JP2003040965A - Unsaturated group-containing urethane resin and active energy ray-curing composition using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an unsaturated group-containing urethane resin for an active energy ray-curing which gives a coating film performance excellent in flexibility, softness, surface hardness, fouling resistance, weather resistance and the like, an active energy ray-curing composition using the resin and a method for forming a resist pattern using the composition. SOLUTION: The unsaturated group-containing urethane resin is characterized by reacting (a) a specific alicyclic compound containing two hydroxy groups and an ethylenically unsaturated group in a molecule, (b) an isocyanate compound and, if necessary, (c) a polyol compound.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel unsaturated group-containing urethane resin for curing active energy rays. Furthermore, the present invention has a high photocuring speed, and in particular, has excellent scratch resistance, stain resistance, flexibility and weather resistance (light resistance) of a film after resin curing, and is used for paints, surface modifiers, printing. The present invention relates to an active energy ray-curable composition suitable for inks, shaped articles such as optical disks, and also for photoresists.

[0002]

2. Description of the Related Art In recent years, active energy ray curable resins have been widely used as ultraviolet curable resins including surface treatment agents such as paints from the viewpoints of pollution prevention, environmental protection, work environment improvement, etc. Became.

Compared with the conventional heat-curing method, it has a significantly faster curability, is a non-heat-curing type, can be solvent-free, and can save space in a line.
This is because it has many advantages such as high energy efficiency in curing. In particular, the unsaturated group-containing urethane resin according to the present invention has high chemical resistance in addition to mechanical properties such as flexibility, flexibility, and elongation, and therefore has general chemical resistance, general ink, printing ink, plastic coating agent, adhesive, surface treatment. It is widely used as an agent.

Further, with the recent development of the information industry, for optical fiber coating (Japanese Patent Laid-Open No. 05-306147), optical disk manufacturing (Japanese Patent Laid-Open No. 05-125142), hologram display element (Japanese Patent Laid-Open No. 11-202744), photoresist. The range of use has expanded greatly for business purposes.

[0005]

These unsaturated group-containing urethane resins usually have a radically polymerizable unsaturated group such as a (meth) acryloyl group introduced at the terminal via a urethane bond. Therefore, in the case of increasing the molecular weight in order to improve the coating performance, the concentration of unsaturated groups in the resin decreases,
There is a problem in that the curing speed due to light irradiation decreases and the crosslink density decreases, and it is difficult to obtain coating film performance such as surface hardness, stain resistance, and weather resistance.

The object of the present invention is to obtain an unsaturated group-containing urethane resin for curing active energy rays, which is excellent in flexibility, flexibility and the like, and can obtain coating film performance which is also excellent in surface hardness, stain resistance and weather resistance. To provide.

[0007]

Means for Solving the Problems The inventors of the present invention have made earnest studies on the problems to be solved by the invention as described above, and as a result, have two hydroxyl groups and one ethylenic unsaturated group in one molecule. The present invention has now been completed by finding an unsaturated group-containing urethane resin obtained from a specific alicyclic compound containing a group and an isocyanate compound.

That is, (a) the following general formulas (I) to (V)
Unsaturated group-containing urethane resin obtained by reacting at least one alicyclic compound selected from I) and (b) an isocyanate compound

[0009]

[Chemical 3]

In the formula, R1 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,

[0011]

[Chemical 4]

In the formula, R ₂ represents an ethylene group or a propylene group, m represents an integer of 0 to 10 and n represents an integer of 1 to 10. The present invention provides an active energy ray-curable composition using the unsaturated group-containing urethane resin, and a resist pattern forming method using the active energy ray-curable composition. .

The unsaturated group-containing urethane resin of the present invention and the active energy ray-curable composition using the unsaturated group-containing urethane resin will be described below.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The unsaturated group-containing urethane resin of the present invention comprises an alicyclic compound (a) containing two hydroxyl groups and one ethylenically unsaturated group in one molecule and, if necessary, It contains a polyol compound (c) and is obtained by reacting these compounds with an isocyanate compound (b).

Alicyclic compound (a) The alicyclic compound (a), which is a raw material of the unsaturated group-containing urethane resin of the present invention, contains two hydroxyl groups and one ethylenically unsaturated group in one molecule. The compound is represented by the following formulas (I) to (VI).

[0016]

[Chemical 5]

In the formula, R ₁ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and Y has the following meaning.

[0018]

[Chemical 6]

In the formula, R ₂ represents an ethylene group or a propylene group, m represents an integer of 0 to 10 and n represents an integer of 1 to 10.

Among them, the compounds represented by the chemical formulas (I) and (II), and more particularly, the compound in which R ₁ is a hydrogen atom or a methyl group and Y is a methylene group are curable, the production stability of the resin, etc. preferable.

Isocyanate Compound (b) The isocyanate compound (b), which is a raw material for the unsaturated group-containing urethane resin of the present invention, is a compound containing one or more isocyanate groups in one molecule. Examples of the isocyanate compound include monoisocyanate compounds, diisocyanate compounds and other isocyanate compounds, and among them, diisocyanate compounds are preferably used.

Examples of the diisocyanate compound include an aliphatic diisocyanate compound, an alicyclic diisocyanate compound and an aromatic diisocyanate compound. Examples thereof include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate and xylene. Diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, 4,4 '
-Methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4 (or 2,6) -diisocyanate, 1,3- (isocyanatomethyl) cyclohexane, isophorone diisocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate, dianisidine diisocyanate, phenyl diisocyanate , Halogenated phenyl diisocyanate, methylene diisocyanate, ethylene diisocyanate,
Butylene diisocyanate, propylene diisocyanate, octadecylene diisocyanate, 1,5-naphthalene diisocyanate, polymethylene polyphenylene diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, tolylene diisocyanate polymer, diphenylmethane diisocyanate polymer, hexamethylene diisocyanate polymer , 3-
Phenyl-2-ethylene diisocyanate, cumene
2,4-diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, 4-ethoxy-1,3-phenylene diisocyanate, 2,4'-diisocyanate diphenyl ether, 5,6-dimethyl-1,3-phenylene diisocyanate, 4 , 4'-diisocyanate diphenyl ether, benzidine diisocyanate,
9,10-anthracene diisocyanate, 4,4'-
Diisocyanate benzyl, 3,3′-dimethyl-4,
4'-diisocyanate diphenylmethane, 2,6-dimethyl-4,4'-diisocyanate diphenyl, 3,
3'-dimethoxy-4,4'-diisocyanate diphenyl, 1,4-anthracene diisocyanate, phenylene diisocyanate, 2,4,6-tolylene triisocyanate, 2,4,4'-triisocyanate diphenyl ether, 1,4- Tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,1
Examples thereof include 0-decamethylene diisocyanate, 1,3-cyclohexylene diisocyanate and 4,4′-methylene-bis (cyclohexyl isocyanate).

As the above-mentioned monoisocyanate compound,
Examples thereof include those obtained by reacting a hydroxyl group-containing compound with one isocyanate group of the above diisocyanate compound, methyl isocyanate, ethyl isocyanate, propyl isocyanate, phenyl isocyanate, and Additive TI (trade name, manufactured by Sumitomo Bayer Urethane Co., Ltd.).

Other polyisocyanate compounds include, for example, triphenylmethane-4,4 ', 4 ".
-Triisocyanate, 1,3,5-triisocyanatobenzene, 2,4,6-triisocyanatotoluene,
4,4'-dimethyldiphenylmethane-2,2 ', 5
Polyisocyanate compounds having three or more isocyanate groups such as 5'-tetraisocyanate; ethylene glycol, propylene glycol, 1,4-butylene glycol, polyalkylene glycol, trimethylo-
Addition products obtained by reacting polyisocyanate compounds in excess of isocyanate groups with respect to hydroxyl groups of polyols such as propane and hexanetriol; hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, xylylene diisocyanate, 4 , 4'-diphenylmethane diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate) and other buret type adducts, isocyanuric ring type adducts and the like.

The above isocyanate compounds may be used alone or in combination of two or more.

Polyol compound (c) The polyol compound (c) optionally used in the production of an unsaturated group-containing urethane resin is one containing at least two alcoholic or phenolic hydroxyl groups in one molecule. It is also possible to use an ethylenically unsaturated group-containing polyol compound other than the alicyclic compound (a).

Further, it is suitable that the unsaturated group-containing urethane resin has a carboxyl group for water-dispersion of the unsaturated group-containing urethane resin, or for photoresists. Preference is given to using polyol compounds.

