JPH089644B2 - Photopolymerizable composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a photopolymerizable composition, which has a high photosensitivity to visible light and is cured by a visible laser such as an argon ion laser. It relates to possible photopolymerizable compositions.

[Prior Art] A conventional photopolymerizable composition comprising an addition-polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator, and a binder polymer having a film-forming ability, which is added as necessary, As the initiator, photopolymerization initiators such as benzophenone, benzoin alkyl ether, benzyl dialkyl ketal and anthraquinone are widely used.

[Problems to be Solved by the Invention] However, although this initiator is sensitive to ultraviolet rays, it is hardly sensitive to visible rays.

In recent years, with the progress of laser scanning exposure technology, it has been desired to develop a photopolymerizable composition having high photosensitivity to the emission wavelength of a visible laser such as an argon laser. However, the photopolymerizable composition as described above is not economical because the compatibility with the laser emission wavelength is not sufficient and a high-power argon laser is required.

Further, various photosensitive resins and initiator compounds that are sensitive to visible light have been proposed, but none of them have sufficient practicality in terms of sensitivity, stability, economy and the like. Is the actual situation.

For example, the compound (a) which is one component of the initiator composition used in the photopolymerizable composition of the present invention is disclosed in JP-A-63-
It is described in Japanese Patent No. 10602, and even by itself it is sensitive to visible light and can be cured by a visible laser, for example, an argon ion laser, but it cannot be said that sufficiently high sensitivity is obtained. .

Further, JP-A-63-221110 discloses a compound (a) and a compound (a) which are one component of an initiator composition of the photopolymerizable composition of the present invention.
-It is described that the use of ketocoumarin in combination can solve the problem of scattering without lowering the sensitivity, but sufficient sensitivity to visible light has not been obtained.

An object of the present invention is to provide a photopolymerizable composition which has a high photosensitivity to visible light and can be exposed by scanning with a visible laser, for example, an argon ion laser.

[Means for Solving the Problems] As a result of intensive studies to achieve the above object, the present inventors have found that the following photopolymerizable composition containing a 3-substituted coumarin having a specific structure is: The inventors have found that they have high photosensitivity to visible light, and in particular, they are capable of scanning exposure with a visible laser, for example, an argon ion laser, and have completed the present invention.

That is, the present invention relates to a photosensitive resin 90-containing at least one addition-polymerizable compound having an ethylenically unsaturated bond.
A photopolymerizable composition comprising 99.99 parts by weight and 0.01 to 10 parts by weight of a photopolymerization initiator, wherein the photopolymerization initiator comprises the following compound (a) and compound (b) in combination. It is a polymerizable composition.

The compound (a) is a compound represented by the following general formula.

 Where R¹Are each independently unsubstituted or C₁~ C₆Alkyl or
C₁~ C₆Alkoxy-substituted cyclopentadienyl , Inn
Denil Or 4,5,6,7-tetrahydroindenyl And
Or formula(Where R^Four, And R^FiveAre each independently hydrogen or methyl
It ) Is a group represented by R²Is a 6-membered carbocyclic aromatic ring or a 5- or 6-membered heterocycle
Cyclic aromatic ring, two ortho of metal-carbon bond
At least one of the positions is a fluorine atom or --CF₂R group (in the formula,
R is a fluorine atom or methyl. ) Has also been replaced
Because R³Is R²Similar to or even -OR⁶Or -OR⁷
(R in the formula⁶Is hydrogen, C₁~ C₆Alkyl, phenyl, acetyl
Or trifluoroacetyl, R⁷Is C₁~ C₆Alkyl
Or phenyl. ), Or R²And R³Are linked to form a formula -Q-Y-Q- (wherein Q is a 6-membered carbocyclic aromatic group, or a 5-membered or
A 6-membered heterocyclic aromatic group in which each of the two bonds is Y
In ortho position with respect to Y, and each meta position with respect to Y
Is one fluorine atom or one --CF₂Substituted with R group
And Y is a direct bond, -O-, -S-, -SO.
₂−, −CO−, −CH₂-Or-C (CH₃)_Two− ) Is a group represented by.

