the same manner as in Example 1 except that 100P (number average molecular weight: 23,000) was used. The results of the test according to the method described above are shown in Table 1.

[Example 4] Copolymer of methyl methacrylate/methyl acrylate/methacrylic acid (55/20/25 weight ratio) [acid value 15
3 ■KOR/71, number average molecular weight 520001150/
, tetrahedral furfuryl acrylate (”/nl
= 8/l) After completely dissolving in 450 P, succinic acid/trimethylolethane/acrylic acid (1/2
A liquid photosensitive resin composition Ex4 was prepared by adding and mixing 400 t of benzyl dimethyl ketal 10F (oligoester acrylate) obtained by cocondensation at a molar ratio of /4. The results of the test according to the method described above are shown in Table 1.

[Example 5] Copolymer of methyl methacrylate/methyl acrylate/methacrylic acid (55/20/25 weight ratio) [acid value 15
3 m9KOH/f, number average molecular weight 5.2000110
0 F as tetrahydrofurfuryl methacrylate (n
1/n! = 971) After completely dissolving in 500 P, succinic acid/trimethylolethane/methacrylic acid (1/
400 tons of oligoester methacrylate obtained by cocondensation (2/4 molar ratio) and 40/40 tons of benzyl dimethyl ketal were added and mixed to prepare a liquid photosensitive resin composition Ex5. The results of the test according to the method described above are shown in Table 1.

[Example 6] Copolymer of methyl methacrylate/methyl acrylate/methacrylic acid (55/25/20 weight ratio) [acid value 12
7■KOH//, number average molecular weight 52000] 100P, triethylene glycol diacrylate ("s/n,
= 6/l) Hydroxypivalic acid neopentyl glycol ester diacrylate 2001 dicyclopentenyloxyethyl acrylate 200t Benzyl dimethyl ketal 40/p-methoxyphenol l/Phthalocyanine green 1t Talc
100t (LM8100 manufactured by Fuji Talc Industries Co., Ltd.) Amorphous silica
60F (Aerosil +#200, manufactured by Nippon Aerosil Co., Ltd.) was added and mixed, and mixed using three rolls to prepare a liquid photosensitive resin composition Ex6. Table 1 shows the results of the test according to the test method described above.

[Example 7] Copolymer of methyl methacrylate/1-butyl acrylate/acrylic acid (55/25/20 weight ratio) [acid value 1
33119KOH//, number average molecular weight 45000'18
0/, tetraethylene glycol dimethacrylate (
nt/nl = 5-3/1) 250t and tetraethylene glycol diacrylate (nt/, = 4.77
1) Trimethylolpropane triacrylate 50 after completely dissolving in a mixture with 250 P
/human cylinder xypivalic acid neopentyl glycol ester diacrylate) 100/dicyclopentenyloxyethyl acrylate 250P
Benzyldimethylketer/I/40J'p-methoxyphenol I Taftalodianine Green 1/Talc
1007 (LMS 100 manufactured by Fuji Talc Industries Co., Ltd.) Amorphous silica 60F (A@roail $200 manufactured by Nippon Aerosil Co., Ltd.) Silicone oil 0.057'
((l!KF 96 manufactured by Etsu Kagaku Kogyo Co., Ltd.) was added and mixed and cross-wired using three rolls to prepare a liquid photosensitive resin composition Bx7. The results of the test according to the above-mentioned test method are shown below. Shown in 1.

[Example 8] Copolymer of methyl methacrylate/methyl acrylate/methacrylic acid (55/30/15 weight ratio) [acid value 90
■KOH/71, number average molecular weight 29000] 100J
', tripropylene glycol diacrylate (''/
n, −”/1) After completely dissolving in 5001, dicyclopentenyloxyethyl acrylate 40
0/Benzyl dimethyl ketal
40/p-methoxyphenol
IP Phthalocyanine Green
IP mica (manufactured by Yamaro Mica Industries Co., Ltd. A)
-11) 2007'Amorphous Silica
70J' (Aerosll $200, manufactured by Nippon Aerosil Co., Ltd.) was added and mixed, and mixed with three rolls to form a liquid photosensitive resin composition Ex8.
was created. Table 1 shows the results of the test according to the test method described above.

[Comparative Example 1] Using 2-ethylhexyl acrylate in place of the tetrahydrofurfuryl acrylate of Example 1, Example 1
An attempt was made to dissolve the polymer shown in the figure, but it was not possible to dissolve it.

[Comparative Example 2] Instead of the tetrahydrofurfuryl acrylate of Example 1, an acrylate (manufactured by Nippon Kayaku Co., Ltd., manufactured by Nippon Kayaku Co., Ltd., KAYARAD■TC
-110) ("!/n, "13/l) to dissolve the linear polymer shown in Example 1, but
Uniform dissolution could not be achieved.

[Comparative Example 3] C. liquid photosensitive resin composition R.3 was prepared and tested in the same manner as in Example 1 except that hydroxyethyl acrylate was used in place of the tetrahydrofurfuryl acrylate in Example 1. The results are shown in Table 1.

[Comparative Example 4] Instead of the polymer of Example 1, a copolymer of methyl methacrylate/methyl acrylate/methacrylic acid (A5/l 5/40 weight ratio) [acid value 240119 KOH//,
An attempt was made to dissolve it in tetrahydrofurfuryl acrylate 5001 using number average molecular weight xtooolxoop, but uniform dissolution could not be achieved.

