JP3414058B2 - Active energy ray-curable resin composition and water developing method - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an active energy ray-curable resin composition used as a resist material by active energy ray curing and a water developing method . More specifically, it has excellent sensitivity and resolution,
The present invention relates to an active energy ray-curable resin composition excellent in water developability and water resistance as well as a non-tacky film, and a water development method .

[0002]

2. Description of the Related Art Negative resists used for printed wiring board materials are distinguished by a developing method for removing an unexposed portion, and a solvent developing type using an organic halogen solvent represented by 1,1,1-trichloroethane. Alkali development type using an aqueous alkali solution such as an aqueous solution of sodium carbonate or an aqueous solution of tetramethylammonium hydroxide,
And three types of water development type using neutral water.
At the time when the use of photoresist was started, solvent developing type was the mainstream, but due to problems of working environment and natural environment, this type of resist has not been used much in recent years, and instead, alkali developing type photoresist is used. It is used.

In recent years, in consideration of cost reduction such as neutralization of a developing solution after use, simplification of developing equipment, and influence of an alkaline aqueous solution on an operator, a resist which can be developed with neutral water has been developed. The need is growing.

At present, the water-developable resist is widely used as a printing plate material such as a flexographic plate and a screen printing plate. As these water-developable resists, polyvinyl alcohol (for example, JP-A-5-119476) and water-soluble nylon (for example, JP-A-5-210241) have been proposed.

Further, in JP-A-6-27664,
A photocurable elastomer composition for plate-making comprising x), y) and z) is disclosed. That is, the hydrophobic soft segment (X) having a glass transition temperature (Tg) of -30 ° C or lower
And a hydrophilic hard segment (Y) having a glass transition temperature of + 30 ° C. or higher, or a glass transition temperature of + 50 ° C. in addition to (X) and (Y).
It is an amphipathic elastomer binder which is a block copolymer composed of three segments of the above hydrophobic hard segment (Z). y) is a low molecular weight compound that can be polymerized by the free radical mechanism, is compatible with the binder, has at least one ethylenically unsaturated end group and has a boiling point above 100 ° C. under normal pressure. z) is a compound capable of initiating the polymerization of compound y) under the action of actinic radiation.

With a composition using such an amphipathic elastomer binder, an exposed printing plate excellent in printing ink resistance and Shore hardness can be obtained by aqueous development after moderate exposure.

[0007]

However, it is necessary to use 1% sodium hydroxide as the aqueous medium used for this development. This is because the water-soluble segment is composed of an unsaturated carboxylic acid, so that development with neutral water is difficult. Moreover, since this amphiphilic elastomer binder contains the hydrophobic soft segment (X) having a glass transition temperature (Tg) of -30 ° C or less as an essential component, the coating film has tackiness and the image shape is It is difficult to expose the recorded photomask closely.

As described above, according to the conventional techniques, most resist materials which can be developed with neutral water can obtain a coating film which is non-tacky in addition to sensitivity and resolution and which is excellent in water resistance. Not found.

The present invention has been made by paying attention to the problems existing in the prior art as described above. An object of the invention is to provide an active energy ray-curable resin composition having excellent water developability, that is, easy to develop with neutral water.

Another object of the present invention is that when it is used as a resist material or the like, it has good sensitivity to active energy rays, a clear image can be obtained, and a non-tacky film can be obtained and cured. An object of the present invention is to provide an active energy ray-curable resin composition which is excellent in water resistance of the resin to be obtained later.

[0011]

In order to achieve the above object, in the invention of the active energy ray-curable resin composition according to claim 1, (A) the water-soluble segment (I) and the hydrophobic segment (II). ) And a block copolymer, (B)
In the block copolymer (A), the block copolymer (A) contains a polymerizable monomer that is polymerized by irradiation with an active energy ray and (C) a polymerization initiator for initiating the polymerization of the polymerizable monomer by an active energy ray. the glass transition temperature of the hydrophobic segment (II) (Tg) is not less -5 ° C. or higher, and Ri der glass transition temperature (Tg) of 80 ° C. or less of the water-soluble segment (I) or a hydrophobic segment (II), The block copolymer
The water-soluble segment (I) of (A) is (meth) acrylic
Amide, polyoxyethylene mono (meth) acrylate
Alkali metal salt of acid group-containing monomer, quaternary ammonium
A base-containing (meth) acrylate or reactive emulsifier
And a resist material that can be developed with neutral water.
And used.

According to the invention of claim 2, in the invention of claim 1, the water solubility in the block copolymer (A) is
The content of the segment (I) is 15 to 85% by weight, and the composition
The content of the block copolymer (A) in the product is 35 to 80
The amount is%.