Examples of the polyol compound (c) include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol (molecular weight 6,
000 or less), trimethylene glycol, polypropylene glycol (molecular weight 6,000 or less), tetramethylene glycol, polytetramethylene glycol, 1,2
-Butylene glycol, 1,3-butanediol, 1,
4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,2-hexylene glycol,
1,6-hexanediol, heptanediol, 1,1
0-decanediol, cyclohexanediol, 2-butene-1,4-diol, 3-cyclohexene-1,1
-Dimethanol, 4-methyl-3-cyclohexene-
1,1-dimethanol, 3-methylene-1,5-pentanediol, (2-hydroxyethoxy) -1-propanol, 4- (2-hydroxyethoxy) -1-butanol, 5- (2-hydroxyethoxy) -Pentanol, 3- (2-hydroxypropoxy) -1-propanol, 4- (2-hydroxypropoxy) -1-butanol, 5- (2-hydroxypropoxy) -1-pentanol, 1- (2-hydroxy Ethoxyl) -2-butanol, 1- (2-hydroxyethoxy) -2-pentanol, hydrogenated bisphenol A, glycerin, polycaprolactone diol, polycaprolactone triol, 1,2,6-hexanetriol, trimethylolpropane, Trimethylolethane, pentanetriol, trishydroxyme Ruaminometan, 3- (2-
Hydroxyethoxy) -1,2-propanediol, 3
Examples thereof include-(2-hydroxypropoxy) -1,2-propanediol, 6- (2-hydroxyethoxy) -1,2-hexanediol, pentaerythritol, dipentaerythritol, mannitol and glucose.

Examples of the above-mentioned ethylenically unsaturated group-containing polyol compound include glycerin mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, pentaerythritol mono (meth) acrylate, dipentaerythritol mono (meth) acrylate, Examples thereof include hydroxyisocyanurate mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, pentaerythritol monoallyl ether and the like.

As the carboxyl group-containing polyol compound, a carboxyl group-containing diol is suitable from the viewpoint of production stability, and examples thereof include dimethylolpropionic acid, dimethylolbutanoic acid, and dimethylolvaleric acid. However, it is not particularly limited thereto. These can be used alone or in combination of two or more, but dimethylolpropionic acid and dimethylolbutanoic acid are particularly preferable because they are easily dissolved in an organic solvent.

The unsaturated group-containing urethane resin of the present invention is produced by mixing the above-mentioned components (a) and (b) and, if necessary, (c), and by reacting the conventionally known isocyanate group and hydroxyl group. can do.

In the above reaction, an inert organic solvent which dissolves or disperses these components and does not inhibit these reactions can be used as a solvent, if necessary. Examples of the organic solvent include hydrocarbon-based, ketone-based, ether-based, and ester-based solvents.

In the reaction of an isocyanate group and a hydroxyl group, the reaction temperature is usually about 20 to 250 ° C., especially 50 to 15 ° C.
Suitably, the reaction is carried out in the range of 0 ° C. and the reaction time is in the range of about 10 minutes to about 24 hours, particularly about 20 minutes to about 12 hours.

In the above reaction, a known reaction catalyst of an isocyanate group and a hydroxyl group can be added, if necessary, and examples of the reaction catalyst include lead oleate, tetrabutyltin, antimony trichloride, triphenylaluminum, Trioctylaluminum, zinc naphthenate, zirconium naphthenate, dibutyltin dilaurate, tetra-n-butyl-1,3-diacetyloxydistannoxane, 1,4-diaza [2,2,2] bicyclooctane, N-ethyl Examples thereof include morpholine. The reaction catalyst is usually 0.01 to 10 parts by weight based on 100 parts by weight of the total solid content of the components (a) to (c),
It is preferably used in the range of 0.02 to 5 parts by weight.

When the resin obtained by reacting the above-mentioned components (a) and (b) and optionally (c) has an isocyanate group, it is optionally reacted with a hydroxyl group-containing ethylenically unsaturated monomer. Thus, an ethylenically unsaturated group can be introduced at the molecular chain end of the resin. Examples of the hydroxyl group-containing ethylenically unsaturated monomer include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, allyl alcohol, butanediol mono (meth) acrylate, N-methylol (meth) acrylamide, and crotyl. Examples thereof include alcohol, propylene glycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate and pentaerythritol tri (meth) acrylate.
In addition to the above, addition products of glycidyl acrylate or glycidyl methacrylate with a monocarboxylic acid compound (eg, acetic acid, propionic acid, crotonic acid, etc.), (meth) acrylic acid with an epoxy compound (eg, epichlorohydrin, etc.) Additives and the like can also be used. These may be used alone or in combination of two or more.

When the resin obtained by reacting the above-mentioned components (a) and (b) and, if necessary, (c) has a hydroxyl group, an isocyanate group-containing ethylenically unsaturated group is optionally added. An ethylenically unsaturated group can be introduced at the terminal of the molecular chain of the resin by reacting with a monomer.
As the isocyanate group-containing ethylenically unsaturated monomer, for example, ethyl isocyanate, an adduct obtained by adding a monomer having a hydroxyl group and an ethylenically unsaturated group to one isocyanate group of a diisocyanate compound (for example, , A monoadduct of isophorone diisocyanate and hydroxyethyl (meth) acrylate, etc.).

The unsaturated group-containing urethane resin of the present invention thus obtained has an unsaturation degree of 0.2 to 5.0 mol / k.
g, preferably 0.7 to 4.0 mol / kg, number average molecular weight of 400 to 100,000, preferably 500 to
Within the range of 50,000, the heat stability of the resin, the photosensitivity, and the processability of the cured coating film are suitable.

The mixing ratios of the above-mentioned components (a), (b) and (c) fall within the ranges of the above-mentioned degree of unsaturation and the number average molecular weight of the unsaturated group-containing urethane resin finally obtained. As described above, in general, based on the total solid content of the components (a) to (c), (a)
5-80% by weight of components, preferably 10-70% by weight,
The component (b) is 3 to 70% by weight, preferably 5 to 50% by weight, and the component (c) is 0 to 50% by weight, preferably 1 to 40% by weight.
A weight% range is suitable.

When the unsaturated group-containing urethane resin is used in an aqueous system, or when it is used for a photoresist, the component (a) is based on the total solid content of the components (a) to (c). Is 5 to 50% by weight, preferably 1
0 to 40% by weight, the component (b) is 3 to 50% by weight, preferably 5 to 30% by weight, and the carboxyl group-containing polyol compound in the component (c) is 3 to 50% by weight, preferably 5 to 3%.
0% by weight, and 0 to 50% by weight, preferably 0 to 50% by weight of the polyol compound having no carboxyl group in the component (c).
A range of 40% by weight is suitable.

Next, an active energy ray-curable composition using the unsaturated group-containing urethane resin of the present invention will be described.

Active energy ray-curable composition An active energy ray-curable composition can be obtained by adding a photopolymerization initiator to the unsaturated group-containing urethane resin of the present invention.

As the above-mentioned photopolymerization initiator, conventionally known ones can be used without particular limitation. Specifically, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 1-hydroxycyclohexyl. -Phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, 2,4,6-trimethyl Benzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide, benzophenone, methyl O-benzoylbenzoate, hydroxybenzophenone, 2-isopropylthioxanthone, 2,
4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 2,4
6-tris (trichloromethyl) -S-triazine, 2
-Methyl-4,6-bis (trichloro) -S-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -S-triazine, iron-allene complex,
Examples thereof include titanocene compounds, but the invention is not limited thereto. These photopolymerization initiators may be used alone or in admixture of two or more. The compounding amount thereof is preferably 0.1 to 15 parts by weight, and particularly preferably 0.2 to 8 parts by weight with respect to 100 parts by weight (solid content) of the above-mentioned unsaturated group-containing urethane resin.

Further, in the active energy ray-curable composition of the present invention, a sensitizing dye may be used in combination with the photopolymerization initiator. Specific examples thereof include thioxanthene-based, xanthene-based, ketone-based, thiopyrylium salt-based, base styryl-based, merocyanine-based, 3-substituted coumarin-based, cyanine-based, acridine-based, and thiazine-based dyes. These may be used alone or in admixture of two or more. The compounding amount of the sensitizing dye is preferably 0.1 to 10 parts by weight, and particularly preferably 0.2 to 8 parts by weight with respect to 100 parts by weight of the above-mentioned unsaturated group-containing urethane resin.

In the active energy ray-curable composition of the present invention, a conventionally known polymerizable unsaturated group-containing resin other than the unsaturated group-containing urethane resin is used in order to improve performances such as photocurability and mechanical strength of a cured film. A polymerizable unsaturated monomer and the like can be used as necessary.

Examples of the above-mentioned polymerizable unsaturated group-containing resin include resins obtained by condensing (meth) acrylic acid with polyester, unsaturated group-containing epoxy resins, unsaturated group-containing acrylic resins, and the like.

