JP2001342232A - Active ray-curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active ray-curable composition containing a photosensitive liquid having better storage stability than a conventional photosensitive liquid and excellent in adhesivity to a base material. SOLUTION: The active ray-curable composition comprises a polyurethane resin (A) and a photopolymerization initiator (B). The component (A) is a polyurethane resin derived from an organic polyisocyanate (A1) and a polyol (A2) consisting of a polydienepolyol.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an actinic ray-curable composition. More specifically, the present invention relates to an actinic ray curable composition that can be suitably used for a photosensitive layer such as a photosensitive resist film, a photoresist, a photosensitive resin relief plate, a photosensitive flexographic plate, a screen plate, an optical adhesive, and a hard coat agent. .

[0002]

2. Description of the Related Art Conventionally, for example, an actinic ray-curable composition used for a photosensitive resin relief printing plate is a photosensitive composition containing a polyurethane resin having an allyl group in a side chain, an ethylenically unsaturated compound and a photopolymerization initiator. Objects are known (for example, JP-A-3-4225).

[0003]

However, this has a problem that storage stability is poor.

[0004]

Means for Solving the Problems The inventors of the present invention have sincerely studied to solve the above problems, and as a result, the storage stability of a photosensitive solution has been remarkably improved by using a polyurethane resin containing a polydiene polyol as a polyol component. And reached the present invention.

That is, the present invention relates to an actinic ray-curable composition comprising a polyurethane resin (A) and a photopolymerization initiator (B), wherein (A) comprises an organic polyisocyanate (A1) and a polydiene polyol (a1). ), Which is a polyurethane resin derived from a polyol (A2) comprising: a cured product obtained by curing the composition with actinic light; and visible light applied to the composition. And a method of producing a cured resin by irradiating at least one type of active light selected from the group consisting of UV light and laser light.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION As the organic polyisocyanate (A1) constituting the polyurethane resin (A) in the present invention, those conventionally used for producing polyurethane can be used. Such polyisocyanates include:
For example, carbon number (excluding carbon in NCO group, and so on)
6-20 aromatic polyisocyanates [1,3- and / or 1,4-phenylene diisocyanate, 2,4
-And / or 2,6-tolylene diisocyanate (TDI), 2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI) and the like]; an aliphatic polyisocyanate having 2 to 18 carbon atoms [ethylene diisocyanate, Hexamethylene diisocyanate (HD
I), lysine diisocyanate, etc.]; an alicyclic polyisocyanate having 4 to 15 carbon atoms [isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-
Diisocyanate (hydrogenated MDI), methylcyclohexylene diisocyanate, etc .; araliphatic polyisocyanate having 8 to 15 carbon atoms [xylene diisocyanate (X
DI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI) and the like]; modified products of these polyisocyanates (urethane group, carbodiimide group, uretoimine group, isocyanurate group, and oxazoline group-containing modified products) Etc.) and mixtures of two or more of these.

The diene constituting the polydiene polyol (a1) used for the polyol (A2) in the present invention includes alkadiene having 4 to 10 carbon atoms [conjugated diene (butadiene, isoprene, etc.), non-conjugated diene (pentadiene, Hexadiene, octadiene, etc.], carbon number 5
To 10 cyclic dienes (cyclopentadiene, dicyclopentadiene, ethylidene norbornene, etc.) and the like. Preferred are conjugated alkadienes. (A1)
Contains a polydiene polyol (functional group number: 2 to 3) composed of at least one of the above-mentioned dienes and a hydride thereof (hydrogenation ratio: 50% or less). Specific examples include polybutadiene polyol, partial hydrogenation (hydrogenation rate 50
% Or less) polybutadiene polyol, polyisoprene polyol, partially hydrogenated (hydrogenation rate 50% or less) polyisoprene polyol, and the like.

[0008] Of those exemplified as the above (a1), preferred are polybutadiene polyols, and particularly preferred are those having a 1,2-butadiene unit microstructure.
50 mol% or more of vinyl (preferably 70 mol% or more,
Particularly preferably, it is 90 mol% or more). The content of the 1,2-vinyl compound is, for example, NM
It can be measured by R.

The number average molecular weight of (a1) [based on GPC method (in terms of polystyrene). The same applies to the following.
000, preferably 600 to 4,000, and more preferably 700 to 3,000. Number average molecular weight is 500
If less than 5, there is a problem that the resin properties after curing become brittle,
If it exceeds 000, the adhesion to the substrate will be reduced. The (a
The hydroxyl value of 1) is usually 25 to 300, preferably 30 to 300.
200. The double bond content is usually 10 to 50% by weight, preferably 30 to 45% by weight.

The content of the polydiene polyol (a1) in the polyol (A2) is usually at least 1% by weight, preferably at least 3% by weight, more preferably at least 5% by weight, based on the weight of the polyol component (A2). It is. If the content of (a1) is less than 1% by weight, the adhesion to the substrate will be reduced.