In the invention described in claim 3, in the invention described in claim 1 , the polymerizable monomer (B) is a polyfunctional radical.
Is a curable polymerizable monomer or vinyl ether, and
Content of the polymerizable monomer (B) in the product is 20 to 60 weight
%. In the invention described in claim 4, claim 1 to claim
Item 5. The active energy ray-curable resin group according to any one of Items 3.
Form a film using the composition and expose it through a photomask
After that, develop with neutral water at a temperature of 80 ° C or less.
Characteristic water development method.

The present invention will be described in detail below. The block copolymer used in this invention is
It is composed of a water-soluble segment (I) and a hydrophobic segment (II). By using such a block copolymer, as a resist material, water developability,
The sensitivity, resolution, water resistance and non-tackiness are improved.
It is estimated that this is due to the following reasons.

That is, the water developability is improved on the basis of the water-soluble segment (I). In addition, the hydrophobic segment (I
By having I), water resistance is improved. Moreover,
Since it is a block copolymer, both segments (I) and (II) form a so-called sea-island structure and are locally bonded, so that both water developability and water resistance can be achieved, The solubility difference between the active energy ray-irradiated portion and the non-irradiated portion becomes remarkable, and the sensitivity and resolution are improved.
In addition, the glass transition temperature of the hydrophobic segment (II) (T
Since g) is set to −5 ° C. or higher, the surface of the coating film formed from the resin composition becomes non-tacky.

Next, in order to introduce the water-soluble segment (I) into this block copolymer, it is necessary to use a water-soluble vinyl monomer. Examples of the water-soluble vinyl monomer include the following monomers (1) to (10), and one of these monomers may be used alone or in combination of two or more. Can be used. (1) Acrylamide-t-butylsulfonic acid, N, N-
(Meth) acrylamides such as dimethylacrylamide, acrylamide, N, N-diethylacrylamide, N-isopropylacrylamide, acryloylmorpholine, N, N-dimethylaminipropylacrylamide, methacrylamide, N-methylolacrylamide. (2) N, N-diethylaminoethyl methacrylate,
N, N-dimethylaminoethyl methacrylate, N, N
-Aminoalkyl (meth) acrylates such as diethylaminoethyl acrylate, N, N-dimethylaminoethyl acrylate. (3) 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate,
Hydroxyalkyl (meth) acrylates such as 2,3-dihydroxypropyl methacrylate. (4) Polyethylene glycol monomethacrylate having 2 to 98 added moles of EO, 2 to 98 added moles of EO
Of methoxy polyethylene glycol monomethacrylate, EO-added moles of 2-98 phenoxy polyethylene glycol monoacrylate, EO-added moles of 1-
4, nonylphenol monoethoxylate acrylate, methoxyethyl acrylate, ethoxydiethylene glycol acrylate and other polyoxyethylene mono (meth) acrylates. (5) Sodium salt of methacrylic acid, sodium salt of acrylic acid, sodium styrene sulfonate, sodium ethoxy methacrylate sulfonate, sodium ethoxy acrylate sulfonate, sodium salt of mono-2-methacryloyloxyethyl acid phosphate, mono 2
An alkali metal salt of an acid group-containing monomer, such as the sodium salt of acryloyloxyethyl acid phosphate. (6) Quaternary ammonium base-containing (meth) acrylates such as hydroxyethyl trimethyl ammonium chloride methacrylate, hydroxypropyl trimethyl ammonium chloride methacrylate, and hydroxyethyl trimethyl ammonium chloride acrylate. (7) Water-soluble (meth) allyl compounds such as allyl glycol, polyethylene glycol monoallyl ether having an EO addition mole number of 3 to 32, methoxypolyethylene glycol monoallyl ether, and a salt of methallylsulfonic acid. (8) A compound containing a cyclic heterocycle such as N-vinylpyrrolidone and N-vinylcaprolactam. (9) Vinyl cyanide such as acrylonitrile, methacrylonitrile and vinylidene cyanide. (10) Illustrated by the chemical formulas (1) to (7), specifically, Lapizole AIS-112 and AIS manufactured by NOF CORPORATION.
-212, Latemur S-180, 180 manufactured by Kao Corporation
-A, Antox-MS-2N manufactured by Nippon Emulsifier Co., Ltd.,
Antox-MS-60, RA-4211, Sanyo Kasei Co., Ltd. eleminol JS-2, RS-30, Dai-ichi Kogyo Seiyaku Co., Ltd.'s Aqualon HS-20, HS-10,
Reactive emulsifiers sold by each company under trade names such as HS-5, New Frontea A-229E, and SE-10N manufactured by Asahi Denka Co., Ltd.

In the following formulas, Φ represents an aromatic ring.

[0018]

[Chemical 1]

However, (OA) _m and (AO) _n are polyoxyalkylene groups, and R and R ′ are alkyl groups.