Alternatively, both R ¹ are independently cyclopentadienyl, which is unsubstituted or substituted with 1 to 2 methyl groups, and R ² and R ³ are each independently of the formula (In the formula, R ¹² is a fluorine atom or —CF ₂ R, and R ¹³ , R ¹⁴ , and R ^{15 are}
And R ¹⁶ are each independently a fluorine atom, a —CF ₂ R group, hydrogen, C ₁
-C is a ₆ alkyl or C ₁ -C ₆ alkoxy. ), Or R ² and R ³ are linked together to form (In the formula, R ¹⁰ and R ¹¹ are each independently a fluorine atom or —CF
₂ R group, Y is a direct bond, -O-, -S-, -SO
_{2 -, - CO -, -} CH 2 - or -C (CH _{3) 2} - a. )
Or R ³ is a chlorine atom or a cyanide group.

Alternatively, R ¹ and R ² are each independently cyclopentadienyl or methylcyclopentadienyl, and R ³ is of the formula (In the formula, R ¹⁷ and R ¹⁸ are each independently a fluorine atom or —CF ₃
And R ¹⁹ , R ²⁰ and R ²¹ are each independently a hydrogen atom, a fluorine atom or a —CF ₃ group. ) May be.

The compound (b) is a compound represented by the following general formula.

In the formula, R ²² , R ²³ and R ²⁴ each independently represent a hydrogen atom; a chlorine atom; a lower alkoxy group; a lower dialkylamino group; a lower dialkenylamino group or an alicyclic amino group, or Linked to represent a substituted or unsubstituted alicyclic amino group. X has a total number of carbon and heteroatoms of 5
~ 9 represents a substituted or unsubstituted heterocyclic group. Z represents a hydrogen atom or an amino group.

 The present invention will be described in detail below.

The photosensitive resin having at least one addition-polymerizable compound having an ethylenically unsaturated bond may be composed of only an addition-polymerizable compound having an ethylenically unsaturated bond, or a polymer of these compounds and a polymer. It may be composed of a binder resin such as.

The addition-polymerizable compound having an ethylenically unsaturated bond may be a monomer, an oligomer, or a prepolymer having an ethylenically unsaturated bond that causes addition polymerization by the action of a photopolymerization initiator, but is high. In terms of polymerization reactivity, those having an acryloyloxy group or a methacryloyloxy group (hereinafter abbreviated as (meth) acryloyloxy group) are particularly preferable.

Examples of the monomer having a (meth) acryloyloxy group include polyether acrylate or polyether methacrylate (hereinafter, "acrylate or methacrylate" is simply referred to as "(meth) acrylate").
Is abbreviated. ), Polyester (meth) acrylate-based, polyol (meth) acrylate-based, epoxy (meth) acrylate-based, amidourethane (meth) acrylate-based, urethane (meth) acrylate-based, spiroacetal (meth) acrylate-based and polybutadiene (meth) Examples thereof include acrylate-based monomers and oligomers.

Specific examples of such a monomer or oligomer include triethylene glycol diacrylate, hexapropylene glycol diacrylate, or 1,2,6-hexanetriol / propylene oxide / acrylic acid,
Polyether (meth) acrylate synthesized from trimethylolpropane / propylene oxide / acrylic acid; polyester synthesized from adipic acid / 1,6-hexanediol / acrylic acid, succinic acid / trimethylolethane / acrylic acid (meth ) Acrylate; neopentyl glycol diacrylate, 1,4-butanediol dimethacrylate, 2-ethylhexyl acrylate, tetrahydrofurfuryl acrylate, 2-
Hydroxyethyl methacrylate, ethylcarbitol acrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, 2,2-bis (4-acryloyloxydiethoxyphenyl) propane, 2, 2-Bis (4-acryloyloxypropoxyphenyl) propane and other (meth) acrylates or polyols (meth)
Acrylate; Epoxy (meth) acrylate synthesized from diglycidyl etherified bisphenol A / acrylic acid, diglycidyl etherified polybisphenol A / acrylic acid, triglycidyl etherified glycerin / acrylic acid, and the like; γ-butyrolactone / N-methyl ethanol Synthesized from amine / bis (4-isocyanatocyclohexyl) methane / 2-hydroxyethyl acrylate, γ-butyrolactone / N-methylethanolamine / 2,6-tolylene diisocyanate / tetraethylene glycol / 2-hydroxyethyl acrylate, etc. Amidourethane (meth) acrylate; Urethane acryl such as 2,6-tolylene diisocyanate diacrylate, isophorone diisocyanate diacrylate, and hexamethylene diisocyanate diacrylate Spiro acetal acrylate synthesized from diallylidene pentaerythritol / 2-hydroxyethyl acrylate; acrylated polybutadiene synthesized from epoxidized butadiene / 2-hydroxyethyl acrylate, etc., and these monomers and oligomers may be used alone or Used in combination with more than one species.