As the polyol (A2), an organic acid (salt) group-containing polyol (a2) is preferably used together with the above (a1) for the purpose of further improving the adhesion of the polyurethane resin (A) to the substrate. . Examples of the organic acid (salt) group include a carboxylic acid (salt) group and a sulfamic acid (salt)
Groups, sulfonic acid (salt) groups and phosphate (salt) groups.

The salts include alkali metal salts, tertiary amine salts and quaternary ammonium salts. Examples of the alkali metal include potassium, sodium, and lithium. As the tertiary amine, the alkyl group has 1 to 8 carbon atoms.
(Trimethylamine, triethylamine, tributylamine, etc.), mono-, di- and trialkanolamines having 2 to 4 carbon atoms of a hydroxyalkyl group (triethanolamine, etc.). Examples of the quaternary ammonium salt include a tetraalkylammonium salt of an alkyl group having 1 to 8 carbon atoms, such as a methyltriethylammonium salt and a methyltributylammonium salt. Of these, preferred are alkali metals, and particularly preferred are potassium and sodium.

The (a2) includes a carboxylic acid (salt) group-containing polyol (a21), a sulfamic acid (salt) group-containing polyol (a22), a sulfonic acid (salt) group-containing polyol (a23), and a phosphate ester (salt). ) Group-containing polyol (a24).

The polyol (a21) containing a carboxylic acid group is, for example, an alkane group having 2 to 2 carbon atoms.
12 α, α-dimethylolalkanoic acids (α, α-dimethylolpropionic acid, α, α-dimethylolbutanoic acid, α, α-dimethylolnonanoic acid, etc.);
Alkylene (e.g., C2-6) glycol (e.g., ethylene glycol, propylene glycol, etc.) monoester of oxycarboxylic acid (e.g., tartaric acid, citric acid, malic acid, etc.), e.g., 1 mole of citric acid and 1 mole of ethylene glycol Ester (molecular weight 240, acid value 468, hydroxyl value 468), ester of malic acid 1 mol and ethylene glycol 1 mol (molecular weight 178, acid value 3)
15, hydroxyl value 630); and salts thereof. Of these, preferred are α, α-dimethylolalkanoic acids, and more preferred are α, α-dimethylolpropionic acid (hereinafter abbreviated as DMPA) and α, α-dimethylolbutanoic acid.

The sulfamic acid (salt) group in the polyol (a22) containing the sulfamic acid (salt) group is represented by the following general formula: [In the formula, X represents hydrogen, an alkali metal, a tertiary amine or a quaternary ammonium cation. ] It is a group shown by these.

As (a22), for example, N, N
-Dihydroxyalkylsulfamic acid (having 2 to 4 carbon atoms in the hydroxyalkyl group); a polyether polyol having a sulfamic acid (salt) group (number average molecular weight of 300 to
5,000, preferably 400 to 4,000, more preferably 500 to 3,000), for example, the above-mentioned (poly) oxyalkylene (C2-4) ether; sulfamic acid (salt) group-containing polyester polyol (number Average molecular weight 500-5,000, preferably 600-
4,000), for example, a polyester of the above and / or with a dicarboxylic acid (for example, one used as a raw material for a condensed polyester polyol described later), and a sulfamic acid (salt) group-containing dicarboxylic acid (having 8 to 1 carbon atoms)
2, for example, 2-sulfaminoterephthalic acid, 3-sulfaminophthalic acid, 5-sulfaminoisophthalic acid, etc.)
And polyesters of polyols; and lactones of the above and / or (C4-12, e.g.
Adducts such as caprolactone). Among these, preferred are sulfamic acid (salt) group-containing diols and sulfamic acid (salt) group-containing polyether polyols.

The above-mentioned raw material sulfamic acid (salt)
Examples thereof include sulfamic acid, sodium sulfamate, triethylamine sulfamate, triethanolamine sulfamate, methyltriethylammonium sulfamate and the like. As the synthesis method, for example, sulfamic acid (salt) is mixed in an alkylene oxide, and gradually heated at normal pressure or under pressure in the presence of an alkaline catalyst (for example, potassium hydroxide or the like), usually at 80 to 200 ° C. Can be exemplified.

In the above and below, the alkylene oxide is an alkylene oxide having 2 to 4 carbon atoms,
For example, ethylene oxide (EO), propylene oxide (PO), 1,2-, 2,3-, 1,3- or 1,4-butylene oxide and a combination of two or more thereof (random and / or block addition) Is mentioned. Preferred are EO, PO and combinations thereof (block and / or random addition).

The sulfamic acid (salt) group-containing polyester polyol can be obtained by esterification by a known method. The equivalent ratio (OH / COOH) of the hydroxyl group to the carboxyl group during the esterification is usually (1.1 to 5) / 1, preferably (1.5 to 3) / 1.