Examples of the above-mentioned polymerizable unsaturated group-containing monomer include the following polymerizable unsaturated monomers having 1 to 3 polymerizable unsaturated groups in one molecule.

Examples of the monomer having one polymerizable unsaturated group in one molecule include styrene, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth).
Acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate,
Tetrahydrofurfuryl (meth) acrylate, ε-caprolactone-modified tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth ) Acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, ε-caprolactone-modified hydroxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (Meth) acrylate, 2-hydroxy-3
-Butoxypropyl (meth) acrylate, monohydroxyethyl phthalate (meth) acrylate, Aronix M-110 (manufactured by Toagosei Co., Ltd.), N-methylol (meth) acrylamide, N-methylol (meth) acrylamide butyl ether, acryloyl morroline, Dimethylaminoethyl (meth) acrylate, N-vinyl-
2-pyrrolidone and the like can be mentioned. These may be used alone or in combination of two or more.

Examples of the monomer having two polymerizable unsaturated groups in one molecule include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate and polyethylene glycol di (meth).
Acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate,
1,4-butanediol di (meth) acrylate, 1,
6-hexanediol di (meth) acrylate, bisphenol A polyethylene oxide modified di (meth) acrylate, bisphenol A polypropylene oxide modified di (meth) acrylate, 2-hydroxy-1
-Acryloxy-3-methacryloxypropane, tricyclodecane dimethanol di (meth) acrylate, di (meth) acryloyloxyethyl acid phosphate, Kayarad HX-220, 620, R-60.
4, MANDA (all manufactured by Nippon Kayaku Co., Ltd.) and the like.

Examples of the monomer containing three or more polymerizable unsaturated groups in one molecule include trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide-modified tri (meth) acrylate,
Trimethylol propane propylene oxide modified tri (meth) acrylate, glycerin tri (meth) acrylate, glycerin ethylene oxide modified tri (meth) acrylate, glycerin propylene oxide modified tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra Examples include (meth) acrylate, isocyanuric acid ethylene oxide-modified triacrylate, and dipentaerythritol hexa (meth) acrylate. These monomers may be used alone or in any mixture of two or more.

The above-mentioned other resins and monomers can be added in an amount of about 200 parts by weight or less based on 100 parts by weight of the unsaturated group-containing urethane resin.

In addition to the above, the active energy ray-curable composition of the present invention contains dyes, pigments, various additives (polymerization inhibitor, leveling agent, defoaming agent, anti-sagging agent), if necessary.
Addition of adhesion improvers, paint surface modifiers, plasticizers, nitrogen-containing compounds, etc.), cross-linking agents (eg epoxy resins, etc.), other resins, or solvents such as organic solvents to facilitate coating. You can

The active energy ray-curable composition of the present invention is
It can be used as an organic solvent-based active energy ray-curable composition, a solventless (low solvent-based) active energy ray-curable composition, and a water-based active energy ray-curable composition. The organic solvent-based active energy ray-curable composition is obtained by dissolving or dispersing the above-mentioned unsaturated group-containing urethane resin and photopolymerization initiator in an organic solvent. Further, the solventless active energy ray-curable composition can be produced by producing the alicyclic compound (a) without using an organic solvent. When the alicyclic compound (a) is produced using an organic solvent, the alicyclic compound (a) can be obtained by decompressing this with a vacuum pump or the like to remove a part or all of the organic solvent.

The aqueous active energy ray-curable composition is obtained by neutralizing the carboxyl group of an unsaturated group-containing urethane resin containing or not containing an organic solvent with a basic neutralizing agent, and then dissolving or dispersing it in water. . In the water-based active energy ray-curable composition, when an organic solvent is used, it is neutralized, diluted with water, and then reduced in pressure with a vacuum pump or the like to remove a part or all of the organic solvent to obtain a low solvent or no solvent. The water-based active energy ray-curable composition can be produced.

As the above-mentioned basic neutralizing agent, for example,
Sodium hydroxide, potassium hydroxide, lithium hydroxide,
Hydroxides of alkali metals or alkaline earth metals such as calcium hydroxide and barium hydroxide; ammonia; triethylamine, tripropylamine, tributylamine,
Examples thereof include monomethyldimethylethanolamine and triethanolamine. These may be used alone or in combination of two or more. The mixing ratio of the basic neutralizing agent is preferably in the range of 0.1 to 2 equivalents, particularly 0.2 to 1.5 equivalents based on the acid groups of the unsaturated group-containing urethane resin.

The active energy ray-curable composition of the present invention comprises
Well-known photosensitive materials that are generally used, such as paints, inks, adhesives, etching resist materials, solder resist materials, plating resist materials, photo via build-up insulating materials, printing plate materials (plate-making materials for flat plates and letterpress, offset It can be used for a wide range of applications such as printing PS plates) information recording materials, relief image making materials, and coating materials for optical fibers.

The active energy ray-curable composition is applied to the surface of the substrate by spray coating, electrostatic coating, spin coating, dip coating,
It is painted by means of roller painting, curtain flow painting, silk printing, etc.

When the object to be coated is electrically conductive (eg, a copper-clad substrate), it can be applied by the anion electrodeposition coating method. The anion electrodeposition coating used in the anion electrodeposition coating has the above-mentioned aqueous active energy ray-curable composition in a concentration (solid content) of 3 to 25% by weight, particularly 5 to 15% by weight and a pH of 7 to 9. The thing adjusted to the range can be used as a bath paint. The anion electrodeposition paint can be applied to the surface of the conductor, which is the object to be coated, in the following manner, for example. That is, first, the pH and bath concentration of the bath are adjusted within the above ranges, and the bath temperature is controlled at about 15 ° C to about 40 ° C, preferably about 15 ° C to about 30 ° C. Next, the conductor to be coated is immersed as an anode in the electrodeposition coating bath controlled in this way, and a direct current is passed between the cathode and the cathode so that the electrodeposition voltage is in the range of about 5V to about 300V. A suitable energization time is about 10 seconds to about 5 minutes. The aqueous active energy ray-curable composition can be coated by electrodeposition coating, followed by draining, air blowing, etc., and if necessary, drying at a temperature in the range of about 50 to 130 ° C.

The film thickness of the active energy ray-curable composition coating film is generally in the range of about 0.5 to 100 μm, preferably about 1 to 50 μm.

The light ray used for curing the active energy ray-curable composition is not particularly limited as long as it cures the active energy ray-curable composition of the present invention, and conventionally known rays can be used. Examples of the light beam include ultraviolet light, visible light, and laser light (near infrared light, visible light laser, ultraviolet laser, etc.).

The irradiation amount is usually 0.2 to 2,000 m.
J / cm ² , preferably within the range of 1 to 1,000 mJ / cm ² .

The organic solvent-based active energy ray-curable composition, the low solvent-based active energy ray-curable composition and the water-based active energy ray-curable composition of the present invention are applied to a support substrate and dried to obtain a dry film. Can be used.

The active energy ray-curable composition coating film on the surface of the dry film is preferably formed of a resin which does not adhere to the coating film or the coating film or the supporting substrate when wound and stored. For this, the softening temperature of the resin is preferably in the range of about 10 to 200 ° C, particularly 15 to 100 ° C.

The supporting base material used in the present invention can be easily attached to the surface of an adherend (for example, a printed circuit board) while fixing the active energy ray-curable resin layer on the supporting base material. It is a base material provided so that it can be. As the substrate, for example, any of polyethylene terephthalate film, aramid, Kapton, polymethylpentene, polyethylene, polypropylene and the like films can be used, but in particular, using polyethylene terephthalate film is cost and active energy ray curable. It is suitable for obtaining good characteristics as a dry film.

The thickness of the supporting substrate is usually about 10 μm to about 5 μm.
mm, particularly preferably in the range of about 15 μm to about 500 μm.

An active energy ray-curable resin dry film is produced by applying or printing the above-mentioned active energy ray-curable composition on these supporting substrates by a roller method, a spray method, a silk screen method or the like. be able to. Of course, a release agent (silicone, wax, etc.) may be applied to the supporting substrate in advance in order to enhance the releasability of the coating film of the active energy ray-curable composition from the substrate.

The film thickness of the active energy ray-curable resin layer is
Usually 10 μm to 200 μm, especially 15 μm to 150 μm
The range of is preferable. The resin composition applied or printed on the surface of the supporting substrate can be heat-laminated and attached to a substrate or the like.

After the dry film is attached to the substrate, the base material is peeled off and developed.

Method for forming resist pattern Next, one example of forming a resist pattern using the active energy ray-curable composition of the present invention will be described.

The active energy ray-curable composition of the present invention used for forming a resist pattern is preferably one using an unsaturated group-containing urethane resin having a carboxyl group as a raw material of the composition.