[0020]

[Chemical 2]

However, R represents an alkyl group.

[0022]

[Chemical 3]

[0023]

[Chemical 4]

[0024]

[Chemical 5]

However, the substituent bonded to the aromatic ring (Φ) is in the para position.

[0026]

[Chemical 6]

[0027]

[Chemical 7]

However, the substituent bonded to the aromatic ring (Φ) is in the para position. And so on. Among these vinyl monomers, the monomers (1), (4), (5), (6) and (10) which have high water solubility and good radical polymerizability are preferable.

The proportion of the water-soluble segment (I) is preferably 15 to 85% by weight of the whole block copolymer, and 30 to 30% by weight.
60% by weight is more preferred. If this ratio is less than 15% by weight, good results cannot be obtained in water developability, sensitivity and resolution as a resist material, and if it is more than 85% by weight, good results cannot be obtained in sensitivity and water resistance.

Examples of the hydrophobic vinyl monomer required for introducing the hydrophobic segment (II) into the block copolymer include the following monomers (a) to (j). From the monomers, one of them can be used alone or two or more of them can be mixed and used. (a) 1 to 2 carbon atoms such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, octadecyl acrylate, and docosyl acrylate
Acrylic ester with 2 alkyl groups. (b) Methacrylic acid ester having an alkyl group having 1 to 22 carbon atoms such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, octadecyl methacrylate, and docosyl methacrylate. (c) Unsaturated dicarboxylic acid esters such as dimethyl fumarate, diethyl fumarate, dibutyl fumarate, dimethyl itaconate, dibutyl itaconate, methyl ethyl fumarate, methyl butyl fumarate and methyl ethyl itaconate. (d) Styrene derivatives such as styrene, α-methylstyrene and chlorostyrene. (e) Unsaturated ketones such as methyl vinyl ketone and butyl vinyl ketone. (f) Vinyl esters such as vinyl acetate and vinyl butyrate. (g) Vinyl ethers such as methyl vinyl ether and butyl vinyl ether. (h) N-substituted maleimides such as N-phenolmaleimide and N-cyclohexylmaleimide. (i) Vinyl halides and vinylidene halides such as vinyl chloride, vinyl bromide, vinyl fluoride and vinylidene chloride. (j) allyl phenyl ether, allyl methyl ether,
Allyl compounds such as allyl propionate, allyl myristate, allyl cyclohexyl propionate.

Among these vinyl monomers, (a), (b), (c), (d) and (f) having good radical polymerizability are preferable. The content of the hydrophobic segment (II) is preferably 15 to 85% by weight, more preferably 30 to 60% by weight, based on the whole block copolymer. If the content is less than 15% by weight, good results cannot be obtained in sensitivity and water resistance as a resist material, and if it is more than 85% by weight, good results cannot be obtained in water developability, sensitivity and resolution.

Further, the glass transition temperature (Tg) of the hydrophobic segment (II) of the block copolymer is required to be -5 ° C or higher at the temperature measured by the differential scanning calorimetry (DSC), It is preferably 0 ° C or higher. When the glass transition temperature is lower than -5 ° C, the coating film of the formed composition has tackiness and is not suitable.

Furthermore, the glass transition temperature of at least one of the water-soluble segment (I) and the hydrophobic segment (II) must be 80 ° C. or lower, preferably 60 ° C. or lower. When the glass transition temperatures of both segments (I) and (II) both exceed 80 ° C., water developability,
It is not suitable because the sensitivity deteriorates.

Next, the block copolymer is synthesized by a conventional method. Specifically, the anion living method, the sequential addition method, the polymer reaction method, the polymeric peroxide method, the polymeric azo compound method, etc. are adopted, but the most preferred is polymeric peroxide from the viewpoint of ease of production and improvement of yield. Is the law.

The polymerization method may be any of a bulk polymerization method, a solution polymerization method, a suspension polymerization method and an emulsion polymerization method. Here, the polymeric peroxide refers to a compound having a plurality of peroxide bonds in one molecule.
The block copolymer is obtained by two-step polymerization using this polymeric peroxide as a polymerization initiator. As the polymeric peroxide, conventionally known ones can be used. Preferably, one or more hydrophobic vinyl monomers are used by using a polymeric peroxide represented by the following chemical formulas (8) to (12). Polymerize.

[0036]

[Chemical 8]

[0037]

[Chemical 9]

[0038]

[Chemical 10]

[0039]

[Chemical 11]

[0040]

[Chemical 12]

During polymerization, a hydrophobic polymer containing a peroxide bond can be obtained by stopping the polymerization when about 50% of active oxygen in the polymeric peroxide remains. The desired block copolymer can be synthesized by polymerizing one or more water-soluble vinyl monomers using the obtained polymer as a polymerization initiator.