Examples of the sulfamic acid (salt) group-containing dicarboxylic acid include an amino group of an amino group-containing dicarboxylic acid having 8 to 12 carbon atoms (eg, 2-aminoterephthalic acid, 3-aminophthalic acid, 5-aminoisophthalic acid, etc.). -NH-
A compound having a structure in which SO ₃ X is substituted is exemplified. As a synthesis method, for example, after reacting the amino group-containing dicarboxylic acid with a pyridine-sulfur trioxide complex in an aqueous alkaline solution at a temperature of about 0 to 40 ° C., the reaction product is re-used with a solvent (ethanol, acetone, etc.). An example is a method of obtaining the desired product by purification by a method such as crystallization. Examples of the polyol include glycols, for example, those exemplified as dihydric alcohols described below, and combinations of these with trihydric alcohols described below (equivalent ratio: 100/0 to 95/5).

As the polyol (a23) containing a sulfonic acid (salt) group, a polyester of a dicarboxylic acid containing a sulfonic acid (salt) group and a polyol (number average molecular weight of 400 to 5,000, preferably 500 to 3) , 00
0).

Examples of the dicarboxylic acid containing a sulfonic acid (salt) group include 5-sulfoisophthalic acid, 2-sulfoterephthalic acid, sodium 5-sulfoisophthalate,
-Sulfoisophthalic acid potassium salt, 2-sulfoterephthalic acid sodium salt, 2-sulfophthalic acid potassium salt and the like. Of these, preferred are sodium 5-sulfoisophthalate and potassium 5-sulfoisophthalate. The equivalent ratio (OH / COOH) of the hydroxyl group of the glycol component and the carboxyl group of the sulfonic acid (salt) group-containing dicarboxylic acid in (a23) is usually (1.
1-5) / 1, preferably (1.5-3) / 1.

The phosphate (salt) group in the phosphate (salt) group-containing polyol (a24) has the following general formula: [Wherein, R ′ represents an alkyl group having 1 to 24 carbon atoms;
X is the same as in the general formula (1). ] It is a group represented by these. Preferred as R 'is an alkyl group having 3 to 18 carbon atoms. Particularly preferred as X are potassium and sodium. Examples of the (a24) include a trihydric or higher polyol [trihydric alcohol (for example, glycerin, trimethylolpropane, triethanolamine, etc.) and / or a (poly) oxyalkylene (C2-4) triol [ For example, the above-mentioned alkylene oxide (co) adduct of trihydric alcohol]] and an ester of monoalkyl phosphoric acid (number average molecular weight 250
To 3,000, preferably 500 to 2,000). Of these, preferred are esters of propylene oxide adduct of glycerin (molecular weight 250 to 1,000 or more) with monoalkyl phosphoric acid and sodium salts thereof. Examples of the monoalkyl phosphoric acid include monoalkyl phosphates having 1 to 24 carbon atoms in the alkyl group (eg, monomethyl phosphate, monobutyl phosphate, monohexyl phosphate, monooctyl phosphate, monolauryl phosphate, monostearyl phosphate, etc.).

As a method for synthesizing (a24), for example, 1 mol of triol (for example, 1 to 5 mol of PO of glycerin, preferably 1.2 to 4 mol of adduct) and 1 mol of monoalkylphosphoric acid (for example, monobutyl phosphate) Can be heated in a solvent inert to both (eg, methyl ethyl ketone) or in the absence of a solvent. The reaction temperature is usually from 40 to 160 ° C.

(A2) [(a21) to (a21)]
(A24)] may be used in combination of two or more. (A2)
(A21) and (a22) are preferred. The number of functional groups (the number of hydroxyl groups) of the (a2) is usually 2 to 3,
It is preferably from 2 to 2.5, and the hydroxyl value is usually from 50 to 9
00, preferably 80 to 850.

If necessary, other high molecular polyol (a3) and / or low molecular polyol (a4) can be used together with (a1) or (a1) and (a2). (A3) includes polyether polyols, polyester polyols, and mixtures thereof. The number average molecular weight of the (a3) is usually 500 to
It is 5,000, preferably 600-4,000.

Examples of the polyether polyol include low molecular polyols [aliphatic dihydric alcohols having 2 to 20 carbon atoms (ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, neopentyl glycol, Methyl-
1,5-pentanediol, 1,6-hexanediol, etc.), an alicyclic dihydric alcohol having 6 to 15 carbon atoms (such as cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol A), and an aromatic compound having 8 to 15 carbon atoms Ring-containing dihydric alcohols (such as xylylene glycol) and trihydric alcohols (such as glycerin and trimethylolpropane);
Dihydric phenols [monocyclic dihydric phenols (catechol,
Hydroquinone, etc.), bisphenols (bisphenol A, bisphenol S, bisphenol F, etc.)] etc.]
And mixtures of two or more of these. Preferred specific examples of the polyether polyol include polypropylene glycol, polyoxyethylene polyoxypropylene (block and / or random) glycol, polyoxytetramethylene glycol, and the like.