The binder resin has various improving purposes such as compatibility, developability and adhesiveness, and may be appropriately selected depending on the purpose, for example, polyvinylpyrrolidone,
Polyvinyl alcohol, (meth) acrylic acid ester
(Meth) acrylic acid copolymer, styrene / (meth) acrylic acid copolymer, styrene / maleic acid copolymer, (meth) acrylic acid ester / (meth) acrylamide copolymer and the like can be used. One kind of these polymers may be used, or two or more kinds may be mixed and used at an appropriate ratio. For example, in the case of an alkali-developable photopolymerizable resin composition that develops and removes the unexposed area with an aqueous alkali solution, an α, β-unsaturated carboxyl group-containing monomer containing 3 to 15 carbon atoms is used as What is contained as a polymerization component is preferable, and acrylic acid and methacrylic acid are most preferable.

Next, the photopolymerization initiator used in the photopolymerizable composition of the present invention will be described. In the photopolymerizable composition of the present invention,
Two compounds (a) and (b) as photopolymerization initiators
The ingredients are used together.

When irradiated with visible light, the compound (a) and the compound (b) each absorb light to generate a radical independently, but when the compound (a) and the compound (b) are used together, the compound (b) component Absorbs light, forms an exciplex with compound (a), then undergoes electron transfer to generate radicals, and these radicals react with the ethylenic compound in the photopolymerizable composition to add. Since the polymerization is initiated, the photosensitivity can be greatly improved.

The compound (a) is a compound represented by the following general formula.

 Where R¹Are each independently unsubstituted or C₁~ C₆Alkyl or
C₁~ C₆Alkoxy-substituted cyclopentadienyl , Inn
Denil Or 4,5,6,7-tetrahydroindenyl And
Or formula(Where R^Four, And R^FiveAre each independently hydrogen or methyl
It ) Is a group represented by R²Is a 6-membered carbocyclic aromatic ring or a 5- or 6-membered heterocycle
Cyclic aromatic ring, two ortho of metal-carbon bond
At least one of the positions is a fluorine atom or --CF₂R group (in the formula,
R is a fluorine atom or methyl. ) Has also been replaced
Because R³Is R²Similar to or even -OR⁶Or -OR⁷
(R in the formula⁶Is hydrogen, C₁~ C₆Alkyl, phenyl, acetyl
Or trifluoroacetyl, R⁷Is C₁~ C₆Alkyl
Or phenyl. ), Or R²And R³Are linked to form a formula -Q-Y-Q- (wherein Q is a 6-membered carbocyclic aromatic group, or a 5-membered or
A 6-membered heterocyclic aromatic group in which each of the two bonds is Y
In ortho position with respect to Y, and each meta position with respect to Y
Is one fluorine atom or one --CF₂Substituted with R group
And Y is a direct bond, -O-, -S-, -SO.
₂−, −CO−, −CH₂-Or-C (CH₃)_Two− ) Is a group represented by.

Alternatively, both R ¹ are independently cyclopentadienyl, which is unsubstituted or substituted with 1 to 2 methyl groups, and R ² and R ³ are each independently of the formula (In the formula, R ¹² is a fluorine atom or —CF ₂ R, and R ¹³ , R ¹⁴ , and R ^{15 are}
And R ¹⁶ are each independently a fluorine atom, a —CF ₂ R group, hydrogen, C ₁
-C is a ₆ alkyl or C ₁ -C ₆ alkoxy. ), Or R ² and R ³ are linked together to form (In the formula, R ¹⁰ and R ¹¹ are each independently a fluorine atom or —CF
₂ R group, Y is a direct bond, -O-, -S-, -SO
_{2 -, - CO -, -} CH 2 - or -C (CH _{3) 2} - a. )
Or R ³ is a chlorine atom or a cyanide group.

Alternatively, R ¹ and R ² are each independently cyclopentadienyl or methylcyclopentadienyl, and R ³ is of the formula (In the formula, R ¹⁷ and R ¹⁸ are each independently a fluorine atom or —CF ₃
And R ¹⁹ , R ²⁰ and R ²¹ are each independently a hydrogen atom, a fluorine atom or a —CF ₃ group. ) May be.

The compound (b) is a compound represented by the following general formula.

