JP2002145916A - Active energy ray-curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active energy ray-curable resin composition capable of easily producing a cured product having high surface hydrophilicity despite having unswelling tendency to water and giving extremely fine structure through active energy ray pattern exposure. SOLUTION: This active energy ray-curable resin composition comprises (a) an active energy ray-curable compound giving the corresponding homopolymer with its contact angle with water of >=50 deg., (b) an amphipathic polymerizable compound capable of forming a copolymer with the compound (a) on being irradiated with active energy rays and (c) a polymerization retarder and/or polymerization inhibitor.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an active energy ray-curable resin composition providing a hydrophilic surface, and more particularly to a resin composition suitable for forming a microstructure by patterning irradiation of active energy rays. The active energy ray-curable resin composition of the present invention is preferably used for a microchemical device such as a DNA chip, a microreactor, and a microelectrophoresis device, and a biosensor such as an immunodiagnostic device.

[0002]

2. Description of the Related Art It is known that microchemical devices such as DNA chips, microelectrophoresis devices, and microPCR devices can not only perform analysis and diagnosis with a small sample amount but also significantly improve the speed of analysis and diagnosis. Have been. However, most of the microchemical devices known so far are expensive devices made of silicon, glass, quartz or the like.

Recently, attempts have been made to make devices made of plastic as inexpensive devices. However, plastics are more likely to adsorb biochemical substances such as proteins than glass or silicon, and have a trace amount or a very low dilution. When handling a sample having a concentration, there is a problem that a part or a substantial part of the sample is lost due to adsorption.

As a solution to this drawback, attempts have been made to make the plastic surface hydrophilic. Examples of general methods for hydrophilizing plastics include physical surface treatments such as corona treatment, plasma treatment, and ultraviolet treatment; chemical surface treatments such as sulfonation; kneading methods of surfactants and hydrophilic substances; Use of a polymer having a hydrophilic group; coating with a hydrophilic polymer and the like are known.

[0005] Among these hydrophilization methods, it is applicable to hydrophilization of the surface of minute concaves (grooves and wells) or minute cavities serving as a liquid contacting part of a microchemical device, and adsorbs biochemical substances. Chemical surface treatment and surface grafting can be mentioned as methods that can achieve high hydrophilicity enough to suppress the occurrence of low hydrophilicity. However, there was a problem that it was difficult to form a hydrophilic portion.

[0006]

The problem to be solved by the present invention is to exhibit high surface hydrophilicity while being non-swelling with water and to have an extremely fine structure by pattern exposure to active energy rays. An object of the present invention is to provide an active energy ray-curable resin composition which can easily form a cured product.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a composition comprising an active energy ray-polymerizable compound and an amphiphilic polymerizable compound has a polymerization delay. The present inventors have found that a resin composition to which an agent and / or a polymerization inhibitor has been added can solve the above-mentioned problems, and have completed the present invention.

That is, the present invention relates to (1) an active energy ray polymerizable compound (a) in which the contact angle of the homopolymer with water is 50 ° or more; An active energy ray-curable resin composition containing an amphiphilic polymerizable compound (b) capable of forming a copolymer with the compound (a) and a polymerization retarder and / or a polymerization inhibitor;

(2) The amount of the polymerization retarder and / or the polymerization inhibitor contained in the active energy ray-curable resin composition is adjusted so that the active energy ray-curable resin composition has fluidity by irradiation with the active energy ray. The active energy ray-curable resin composition according to (1), wherein the dose of the active energy ray required for the loss is 1.5 to 50 times that of the system without the polymerization retarder and / or the polymerization inhibitor. ,

(3) The active energy ray polymerizable compound (a) is a compound having two or more polymerizable carbon-carbon unsaturated bonds in one molecule, and is an amphiphilic polymerizable compound (b). Is an active energy ray-curable resin composition according to (1) or (2), which is a compound having one or more polymerizable carbon-carbon unsaturated bonds in one molecule.

(4) The amphiphilic polymerizable compound (b) is
Cyclohexane: toluene at 25 ° C. = 5: 1 (weight ratio)
The active energy ray-curable resin composition according to any one of (1) to (3), which is soluble in a mixed solvent of 25% by weight or more and 0.5% by weight or more in water at 0 ° C. When,

(5) The HLB value of the glycine of the amphiphilic polymerizable compound (b) is from 10 to 16.
(4) The active energy ray-curable resin composition according to any one of (4),

(6) The amphiphilic polymerizable compound (b) is
The active energy ray-curable resin composition according to any one of (1) to (5), which is a compound having a polyethylene glycol chain having 6 to 20 repetitions,

(7) The amphiphilic polymerizable compound (b) is
The active energy ray-curable resin composition according to any one of (1) to (6), which is a compound having an alkyl group or an alkylene group having 6 to 20 carbon atoms,

(8) The amphiphilic polymerizable compound (b) is
The active energy ray-curable resin composition according to any one of (1) to (7), which is an alkylphenyl group-containing compound having an alkyl group having 6 to 20 carbon atoms,

(9) The amount of the amphiphilic polymerizable compound (b) contained in the active energy ray-curable resin composition is 0.1 to 1 part by weight of the active energy ray-polymerizable compound (a). And the active energy ray-curable resin composition according to any one of (1) to (8), which is 5 to 5 parts by weight.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The active energy ray-curable resin composition of the present invention comprises an active energy ray-polymerizable compound (a).
And an amphiphilic polymerizable compound (b) capable of forming a copolymer with the active energy ray polymerizable compound (a) upon irradiation with active energy rays, and a polymerization retarder and / or a polymerization inhibitor. .

The active energy ray polymerizable compound (a) is a compound which is polymerized by an active energy ray to form a crosslinked polymer, and the homopolymer has a contact angle with water of 50 ° or more, preferably 60 ° or more. And more preferably 70 ° or more. When the contact angle of the homopolymer with water is less than this value, the obtained molded product becomes swellable with water, or has poor water resistance, or has a low degree of surface hydrophilicity. It tends to be something.