Examples of the polyester polyol include dicarboxylic acids [aliphatic dicarboxylic acids having 4 to 36 carbon atoms (adipic acid, sebacic acid, azelaic acid, maleic acid, dimer acid, etc.), aromatic dicarboxylic acids having 8 to 15 carbon atoms] (Phthalic acid, terephthalic acid, isophthalic acid, etc.), their ester-forming derivatives [anhydrides, lower alkyl (C1-4) esters, acid halides, etc.] etc.] and the polyether polyol. Condensed polyester polyols obtained by polycondensation with one or more of the low-molecular polyols exemplified as the starting material (for example, polyethylene adipate diol, polyethylene butylene adipate diol, polyhexamethylene isophthalate diol, etc.); More than 4 to 12 carbon atoms Ton (γ- butyrolactone, ε
Polylactone polyols (eg, polycaprolactone diol, etc.) obtained by ring-opening addition of -caprolactone, γ-valerolactone, etc .; obtained by reacting at least one of the above low molecular weight polyols with a carbonate ester (dimethyl carbonate, etc.) Castor oil-based polyols (castor oil, a transesterification product of castor oil with a di- to tri-hydric alcohol, etc.).

Examples of the low molecular polyol (a4) include those described in the above examples as starting materials for the polyether polyol.
And low-molar adducts of alkylene oxides and alkylene oxides (molecular weight less than 500) and low-molar adducts of alkylene oxides of dihydric phenols (molecular weight less than 500). When (a4) is used in combination, the amount used is generally 20% by weight or less, preferably 15% by weight or less, based on the weight of the polyol (A2).

The proportion of (a2) in the polyol (A2) is 98% by weight or less, preferably 40 to 95% by weight,
The ratio of (a3) is 40 equivalent% or less, preferably 2-35%.
Equivalent%. The average number of functional groups of (A2) is usually 2 to
2.5, preferably 2 to 2.3. The (A)
The average hydroxyl value of 2) is usually from 80 to 600, preferably 1
And the content of the organic acid (salt) group is (A)
2) less than 7 meq / g, preferably 1.5-6
It is a milliequivalent.

In producing the polyurethane resin (A) by reacting the organic polyisocyanate (A1) with the polyol (A2), the equivalent ratio (NCO) of (A1) to (A2)
/ OH ratio) is usually 0.6 to 1.7, preferably 0.8 to 1.7.
1.3. When the equivalent ratio is less than 0.6 or more than 1.7, the resin strength of (A) is insufficient, and the abrasion resistance of the cured resin,
Scratch resistance, hydrolysis resistance, etc. decrease. The urethanization reaction can be performed in the presence or absence of a solvent inert to isocyanate. Examples of the solvent include ester solvents (such as ethyl acetate and butyl acetate), ether solvents (such as dioxane and tetrahydrofuran),
Ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), aromatic hydrocarbon solvents (toluene, xylene, etc.) and their two
A mixed solvent of at least one kind is exemplified. Of these, ether solvents, particularly tetrahydrofuran, are preferred.
When a solvent is used, the amount thereof is such that the concentration of (A) becomes 50% or less, preferably 5 to 25% by weight.

As a reaction method, a method in which (A1) and (A2) are charged into a reaction vessel at once and a reaction is performed; a method in which (A1) and (A2) are divided and subjected to a multi-stage reaction; ) And (A2) through a heated multi-screw extruder to cause a reaction. The reaction temperature is usually 30 to 180 ° C, preferably 60 to 120 ° C.
Further, catalysts usually used in urethane reactions to accelerate the reaction, such as tin-based catalysts (trimethyltin laurate, trimethyltin hydroxide, dimethyltin dilaurate, dibutyltin dilaurate, stannas octoate, etc.), lead-based catalysts (red Olate, Red 2
-Ethylhexoate), an amine catalyst (such as triethylenediamine) and the like may be used. The amount of the catalyst used is 3% by weight or less, preferably 1% by weight or less based on the weight of (A).

In the above reaction, a reaction terminator (a5) can be used if necessary. As (a5), 1
Polyhydric alcohol [aliphatic monohydric alcohol having 1 to 10 carbon atoms (eg, methanol, ethanol, propanol, butanol, octanol, ethyl cellosolve, ethyl carbitol, etc.), alicyclic monohydric alcohol having 6 to 12 carbon atoms (eg, cycloalkyl) Hexanol, etc.), an aromatic ring-containing monohydric alcohol having 7 to 20 carbon atoms [for example, benzyl alcohol,
(Poly) oxyalkylene of phenols (2 to 2 carbon atoms)
4) ethers etc.]; primary or secondary monoamines [mono- and dialkylamines having 1 to 10 carbon atoms in the alkyl group (eg, monoethylamine, diethylamine, monobutylamine, dibutylamine, etc.), 6 carbon atoms]
To 12 alicyclic monoamines (e.g., cyclohexylamine, etc.), C6-C15 aromatic ring-containing monoamines (e.g., aniline, benzylamine, etc.), heterocyclic monoamines (e.g., morpholine, etc.), hydroxyalkyl group having 2 to 2 carbon atoms 4 mono- and dialkanolamines (eg, monoethanolamine, diethanolamine, etc.) and the like];
And mixtures of two or more of these. Of these, preferred are monohydric alcohols, and more preferred are aliphatic monohydric alcohols, particularly methanol.