The resist pattern comprises (1) a step of coating the active energy ray-curable composition of the present invention on a substrate to form a film, (2) active energy ray curing for a photoresist formed on the substrate. A step of exposing and curing with a laser beam directly or through a negative mask so as to obtain a desired resist film (image) on the surface of the composition film; (3) alkali developing treatment of the resist film formed in the above step (2) Then, it can be formed by the step of forming a resist pattern on the substrate.

Examples of the above-mentioned substrate include plastic films and plastic plates such as electrically insulating glass-epoxy plates, polyethylene terephthalate films, and polyimide films; metal foils such as copper and aluminum on the surfaces of these plastic plates and plastic films. Or a metal such as copper, nickel, or silver, or a compound such as a conductive oxide represented by indium-tin oxide (ITO) by vacuum deposition, chemical vapor deposition, plating, or the like to form a conductive film. Formed: Plastic plate or plastic film provided with through holes and conductive film formed on the surface and through holes: Metal plate such as copper plate: Patterned copper through hole printed wiring board, etc. To be

When the active energy ray-curable composition is an organic solvent-based or water-based composition in the coating (1) step, spray coating, electrostatic coating, spin coating, dip coating, roller coating, curtain flow coating on the surface of the substrate. It is possible to form an active energy ray-curable composition coating film by coating by means such as silk printing, performing setting if necessary, and drying at a temperature in the range of about 50 to 130 ° C.

The film thus formed is then exposed in the step (2). If necessary, oxygen is blocked from the surface of the film in order to prevent the curing of the photosensitive film due to the exposure. A publicly known non-photosensitive cover coat layer can be provided.

The exposure is performed by a photomask method in which an image is formed by irradiating an actinic ray such as an ultraviolet ray through a film (photomask) on which a pattern is drawn, or an image is formed by directly drawing with a laser beam or the like. The resist pattern can be formed by the LDI method.

When the active energy ray-curable composition is an electrodeposition coating composition, it is subjected to electrodeposition coating followed by draining, air blowing, etc., and if necessary dried at a temperature in the range of about 50 to 130 ° C. By performing the above, the photosensitive resin film can be formed. The film thickness of the above-mentioned photosensitive resin film is preferably about 0.5 to 100 μm, particularly preferably about 1 to 50 μm.

The light beam used in the exposure step (2) is
Any conventionally known one can be used without particular limitation as long as it cures the active energy ray-curable composition of the present invention. Examples of the light beam include ultraviolet light, visible light, and laser light (near infrared light, visible light laser, ultraviolet laser, etc.).

The irradiation amount is usually 0.5 to 2,000 m.
J / cm ² , preferably within the range of 1 to 1,000 mJ / cm ² .

Further, as the light irradiation source, those which have been conventionally used, for example, ultra-high pressure, high pressure, medium pressure and low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, fluorescent lamps, A light source obtained by each light source such as a tungsten lamp or sunlight, a light ray in the visible region cut by an ultraviolet cut filter, or various lasers having an oscillation line in the visible region can be used. As a high-power and stable laser light source, for example, an argon ion laser (488 nm) or a second harmonic wave (532 nm) of a YAG laser is preferable.

To wash out the uncured film in the developing treatment (3), a weak alkaline aqueous solution obtained by diluting caustic soda, sodium carbonate, caustic potash, ammonia, amine and the like in water is usually used. When the cover coat is provided, it is preferable to remove the cover coat before the development processing.

When a copper-clad base material is used, the exposed copper layer (non-circuit portion) is removed by etching with an aqueous solution of ferric chloride or cupric chloride. Also,
The resist film is removed with a strong alkali such as caustic soda or a solvent such as methylene chloride.

[0081]

EFFECTS OF THE INVENTION A coating composition using an unsaturated group-containing urethane resin for curing active energy rays of the present invention has a high photocuring rate, and in particular, has scratch resistance, stain resistance after resin curing,
Excellent flexibility and weather resistance (light resistance), for paints,
It can be used as a surface modifier or printing ink, a molded article such as an optical disk, a photoresist, etc., and is extremely practical.

[0082]

EXAMPLES The present invention will be described in more detail below with reference to examples. The present invention is not limited to the examples described below, and the "parts" in the synthesis examples and examples
And "%" are based on weight.

Synthesis of Unsaturated Group-Containing Urethane Resin Example 1 600 parts of the following alicyclic compound (a1) was placed in a four-necked flask equipped with a cooling tube, a thermometer and a stirrer.

[0084]

[Chemical 7]

Hexamethylene diisocyanate (336 parts) and hydroquinone (0.2 parts) were added, and the mixture was stirred while blowing air, heated to 80 ° C., and kept at 80 ° C. for 3 hours while controlling heat generation with cold water for reaction. Next, 0.2 part of dibutyltin dilaurate was added, and the mixture was further added at 80 ° C. for 6 hours.
After maintaining for a while, it was confirmed that almost no residual isocyanate group was observed, and the unsaturated group-containing urethane resin A-
1 (unsaturation degree 3.2 mol / kg; number average molecular weight 940)
Got

Example 2 400 parts of the alicyclic compound (a1) used in Example 1 was placed in a four-necked flask equipped with a cooling tube, a thermometer and a stirrer.
Hexamethylene diisocyanate (504 parts) and hydroquinone (0.2 parts) were added and stirred while blowing air,
After raising the temperature to 80 ℃, control the heat generation with cold water.
The reaction was carried out by holding at 3 ° C for 3 hours. Next, 0.2 part of dibutyltin dilaurate was added, and after holding at 80 ° C. for 3 hours, 232 parts of 2-hydroxyethyl acrylate was added and reacted at that temperature for 5 hours. It was confirmed that almost no residual isocyanate group was observed, and the unsaturated group-containing urethane resin A-2 (unsaturation degree: 3.5 mol / kg;
A number average molecular weight of 1,200) was obtained.

Example 3 The alicyclic compound (a1) 1,000 used in Example 1 was placed in a four-necked flask equipped with a cooling tube, a thermometer and a stirrer.
Parts, 1,008 parts of hexamethylene diisocyanate and 0.4 parts of hydroquinone were placed in a four-necked flask, stirred while blowing air, heated to 80 ° C, and then heated to 80 ° C for 3 hours while controlling heat generation with cold water. Hold and react. Next, 0.4 part of dibutyltin dilaurate was added, and after holding at 80 ° C. for 3 hours, 232 parts of 2-hydroxyethyl acrylate was added and reacted at that temperature for 5 hours. It was confirmed that almost no residual isocyanate group was observed, and unsaturated group-containing urethane resin A-3
(Unsaturation degree 3.1 mol / kg; number average molecular weight 2,20
0) was obtained.

Example 4 100 parts of the alicyclic compound (a1) used in Example 1, 252 parts of hexamethylene diisocyanate and PP-200 were placed in a four-necked flask equipped with a cooling tube, a thermometer and a stirrer.
0 (manufactured by Sanyo Kasei Sannix Co., polypropylene glycol having a molecular weight of 2,000) (1,000 parts) and hydroquinone (0.3 parts) were added, and the mixture was stirred while blowing air,
After heating up to 0 ℃, control the heat generation with cold water to 80 ℃
It was kept for 3 hours to react. Next, 0.3 part of dibutyltin dilaurate was added, and after holding at 80 ° C. for 3 hours, 116 parts of 2-hydroxyethyl acrylate was added and reacted at that temperature for 5 hours. It was confirmed that almost no residual isocyanate group was observed, and the unsaturated group-containing urethane resin A-4 (unsaturation degree 1.0 mol / k) was used.
g; number average molecular weight 3,000) was obtained.

Example 5 400 parts of the alicyclic compound (a1) used in Example 1, 666 parts of isophorone diisocyanate and 0.3 part of hydroquinone were placed in a four-necked flask equipped with a cooling tube, a thermometer and a stirrer. Agitate while blowing air at 80 ℃
After heating up to 80 ℃, control the heat generation with cold water to 3 ℃.
Hold for time to react. Next, 0.3 part of dibutyltin dilaurate was added, and the mixture was kept at 80 ° C. for 3 hours, and then 2
232 parts of hydroxyethyl acrylate were added and reacted at that temperature for 5 hours. It was confirmed that almost no residual isocyanate group was observed, and thus an unsaturated group-containing urethane resin A-5 (unsaturation degree 3.1 mol / kg; number average molecular weight 1,300) was obtained.