Conversely, using polymeric peroxide,
It is also possible to polymerize one or more water-soluble vinyl monomers to obtain a water-soluble polymer containing a peroxide bond, and then polymerize one or more hydrophobic vinyl monomers. .

By the way, the active energy ray-curable resin composition usually contains a base resin, a monomer, and a polymerization initiator for initiating polymerization by active energy rays as essential components.

The block copolymer is used as a base resin in the active energy ray-curable resin composition, and the content thereof is preferably 35 to 80% by weight, more preferably 40 to 70% by weight in the composition. .

Next, the polymerizable monomer (B) is a monomer which is polymerized by irradiation with an active energy ray, and generally known ones can be used. Examples of the polymerizable monomer (B) include the monofunctional radically polymerizable monomers (1) to (10) and (a) to (j) exemplified in the production of the block copolymer, Examples thereof include polyfunctional radically polymerizable monomers exemplified by (α) below and monofunctional and polyfunctional cationic polymerizable monomers exemplified by (β) to (δ). One of these monomers is used alone,
Alternatively, two or more kinds can be mixed and used. (Α) Polyfunctional radically polymerizable monomer hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl hydroxypivalate Glycol ester di (meth) acrylate, acrylic acid adduct of diglycidyl ether of 1,6-hexanediol, di (meth) acrylate of acetalization product of hydroxypivalaldehyde and trimethylolpropane, 2,2-bis [4- (Acryloyloxy)
Phenyl] propane, hydrogenated bisphenol A ethylene oxide adduct di (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane Propylene oxide adduct tri (meth) acrylate, glycerin Propylene oxide adduct tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol lower fatty acid and acrylic acid ester , Tris (acryloyloxyethyl) isocyanate, dipentaerythritol caprolactone adduct (meth) acrylate, dipropionate Erythritol penta (meth) acrylate, a radical polymerizable polyfunctional monomers such as caprolactone adduct of hydroxypivalic acid neopentyl glycol di (meth) acrylate. (Β) Epoxy compound Epoxy resin represented by reaction of polyhydric phenol such as bisphenol A and bisphenol F or its alkylene oxide adduct with epichlorohydrin, and novolak type epoxy resin such as phenol novolac type and cresol novolac type Aromatic epoxy resin, epoxy resin obtained by reaction of hydrogenated bisphenol A or its alkylene oxide adduct with epichlorohydrin, and cyclohexene oxide group such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate,
Alicyclic epoxy resin having alicyclic ring such as tricyclodecene oxide group and cyclopentene oxide group, 1,4-
Typical examples are polyglycidyl ethers obtained by reaction of alicyclic polyhydric alcohols such as butanediol and 1,6-hexanediol, and their alkylene oxide adducts with epichlorohydrin, and diglycidyl esters of aliphatic long-chain dibasic acids. Aliphatic epoxy resin. (Γ) Glycidyl compound Methyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, and other glycidyl ethers, diglycidyl phthalate, diglycidyl tetrahydrophthalate, and other glycidyl esters, N, N-di Glycidyl amines such as glycidyl aniline, tetraglycidyl diaminophenylmethane, and triglycidyl p-aminophenol. (Δ) Vinyl ether 2-ethylhexyl vinyl ether, octyl vinyl ether, phenyl vinyl ether, naphthyl vinyl ether, 2-chloroethyl vinyl ether, 2-vinyloxyethyl acrylate, 2-vinyloxyethyl methacrylate, diethylene glycol divinyl ether.

Among these monomers, (α) polyfunctional radical-polymerizable monomer having good active energy ray curability,
(Δ) Vinyl ether is preferable from the viewpoint of improving curability by active energy rays.

The content of the polymerizable monomer (B) is preferably 20 to 60% by weight in the active energy ray-curable resin composition in order to maintain the curability by the active energy ray.
Next, the polymerization initiator (C) for initiating the polymerization of the polymerizable monomer (B) with an active energy ray has an appropriate thermal stability during processing of the resin composition, and It is a compound that produces active species such as radicals and cations necessary for initiating polymerization or curing by active energy rays. As the polymerization initiator (C), conventionally known ones can be used, and examples thereof include the radical polymerization type and the cationic polymerization type shown below. The 1 type can be used individually or in mixture of 2 or more types. (A) Radical polymerization system diethylthioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone,
Benzoin isopropyl ether, benzoin ethyl ether, benzophenone, benzophenone methyl ether, 2-ethylanthraquinone, 2,4-dimethylthioxanthone, 2,2-dimethoxy-2-phenylacetophenone, pt-butyltrichloroacetophenone,
Hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one. (A) Cationic polymerization system triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrafluoroborate, tris (3,5-dimethyl-4-hydroxyphenyl) sulfonium hexafluoroantimonate, (η
6-benzene) (η5-cyclopentadienyl) iron (2
Value) hexafluorophosphate salt, diphenyliodonium tetrafluoroborate, phenyl-4-methoxyphenyliodonium hexafluoroantimonate.