The polyurethane resin (A) thus obtained
Has a number average molecular weight of usually 5,000 to 80,000, preferably 8,000 to 50,000. If the number average molecular weight is less than 5,000, the resin properties deteriorate, and the durability of the cured product becomes poor. If it exceeds 80,000, the viscosity of the composition increases, and the workability decreases. The double bond content in (A) is usually 0.5 to 20% by weight, preferably 1 to 10% by weight from the viewpoint of obtaining good photocurability and adhesion.

By introducing the above-mentioned organic acid (salt) group into (A), the adhesion to the substrate is further improved.
The content of the organic acid (salt) group in (A) is preferably 3 meq. Or less, more preferably 0.7 to 3 meq., Particularly preferably 1 to 2.9 meq.

(A) in the actinic ray-curable composition of the present invention
Is usually 20-98% by weight, preferably 25-95% by weight, more preferably 3% by weight, based on the weight of the composition.
0 to 90% by weight. When the amount of (A) is less than 20% by weight, the adhesion to the substrate is reduced, and when it exceeds 98% by weight, the curability becomes poor.

The photopolymerization initiator (B) in the present invention includes, for example, benzoinalkyl (C1-4) ether, benzylalkyl (C1-4) ketanol,
-Hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1 phenylpropan-1-one,
Benzophenone, methylbenzoylformate, isopropylthiochitosan, α-carbonyl compound described in U.S. Pat. No. 2,367,661, U.S. Pat.
No. 8, acyloin ether described in US Pat.
No. 512, an α-hydrocarbon-substituted aromatic acyloin compound, a polycyclic quinone compound described in US Pat. No. 3,046,427, a triarylbiimidazole / p-aminophenyl ketone described in US Pat. No. 3,549,367, US Trihalomethyl-s-triazine compounds described in Japanese Patent No. 4239850, U.S. Pat.
Oxadiazole compounds described in No. 0, US Pat.
And the benzothiazole compounds described in JP-B-51-48516. Two or more of these photopolymerization initiators may be used in combination.

The amount of (B) is usually 0.05 to 5% by weight, preferably 0.1 to 3% by weight, based on the weight of the composition. When the amount of (B) is less than 0.05% by weight,
The resin after irradiation with actinic radiation becomes hard to cure, and if it exceeds 5% by weight, the storage stability of the photosensitive solution decreases.

In the present invention, the polyurethane resin (A)
If necessary, an addition-polymerizable ethylenically unsaturated compound (C) in an amount not exceeding 400% by weight based on the weight of (A) can be used together with the photopolymerization initiator (B). The (C) is a vinyl monomer or oligomer containing at least one, preferably two or more, more preferably four or more addition-polymerizable ethylenically unsaturated groups in the molecule. .

When the composition comprises (A), (B) and (C), each component is (A) in an amount of 20 to 98% by weight and (B) in an amount of 0.05 to 98% by weight based on the weight of the composition. 5% by weight, and (C) 1.95 to 80% by weight, preferably (A)
, 40 to 98% by weight, (B) 0.1 to 3% by weight, and (C) 1.9 to 60% by weight. If the weight ratio of (A) is less than 20%, the cured resin film becomes brittle, and if it exceeds 98%, the hardness of the cured resin film tends to decrease.