The active energy ray polymerizable compound (a) is
The upper limit of the contact angle with water represented by the homopolymer is not particularly limited and may be 180 degrees, but is preferably 100 degrees or less so as not to reduce the hydrophilicity of the obtained molded product. , 90 ° or less.

The active energy ray polymerizable compound (a) is
The polymer may be a crosslinked polymer in any polymerization mode such as addition polymerization, ring-opening polymerization, and condensation polymerization. When the polymerization mode is addition polymerization, ring-opening polymerization may be any of radical polymerization, anion polymerization, and cation polymerization.
When the polymerization mode is condensation polymerization, the active energy ray polymerizable compound (a) may be a set of compounds. These are not limited to those that polymerize in the absence of a polymerization initiator,
Those which polymerize with active energy rays only in the presence of a polymerization initiator can also be used.

As the active energy ray polymerizable compound (a), a compound having two or more polymerizable carbon-carbon double bonds in one molecule is preferable, and a polymerizable compound having at least two terminal ethylene groups is preferable. Saturated compounds are preferred, and among others,
Compound having a highly reactive (meth) acryloyl group [hereinafter, “(meth) acryloyl” means “methacryloyl or acryloyl”. The same applies to (meth) acrylate, (meth) acryl and the like. And vinyl ethers, and a maleimide compound which is cured by ultraviolet light even in the absence of a photopolymerization initiator.

Examples of the (meth) acrylic monomer [that is, a monomer having a (meth) acryloyl group] which can be used as the active energy ray polymerizable compound (a) include, for example, diethylene glycol di (meth) acrylate, neopentyl glycol Di (meth) acrylate, 1,6
-Hexanediol di (meth) acrylate, 2,2 ′
-Bis (4- (meth) acryloyloxypolyethyleneoxyphenyl) propane, 2,2'-bis (4- (meth) acryloyloxypolypropyleneoxyphenyl) propane, neopentylglycol hydroxydipivalate di (meth) acrylate, di Bifunctional monomers such as cyclopentanyl diacrylate, bis (acryloxyethyl) hydroxyethyl isocyanurate;

Trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate,
Trifunctional monomers such as caprolactone-modified tris (acryloxyethyl) isocyanurate; tetrafunctional monomers such as pentaerythritol tetra (meth) acrylate;
Hexafunctional monomers such as dipentaerythritol hexa (meth) acrylate are exemplified.

Further, as the active energy ray polymerizable compound (a), a polymerizable oligomer (also referred to as a prepolymer) can be used, and examples thereof include those having a weight average molecular weight of 500 to 50,000. Such polymerizable oligomers include, for example, (meth) acrylates of epoxy resins and (meth) acrylates of polyether resins.
Acrylic esters, (meth) acrylic esters of polybutadiene resins, polyurethane resins having (meth) acryloyl groups at molecular terminals, and the like.

These compounds can be used alone or
Two or more types can be used in combination. In particular, the high molecular weight oligomer is preferably used in combination with the low molecular weight active energy ray polymerizable compound (a).

Examples of the maleimide-based crosslinkable polymerizable monomer include 4,4'-methylenebis (N-phenylmaleimide) and 2,3-bis (2,4,5-trimethyl-
3-thienyl) maleimide, 1,2-bismaleimideethane, 1,6-bismaleimidehexane, triethylene glycol bismaleimide, N, N'-m-phenylenedimaleimide, m-tolylenedimaleimide, N, N'-
1,4-phenylenedimaleimide, N, N′-diphenylmethane dimaleimide,

N, N'-diphenylether dimaleimide, N, N'-diphenylsulfone dimaleimide, 1,
4-bis (maleimidoethyl) -1,4-diazoniabicyclo- [2,2,2] octane dichloride, 4,4 ′
-Isopropylidenediphenyl dicyanate-N,
Bifunctional maleimides such as N '-(methylenedi-p-phenylene) dimaleimide; and maleimides having a maleimide group such as N- (9-acridinyl) maleimide and a polymerizable functional group other than the maleimide group.

Examples of the maleimide-based crosslinked polymerizable oligomer include polytetramethylene glycol maleimide alkylate such as polytetramethylene glycol maleimide capriate and polytetramethylene glycol maleimide acetate.

These maleimide-based monomers and oligomers can be used alone or as a mixture of two or more kinds. For example, polymerizable carbon-carbon double bonds such as vinyl monomers, vinyl ethers and acrylic monomers can be used. Can also be used in combination with a compound having the following.

The amphiphilic polymerizable compound (b), which can form a copolymer with the active energy ray polymerizable compound (a) upon irradiation with active energy rays, is selected from the active energy ray polymerizable compound (a) ) And a polymerizable functional group copolymerizable therewith.

When the active energy ray polymerizable compound (a) is 1
In the case of a compound having two or more polymerizable carbon-carbon unsaturated bonds in a molecule, the amphiphilic polymerizable compound (b) may have one or more polymerizable carbon-carbon unsaturated bonds in one molecule. Preferably, the compound has a saturated bond. The amphiphilic polymerizable compound (b) does not need to be a cross-linked polymer, but may be a cross-linked polymer.

The amphiphilic polymerizable compound (b) is
It is uniformly compatible with the active energy ray polymerizable compound (a). Compatibility in this case refers to no macroscopic phase separation, and includes a state where micelles are formed and dispersed stably.

The polymerizable compound (b) is an amphiphilic compound. An amphiphilic compound is a compound having a hydrophilic group and a hydrophobic group in a molecule, and is combined with both water and a hydrophobic solvent. Refers to compatible compounds. In this case as well, the term "compatible" means that no phase separation occurs macroscopically, and also includes a state where micelles are formed and dispersed stably. The amphiphilic polymerizable compound (b) has a solubility in water of 0.5 at 0 ° C.
The solubility in cyclohexane: toluene = 5: 1 (weight ratio) mixed solvent at 25 ° C. is preferably 25% by weight or more at 25% by weight or more.