Example 6 A four-necked flask equipped with a cooling tube, a thermometer and a stirrer was charged with 400 parts of the alicyclic compound (a1) used in Example 1, 522 parts of tolylene diisocyanate and 0.2 part of hydroquinone. Put it in and stir it while blowing air at 80 ℃
After heating up to 80 ℃, control the heat generation with cold water to 3 ℃.
Hold for time to react. Next, 0.2 part of dibutyltin dilaurate was added, and the mixture was kept at 80 ° C. for 3 hours, and then 2
232 parts of hydroxyethyl acrylate were added and reacted at that temperature for 5 hours. It was confirmed that almost no residual isocyanate group was observed, and thus an unsaturated group-containing urethane resin A-6 (unsaturation degree 3.1 mol / kg; number average molecular weight 1,200) was obtained.

Example 7 400 parts of the alicyclic compound (a1) used in Example 1, 504 parts of hexamethylene diisocyanate and 0.3 part of hydroquinone were placed in a four-necked flask equipped with a cooling tube, a thermometer and a stirrer. And stir while blowing air, 80
After the temperature was raised to 0 ° C., the temperature was kept at 80 ° C. for 3 hours to control the reaction while controlling the heat generation with cold water. Next, 0.3 part of dibutyltin dilaurate was added, and after holding at 80 ° C. for 5 hours,
Aronix M-305: 1,026 parts (Pentaerythritol triacrylate manufactured by Toagosei Co., Ltd.) was added, and the reaction was carried out at that temperature for 5 hours. It was confirmed that almost no residual isocyanate group was observed, and the unsaturated group-containing urethane resin A-7 (unsaturation degree 4.3 mol / k) was used.
g; number average molecular weight 1,500) was obtained.

Example 8 In a four-necked flask equipped with a cooling tube, a thermometer and a stirrer, 300 parts of the alicyclic compound (a1) used in Example 1, 80 parts of glycerin monomethacrylate, 504 parts of hexamethylene diisocyanate and Hydroquinone (0.2 parts) was added, the mixture was stirred while blowing air, and the temperature was raised to 80 ° C., and then the temperature was maintained at 80 ° C. for 3 hours to control the reaction while controlling the heat generation with cold water. Next, 0.2 part of dibutyltin dilaurate was added, and the mixture was further held at 80 ° C. for 3 hours, and then 232 parts of 2-hydroxyethyl acrylate was added, and the mixture was heated at that temperature for 5 hours.
Reacted for hours. It was confirmed that almost no residual isocyanate groups were observed, and an unsaturated group-containing urethane resin A-8 (unsaturation degree 3.1 mol / kg; number average molecular weight 1,100) was obtained.

Example 9 428 parts of the following alicyclic compound (a2) was placed in a four-necked flask equipped with a cooling tube, a thermometer and a stirrer.

[0094]

[Chemical 8]

Hexamethylene diisocyanate (504 parts) and hydroquinone (0.2 parts) were added, and the mixture was stirred while blowing in air, heated to 80 ° C., and kept at 80 ° C. for 3 hours while controlling heat generation with cold water for reaction. Next, 0.2 part of dibutyltin dilaurate was added, and the mixture was further held at 80 ° C. for 3 hours, and then 2-hydroxyethyl acrylate 23
Two parts were added and the reaction was carried out at that temperature for 5 hours. It was confirmed that almost no residual isocyanate group was observed, and the unsaturated group-containing urethane resin A-9 (unsaturation degree 3.4) was used.
Mol / kg; number average molecular weight 1,200) was obtained.

Example 10 In a four-necked flask equipped with a cooling tube, a thermometer and a stirrer, 428 parts of the following alicyclic compound (a3),

[0097]

[Chemical 9]

Hexamethylene diisocyanate (504 parts) and hydroquinone (0.2 parts) were added, and the mixture was stirred while blowing in air, heated to 80 ° C., and kept at 80 ° C. for 3 hours while controlling heat generation with cold water to react. Next, 0.2 part of dibutyltin dilaurate was added, and the mixture was further mixed at 80 ° C. for 3 days.
After holding for 2 hours, 2-hydroxyethyl acrylate 2
32 parts was added and the reaction was carried out at that temperature for 5 hours. It was confirmed that almost no isocyanate group remained, and thus an unsaturated group-containing urethane resin A-10 (unsaturation degree: 3.4 mol / kg; number average molecular weight: 1,200) was obtained.

Example 11 The alicyclic compound (a1) 1,000 used in Example 1 was placed in a four-necked flask equipped with a cooling tube, a thermometer and a stirrer.
, 840 parts of hexamethylene diisocyanate, 291 parts of Sumidule N-3500 (HMDI isocyanurate manufactured by Sumitomo Bayer Urethane Co., Ltd.), 60 parts of phenyl isocyanate, and hydroquinone 0.
After adding 5 parts and stirring while blowing air, the temperature was raised to 80 ° C., and then the reaction was performed by maintaining the temperature at 80 ° C. for 3 hours while controlling the heat generation with cold water. Next, 0.5 part of dibutyltin dilaurate was added, and the mixture was kept at 80 ° C. for 3 hours.
232 parts of hydroxyethyl acrylate was added and the reaction was carried out at that temperature for 5 hours. It was confirmed that almost no isocyanate group remained, and thus an unsaturated group-containing urethane resin A-11 (unsaturation degree 2.9 mol / kg; number average molecular weight 2,400) was obtained.

Example 12 In a four-necked flask equipped with a cooling tube, a thermometer and a stirrer, 1123 parts of methyl isobutyl ketone, 800 parts of the alicyclic compound (a1) used in Example 1, and 444 parts of dimethylolbutanoic acid were used. Hexamethylene diisocyanate 1,26
After adding 0 part and 0.6 part of hydroquinone to the mixture while stirring and raising the temperature while blowing air, the temperature is adjusted to 80 with cold water.
The reaction was carried out by holding at 3 ° C for 3 hours. Next, 0.6 part of dibutyltin dilaurate was added, and after holding at 80 ° C. for 3 hours, 116 parts of 2-hydroxyethyl acrylate was added and reacted at that temperature for 5 hours. After confirming that almost no remaining isocyanate group was observed, 624 parts of propylene glycol monomethyl ether was added and cooled to obtain an unsaturated group-containing urethane resin solution A-12 having a solid content of 60%. The acid value of the obtained resin is 57 mgKOH
/ G, degree of unsaturation 2.0 mol / kg, number average molecular weight 5,3
It was 00.

Example 13 In a four-necked flask, 672 parts of methyl isobutyl ketone, 600 parts of the alicyclic compound (a1) used in Example 1, 296 parts of dimethylolbutanoic acid, 840 parts of hexamethylene diisocyanate and 0.3 parts of hydroquinone. Add parts and stir while blowing air and heat. While controlling the exotherm with cold water, the mixture is kept at 80 ° C. for 3 hours for reaction. Next, 0.3 part of dibutyltin dilaurate was added, and the mixture was further held at 80 ° C. for 6 hours to confirm that almost no isocyanate group remained, and then 373 parts of propylene glycol monomethyl ether was added and cooled to obtain an unsaturated group. A 60% solution A-1 containing urethane resin (acid value 72 mg KOH / g; degree of unsaturation 1.9 mol / kg; number average molecular weight 1,600)
Got 3.

Example 14 758 parts of methyl isobutyl ketone in a four-necked flask, 400 parts of the alicyclic compound (a1) used in Example 1, 296 parts of dimethylolbutanoic acid, 840 parts of hexamethylene diisocyanate, 0.4 parts of hydroquinone. Part of the mixture is stirred and blown with air to raise the temperature. While controlling the exotherm with cold water, the mixture is kept at 80 ° C. for 3 hours for reaction. Next, 0.4 part of dibutyltin dilaurate was added, and the mixture was further held at 80 ° C. for 3 hours, and then 2-hydroxyethyl acrylate 232
Parts are added and reacted at that temperature for 5 hours. After confirming that almost no remaining isocyanate group was observed, propylene glycol monomethyl ether 421
Parts and cool, and then unsaturated group-containing urethane resin (acid value 64
A 60% solution A-14 having a degree of unsaturation of 2.3 mol / kg and a number average molecular weight of 1,800 was obtained.

Example 15 1123 parts of methyl isobutyl ketone in a four-necked flask,
The alicyclic compound (a1) used in Example 1 (800 parts), dimethylolbutanoic acid (444 parts), hexamethylene diisocyanate (1,260 parts), and hydroquinone (0.6 parts) were added, and the mixture was stirred while blowing air to raise the temperature. While controlling the exotherm with cold water, the mixture is kept at 80 ° C. for 3 hours for reaction. Next, 0.6 part of dibutyltin dilaurate is added, and after holding at 80 ° C. for 3 hours, 116 parts of 2-hydroxyethyl acrylate is added and reacted at that temperature for 5 hours. After confirming that almost no remaining isocyanate group was observed, 624 parts of propylene glycol monomethyl ether was added and cooled, and an unsaturated group-containing urethane resin (acid value 57 mgKOH / g; degree of unsaturation 2.0 mol / kg; A 60% solution A-15 having a number average molecular weight of 5,300 was obtained.