Among these polymerization initiators (C), 2-methyl-1-, which has good sensitivity to active energy rays.
[4- (methylthio) phenyl] -2-morpholinopropanone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,4,6-Trimethylbenzoyldiphenylphosphine oxide and triphenylsulfonium hexafluoroantimonate are preferred.

The content of the polymerization initiator (C) is preferably 0.1 to 20% by weight in the active energy ray-curable resin composition from the viewpoint of rapid curability by active energy rays.

If necessary, the active energy ray-curable resin composition of the present invention contains thioxanthone, anthracene,
Photosensitizers such as perylene, antioxidants, thermosetting catalysts,
Dyes, pigments, thixotropic agents, plasticizers, surfactants and the like may be included. Further, a thermosetting resin such as phenol resin, melamine resin or polyimide, a thermoplastic resin such as polyolefin resin, polystyrene resin, nylon, polyethylene terephthalate or polycarbonate may be added.

By mixing the components described above,
An active energy ray curable resin composition can be prepared. Further, when used, the resin composition is dissolved or dispersed in a solvent such as methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, or water. By doing so, the viscosity and coatability can be adjusted.

This active energy ray-curable resin composition, when used, is made of a transfer plate, bar coater, roll coater, spin coater, or the like, the surface of which is used for a printing base plate and has a grained aluminum plate, copper plate or aluminum plate. It is applied to adherends such as semiconductor substrates and liquid crystal display substrates. Alternatively, it may be applied to a release paper, a film or the like to form a sheet and then attached to the adherend.

After this coating or pasting, active energy rays such as ultraviolet rays, electron beams, X-rays and γ-rays are irradiated through a photomask to cure. After that, development is performed with neutral water to remove the non-irradiated portion, whereby an image in the shape of the photomask is formed. Usually 8 for development
Neutral water at temperatures below 0 ° C. is used.

According to this resin composition, the development with neutral water is easy, the above operation makes it possible to form a clear image with good sensitivity, and the cured image has excellent water resistance.

[0055]

EXAMPLES The present invention will be described more specifically with reference to Reference Examples, Comparative Reference Examples, Examples and Comparative Examples.
The polymers a to i and the elastomer block copolymers used in Examples and Comparative Examples are described in Reference Examples 1 to 1 below.
5, manufactured by the method of Comparative Reference Examples 1-5.
In addition, parts and% in each example are by weight unless otherwise specified.

The analytical values of the peroxide bond-containing polymers and block copolymers produced by the methods of Reference Example and Comparative Reference Example are obtained by the following method. (Amount of active oxygen) It was determined by an iodometry method. (Weight average molecular weight Mw) Measurement was carried out by the SEC method (size exclusion chromatography). (Glass transition temperature) The measurement was performed by a differential scanning calorimetry (DSC). [Reference Example 1] (1-a, method for producing polymer containing peroxide bond) 60 g of propylene glycol monomethyl ether was charged into a reactor equipped with a thermometer, a stirrer and a reflux condenser, and 70 ° C while blowing nitrogen gas. Heat to. Next, 4 g of the compound represented by the chemical formula (12) and 40 g of butyl methacrylate.
The mixed solution consisting of was prepared over 2 hours, and the polymerization reaction was further carried out for 2 hours. The obtained solution was a transparent liquid containing 42% by weight of the polymer containing a peroxide bond (precursor a). In addition, as a result of measurement of active oxygen, 51% of peroxide bonds remained with respect to the charged amount. The polymerization results are shown in Table 1 together with the analysis results.

The abbreviations in Tables 1 to 7 are as follows. DMA: N, N-dimethylacrylamide, HEM
A: 2-hydroxyethyl methacrylate, DMAEM
A: N, N-dimethylaminoethyl methacrylate, P
ME-400: methoxypolyoxyethylene methacrylate (the number of moles of EO added: 9), MAA: methacrylic acid, AIS-112: Nippon Oil & Fats Co., Ltd. reactive emulsifier Lapizole AIS-112, BMA: butyl methacrylate, EA: ethyl. Acrylate, St: Styrene, B
A: butyl acrylate, MMA: methyl methacrylate, VAc: vinyl acetate, DLPO: dilauroyl peroxide

[0058]

[Table 1]

[0059]

[Table 2]

(1-b, Production of Block Copolymer) A propylene glycol monomethyl ether of the peroxy bond-containing polymer (precursor a) of Reference Example 1 was placed in a reactor equipped with a thermometer, a stirrer and a reflux condenser. Solution 104g, N, N
20 g of dimethyl acrylamide, 20 g of 2-hydroxyethyl methacrylate and 60 g of propylene glycol monomethyl ether were charged. Then, the mixture was heated to 70 ° C. while blowing nitrogen gas, and the block copolymerization reaction was carried out for 6 hours to obtain a translucent polymer mixed liquid containing the block copolymer.