In the formula, R ²² , R ²³ and R ²⁴ each independently represent a hydrogen atom; a chlorine atom; a lower alkoxy group; a lower dialkylamino group; a lower dialkenylamino group or an alicyclic amino group, or Linked to represent a substituted or unsubstituted alicyclic amino group. X has a total number of carbon and heteroatoms of 5
~ 9 represents a substituted or unsubstituted heterocyclic group. Z represents a hydrogen atom or an amino group.

Particularly preferred as such compound (b) is And the most preferred of these is Is.

The amount of the photopolymerizable initiator in the photopolymerizable composition of the present invention is 0.01 to 1 with respect to 90 to 99.99 parts by weight of the photosensitive resin.
It is preferably 0 parts by weight. The compounding ratio (weight ratio) of the compound (a) and the compound (b) is (a) / (b) = 50.
It is desirable to set in the range of 1 to 1. If the ratio of use of any one of these two components is less than the lower limit of the above range, the photosensitivity is lowered and it takes a long time to insolubilize the composition. Further, if the use ratio of any of the components exceeds the upper limit of the above range, the storage stability will be reduced and the physical properties after curing will be reduced.

The photopolymerizable composition of the present invention contains the above-described addition-polymerizable compound having an ethylenically unsaturated bond and the compounds (a) and (b) as essential components, but may further be thermally polymerized as necessary. Various additives such as inhibitors, colorants, adhesion promoters, fillers and plasticizers can be included.

The photopolymerizable composition of the present invention can be used for applications such as printing plates, photoresists, paints, etc., but particularly useful are plate-making materials and photosensitive image forming materials such as photoresists. In these applications, generally, the photopolymerizable composition of the present invention, after dissolving in a solvent, coated on a support,
It is used by drying, forming a film, exposing and curing.

The photopolymerizable composition of the present invention shows high photosensitivity as it is, but when particularly high sensitivity is required, in order to prevent polymerization inhibition by oxygen, exposure is performed under vacuum degassing or nitrogen substitution, or It is advisable to form a coating film of polyvinyl alcohol or the like on the photopolymerizable composition, or laminate a plastic film having a low oxygen transmission rate on the surface and expose.

Since the photopolymerizable composition of the present invention exhibits a spectral sensitivity distribution extending to a wavelength of about 200 to 550 nm, it can be cured with a light source such as a conventionally used high pressure mercury lamp, xenon lamp, metal halide lamp, etc. The most important feature of the present invention is that it has high photosensitivity to visible light, particularly 488 nm and 514.5 nm, which are the emission wavelengths of an argon ion laser. Therefore, it is preferable to use an argon laser for scanning exposure.

〔Example〕

 Hereinafter, the present invention will be described in detail based on examples.

The photopolymerizable composition of the present invention was prepared and coated on a polyester film to prepare a test plate, and the scanning exposure sensitivity was measured.

Preparation of photosensitive layer (test plate) Methyl methacrylate / methyl acrylate / methacrylic acid / styrene copolymer solution monomer composition ratio = 50/2
2.5 / 22.5 / 5 (weight ratio), average molecular weight about 90,000 (polystyrene equivalent), solid content weight 35%. As shown in Table 1, compound (a), compound (b), and ethylenic compound are shown in the table for 150 parts containing isopropyl alcohol and methyl ethyl ketone as a solvent in a ratio of 1: 4. Various photopolymerizable compositions were prepared by mixing in parts by weight and stirring.

The obtained composition was applied onto a 25 μ polyester film with an applicator. Then, it was dried for 30 minutes in a dryer at 60 ° C. to obtain a photopolymerizable composition layer having a thickness of 30 μm.

The photopolymerizable composition layer thus obtained was heat-laminated on a copper clad laminate with the polyester film side facing up to obtain a test plate.

Scanning exposure sensitivity measurement Using an NEC laser (GLG3028) as a light source, the emission wavelength of 488 nm was picked up by an interference filter, and the laser beam that focused the beam system to 35μ through the optical system was used.
Scanning exposure (10 lines / 1 mm) was performed on the test plate. Then after exposure
After standing for 20 minutes, the polyester film was peeled off, and then the uncured portion was dissolved and removed using a 1% sodium carbonate aqueous solution. The spray pressure was 1.4 km / cm ² , the distance between the spray and the substrate was 10 cm, and processing was performed for 40 seconds at a temperature of 30 ° C. to obtain a scanning pattern.