Example 16 873 parts of methyl isobutyl ketone, 600 parts of the alicyclic compound (a1) used in Example 1, 296 parts of dimethylolbutanoic acid, 1100 parts of isophorone diisocyanate, and 0.10 parts of hydroquinone were placed in a four-necked flask. Add 4 parts, stir while blowing air, and heat. While controlling the exotherm with cold water, the mixture is kept at 80 ° C. for 3 hours for reaction. Next, 0.4 part of dibutyltin dilaurate was added, and the mixture was further held at 80 ° C. for 5 hours, and then 2-hydroxyethyl acrylate 232
Parts are added and the temperature is allowed to react for 5 hours. After confirming that almost no remaining isocyanate groups were observed, 485 parts of propylene glycol monomethyl ether were added and cooled, and an unsaturated group-containing urethane resin (acid value 55 m
A 60% solution A-16 having a degree of unsaturation of 2.0 mol / kg; a number average molecular weight of 2,000) was obtained.

Example 17 771 parts of methyl isobutyl ketone, 400 parts of the alicyclic compound (a1) used in Example 1, 296 parts of dimethylolbutanoic acid and 3 parts of tolylene diisocyanate were placed in a four-necked flask.
48 parts and 0.4 parts of hydroquinone are added and stirred while blowing air to raise the temperature. Controlling heat generation with cold water 8
Hold at 0 ° C. for 3 hours to react. Next, 0.4 part of dibutyltin dilaurate was added, and after holding at 80 ° C. for 5 hours, 232 parts of 2-hydroxyethyl acrylate was added and reacted at that temperature for 5 hours. After confirming that almost no residual isocyanate groups were observed,
428 parts of propylene glycol monomethyl ether was added and cooled, and an unsaturated group-containing urethane resin (acid value 62 mgK
A 60% solution A-17 having an OH / g; an unsaturation degree of 2.2 mol / kg; a number average molecular weight of 1,800) was obtained.

Example 18 981 parts of methyl isobutyl ketone, 400 parts of the alicyclic compound (a1) used in Example 1, 370 parts of dimethylolbutanoic acid, 924 parts of hexamethylene diisocyanate and 0.5 parts of hydroquinone were placed in a four-necked flask. Add parts and stir while blowing air and heat. While controlling the exotherm with cold water, the mixture is kept at 80 ° C. for 3 hours for reaction. Next, 0.5 part of dibutyltin dilaurate was added, and the mixture was further held at 80 ° C. for 5 hours, then, 1,026 parts of pentaerythritol triacrylate (Toagosei M-305) was added, and the reaction was carried out at that temperature for 5 hours. After confirming that almost no residual isocyanate group was observed, 703 parts of propylene glycol monomethyl ether was added and cooled, and an unsaturated group-containing urethane resin (acid value 41 mg KOH / g; unsaturated degree 3.2 mol / kg; A 60% solution A-18 having a number average molecular weight of 2,300 was obtained.

Example 19 749 parts of methyl isobutyl ketone, 300 parts of the alicyclic compound (a1) used in Example 1, 296 parts of dimethylolbutanoic acid, 80 parts of glycerin monomethacrylate and 840 parts of hexamethylene diisocyanate were placed in a four-necked flask. Department,
Add 0.3 parts of hydroquinone, stir while blowing air, and heat. While controlling heat generation with cold water, 3 at 80 ℃
Hold for time to react. Next, 0.3 part of dibutyltin dilaurate was added, and the mixture was kept at 80 ° C. for 5 hours, and then 2
232 parts of hydroxyethyl acrylate are added and reacted at that temperature for 5 hours. After confirming that almost no residual isocyanate group was observed, 416 parts of propylene glycol monomethyl ether were added and cooled, and an unsaturated group-containing urethane resin (acid value 64 mgKOH /
g; Unsaturation degree: 2.0 mol / kg; Number average molecular weight: 1,80
A 60% solution A-19 of 0) was obtained.

Example 20 In a four-necked flask, 770 parts of methyl isobutyl ketone, 428 parts of the alicyclic compound (a2) used in Example 9, 296 parts of dimethylolbutanoic acid, 840 parts of hexamethylene diisocyanate and 0.4 parts of hydroquinone. Part of the mixture is stirred and blown with air to raise the temperature. While controlling the exotherm with cold water, the mixture is kept at 80 ° C. for 3 hours for reaction. Next, 0.4 part of dibutyltin dilaurate was added, and the mixture was further held at 80 ° C. for 3 hours, and then 2-hydroxyethyl acrylate 232
Parts are added and reacted at that temperature for 5 hours. After confirming that almost no remaining isocyanate group was observed, propylene glycol monomethyl ether 428
Parts and cooled, and the unsaturated group-containing urethane resin (acid value 62
A 60% solution A-20 having a mgKOH / g; an unsaturation degree of 2.2 mol / kg; a number average molecular weight of 1,800) was obtained.

Example 21 In a four-necked flask, 768 parts of methyl isobutyl ketone, 424 parts of the alicyclic compound (a3) used in Example 10, 296 parts of dimethylolbutanoic acid, 840 parts of hexamethylene diisocyanate and 0.4 parts of hydroquinone. Part of the mixture is stirred and blown with air to raise the temperature. While controlling the exotherm with cold water, the mixture is kept at 80 ° C. for 3 hours for reaction. Next, 0.4 part of dibutyltin dilaurate was added, and the mixture was further held at 80 ° C. for 3 hours, and then 2-hydroxyethyl acrylate 23
Add 2 parts and react at that temperature for 5 hours. After confirming that almost no remaining isocyanate group was observed, propylene glycol monomethyl ether 42
7 parts were put and cooled, and unsaturated group-containing urethane resin (acid value 6
A 60% solution A-21 having a degree of unsaturation of 2.2 mol / kg and a number average molecular weight of 1,800 was obtained.

Example 22 The alicyclic compound (a used in Example 1 was used in a four-necked flask.
1) 600 parts, 296 parts of dimethylolbutanoic acid, 840 parts of hexamethylene diisocyanate in a four-necked flask,
Sumijour N-3500 (Sumitomo Bayer Urethane Co., Ltd., HMDI isocyanurate) 291 parts, phenyl isocyanate 60 parts, and hydroquinone 0.5 part are put and stirred while blowing air, and heated to 80 ° C., and then with cold water. While controlling the exotherm, the mixture was kept at 80 ° C. for 3 hours for reaction. Next, 0.5 part of dibutyltin dilaurate was added, and the mixture was further held at 80 ° C. for 3 hours, then 232 parts of 2-hydroxyethyl acrylate was added and reacted at that temperature for 5 hours. It was confirmed that almost no residual isocyanate groups were found, and unsaturated group-containing urethane resin A
-22 (acid value 57 mg KOH / g; degree of unsaturation 2.5 mol / kg; number average molecular weight 2,000) was obtained.

Synthesis of Resin Containing Unsaturated Group for Comparative Example Synthesis Example 1 168 parts of hexamethylene diisocyanate and molecular weight of 2 in a four-necked flask equipped with a cooling tube, a thermometer and a stirrer.
1000 parts of polypropylene glycol (Sanyo Kasei Sannix, PP-2000) and 0.5 parts of hydroquinone were added and stirred while blowing air, and the temperature was raised to 80 ° C. Hold for time to react. Next, 0.5 part of dibutyltin dilaurate was added, and the mixture was kept at 80 ° C. for 3 hours.
116 parts of hydroxyethyl acrylate was added, and the mixture was reacted at that temperature for 5 hours. It was confirmed that almost no residual isocyanate groups were observed, and an unsaturated group-containing urethane resin B-1 (unsaturation degree 0.8 mol / kg; number average molecular weight 2,700) was obtained.

Synthetic Example 2 The same procedure as in Synthetic Example 1 was carried out except that 222 parts of isophorone diisocyanate was used instead of 168 parts of hexamethylene diisocyanate. Unsaturated group-containing urethane resin B-2
(Unsaturation degree 0.7 mol / kg; number average molecular weight 2,70
0) was obtained.

Synthesis Example 3 Unsaturated group-containing urethane resin B-3 (unsaturation degree 0.8 mol / kg) except that 174 parts of tolylene diisocyanate was used instead of 168 parts of hexamethylene diisocyanate in Synthesis Example 1. A number average molecular weight of 2,600) was obtained.