The solubility mentioned here, for example, the solubility is 0.
The content of 5% by weight or more means that at least 0.5% by weight of the compound is soluble, and although 0.5% by weight of the compound is not soluble in the solvent, only a small amount of the compound is contained in the compound. Does not include those in which the solvent is soluble. Solubility in water, or cyclohexane: toluene =
When a compound having at least one of solubility in a 5: 1 (weight ratio) mixed solvent lower than these values is used, it is difficult to satisfy both high surface hydrophilicity and high water resistance.

When the amphiphilic polymerizable compound (b) has a nonionic hydrophilic group, particularly a polyether-based hydrophilic group, the balance between hydrophilicity and hydrophobicity is HL of glycine.
Those having a B (HLB) value in the range of 10 to 16 are preferable, and those having the value of 11 to 15 are more preferable. Outside this range, it is difficult to obtain a molded article having high hydrophilicity and excellent water resistance, or the combination and mixing ratio of the compounds for obtaining the molded article are extremely limited, and the performance of the molded article is poor. It tends to be stable.

The hydrophilic group possessed by the amphiphilic polymerizable compound (b) is optional, and includes, for example, a cationic group such as an amino group, a quaternary ammonium group and a phosphonium group; a sulfone group, a phosphate group and a carbonyl group. Anionic groups such as; hydroxyl groups,
It may be a nonionic group such as a polyether group such as a polyethylene glycol group or an amide group; or a zwitterionic group such as an amino acid group. Preferred as the hydrophilic group are compounds having a polyether group, particularly preferably a polyethylene glycol chain having a repeating number of 6 to 20.

Examples of the hydrophobic group of the amphiphilic polymerizable compound (b) include an alkyl group, an alkylene group, an alkylphenyl group, a long-chain alkoxy group, a fluorine-substituted alkyl group, and a siloxane group. The amphiphilic polymerizable compound (b) preferably contains an alkyl group or an alkylene group having 6 to 20 carbon atoms as a hydrophobic group. The alkyl group or alkylene group having 6 to 20 carbon atoms may be contained, for example, in the form of an alkylphenyl group, an alkylphenoxy group, an alkoxy group, a phenylalkyl group, or the like.

The amphiphilic polymerizable compound (b) has a polyethylene glycol chain having a repeating number of 6 to 20 as a hydrophilic group and an alkyl or alkylene group having 6 to 20 carbon atoms as a hydrophobic group. Preferably, it is a compound. As the amphiphilic polymerizable compound (b) which can be more preferably used, a compound represented by the general formula (1) can be mentioned.

Formula (1) CH ₂ CR ¹ COO (R ² O) _n -φ-R ³ (wherein R ¹ represents hydrogen, a halogen atom or a lower alkyl group, and R ² has 1 to 1 carbon atoms) 3 represents an alkylene group, n represents an integer of 6 to 20, φ represents a phenylene group, and R ³ represents an alkyl group having 6 to 20 carbon atoms.)

Here, R ³ is specifically a hexyl group,
A heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, or a pentadecyl group, preferably a nonyl group or a dodecyl group. In the general formula (1), it is preferable that the larger the number of n, the larger the number of carbon atoms of R ³ .

The relationship between the number n and the number of carbon atoms in R ³ is preferably in the range of 10 to 16 as HLB value of griffin, and particularly preferably in the range of 11 to 15. Among these amphiphilic polymerizable compounds (b), nonylphenoxypolyethylene glycol (n = 8 to 17) (meth) acrylate, nonylphenoxypolypropylene glycol (n = 8 to 17)
(Meth) acrylates are particularly preferred.

The preferred compounding ratio of the active energy ray polymerizable compound (a) and the amphiphilic polymerizable compound (b) is as follows:
Depending on the type and combination of the active energy ray polymerizable compound (a) and the amphiphilic polymerizable compound (b),
The amphiphilic polymerizable compound (b) is preferably at least 0.2 part by weight, more preferably at least 0.5 part by weight, based on 1 part by weight of the active energy ray polymerizable compound (a). . When the ratio of the amphiphilic polymerizable compound (b) to 1 part by weight of the active energy ray polymerizable compound (a) is less than 0.2 part by weight, a hydrophilic surface having a small contact angle with water is formed. Becomes difficult.

The proportion of the amphiphilic polymerizable compound (b) is preferably 5 parts by weight or less, more preferably 3 parts by weight or less, based on 1 part by weight of the active energy ray polymerizable compound (a). It is even more preferred. When the ratio of the amphiphilic polymerizable compound (b) to 1 part by weight of the active energy ray polymerizable compound (a) is more than 5 parts by weight, the compound tends to be swellable in water and constitutes a liquid contact part. Polymers tend to gel.

By appropriately selecting the mixing ratio between the active energy ray polymerizable compound (a) and the amphiphilic polymerizable compound (b), the composition does not gel in a wet state and has high hydrophilicity and low adsorptivity. Can be produced. For example,
As the hydrophilicity of the amphiphilic polymerizable compound (b) becomes relatively stronger, for example, as the glycine has a higher HLB value,
The preferred addition amount is lower. The optimal value can be determined by simple experiments.

The active energy ray-curable resin composition of the present invention contains a polymerization retarder and / or a polymerization inhibitor, preferably a polymerization retarder. The term “polymerization retarder” refers to a substance that reduces the rate of polymerization, and the term “polymerization inhibitor” refers to a substance that increases the introduction time until the start of polymerization. Generally, a polymerization retarder does not substantially increase the introduction time until the start of polymerization, and a polymerization inhibitor refers to a substance that does not substantially reduce the polymerization rate after the start of polymerization, but increases the introduction time of polymerization. And those that reduce the rate of polymerization, ie, those that are both polymerization retarders and polymerization inhibitors.

By adding a polymerization retarder or a polymerization inhibitor to the active energy ray-curable resin composition, the resolution when the resin composition is used for photolithography is improved. That is, even in a fine pattern, a wall surface perpendicular to the bottom surface can be formed, and a deep groove can be formed.