Examples of (C) include styrene monomer (C1) (styrene, α-methylstyrene, vinyltoluene, divinylbenzene, etc.), carboxyl group-containing vinyl monomer (C2) [(meta A) Acrylic acid, crotonic acid, etc.], sulfonic acid group-containing vinyl monomer (C3)
[Vinylsulfonic acid (salt), styrenesulfonic acid (salt)
Etc.], a phosphoric acid group-containing vinyl monomer (C4) [2-hydroxyethylethyl (meth) acryloyl phosphate, etc.], a hydroxyl group-containing vinyl monomer (C5) [hydroxyalkyl (2-4 carbon atoms) ( Meth) acrylates, such as hydroxyethyl (meth) acrylate,
Hydroxystyrene etc.], nitrogen-containing vinyl monomer (C6)
[N-dialkyl (C 1-4) aminoethyl (meth) acrylate, vinylpyrrolidone, etc.], epoxy group-containing vinyl monomer (C7) [glycidyl (meth) acrylate, etc.], halogen-containing vinyl monomer (C8)
(Vinyl chloride, etc.), vinyl ester monomer (C9)
(Vinyl acetate, vinyl propionate, etc.), vinyl ether monomer (C10) (vinyl ethyl ether, etc.), vinyl ketone monomer (C11) (vinyl ethyl ketone, etc.), alkyl (meth) acrylate (C12) [alkyl An alkyl (meth) acrylate having 1 to 20 carbon atoms such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, etc.],
Vinyl monomer having a polyoxyalkylene chain (C1
3) [polyethylene glycol (polymerization degree 2 to 10) mono (meth) acrylate, etc.], polyfunctional (meth) acrylates (C14) ｛bifunctional (meth) acrylate [ethylene glycol di (meth) acrylate, 1,2- And 1,3-propylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate,
Di (meth) acrylate of trimethylolpropane, di (meth) acrylate of alkylene oxide (2-4 carbon atoms) adduct (2-10 moles of addition) of bisphenols (bisphenol A, bisphenol S, bisphenol F, etc.), Polyethylene glycol (degree of polymerization 2
10 to 10) di (meth) acrylate, etc.], trifunctional (meth)
Acrylate [tri (meth) acrylate of glycerin, tri (meth) acrylate of trimethylolpropane, tri (meth) acrylate of pentaeristol,
Dipentaerythol tri (meth) acrylate, alkylene oxide-modified trimethylolpropane tri (meth) acrylate, etc.) and tetrafunctional or higher (meth)
Acrylates [tetra (meth) acrylate of pentaerythritol, tetra-, penta- and hexa (meth) acrylate of dipentaerythol, alkylene oxide-modified pentaerythritol tetra (meth) acrylate, alkylene oxide-modified dipentaerythrol hexa ( Meth) acrylates] and the like.

(C) [(C1) to (C1)
4)] may be used in combination of two or more. Preferred as (C) are (C13) and (C14), more preferably (C14), and particularly preferably (C1).
4) The (meth) acrylate having four or more functional groups.

If necessary, the composition of the present invention may contain a photosensitizer (eg, triethanolamine), a thermal polymerization inhibitor (eg, hydroquinone), an antifoaming agent, a leveling agent, a coupling agent (eg, silane cup). A known additive such as a ring agent) can be contained. The content of the additive is usually 5% by weight based on the weight of the composition.
Or less, preferably 3% by weight or less.

The photosensitive solution comprising the composition of the present invention has good storage stability, and is also excellent in photosensitivity and adhesion to a substrate, so that a photosensitive resist film, a photoresist, a photosensitive resin relief plate, a photosensitive resin It can be suitably used for a photosensitive layer such as a flexographic plate, a screen plate, a light adhesive, and a hard coat agent. Details of each of these uses are described, for example, in "Polysensitive Resin" edited by The Society of Polymer Science, Kyoritsu Shuppan (1988).

The composition of the present invention comprises an actinic ray (visible light,
(UV light, laser beam, etc.). Light sources include sunlight, high-pressure mercury lamps, low-pressure mercury lamps, metal halide lamps, and semiconductor lasers.

The use of the composition of the present invention is illustrated below. For example, a photosensitive resist film is formed by applying and drying the composition of the present invention on a transparent base film (eg, a polyester film having a thickness of 30 to 100 μm), and then forming a coating layer (the coating layer has a thickness of 5 to 100 μm). Is covered with a protective film (for example, a polyethylene film having a thickness of 10 to 50 μm or the like). When manufacturing a printed wiring board using this, the surface (photosensitive layer) from which the protective film of the photosensitive resist film has been peeled off is adhered to the surface copper-clad layer on the substrate, and the ultraviolet ray is passed through the wiring pattern forming film. Exposure (exposure amount 100 to 1,000 mJ / c
m ² ) to cure the exposed portions, and the non-exposed portions to a diluted alkaline aqueous solution (for example, a 0.5 to 5% NaOH aqueous solution).
By this, the wiring pattern is developed on the substrate. After the development, the copper-clad layer in the non-exposed portion is removed by etching, and the exposed portion (cured resin layer) is peeled off to finally obtain a printed wiring board.

In other uses of the composition of the present invention, the objective is achieved by irradiating the active layer with a photosensitive layer obtained by applying the composition to a substrate and drying the composition using a system similar to the above-described photosensitive resist. A cured product is obtained.

[0048]

EXAMPLES The present invention will be further described with reference to examples below, but the present invention is not limited to these examples. In the following, “part” indicates “part by weight” and “%” indicates “% by weight”.