Synthesis Example 4 Methyl methacrylate 40 parts, butyl acrylate 21
Part, acrylic acid 39 parts, and azobisisobutyronitrile 2 parts under a nitrogen gas atmosphere,
It was added dropwise to 90 parts of propylene glycol monomethyl ether kept at 10 ° C. over 3 hours. After the dropping, the mixture was aged for 2 hours, a mixed solution of 1 part of azobisdimethylvaleronitrile and 12 parts of propylene glycol monomethyl ether was added dropwise over 1 hour, and the mixture was aged for 5 hours to obtain a high acid value acrylic resin (acid. Value 155mgKOH / g)
A solution was obtained. Next, 50 parts of glycidyl methacrylate, 0.12 part of hydroquinone and 0.6 part of tetraethylammonium bromide were added to the melted night, and the mixture was reacted at 110 ° C. for 5 hours while blowing air to obtain a photocurable resin (acid value of about 69 mgKOH / g; degree of unsaturation 2.3 mol / kg,
A solution B-4 having a number average molecular weight of about 20,000 was obtained.

Synthesis Example 5 506 parts of methyl isobutyl ketone, 626 parts of tolylene diisocyanate, polyethylene glycol (molecular weight 60
0) 1,080 parts and 178 parts of dimethylolbutanoic acid were placed in four flasks and stirred, and the mixture was kept at 100 ° C for 2 hours and then cooled to 80 ° C. Hydroquinone 0.5 parts and 2-hydroxyethyl methacrylate 13 at 80 ° C
Add 9 parts and stir for 5 hours while blowing air. After confirming that almost no remaining isocyanate groups were observed, 843 parts of propylene glycol monomethyl ether were added and cooled, and an unsaturated group-containing polyurethane resin (acid value 33.2 mg KOH / g; degree of unsaturation 0.59) was added. Mol / kg; A solution B-5 having a number average molecular weight of about 3.372) was obtained.

Active energy ray-curable composition Example 23 100 parts of the unsaturated group-containing urethane resin A-1 obtained in Example 1 and 10 parts of Aronix M-220 (tripropylene glycol diacrylate manufactured by Toagosei Co., Ltd.) Then, a solution of 4 parts of Irgacure 651 (manufactured by Ciba-Geigy, a photopolymerization initiator) dissolved in 10 parts of methyl ethyl ketone was added and mixed by stirring to obtain an active energy ray-curable composition.

Examples 24 to 33 and Comparative Examples 1 to 3 In the same manner as in Example 23, each active energy ray-curing composition was obtained with the composition shown in Table 1 below.

Example 34 Unsaturated group-containing urethane resin solution A obtained in Example 12
-12 parts to 167 parts (100 parts solids) Aronix M
A solution of 10 parts of -220 (Toagosei Co., Ltd., tripropylene glycol diacrylate) and 4 parts of Irgacure 651 (Ciba Geigy Co., photopolymerization initiator) dissolved in 10 parts of methyl ethyl ketone was added, and then 4 parts of triethylamine was added. After neutralizing and stirring well to dissolve the mixture uniformly, 266 parts of deionized water are added to 1,000.
The mixture was gradually added with stirring at ˜3,000 rpm, and after the addition was completed, the mixture was further stirred at 500 rpm for 20 minutes to obtain an aqueous dispersion. Next, the solvent was distilled off under reduced pressure to obtain an aqueous active energy ray-curable composition (solid content 30%).

The active energy ray-curable compositions obtained in Examples 23 to 34 and Comparative Examples 1 to 3 were applied to a thickness of 0.5 mm.
Dry film thickness of 20 μm on dull steel plate of × 70 mm × 150 mm
After coating with a bar coater to 50 mj / cm ² with a 600 W metal halide lamp, the test coated plate 1 is irradiated with 50 mj / cm ² and with a 600 W metal halide lamp for 10 minutes.
Irradiation with 0 mj / cm ² gave a test coated plate 2. In addition, about Example 34, 1 degree at 80 degreeC before active energy ray irradiation.
It was dried for 0 minutes. The coating film performance of the obtained test coated plate was evaluated by the following evaluation methods. The evaluation results are shown in Table 1 below. The formulations in Table 1 are shown by solid content weight ratio.

Evaluation method Coating film curability: For the test coated plates 1 and 2, the coating film was rubbed with gauze impregnated with methyl ethyl ketone, and evaluated according to the following criteria. ◯: Good for rubbing 5 or more reciprocations, Δ: good for rubbing 2 to 4 reciprocations, ×: rubbing is observed after rubbing 1 or 2 reciprocations.

Surface Curability: With respect to the test coated plate 2, the stickiness of the coating film was evaluated by touching with a finger according to the following criteria. ◯: No stickiness when touched for 3 minutes or more, Δ: Sticky feeling when touched within 3 minutes, ×: Sticky feeling immediately after touching the finger.

Pencil hardness: For test coated plate 2, JIS
The pencil scratch test defined in K-5400 8.4.2 (1990) was performed to evaluate the scratches.

Bending test: Test coated plate 2 was bent 180 degrees from the center of the coated plate, and the presence or absence of cracks in the coating film was evaluated according to the following criteria. ◯: No cracks (thin, small cracks pass), ×: Large cracks or cracks occurred.

DuPont type impact test: using test coated plate 2,
A hemispherical weight of 300 g having a diameter of 15 mm was dropped onto the coated plate from a height of 10 cm, and the state of the film due to impact was evaluated according to the following criteria. ◯: No cracks (thin, small cracks pass), ×: Large cracks or cracks occurred.

[0125]

[Table 1]

Use as active energy ray-curable composition for resist as liquid resist Example 35 167 parts of the resin solution (A-13) prepared in Example 13 was mixed with Aronix M-310 (manufactured by Toagosei Co., Ltd., trimethylolpropane propylene). A solution prepared by dissolving 5 parts of oxide-modified triacrylate), 5 parts of Irgacure 907 (trade name, manufactured by Ciba-Geigy Co., Ltd.) and 2 parts of diethylthioxanthone in 10 parts of propylene glycol monomethyl ether is added, and the solid content becomes 50%. like,
Propylene glycol monomethyl ether was added to obtain an active energy ray-curable composition for resist.

Examples 36 to 44 and Comparative Examples 4 and 5 Active energy ray curable compositions for resists were obtained in the same manner as in Example 35 except for the formulation shown in Table 2 below. The compounding amount is shown by the solid content weight.

The active energy ray curable compositions for resists obtained in Examples 35 to 44 and Comparative Examples 4 and 5 had a thickness of 0.
27mm (glass epoxy thickness 0.20mm, copper thickness 0.0
A 35 mm × 2) double-sided copper clad laminate was coated with a bar coater to a dry film thickness of 15 μm and dried at 80 ° C. for 10 minutes. The uncured film was pressed with a finger to check the tackiness, and the tackiness of the uncured film was evaluated.

Then, a test pattern negative mask film (line (μm) / space (μm) = 150/150,
100/100 and 50/50 patterns: exposure has the same meaning below), and this coated plate was brought into close contact with the coated plate by a vacuum device, and a 3 kw ultra high pressure mercury lamp was used.
Irradiated ² times. Next, the substrate was passed through a roller-conveying type spray developing device, and the unexposed portion was washed out with a 1% aqueous solution of sodium carbonate at 30 ° C. for 30 seconds for development. The film state after the roller transportation was examined and the damage to the developing roller transportation was evaluated.

Further, a bending test in which this plate was bent 90 degrees in an arm-bent shape was carried out to evaluate the film breakage, peeling and adhesion of the resist image lines.

Also, a DuPont type impact test (using a DuPont type impact tester: a hemispherical 300 g weight having a diameter of 15 mm is dropped onto a plate from a height of 10 cm), and the resist image line is broken or peeled off. Was evaluated.

After that, the plate was returned to a flat state, and after the etching treatment with cupric chloride, the resist film was peeled off with a 5 wt% caustic soda solution at 50 ° C. to obtain a printed wiring board. The film removal pattern state of this printed wiring board was evaluated.

Exposure was carried out at 150 mJ / cm ² and the exposure sensitivity (the number of steps) was obtained using a 21-step step tablet film after development (the light transmittance was reduced to 1 / √2 as the number of steps increased from 0 to 1 / √2).

The evaluation results are shown in Table 2.

[0135]

[Table 2]

Use as Dry Film Example 45 The active energy ray-curable composition for resist of Example 36 was applied on the surface of polyethylene terephthalate (thickness: 50 μm) with a bar coater to a dry film thickness of 15 μm,
When dried at 80 ° C. for 10 minutes, a dry film having no tackiness was obtained.