Although the reason is not clear, it is considered as follows. That is, when irradiating the energy beam with photolithography or the like, it is ideal that the energy beam irradiation intensity of the energy beam non-irradiation portion is zero, but actually, at the boundary portion between the energy beam irradiation portion and the non-irradiation portion. Varies with a certain slope, and the intensity in the non-irradiated portion is not zero.

For this reason, as the pattern becomes finer, the difference in dose between the irradiated part and the non-irradiated part during exposure becomes smaller. In addition, scattering of active energy rays by the resin composition itself and reflection and scattering at the bottom face also have a greater effect as the pattern becomes finer. For these reasons, in the concavo-convex structure obtained by development after exposure (that is, removal of the uncured resin in the non-irradiated portion), as the pattern becomes finer, the boundary becomes less clear (gentle slope) and the groove becomes shallower. Become.

When a polymerization inhibitor is added to the active energy ray-curable resin composition, the polymerization does not start until a certain dose is reached, so that the polymerization in the portion where the dose is small is suppressed, and the difference in hardness between the irradiated portion and the non-irradiated portion is suppressed. Is estimated to expand.

On the other hand, since the polymerization retarder reduces the slope of the graph of the resin hardness (or viscosity) with respect to the irradiation dose, according to the above mechanism, the hardness difference (or viscosity difference) between the irradiated portion and the non-irradiated portion is reduced. ) Should have the opposite effect as the polymerization inhibitor. However, actually, the same effect as the polymerization inhibitor can be obtained by the polymerization retarder.

Although the reason is unknown, when the polymerization system is a cross-linking polymerization system, the irradiated portion gels and cures to a state where it cannot be removed in the next development step, whereas the non-irradiated portion hardens. The polymerization proceeds only to the extent that it has not been polymerized, so that the unirradiated portion can be removed with a solvent or water pressure during development, and the addition of a polymerization retarder causes gelation even if the difference in hardness is not large. It is presumed that because the irradiation time difference between the state and the non-gel state is increased, it becomes easy to control the irradiation dose to the best. Furthermore, the addition of a polymerization retarder also has the effect of improving reproducibility.

As the polymerization retarder, for example, when the active energy ray polymerizable compound (a) is an acryloyl group-containing compound, styrene, α-methylstyrene, α-phenylstyrene, p-octylstyrene, p- (4 -Pentylcyclohexyl) styrene, p-phenylstyrene,
p- (p-ethoxyphenyl) phenylstyrene,
2,4-diphenyl-4-methyl-1-pentene, 4,
Vinyl monomers having a lower polymerization rate than the active energy ray polymerizable compound (a) used, such as 4'-divinylbiphenyl and 2-vinylnaphthalene, can be mentioned.

As the polymerization inhibitor, for example, when the active energy ray polymerizable compound (a) is a polymerizable compound containing a carbon-carbon double bond, hydroquinone derivatives such as hydroquinone and methoxyhydroquinone; butylhydroxytoluene, tert -Hind phenols such as butyl phenol and dioctyl phenol.

Since the effects of the polymerization retarder and the polymerization inhibitor vary considerably depending on the type, it is difficult to specify their contents in the active energy ray resin composition of the present invention in a unified manner. . The addition amount of the polymerization retarder and the polymerization inhibitor in the active energy ray resin composition of the present invention causes the active energy ray-curable resin composition to lose fluidity (that is, cause gelation) by irradiation with the active energy ray. Dose of the active energy ray required is 1.5 times to 50 times, preferably 2 times, the amount of the system without the polymerization retarder or the polymerization inhibitor.
The amount is 50 times, more preferably 3 times to 50 times, and most preferably 5 times to 40 times.

If the amount is less than the lower limit, the effect is small. If the amount exceeds the upper limit, curing of the active energy ray-curable resin composition tends to be insufficient. As a method of measuring the point at which the active energy ray-curable resin composition loses fluidity (gelation point), for example, a dynamic viscoelasticity measurement during curing is performed, and the intersection of the loss modulus and the storage modulus is determined as the gel point. Can be adopted.

The content of the polymerization retarder or the polymerization inhibitor exhibiting the above-mentioned polymerization retarding property or polymerization inhibiting property is preferably 500 in the case of a vinyl monomer-based polymerization retarder.
~ 1,000,000 weight ppm, more preferably 1000
To 50,000 weight ppm, and in the case of a hydroquinone-based polymerization inhibitor, preferably 500 to 50,000 weight ppm, more preferably 1,000 to 10,000 weight pp.
m, in the case of a hindant phenol polymerization inhibitor, preferably 10 to 1000 ppm by weight, more preferably 2 to 1000 ppm by weight.
0 to 500 ppm by weight.

Commercially available active energy ray polymerizable compounds (a) and amphiphilic polymerizable compounds (b) used in the present invention may contain a polymerization inhibitor in order to prevent spontaneous polymerization. There is. For example, a typical addition amount of a polymerization inhibitor for the purpose of preventing spontaneous polymerization of an acrylic monomer is 10% in the case of a hydroquinone-based polymerization inhibitor.
The amount of the polymerization inhibitor is about 100 to 3000 ppm by weight, and about 10 to 100 ppm by weight in the case of the hindant phenol-based polymerization inhibitor. Varies considerably depending on the type, storage conditions and elapsed time since preparation. Usually, a polymerization retarder is not added to commercially available monomers for the purpose of preventing natural polymerization.

The concentration of these polymerization retarders and polymerization inhibitors is
If necessary, it can be measured by, for example, gas chromatography, liquid chromatography, mass spectroscopy, infrared absorption, visible / ultraviolet absorption, nuclear magnetic resonance (NMR), or the like.