The propylene glycol monomethyl ether solution of the polymer a thus obtained was adjusted to a solid content of 30% by weight after the polymerization reaction. The polymerization conditions are shown in Table 3,
The results are shown in Table 4 together with the analysis values. [Reference Examples 2 to 5 and Comparative Reference Examples 1 and 2] Tables 1 to 3 show the types and charging amounts of monomers, the types and charging amounts of polymerization initiators, and the types of precursors into a reactor. A 30 wt% propylene glycol monomethyl ether solution of the precursors b to g and the polymers b to g was obtained in the same manner as in Reference Example 1 except that the above was changed to. The results of the polymerization are combined with the results of the precursor a and the polymer a, and
It was shown to.

[0062]

[Table 3]

[0063]

[Table 4]

[0064]

[Table 5]

[0065]

[Table 6]

Comparative Reference Example 3 A reactor equipped with a thermometer, a stirrer and a reflux condenser was charged with 120 g of a propylene glycol monomethyl ether solution and heated to 70 ° C. while blowing nitrogen gas. Then, a previously prepared mixed solution of 40 g of butyl methacrylate, 40 g of N, N-dimethylacrylamide and 5 g of dilauroyl peroxide was charged over 2 hours, and a polymerization reaction was further performed for 8 hours to contain a random copolymer. A clear solution was obtained.

The propylene glycol monomethyl ether solution of the polymer h thus obtained was adjusted to a solid content of 30% by weight after the polymerization reaction. The results of polymerization are shown in Table 7.
It was shown to. Comparative Reference Example 4 A reactor equipped with a thermometer, a stirrer and a reflux condenser was charged with 120 g of a propylene glycol monomethyl ether solution, and heated to 70 ° C. while blowing nitrogen gas. Next, 72 g of butyl methacrylate prepared in advance,
A mixed solution of 8 g of N, N-dimethylacrylamide and 5 g of dilauroyl peroxide was charged over 2 hours, and a polymerization reaction was further performed for 8 hours to obtain a transparent solution containing a random copolymer.

The propylene glycol monomethyl ether solution of the polymer i thus obtained was adjusted to a solid content of 30% by weight after the polymerization reaction. The results of the polymerization are shown in Table 7 together with the results of the polymer h.

[0069]

[Table 7]

Comparative Reference Example 5 (5-a Anionic Polymerization) To a glass autoclave equipped with a thermometer and a stirrer, 34.6 g of toluene and 73.0 g of styrene were charged, and nitrogen gas was blown into the autoclave to blow nitrogen gas into the container. After setting the atmosphere, a mixed solution of 0.13 g of butyllithium and 0.9 g of hexane was charged. Then, after stirring for 2 hours while heating, 138.6 g of toluene
Diluted with. Next, 34.1 g of isoprene was charged and the mixture was further stirred for 2.5 hours, and then a mixed liquid of 0.68 g of 1,1-diphenylethene and 178 g of tetrahydrofuran was added.

Subsequently, it was cooled with a sodium chloride / ice water mixture. Furthermore, t-butyl methacrylate 1
After adding 4.1 g and continuing stirring for 1 hour in the cold bath,
Polymerization was stopped by adding 0.79 g of methanol. Then, the obtained reaction solution was added dropwise to 5000 g of methanol to precipitate the polymer produced. The precipitated polymer was suction filtered, washed and dried. (Removal reaction of 5-b, t-butyl protecting group) To a reactor equipped with a thermometer, a stirrer and a reflux condenser, 100 g of the isolated polymer and 230 g of toluene were added and uniformly dissolved. To this, 0.6 g of p-toluenesulfonic acid was added to obtain 8
Heated at 0 ° C. for 6 hours. After cooling, the reaction mass is 250
The polymer was precipitated by dropping into 0 g of methanol. Further, this was washed and dried at room temperature under vacuum to obtain an elastomer block copolymer. [Example 1] To 20 g of a propylene glycol monomethyl ether solution of polymer a (solid content: 30%), a triacrylate of a 6-mole ethoxide adduct of trimethylolpropane as a monomer (TMP-6EO manufactured by Kyoeisha Yushi Co., Ltd.) was added.
-3A) 3 g, and 1.5 g of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone (Irgacure 907 manufactured by Ciba-Geigy) as an initiator for initiating polymerization with active energy rays. Were mixed. This was stirred at room temperature for 10 minutes to prepare an active energy ray-curable resin composition. The compositions thereof are summarized in Table 8. [Examples 2 to 12 and Comparative Examples 1 to 4] The type and addition amount of the block copolymer, the type and addition amount of the monomer, and the type and addition amount of the initiator for initiating the polymerization by the active energy ray An active energy ray-curable resin composition was prepared in the same manner as in Example 1 except that the changes were made as shown in Table 8.