Example 1 In a pressurized reaction vessel equipped with a pressure gauge, a stirrer and a thermometer,
Polypropylene glycol (number average molecular weight 1,030)
72.7 parts, polybutadiene polyol (number-average molecular weight 1,350, hydroxyl value 74, butadiene unit fine structure is 90 mol% or more of 1,2-vinyl compound) 8.1 parts, DMP
A36.3 parts, HDI 16.2 parts, MDI 71.0 parts,
800 parts of a solvent (tetrahydrofuran) and 0.6 part of a urethanation catalyst (dibutyltin dilaurate) were charged,
After the reaction at 80 ° C. for 24 hours, 10 parts of methanol was injected to stop the urethane reaction, and a polyurethane resin solution (A-1) having a solid content of 20% and a viscosity of 150 mPa · s (25 ° C.) was obtained. The resulting polyurethane resin had a number average molecular weight of 18,000 and a carboxylic acid group content of 1.35 meq / g of resin. This (A-1)
Was used to prepare a photosensitive solution (D-1) according to the following formulation. Polyurethane resin solution (A-1) 75 parts Dipentaerythrol hexaacrylate 10 parts 2- (4-styrylphenyl-4,6-bis (trichloromethyl) -s-triazine 0.5 part The (D-1) Applicator on aluminum plate with film thickness of 10μ
m, and then irradiated with ultraviolet light at 800 mJ / cm ² using a high-pressure mercury lamp to obtain a cured film (E-1).
I got

Example 2 37.6 parts of polypropylene glycol (number average molecular weight 1,030), polybutadiene polyol (number average molecular weight 1,350, hydroxyl number 7) were placed in the same reaction vessel as in Example 1.
4. The butadiene unit has a fine structure of 1,2-vinyl 90
50.8 parts, 33.7 parts of DMPA, HDI
11.1 parts, MDI 66.1 parts, tetrahydrofuran 8
After the reaction was carried out at 80 ° C. for 24 hours, methanol 10
Part to inject the urethane reaction, solid content 20%,
A polyurethane resin solution (A-2) having a viscosity of 145 mPa · s (25 ° C.) was obtained. The resulting polyurethane resin had a number average molecular weight of 18,500 and a carboxylic acid group content of 1.26 meq / g of resin. (A) of Example 1
Example 1 except that (A-2) was used instead of -1)
A photosensitive solution (D-2) was prepared according to the same formulation as described above. (D-2) is coated on an aluminum plate with an applicator to a thickness of 10 μm.
After coating and drying, a cured film (E-2) was obtained by irradiating with ultraviolet light at 800 mJ / cm ² using a high-pressure mercury lamp.

Example 3 In a reaction vessel similar to that of Example 1, 72.7 parts of polypropylene glycol (number average molecular weight 1,030), polybutadiene polyol (number average molecular weight 1,350, hydroxyl value 7
4. The butadiene unit has a fine structure of 1,2-vinyl 90
Mol% or more) 8.1 parts, [H- [OCH (CH ₃ ) C
H _{2] 4 (OCH 2 CH 2) 2} ] 209.7 parts of sulfamic acid base-containing diol having the structure of ₂ NSO ₃ K, HDI
16.2 parts, MDI 71.0 parts, tetrahydrofuran 8
After the reaction was carried out at 80 ° C. for 24 hours, methanol 10
Part to inject the urethane reaction, solid content 20%,
A polyurethane resin solution (A-3) having a viscosity of 155 mPa · s (25 ° C.) was obtained. The number average molecular weight of the obtained polyurethane resin was 16,000, and the content of potassium sulfamate group was 1.34 meq / g of resin.
A photosensitive solution (D-3) was prepared in the same manner as in Example 1 except that this (A-3) was used instead of (A-1) in Example 1. The (D-3) was applied to an aluminum plate with an applicator to a thickness of 10 μm and dried, and then irradiated with ultraviolet light at 800 mJ / cm ² using a high-pressure mercury lamp to obtain a cured film (E-3). Was.

Comparative Example 1 Based on the description in Example 1 of JP-A-3-4225, glycerol-
72.7 parts of α-monoallyl ether, DMPA 60.3
Parts, 250 parts of MDI, 1532 parts of solvent (dioxane) and 0.5 part of dibutyltin dilaurate.
After the reaction at 20 ° C. for 20 hours, 10 parts of methanol was injected to stop the urethane reaction, and the solid content was 20% and the viscosity was 22%.
0 mPa · s (25 ° C) polyurethane resin solution (A-
4) was obtained. The number average molecular weight of the obtained polyurethane resin was 11,000, and the content of the carboxylic acid group was 1.175 meq / g of the resin. (A-1) of Example 1
A comparative photosensitive solution (D-4) was prepared in the same manner as in Example 1 except that this (A-4) was used instead of (A-4). (D-4) is applied on an aluminum plate with an applicator to a thickness of 10 μm.
After coating and drying, a UV ray was irradiated at 800 mJ / cm ² using a high-pressure mercury lamp to obtain a cured film (E-4).