However, in order to form a cured product having a fine structure by patterning irradiation with an active energy ray, the amount of a polymerization inhibitor for preventing natural polymerization is insufficient. When the active energy ray-curable resin composition of the present invention contains a polymerization inhibitor for the purpose of preventing spontaneous polymerization, the active energy ray-polymerizable compound (a) or the amphiphilic polymerizable compound (b) contains And a polymerization retarder and / or a polymerization inhibitor.

The preferred addition amounts of the polymerization retarder and / or the polymerization inhibitor to be added in the present invention are determined based on the active energy ray polymerizable compound (a) and the amphiphilic polymerizable compound (b).
In the case where contains a polymerization inhibitor for preventing natural polymerization, it means the amount to be added additionally thereto.

In the present invention, the polymerization inhibitor added to the active energy ray-curable resin composition is an active energy ray-polymerizable compound (a) or an amphiphilic polymerizable compound (b) for preventing natural polymerization. If the same as the polymerization inhibitor contained as, among the polymerization inhibitors contained in the active energy ray-curable resin composition of the present invention, the amount derived from the raw materials, and for the purpose of the present invention In some cases, it cannot be distinguished from the added amount.

That is, when the product names of the active energy ray polymerizable compound (a) and the amphiphilic polymerizable compound (b) used as a raw material of the active energy ray curable resin composition of the present invention are known. Can be determined, but cannot be determined if the product name of the raw material is unknown.

In such a case, the amount of the polymerization inhibitor added to the active energy ray polymerizable compound (a) or the amphiphilic polymerizable compound (b) for the purpose of preventing natural polymerization is as follows:
It may be 1.5 times (including the safety factor) the minimum addition amount at which these spontaneous polymerizations do not substantially occur after storage at 15 ° C. for 6 months without addition of a polymerization initiator. In this case, the addition amount of the polymerization inhibitor in the present invention is preferably 2 to 3 times the amount added for the purpose of preventing natural polymerization.
00 times, more preferably 3 times to 100 times, most preferably 4 times to 30 times.

In the present invention, the amount of the polymerization retarder and / or the polymerization inhibitor contained in the active energy ray-curable resin composition is adjusted so that the active energy ray-curable resin composition has fluidity by irradiation with the active energy ray. It is preferable that the dose of the active energy ray required for the loss be 1.5 to 50 times that of the system without the polymerization retarder and / or the polymerization inhibitor.

Here, when the active energy ray polymerizable compound (a) or the amphiphilic polymerizable compound (b) contains an amount of polymerization inhibitor for the purpose of preventing spontaneous polymerization, the polymerization inhibitor The dose of the active energy ray required to cause the active energy ray-curable resin composition containing the composition to lose fluidity is set to 1.0, and the amount of the polymerization retarder and / or the polymerization is 1.5 to 50 times the dose. It is preferable to add an inhibitor to the active energy ray-curable resin composition.

These amounts depend on the type of polymerization retarder and polymerization inhibitor, and whether the polymerization inhibitor is already contained in the active energy ray polymerizable compound (a) or the amphiphilic polymerizable compound (b). However, in general, in the case of a polymerization retarder, it is preferably 500 to 10
00000 weight ppm, more preferably 1000-50
000 ppm by weight, and in the case of a polymerization inhibitor, preferably 10 to 50,000 ppm by weight, more preferably 20
-10,000 ppm by weight.

By including a polymerization retarder or a polymerization inhibitor at the above concentration, a fine pattern can be formed satisfactorily. When a light beam is used as the energy ray, it is preferable to use a photopolymerization initiator together with a polymerization retarder and / or a polymerization inhibitor. When the active energy ray-curable resin composition of the present invention contains a photopolymerization initiator, or when a photopolymerization initiator is added at the time of use, the larger the content or the amount of addition, the more the polymerization retarder or polymerization. It is preferred to increase the amount of inhibitor added.

The amount of the photopolymerization initiator added is preferably 0.05 to ² mJ / cm ² , more preferably 0.1 to ² mJ / cm ² , up to the gel point when no polymerization retarder or polymerization inhibitor is added. The amount is ¹ to 1 mJ / cm ² . In the present invention, the amount of the polymerization retarder and / or polymerization inhibitor added is such that the dose of the active energy ray required for gelation is 1.5 to 50 times that of the non-addition system of the polymerization retarder and the polymerization inhibitor. The amount is preferably 2 to 50 times, more preferably 3 to 50 times, and most preferably 5 to 40 times. Therefore, when the photopolymerization initiator is contained, the amount of the polymerization retarder or polymerization inhibitor to be added is such that the light irradiation amount required for gelation is preferably 0.15 to 50 mJ / c.
m ² , more preferably 0.5 to 40 mJ / cm ² , most preferably 1 to 10 mJ / cm ² .

The active energy ray-curable resin composition of the present invention may further contain other components, if necessary. Other components include, for example, other polymerizable compounds, photopolymerization initiators, solvents, thickeners, modifiers, colorants, and the like.

The other polymerizable compounds that can be contained in the active energy ray-curable resin composition of the present invention include an active energy ray polymerizable compound (a) and an amphiphilic polymerizable compound when irradiated with active energy rays. It is a polymerizable compound copolymerizable with the compound (b), and examples thereof include a monofunctional monomer capable of such copolymerization. The addition of the polymerizable compound can be suitably performed for adjusting the viscosity of the active energy ray-curable resin composition.

These copolymerizable monofunctional monomers include monofunctional (meth) acrylic monomers, such as methyl methacrylate, alkyl (meth) acrylate, isobornyl (meth) acrylate, and alkoxy polyethylene glycol (meth). Acrylate, phenoxydialkyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, alkylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol acrylate methacrylate, butanediol mono ( Meth) acrylates,

2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethyl-2-hydroxypropyl acrylate, ethylenoxide-modified phthalic acid acrylate, w-carboxyaprolactone monoacrylate, 2-acryloyloxypropyl hydrogen phthalate , 2-acryloyloxyethylsuccinic acid, acrylic acid dimer, 2-acryloysoxypropylhexahydrohydrogen phthalate,
Fluorine-substituted alkyl (meth) acrylate,

A chlorine-substituted alkyl (meth) acrylate,
Sodium sulfonic acid (meth) acrylate, sulfonic acid-2-methylpropane-2-acrylamide, (meth) acrylate having a phosphoric ester group, (meth) acrylate having a sulfonic ester group, (meth) acrylate having a silano group (Meth) acrylate having ((di) alkyl) amino group, (meth) acrylate having quaternary ((di) alkyl) ammonium group, (N-alkyl) acrylamide, (N, N-dialkyl) acrylamide, acro Loyl morifolin and the like.