The abbreviations in Table 8 are as follows. TMP-6EO-3A: triacrylate of a 6-mol ethyroxide adduct of trimethylolpropane, 9EG-DA: diacrylate of polyethylene glycol (the number of moles of EO added: 9), 907: 2-methyl-1- [4- (Methylthio) phenyl] -2-morpholinopropanone (Irgacure 907 manufactured by Ciba Geigy) 651: 2,2-dimethoxy-1,2-diphenylethan-1-one (Irgacure 65 manufactured by Ciba Geigy
1), 1173: 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Darocur 11 manufactured by Ciba-Geigy)
73) TPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Lucillin TPO manufactured by BASF) PVA: acid-modified polyvinyl alcohol PAMID synthesized in Comparative Example 5: water-soluble polyamide EBCO synthesized in Comparative Example 6: in Comparative Example 7 Synthesized elastomer block copolymer [Comparative Example 5] Instead of 20 g of a propylene glycol monomethyl ether solution (solid content 30%) of polymer a, 60 g of vinyl acetate and 40 g of maleic anhydride were added in 233 g of propylene glycol monomethyl ether. An acid-modified polyvinyl alcohol obtained by using 0.1 g of dilauroyl peroxide as a polymerization initiator, polymerizing at 65 ° C. for 6 hours in a nitrogen atmosphere, and then saponifying with sodium hydroxide and adjusting the resin content to 30% by weight. Propylene glycol mono Was changed to Chirueteru solution 20g was the case of the active energy ray curable resin composition in the same manner as in Example 1. [Comparative Example 6] α obtained by adding acrylonitrile to both ends of polyethylene oxide having a mole number of addition 12 instead of 20 g of a propylene glycol monomethyl ether solution of polymer a (solid content 30%), and reducing it with hydrogen , Ω
-Propylene glycol monomethyl ether solution of water-soluble polyamide obtained by melt polymerization of 55 g of equimolar salt of diaminopolyoxyethylene and adipic acid, 225 g of ε-caprolactam and 20 g of equimolar salt of hexamethylenediamine and adipic acid (solid content The active energy ray-curable resin composition was prepared in the same manner as in Example 1 except that 20 g of 30%) was used. [Comparative Example 7] 20 g of propylene glycol monomethyl ether solution (solid content 30%) of the elastomer block copolymer synthesized in Comparative Reference Example 5 instead of 20 g of propylene glycol monomethyl ether solution (solid content 30%) of polymer a An active energy ray-curable resin composition was prepared in the same manner as in Example 1 except that was used.

[0073]

[Table 8]

Examples 1 to 12 and Comparative Examples 1 to 7 described above
With respect to each active energy ray-curable resin composition, the water developability, sensitivity, resolution, water resistance and tackiness were examined in the following manner. The results are shown in Table 9. <Water developability> An active energy ray-curable resin composition was applied onto an aluminum plate having a grained surface by a spin coater ASS-300 manufactured by Able Co., Ltd. to a film thickness of 2 μm.

The solvent was removed by drying in a hot air dryer at 70 ° C. for 20 minutes. Through a photomask having lines and spaces of 2 to 40 μm, exposure was performed for 10 seconds in the air using an ultrahigh pressure mercury lamp of 20 mW / cm.

The exposed film is spray-developed with ion-exchanged water at a predetermined temperature shown in Table 8 at a pressure of 3 kg / cm ² by a gas-liquid mixing method to remove the unexposed part and remove the unexposed part. Was measured by the time of development.

In Table 9, the short development time (seconds) in the water developability column indicates that the water developability is good. <Sensitivity> In the water developability test, water was used except that exposure was performed through a gray scale (Photographic step tablet No. 2 manufactured by Eastman Kodak Co., Ltd.) instead of a photomask having a line and space of 2 to 40 μm. The pattern exposure-development was performed by the same operation as in the developability test. The maximum number of remaining gray scale steps was calculated as the sensitivity.

The large number of stages in Table 9 indicates that the sensitivity is high. <Resolution> In the water developability test, the size of the minimum line and space where the image of the photomask line and space is missing after exposure and development was defined as the resolution (μm).
A smaller resolution value in Table 9 indicates a higher resolution. <Water resistance> The appearance of the coating film after immersing the coating film on the substrate after exposure-development in the water developability test for 24 hours in ion-exchanged water whose temperature was adjusted to 60 ° C. was visually observed. . ○, if there is no change compared to the one before immersion
The case where the coating film was destroyed was designated as x. <Tackiness> In the water developability test, when the coating film after coating-drying is touched with a hand, no stickiness is felt, and the photomask does not adhere to the coating film after exposure, ○, coating When the film is sticky when touched by hand, but the photomask does not adhere to the coating film after exposure △, it is sticky when the film is touched by hand, and the photomask adheres to the coating film after exposure The case where it ends up was marked with x.