The scanning speed is changed sequentially, the line width of the cured part of the scanning pattern is measured, and from the obtained scanning speed of the same line width as the beam diameter, the irradiation energy amount per unit area at that time is calculated, Sensitivity. The results are shown in Table 1.

From the results in Table 1, it was confirmed that the sensitivity of the photopolymerizable composition to visible light can be significantly improved by using the compound (a) and the compound (b) together.

[Effect of the Invention] The photopolymerizable composition of the present invention has a high photosensitivity to visible light because it uses the compound (a) and the compound (b) together as a photopolymerization initiator. Scanning exposure with a visible laser such as an argon ion laser is possible. Therefore, according to the photopolymerizable composition of the present invention, using a low-power argon ion laser, a lithographic printing plate,
It is possible to directly expose a resist for making a printed wiring board, a hologram master, etc., and the practical effect thereof is extremely large.

Claims (1)

[Claims] 1. An addition polymerization having an ethylenically unsaturated bond is possible.
Photosensitive resin containing at least one active compound 90-99.9
Light weight consisting of 9 parts by weight and 0.01-10 parts by weight of photopolymerization initiator
In the compatible composition, the following compound (a) and compound are used as the photopolymerization initiator.
Photopolymerizable composition characterized by using (b) together
Stuff. The compound (a) is a compound represented by the following general formula.
ItWhere R¹Are each independently unsubstituted or C₁~ C₆Alkyl or C₁
~ C₆Alkoxy-substituted cyclopentadienyl , Inde
Nil Or 4,5,6,7-tetrahydroindenyl Is
Or, concatenated formula(Where R^Four, And R^FiveAre each independently hydrogen or methyl
It ) Is a group represented by R²Is a 6-membered carbocyclic aromatic ring or a 5- or 6-membered heterocycle
Aromatic ring, two ortho positions of metal-carbon bond
At least one of fluorine atom or --CF₂R group (in the formula, R
Is a fluorine atom or methyl. ) Replaced by
And R³Is R²Similar to or even -OR⁶Or -OR
⁷(R in the formula⁶Is hydrogen, C₁~ C₆Alkyl, phenyl, acetyl
Or trifluoroacetyl, R⁷Is C₁~ C₆Archi
Or phenyl. ), Or R²And R³Are linked to form a formula -Q-Y-Q- (wherein Q is a 6-membered carbocyclic aromatic group, or a 5-membered or
A 6-membered heterocyclic aromatic group in which each of the two bonds is Y
In ortho position with respect to Y, and each meta position with respect to Y
Is one fluorine atom or one --CF₂Substituted with R group
And Y is a direct bond, -O-, -S-, -SO.
₂−, −CO−, −CH₂-Or-C (CH₃)_Two− ) Is a group represented by. Or both R¹Are each independently unsubstituted or 1
With cyclopentadienyl substituted with ~ 2 methyl groups
Yes, R²And R³Are independent expressions(Where R¹²Is a fluorine atom or --CF₂R and R¹³, R¹⁴, R¹⁵
And R¹⁶Are each independently a fluorine atom, --CF₂R group, hydrogen, C₁
~ C₆Alkyl or C₁~ C₆It is an alkoxy. ) Indicated by
Or R²And R³Are connected and the expression(Where R^TenAnd R¹¹Are each independently a fluorine atom or --CF
₂R group, Y is a direct bond, -O-, -S-, -SO
₂−, −CO−, −CH₂-Or-C (CH₃)_Two− )
Forming a group represented by or R³Is a chlorine atom or a cyanide group. Or R¹And R²But each independently cyclopentadiene
Nyl or methylcyclopentadienyl, R³Is the expression(Where R¹⁷And R¹⁸Are each independently a fluorine atom or --CF₃
The base and R¹⁹, R²⁰And R^{twenty one}Are independently hydrogen atom, fluorine
Elementary atom or --CF₃It is a base. ) May be. The compound (b) is a compound represented by the following general formula.
ItWhere R^{twenty two}, R^{twenty three}, R^{twenty four}Are each independently a hydrogen atom;
Chlorine atom; lower alkoxy group; lower dialkylamino
Group; a lower dialkenylamino group or an alicyclic amino group
Represented or linked to a substituted or unsubstituted alicyclic amine
Represents a group. X has a total number of carbon and heteroatoms of 5 to 9
Represents a substituted or unsubstituted heterocyclic group. Z is a hydrogen atom
Alternatively, it represents an amino group.