Examples of monofunctional maleimide monomers that can be used in combination include N-alkylmaleimides such as N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide and N-dodecylmaleimide; and N-alkylmaleimides such as N-cyclohexylmaleimide. Alicyclic maleimide; N-benzylmaleimide; N-phenylmaleimide, N- (alkylphenyl) maleimide, N-dialkoxyphenylmaleimide, N- (2-chlorophenyl) maleimide, 2,3-dichloro-N- (2, N- (substituted or unsubstituted phenyl) maleimides such as 6-diethylphenyl) maleimide, 2,3-dichloro-N- (2-ethyl-6-methylphenyl) maleimide;

Maleimide having a halogen such as N-benzyl-2,3-dichloromaleimide, N- (4'-fluorophenyl) -2,3-dichloromaleimide;
Maleimide having a carboxy group such as (4-carboxy-3-hydroxyphenyl) maleimide; maleimide having an alkoxy group such as N-methoxyphenylmaleimide; maleimide having an amino group such as N- [3- (diethylamino) propyl] maleimide N- (1-
Polycyclic aromatic maleimides such as pyrenyl) maleimide; N
And maleimides having a heterocyclic ring such as-(dimethylamino-4-methyl-3-coumarinyl) maleimide and N- (4-anilino-1-naphthyl) maleimide.

The photopolymerization initiator which can be optionally contained in the active energy ray-curable resin composition is active with respect to the active energy ray used in the present invention, and is used for the active energy ray-curable resin composition. There is no particular limitation as long as it is capable of hardening, and may be a known and commonly used, for example, a radical polymerization initiator, an anionic polymerization initiator, or a cationic polymerization initiator. Of course, the photopolymerization initiator may be added in combination with the photopolymerization initiation aid.

As such a photopolymerization initiator, for example, p-tert-butyltrichloroacetophenone, 2,2
2'-diethoxyacetophenone, 2-hydroxy-2
Acetophenones such as -methyl-1-phenylpropan-1-one; benzophenone, 4,4'-bisdimethylaminobenzophenone, 2-chlorothioxanthone,
Ketones such as 2-methylthioxanthone, 2-ethylthioxanthone and 2-isopropylthioxanthone;

Benzoin, benzoin methyl ether,
Benzoin ethers such as benzoin isopropyl ether and benzoin isobutyl ether; benzyl ketals such as benzyl dimethyl ketal and hydroxycyclohexyl phenyl ketone; and azides such as N-azidosulfonyl phenylmaleimide.

Further, as the photopolymerization initiator, a polymerizable photopolymerization initiator such as a maleimide compound can be used. The polymerizable photopolymerization initiator is, for example, a polyfunctional maleimide such as a polyfunctional maleimide exemplified as a compound that can be used as the energy beam crosslinkable polymerizable compound, and a monofunctional maleimide that can be mixed and used in an active energy ray-curable resin composition. A monofunctional monomer as exemplified as the system monomer may be used.

The amount of the photopolymerization initiator to be added to the active energy ray-curable resin composition is preferably in the range of 0.1 to 20% by weight in the case of a non-polymerizable photopolymerization initiator,
A range of 15% by weight is more preferable, and a range of 1 to 10% by weight is most preferable. The amount of the photopolymerization initiator to be added in the present invention is at least twice that of a usual photocurable composition (that is, no polymerization retarder or polymerization inhibitor more than the purpose of inhibiting natural polymerization is added). It is preferable that However, this does not apply when the photopolymerization initiator is a polymerizable photopolymerization initiator.

Examples of the modifying agent that can be contained in the active energy ray-curable resin composition as required include, for example, a hydrophilic agent, and the hydrophilic agent includes a hydrophilic polymer such as polyacrylamide or polyvinylpyrrolidone. Coalescence: Nonionic, anionic, cationic surfactants and the like can be mentioned.

Examples of the solvent that can be contained in the active energy ray-curable resin composition as needed include any volatile solvent that is uniformly mixed with the active energy ray-curable resin composition. When the viscosity of the active energy ray-curable resin composition is high or a very thin coating film is formed, a volatile solvent is added, and after shaping such as coating,
It is also preferable to volatilize and remove the solvent.

Examples of the thickener which can be added to the active energy ray-curable resin composition as required include linear polymers such as polyvinylpyrrolidone and polyhydroxymethylstyrene; and powders such as clay. .
Examples of the modifying agent that can be contained in the active energy ray-curable resin composition as needed include, for example, inorganic powders such as silica gel and titanium oxide that act as hydrophilicity improvers; and organic powders such as cellulose.

As the coloring agent which can be contained in the active energy ray-curable resin composition as required, a coloring agent or a pigment as a coloring agent, a fluorescent coloring matter such as anthracene or a fluorescent pigment, 2-benzotriazoyl-4 -UV absorbers such as methoxyphenol.

The active energy ray-curable resin composition of the present invention comprises an active energy ray-polymerizable compound (a), an amphiphilic polymerizable compound (b), a polymerization retarder and / or a polymerization inhibitor, and The other polymerizable compounds added accordingly need to be uniformly compatible, but the other components may be in a dispersed state. The viscosity of the active energy ray-curable resin composition of the present invention is arbitrary, but is preferably from 10 to 10,000 mPas (10 to 10) from the viewpoint of workability and resolution.
10,000 cps), more preferably 30 to 1000 m
Pas. For the purpose of completely improving the curing speed and curing, or for the purpose of preventing the generation of bubbles in the cured product, it is also possible to remove dissolved oxygen from the active energy ray-curable resin composition of the present invention. preferable.