Comparative Example 2 80.9 parts of polypropylene glycol (number average molecular weight 1,030) and DMPA3 were placed in the same reaction vessel as in Example 1.
6.3 parts, HDI 11.9 parts, MDI 71.0 parts, tetrahydrofuran 800 parts and dibutyltin dilaurate 0.6 parts were charged and reacted at 80 ° C for 24 hours.
The urethane reaction was stopped by injecting 10 parts of methanol,
A polyurethane resin solution (A-5) having a solid content of 20% and a viscosity of 180 mPa · s (25 ° C.) was obtained. The number average molecular weight of the obtained polyurethane resin was 18,000, and the content of the carboxylic acid group was 1.35 meq / g of the resin.
Comparative photosensitive solution (D-A) was prepared in the same manner as in Example 1 except that (A-5) was used instead of (A-1) in Example 1.
5) was prepared. This (D-5) was applied to an aluminum plate with an applicator to a thickness of 10 μm, dried, and then irradiated with 800 mJ / cm ^{2 of} ultraviolet light using a high-pressure mercury lamp to obtain a cured film (E-5). Was.

Test Example 1 The photosensitive solution (D) obtained in Examples 1 to 3 and Comparative Examples 1 and 2
-1) to (D-5) were examined for storage stability. Table 1 shows the results. The storage stability was expressed as a value after one week, two weeks, and three weeks when the value was set to 100 based on the viscosity immediately after the preparation of the photosensitive solution. The smaller the change in the numerical value, the better the storage stability.

[0055]

[Table 1]

Test Example 2 The cured films (E) obtained in Examples 1 to 3 and Comparative Examples 1 and 2
-1) to (E-5) adhesion (Gobain test: JIS)
K 5400-1990). Table 2 shows the results. The larger the number remaining without being peeled off when the cellotape (registered trademark) is peeled, the better the adhesion.

[0057]

[Table 2]

[0058]

The active ray-curable composition of the present invention has the following effects. (1) The storage stability of the photosensitive solution is good and the storage stability for a long time is excellent. (2) A cured film having good adhesion to the substrate and excellent durability can be obtained. Due to the above effects, the active-curing line composition of the present invention is useful as a photosensitive layer such as a photosensitive resist film, a photoresist, a photosensitive resin relief plate, a photosensitive flexographic plate, a screen plate, an optical adhesive, and a hard coat agent. It is.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/028 G03F 7/028 7/035 7/035 F term (Reference) 2H025 AB02 AB06 AB11 AC01 AD01 BC32 BC42 BC66 BC81 CA01 CA28 FA03 FA17 4J011 QA01 QA02 QA03 QA09 QA12 QA13 QA23 QA24 QA34 QA37 QA39 QA40 QA42 QB11 SA21 SA36 SA51 SA64 SA78 UA01 WA01 4J027 AG05 AG23 AG24 AG25 BA04 BA05 BA18 BA18 BA18 BA18 BA16 BA18 BA16 BA18 BA16 BA18 BA18 BA18 BA18 BA18 BA18 BA18 BA18 BA18 BA18 BA18 BA18 BA18 BA18 CC03 CC09 DF02 DF11 DF12 DF16 DF20 DF22 DF33 DF34 DG02 DG03 DG04 DG14 DG27 DG28 GA06 GA07 GA12 GA23 GA33 HA01 HA07 HB06 HC03 HC09 HC12 HC17 HC22 HC34 HC35 HC46 HC52 HC64 HC67 HC71 HC73 QA05 RA08 RA14

Claims (9)

[Claims] 1. An actinic ray-curable composition comprising a polyurethane resin (A) and a photopolymerization initiator (B), wherein (A) comprises an organic polyisocyanate (A1) and a polydiene polyol (a1). An actinic ray-curable composition, which is a polyurethane resin derived from a polyol (A2). 2. A method according to claim 1, wherein (a1) has a number average molecular weight of 500 to 5,0
00, and the microstructure of butadiene units in the polybutadiene polyol is 1,
The composition according to claim 1, wherein the amount of the 2-vinyl compound is 50 mol% or more. 3. The composition according to claim 1, wherein (A2) further contains an organic acid (salt) group-containing polyol (a2). 4. The organic acid (salt) group in (a2) is selected from the group consisting of a carboxylic acid (salt) group, a sulfamic acid (salt) group, a sulfonic acid (salt) group, and a phosphate ester (salt) group. 4. The composition according to claim 3, which is at least one of the following: 5. The composition according to claim 1, further comprising an addition-polymerizable ethylenically unsaturated compound (C). 6. No more than 400% by weight based on the weight of the composition, 20 to 98% by weight of (A), 0.05 to 5% by weight of (B), and (A). 6. The composition according to claim 5, comprising an amount of (C). 7. The composition according to claim 1, which is used for a photosensitive layer of a photosensitive resist film, a photoresist, a photosensitive resin relief plate, a photosensitive flexographic plate, a screen plate, an optical adhesive or a hard coat agent. object. 8. A cured product obtained by curing the composition according to claim 1 with actinic light. 9. A method for producing a cured resin by irradiating the composition according to claim 1 with at least one actinic ray selected from the group consisting of visible light, ultraviolet light and laser light.