Then, heated to 100 ° C., the thickness is 0.27 m.
m (glass epoxy thickness 0.2 mm, copper thickness 0.035 mm
It was laminated on the copper clad laminate of (2) to form a photosensitive coating on the surface of the copper clad laminate. Further, it was irradiated with 150 mJ / cm ² using a 3 kw ultra-high pressure mercury lamp. Next, the unexposed area was washed with a 1% sodium carbonate aqueous solution at 30 ° C. for 30 seconds and developed. The pattern was not damaged by the transport of the developing roller. Further, when this plate was bent 90 degrees in an arm-bent shape and the state of the resist image line was examined, there was no film breakage or peeling, and the adhesion was good and the good state was maintained. In addition, DuPont type impact test (using DuPont type impact tester: diameter 1
A 5 mm hemispherical 300 g weight is dropped onto the plate from a height of 10 cm. ), The resist image line was not broken or peeled, and a good state was maintained. After that, the plate was returned to a flat state, and after etching with cupric chloride, the resist film was removed with a 5% caustic soda aqueous solution at 80 ° C. to obtain a printed wiring board. The film removal pattern shape was good. Also 150 mJ / cm ²
The exposure sensitivity of the 21-step step tablet film upon irradiation was 8 steps, and the sensitivity was also good.

Example 46 The active energy ray-curable composition for resist of Example 38 was applied on the surface of polyethylene terephthalate (thickness: 50 μm) with a bar coater so that the dry film thickness would be 15 μm.
It was dried at 80 ° C. for 10 minutes to obtain a tack-free dry film.

Then, heated to 100 ° C., the thickness is 0.27 m.
m (glass epoxy thickness 0.2 mm, copper thickness 0.035 mm
It was laminated on the copper clad laminate of (2) and the polyethylene terephthalate was peeled off to form a photosensitive coating on the surface of the copper clad laminate.

Further, using a 3 kw ultra-high pressure mercury lamp, 1
Irradiation was carried out at 50 mJ / cm ² . Next, the unexposed area is 30 ° C.
It was washed with a 1% aqueous solution of sodium carbonate for 30 seconds and developed. The pattern was not damaged by the roller conveyance. Further, when this plate was bent 90 degrees in an arm-bent shape and the state of the resist image line was examined, there was no film breakage or peeling, and the adhesion was good and the good state was maintained. In addition, when a DuPont type impact test (using a DuPont type impact tester: a hemispherical 300 g weight having a diameter of 15 mm is dropped onto a plate from a height of 10 cm), the strength against impact is examined, and a resist image line is formed. There was no breakage or peeling, and it was in good condition. After that, the plate was returned to a flat state, and after etching treatment with cupric chloride, the resist film was removed with a 5% caustic soda solution at 50 ° C. to obtain a printed wiring board. The film removal pattern shape was good.

The exposure sensitivity of the 21-step step tablet film when irradiated with 150 mJ / cm ² is 8
The sensitivity was good as well.

Active energy ray curing composition for aqueous resist
Material and coating film evaluation Example 47 Unsaturated group-containing urethane resin solution obtained in Example 15 (A-
15) To 167 parts, a solution of Aronix M-310: 5 parts, a photopolymerization initiator Irgacure 907: 5 parts and diethylthioxanthone 2 parts in 10 parts of propylene glycol monomethyl ether and 4 parts of a neutralizing agent triethylamine are added. After uniformly dissolving the mixture, 1,408 parts of deionized water is added in an amount of 1,000 to 3,000.
The mixture was gradually added with stirring at 0 rpm, and after the addition was completed, the mixture was further stirred at 500 rpm for 20 minutes to obtain an aqueous dispersion (solid content: 11%). Using a chemical pump, 2 this aqueous dispersion
A circulation stability test was carried out at a circulation rate of 0.5 to 1 / min at 5 ° C. In each of the cases where the circulation time was 24 hours, 120 hours, and 240 hours, there was no precipitation of the initiator, which was good.
Further, when the aqueous dispersion was allowed to stand as it was and a stationary storage stability test was conducted, it was stable in a wide temperature range of 5 to 30 ° C. for 6 months, and precipitation of the initiator was not observed.

Further, using a water dispersion immediately after preparation of the above-mentioned water dispersion, after 240 hours of the above circulation test, and after 6 months of static storage stability test (30 ° C.), the water dispersion has a thickness of 0.2.
7 mm (glass epoxy thickness 0.20 mm, copper thickness 0.03
5mm x 2) copper clad laminate as anode and current density 100
Electric current was applied for 60 seconds at mA / cm ² to perform electrodeposition coating.
The substrate was washed with water after electrodeposition coating, drained and dried at 80 ° C. for 10 minutes to obtain a resist film having a dry film thickness of 5 to 8 μm and no tack. All samples were good with no change in the electrodeposition bath characteristics before and after the test.

Next, a negative film for a printed circuit board pattern was brought into close contact with this coated plate by a vacuum device, and irradiation was performed with a 3 kw ultra-high pressure mercury lamp at an exposure dose of 200 mJ / cm ² , and the film was immersed in a 1% sodium carbonate aqueous solution for development. The pattern was not damaged by the roller conveyance.

When this plate was bent 90 degrees into an arm-bent shape and the state of the image was examined, there was no film breakage or peeling, and the adhesion was good and a good state was maintained. In addition, the DuPont-type impact test (using the DuPont-type impact tester: a hemispherical 300 g weight of 15 mm in diameter is dropped onto the plate from a height of 10 cm) and the strength against impact was examined. It was in good condition with no breakage or peeling.

After that, the plate was flattened and subjected to etching treatment with cupric chloride, and then the resist film was removed with a 1 wt% caustic soda solution at 50 ° C. to obtain a printed wiring board. The film removal pattern shape was good.

The exposure sensitivity of the 21-step step tablet film when irradiated with 150 mJ / cm ² is 8
The sensitivity was good as well.

Continued front page    F-term (reference) 4J027 AA01 AB03 AB36 AC03 AC04                       AC06 AE10 AG04 AG09 AG13                       AG14 AG23 AG24 AG26 AG27                       AG28 AJ01 AJ06 AJ08 AJ09                       BA07 BA08 BA10 BA13 BA14                       BA15 BA19 BA20 BA21 BA24                       BA26 CA32 CA34 CB10 CD08                       CD09 CD10                 4J034 CA03 CA04 CA05 CA13 CA22                       CB03 CB04 CB05 CB07 CB08                       CC02 CC03 CC08 CC23 CC26                       CC45 CC54 CC61 CC65 CC67                       CD04 DA01 DB04 DB07 DF01                       DF12 DG03 DG04 DG06 DG08                       FA02 FA04 FB01 FC01 FC03                       FC04 FC05 FD01 FD07 FE02                       FE04 GA66 GA72 HA02 HA06                       HA07 HA08 HA18 HB05 HB07                       HB08 HB11 HB12 HB17 HC03                       HC11 HC12 HC13 HC17 HC22                       HC35 HC46 HC52 HC61 HC64                       HC67 HC71 HC73 JA02 JA14                       JA30 KA01 KB02 KC08 KC13                       KC16 KC17 KC18 KC23 KD02                       KD12 KD25 KD27 KE01 KE02                       LA13 LA16 LA23 LA33 LA36                       QA05 QA07 QB14 QB17 QC05                       RA07 RA08 RA14 RA16

Claims (7)

[Claims] 1. An unsaturated group-containing compound characterized by being obtained by reacting (a) at least one alicyclic compound selected from the following general formulas (I) to (VI), and (b) an isocyanate compound. Urethane resin. [Chemical 1] In the formula, R1 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and In the formula, R ₂ represents an ethylene group or a propylene group, and m is 0.
The integer of -10, n represents the integer of 1-10. 2. An unsaturated group-containing urethane resin obtained by reacting the alicyclic compound (a), the isocyanate compound (b) and the polyol compound (c). 3. The unsaturated group-containing urethane resin according to claim 2, wherein a part or all of the polyol compound (c) is a carboxyl group-containing polyol. 4. The unsaturated group-containing urethane resin according to claim 3, wherein the carboxyl group in the resin is neutralized with a basic neutralizing agent and dispersed in water. 5. The unsaturated group-containing urethane resin has an unsaturation degree of 0.2 to 5.0 mol / kg and a number average molecular weight of 400 to 1.
Any one of claims 1 to 4, which is in the range of 0,000.
The unsaturated group-containing urethane resin according to the item. 6. A photopolymerization initiator is added in an amount of 0.1 to 15 parts by weight to 100 parts by weight of the unsaturated group-containing urethane resin (solid content) according to any one of claims 1 to 5. An active energy ray-curable composition which is a thing. 7. (1) A step of applying an active energy ray-curable composition comprising the unsaturated group-containing urethane resin according to claim 3 and a photopolymerization initiator onto a substrate, (2) forming on the substrate A step of exposing the active energy ray-curable composition to a desired resist coating (image) on the surface of the composition and exposing it to a laser beam, or exposing the composition through a negative mask to cure the composition; and (3) forming the step (2). Forming a resist pattern on the substrate by subjecting the resist coating film to alkali development.