[0079]

[Table 9]

As is clear from Table 9 above, Example 1
It goes without saying that each of the active energy curable resin compositions of to 12 exhibits excellent sensitivity and resolution.
It gives a non-tacky coating and is excellent in water developability and water resistance.

On the other hand, the active energy ray curability of Comparative Example 1 using the polymer f in which the glass transition temperature (Tg) of each of the water-soluble segment (I) and the hydrophobic segment (II) exceeds 80 ° C. The resin composition has a water developability,
Poor sensitivity. The active energy ray-curable resin composition of Comparative Example 2 using the polymer g in which the glass transition temperature of the hydrophobic segment is lower than −5 ° C. has tackiness in the coating film, and therefore, after exposure, photo The mask adhered to the coating film, and evaluation of water developability, sensitivity, resolution, and water resistance was impossible.

Further, in Comparative Example 3 in which the random copolymer h was used instead of the block copolymer, a part of the exposed portion was also removed during the water development, so that the sensitivity, the resolution and the water resistance were improved. The evaluation was impossible. Comparative Example 4 using the random copolymer i is inferior in water developability, sensitivity, resolution and water resistance.

An active energy ray-curable resin composition using acid-modified polyvinyl alcohol (Comparative Example 5) and water-soluble nylon (Comparative Example 6) in place of the block copolymer has water developability and water resistance. Inferior in sex. Furthermore, the active energy ray-curable resin composition using the elastomer block copolymer (Comparative Example 7) instead of the block copolymer has tack on the coating film and is inferior in water developability.

The technical idea understood from the above embodiment will be described below. (1) Active energy ray polymerization initiator for initiating polymerization of the polymerizable monomer by irradiation of (C) is a radical polymerization initiator or a cationic polymerization initiator, and its content 0.1 The active energy ray-curable composition according to claim 1, which is ˜20% by weight. According to this configuration, the polymerizable monomer can be smoothly polymerized by the active energy ray.

[0085]

As described in detail above, according to the active energy ray-curable resin composition of the first and fourth aspects, the water developability is excellent, that is, the development with water is easy. Moreover, when it is used as a resist material or the like, it has good sensitivity to active energy rays, a clear image can be obtained, a non-tacky film can be formed, and the cured resin has excellent water resistance.

Therefore, the resin composition of the present invention is suitable for a solder resist for a printed wiring board, a printing plate material, and a permanent resist for a color filter, a protective film, a flattening film, etc. for a liquid crystal display. Can be used for.

According to the invention of claim 2, water developability
Water resistance and chemical resistance.
Can be raised. According to the invention of claim 3, the curability of the resin composition by the active energy rays is improved.
Can be made.

Continuation of front page (56) Reference JP-A-6-32997 (JP, A) JP-A-6-107748 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03F 7 / 00-7/42

Claims (4)

(57) [Claims] 1. A block copolymer comprising (A) a water-soluble segment (I) and a hydrophobic segment (II), (B) a polymerizable monomer which is polymerized by irradiation with active energy rays, and (C) an activity. The block copolymer (A) contains a polymerization initiator for initiating the polymerization of the polymerizable monomer by energy rays, and the hydrophobic segment (I
The glass transition temperature (Tg) of I) is -5 ° C or higher, and the water-soluble segment (I) or hydrophobic segment (II)
Water-soluble segments of glass transition temperature (Tg) of Ri der 80 ° C. or less, the block copolymer (A) (I)
However, if (meth) acrylamide or polyoxyethylene
No. (meth) acrylate, acid group-containing monomer alkali gold
Group salt, quaternary ammonium salt group-containing (meth) acrylate
Or formed from a reactive emulsifier and developed with neutral water
An active energy ray-curable resin composition that is used as a possible resist material . 2. A water-soluble segment in the block copolymer (A).
In the composition, the content of ment (I) is 15 to 85% by weight.
Content of the block copolymer (A) of 35 to 80% by weight
The active energy ray-curable resin set according to claim 1.
A product. 3. The polymerizable monomer (B) is a polyfunctional radical.
Polymerizable monomer or vinyl ether, and composition
When the content of the polymerizable monomer (B) is 20 to 60% by weight,
The active energy ray-curable resin composition according to claim 1.
object. 4. The method according to any one of claims 1 to 3.
Form a film using active energy ray curable resin composition
After exposure through a photomask,
A water development method characterized by performing development with neutral water.