[Comparative Example 5] Instead of the polymer of Example 1, a copolymer of methyl methacrylate/methyl acrylate/methacrylic acid (76/20/4 weight ratio) [acid value 25 ■KOH/P, number average molecular weight 41000] 100P A liquid photosensitive resin composition R-5 was prepared and tested in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 6] Polymer 100P shown in Example 4 was mixed with 800t of tetrahydrofurfuryl acrylate (flt/n, = 8/1)
After completely dissolving in succinic acid/trimethylolethane/acrylic acid (1/2
Oligoester acrylate 907'benzyl dimethyl ketal 107' obtained by co-condensation with a ratio of /47%) was added and mixed to prepare a liquid photosensitive resin composition R.6. Table 1 shows the results of testing according to the test method described above.

[Comparative Example 7] Diethylene glycol diacrylate (nl/n!) was used instead of triethylene glycol diacrylate in Example 6.
Although an attempt was made to dissolve the carboxyl group-containing polymer shown in Example 1 using 5ooI (=10/1), uniform dissolution could not be achieved.

[Comparative Example 8] Tetradecaethylene glycol diacrylate ("
A liquid photosensitive resin composition Re 8 was prepared in the same manner as in Example 6 except that t/n, = z, s/l) was used. Table 1 shows the test results according to the above test method.
Shown below.

[Comparative Example 9] Liquid photosensitive resin composition Re9 was prepared in the same manner as in Example 6 except that hydroxyethyl acrylate was used instead of dicyclopentenyloxyethyl acrylate in Example 6.
was created. Table 1 shows the results of testing according to the test method described above.

[Comparative Example 10] Methyl methacrylate/instead of Example 60 linear polymer
Methyl acrylate/methacrylic acid (A5/15/40
Copolymer of triethylene glycol diacrylate (weight ratio) [acid value 240 qKOH//, number average molecular weight 11000) 100 J') (1/lt, = '/1)
I tried to dissolve it in 500 Jl, but it was not possible to dissolve it uniformly.

[Comparative Example 11] Methyl methacrylate/instead of the linear polymer of Example 6
A copolymer of methyl acrylate/methacrylic acid (76/20/4 weight ratio) [acid value 25 my KOH/mu number average molecular weight 41000] 100F was used, and the other conditions were as in Example 6.
Liquid photosensitive resin composition R-11 was prepared in the same manner as above. Table 1 shows the results of the test according to the test method described above.

[Example 9] Methyl methacrylate/in place of the linear polymer in Example 10
Styrene/methyl acrylate/methacrylic acid (30/
25/20/25 weight ratio) copolymer [acid value 14811
A liquid photosensitive resin composition Ex 9 was prepared in the same manner as in Example 1 except that 19KOHh, number average molecular weight 39000) and 100J' were used. The results of the test according to the method described above are shown in Table 1.

[Example 10] Methyl methacrylate/instead of the linear polymer in Example 10
A copolymer of ethyl acrylate/tetrahydrofurfuryl acrylate/itaconic acid (A0/25/10/25 weight ratio) [acid value 118 m9 KOHh, number average molecular weight 47000] 100 J' was used, and the other conditions were the same as in Example 1. A liquid photosensitive resin composition Ex 10 was prepared.

The results of the temperature test according to the method described above are shown in Table 1.

[Example 11] Ethyl methacrylate/instead of the linear polymer of Example 1
Copolymer of methyl acrylate/maleic acid (55/32/13 weight ratio) [acid value 14011I9KOH/, P,
A liquid photosensitive resin composition EXII was prepared in the same manner as in Example 1 except that 100P (number average molecular weight: 31,000) was used. The results of the test according to the method described above are shown in Table 1.

[Example 12] Copper-clad laminate (manufactured by Custom Bakelite Co., Ltd., ELC47)
After cutting 08) into 10 crIL×15 crIL, pretreatment is performed by polishing, washing, and removing moisture. The liquid photosensitive resin composition shown in Example 1 is uniformly coated onto the pretreated copper-clad laminate through a 75 mesh polyester screen. The liquid photosensitive resin composition is coated on a 25μ polyester film in the same manner. The above-mentioned 25μ polyester film is placed on the copper-clad laminate coated with the liquid photosensitive resin composition (the coated surfaces are overlapped) to obtain a hardening coating. Using this cured coating film, evaluation was carried out according to the evaluation methods of (1) and (2) above. The results obtained are shown below.

Optimal - missing exposure energy 120 mJ/cm"Developability ○ Heat resistance ○ Adhesion ○ Solvent resistance ○ Volume resistivity 3.lXl0 Ω・儂 [Effects of the Invention] As explained above, the liquid photosensitive resin of the present invention The composition exhibits excellent effects as a solder resist, etc., which has excellent heat resistance, adhesion, solvent resistance, electrical insulation, and good alkali developability.

Claims (1)

[Claims] 1. (A) has a carboxyl group in the molecule, and has an acid value of 60 to
180, 3 to 20% by weight of an acrylic and/or methacrylic linear polymer with a number average molecular weight of 2000 or more, (B) having one or more etheric oxygen atoms that do not participate in ester bonds in the molecule, and The ratio of the total number of carbon atoms (n_1) to the total number of oxygen atoms (n_2) that do not participate in ester bonds and/or amide bonds in the molecule (n_1
/n_2) is 10 to 60% by weight of an acrylic and/or methacrylic liquid monomer having a ratio of 4/1 to 9/1; (C) an acrylic system that does not substantially dissolve the linear polymer (A) component; and/or methacrylic monomer and/or oligomer 20 to 60% by weight, and (D) photoinitiator and/or photosensitizer 0.05 to 20% by weight as essential components, and the above (B) component and/or (C)
A liquid photosensitive resin composition characterized in that among the components, a crosslinking monomer and/or oligomer is contained in an amount of 10 to 80% by weight based on the total weight of the composition. 2. The viscosity measured with a Brookfield viscometer (spindle #7, 100 rpm) at 25°C is 1,00
The liquid photosensitive resin composition according to claim 1, which has a photopolymerization rate of 0 to 100,000 cps.