The active energy ray for curing the active energy ray-curable resin composition of the present invention is arbitrary, and examples thereof include light rays such as ultraviolet rays, visible light rays, infrared rays, laser rays, and radiated lights; X-rays, gamma rays, and radiated lights. Ionizing radiation; a particle beam such as an electron beam, an ion beam, a beta ray, and a heavy particle beam is exemplified, and ultraviolet rays and visible lights are preferred from the viewpoint of handleability and curing speed, and ultraviolet rays are particularly preferred. For the purpose of accelerating the curing speed and performing the curing completely, it is preferable to carry out the irradiation of the active energy ray in a low oxygen concentration atmosphere. The low oxygen concentration atmosphere is preferably a nitrogen stream, a carbon dioxide stream, an argon stream, a vacuum or a reduced pressure atmosphere.

The method of irradiating the active energy ray-curable resin composition of the present invention with an active energy ray to cure the resin composition is arbitrary. For example, an active energy ray such as a laser is irradiated by masking an unnecessary portion, or a laser. For example, a photolithography technique, such as scanning the beam or focusing only on the irradiated portion, can be used.

The method of irradiating the active energy ray-curable resin composition according to the present invention with active energy rays to cure the irradiated portion and remove the uncured resin in the non-irradiated portion is also optional. Any method such as absorption by a porous body, blowing off by a compressed gas, solvent washing, rinsing with a non-soluble liquid, decomposition and the like can be adopted. Since the active energy ray-curable resin composition of the present invention can be made into a low-viscosity liquid, a suitable one can be selected from the above methods.

The active energy ray-curable resin composition of the present invention gives a cured product having high hydrophilicity. For example, the contact angle with water is 30 degrees or less, further 20 degrees or less, and further 10 degrees.
It can be made highly hydrophilic of a degree or less. Here, the contact angle with water refers to a static angle at 25 ° C. Also,
By making the surface of the cured product highly hydrophilic, proteins and DNA
It is possible to form a cured product with little biochemical substance adsorption.

The active energy ray-curable resin composition of the present invention can impart high hydrophilicity and excellent water resistance to the cured product. For example, a cured product is dried at 25 ° C.
A non-swelling cured product having a weight increase of 10% or less when immersed in water for 24 hours can be given. In addition, the cured product can have water resistance and hot water resistance that do not change in a boiling test at 100 ° C. for 30 minutes.

The active energy ray-curable resin composition of the present invention can form a fine structure on the cured product by patterning irradiation of the active energy ray. For example, the thickness is 5-300 μm, preferably 10-200 μm
m, a width of 20 μm or less,
A fine groove, concave structure, or wall or convex structure having a size of not more than μm, and further not more than 5 μm can be formed.

Further, a groove or concave structure having an aspect ratio (= depth / width) of 0.5 or more, further 1 or more, and further 2 or more is added to the film-shaped cured product having the above thickness. Structures such as walls and convex structures can be formed. The active energy ray-curable resin composition of the present invention can also provide an optically transparent molded product with high productivity.

[0093]

EXAMPLES The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to the scope of the following examples. In the following examples and comparative examples, "parts" are "parts by weight" unless otherwise specified.

[Abbreviations of Compounds] The compounds represented by abbreviations in the following Examples and Comparative Examples mean the following. (1) V-4263: trifunctional urethane acrylate oligomer having an average molecular weight of about 2000 ("Unidick V-4263" manufactured by Dainippon Ink and Chemicals, Inc., contact angle of homopolymer with water: 71 degrees)

(2) HDDA: 1,6-hexanediol diacrylate ("New Frontier HDDA" manufactured by Daiichi Kogyo Seiyaku Co., Ltd., contact angle of water with a homopolymer of 68)
Every time)

(3) M-114: nonylphenoxy polyethylene glycol (n = 8) acrylate (“M-114” manufactured by Toa Gosei Chemical Co., Ltd .; HLB value = 11.2)
5; soluble in both water and a mixed solvent of cyclohexane / toluene) (4) N-177E: Nonylphenoxypolyethylene glycol (n = 17) acrylate (“N-177E” manufactured by Daiichi Kogyo Seiyaku Co., Ltd .; HLB value = 14.64; water,
Soluble in both cyclohexane / toluene mixed solvent)

(5) AMP-10G: Phenoxypolyethylene glycol (n = 1) acrylate (“AMP-10G” manufactured by Shin-Nakamura Chemical Co., Ltd., HLB value: 4.5)
8) (6) M-113: nonylphenoxy polyethylene glycol (n = 4) acrylate (“M-113” manufactured by Toagosei Chemical Co., Ltd., HLB value: 7.82)

(7) M-102: phenoxy polyethylene glycol (n = 4) acrylate (“M-102” manufactured by Toagosei Chemical Co., Ltd., HLB value: 10.86) (8) AM-90G: methoxy polyethylene glycol (N = 9) Acrylate (“AM-90G” manufactured by Shin-Nakamura Chemical Co., Ltd., HLB value: 16.43)

(9) DPMP: 2,4-diphenyl-4-
Methyl-1-pentene (manufactured by Kanto Chemical Co., Ltd.) (10) Irgacure 184: 1-hydroxycyclohexyl phenyl ketone (“Irgacure 184” manufactured by Ciba Geigy)

[Measurement Method] The measurement in the examples was performed by the following method. [Measurement of solubility of polymerizable compound in water] A mixed solution of 0.5 part of amphiphilic polymerizable compound (b) and 99.5 parts of water at 0 ° C was prepared, stirred vigorously, and stirred at 0 ° C. After standing for 24 hours, the presence or absence of phase separation was visually determined.

[Measurement of solubility of polymerizable compound in hydrophobic solvent] 62.5 parts of cyclohexane and 1 part of toluene
A cyclohexane / toluene mixed solvent consisting of 2.5 parts is prepared, and an amphiphilic polymerizable compound (b) (25 parts) and cyclohexane / toluene mixed solvent (75 parts) are mixed and vigorously stirred at 25 ° C. After standing for 24 hours, the presence or absence of phase separation was visually determined.

[Measurement of contact angle with water]
After allowing to stand at 1 ° C. and a humidity of 55 ± 5% for 24 hours, measurement was carried out using a contact angle meter CA-X manufactured by Kyowa Interface Science at the same temperature and humidity as described above for a stabilization time of 3 minutes.

[Measurement of Weight Increase (Swelling Degree) by Immersion in Water] A sample was vacuum-dried at 45 ° C. for 5 hours, and then weighed to obtain a dry weight. After immersing this sample in water at 25 ° C. for 24 hours, the surface was wiped with filter paper and weighed, and the weight increase was measured. The degree of swelling was determined by the following equation. Swelling degree (%) = weight increase (g) / dry weight (g) × 10
0

[Hot Water Resistance Test] The sample was boiled in distilled water at 100 ° C. for 30 minutes, and the color change of the cured coating film and the presence or absence of peeling from the substrate were observed.

[Measurement of UV Irradiation Amount Required for Gelation] As a measuring device, an RS150RheoStress (RS150RheoStress, manufactured by HAAKE) was used.
The measurement was performed at a sample thickness of 0.5 mm and a measurement frequency of 1 Hz using a s-type viscoelasticity measuring device with a P20 sensor. Ushio Spot Cure SP III (SP-III) manufactured by Ushio Electric Co., Ltd. was used as an ultraviolet irradiation device used for curing the resin. The ultraviolet intensity was 1.21 mW / cm ² .

The measurement was carried out by sandwiching an uncured active energy ray-curable resin composition in a predetermined cell, and irradiating ultraviolet rays from the bottom of the glass cell while measuring the viscoelasticity. As the curing progresses, the loss elastic modulus (G ″) increasing from a finite value and the storage elastic modulus (G ′) increasing from zero intersect, but that point is defined as the gel point. The dose of the energy beam was determined as the product of the irradiation intensity and the time to gelation.

[Preparation of active energy ray-curable resin composition] [Active energy ray-curable resin composition (e1)] As an active energy ray-polymerizable compound (a), 10 parts of V-4263 and 10 parts of HDDA were used. Parts, 80 parts of M-114 as an amphiphilic polymerizable compound (b), 0.5 parts of DPMP as a polymerization retarder, and 5 parts of Irgacure 184 as a photopolymerization initiator are uniformly mixed to form an active energy ray. A curable resin composition (e1) was prepared. The gel point of the active energy ray-curable resin composition (e1) was 2.8 seconds (irradiation light amount: 3.4 mJ / cm ² ).

[Active energy ray-curable resin composition (e
2)] As the active energy ray polymerizable compound (a), V
10 parts of 4263, 10 parts of HDDA, 80 parts of M-114 as an amphiphilic polymerizable compound (b), 0.1 part of DPMP as a polymerization retarder, and 2 parts of Irgacure 184 as a photopolymerization initiator. The active energy ray-curable resin composition (e2) was prepared by uniformly mixing the parts. The gel point of the active energy ray-curable resin composition (e2) is as follows.
8 seconds (irradiation light amount: 2.2 mJ / cm ² ).

[Active energy ray-curable resin composition (e
3)] As the active energy ray polymerizable compound (a), V
60 parts of -4263, 20 parts of HDDA, 20 parts of N-177E as an amphiphilic polymerizable compound (b), 0.5 parts of DPMP as a polymerization retarder, and Irgacure 184 as a photopolymerization initiator. Five parts were uniformly mixed to prepare a composition (e3). The gel point of the active energy ray-curable resin composition (e2) was 2.1 seconds (irradiation light amount of 2.5
mJ / cm ² ).

[Active energy ray-curable resin composition (e
4)] As the active energy ray polymerizable compound (a), V
60 parts of -4263, 20 parts of HDDA, 20 parts of N-177E as an amphiphilic polymerizable compound (b), 0.1 part of DPMP as a polymerization retarder, and Irgacure 184 as a photopolymerization initiator. Five parts were uniformly mixed to prepare a composition (e4). The gel point of the active energy ray-curable resin composition (e2) is 0.53 seconds (irradiation light amount 0.6
4 mJ / cm ² ).

[Active energy ray-curable resin composition (e
5)] As the active energy ray polymerizable compound (a), polytetramethylene glycol (average molecular weight: 250) maleimide capriate was synthesized by the method described in Synthesis Example 13 of JP-A-11-124403. 80 parts of contact angle with water), 20 parts of N-177E as an amphiphilic polymerizable compound (b), and 0.1 part of DPMP (manufactured by Kanto Chemical Co., Ltd.) as a polymerization retarder. Preparation (e5) was prepared. The gel point of the active energy ray-curable resin composition (e2) was 4.4 seconds (irradiation light amount: 5.3 mJ / cm ² ).

[Preparation of Photomask for Resolution Test] Widths 4, 6, 8, 10, 20, 30, 40, 50, 60, 7
It has 0, 80, 90, and 100 μm linear mask portions (non-exposed portions), each of which is 4, 6, 8, 10, 2
0, 30, 40, 50, 60, 70, 80, 90, 10
A photomask made of a metal-deposited glass plate having a pattern formed at intervals of 0 μm (exposed portion) was produced.

[Example 1] [Preparation of base material] An active energy ray-curable resin composition (e1) was formed on a 5 cm x 5 cm x 1 mm acrylic resin plate ("Acrylite L" manufactured by Mitsubishi Rayon Co., Ltd.). 50μ
m with a bar coater, and in a nitrogen atmosphere, irradiate with ultraviolet rays of 50 mW / cm ² for 3 seconds without using a photomask to harden the coating film, and apply an activity of about 36 μm thickness to the surface of the acrylic resin plate. Energy ray-curable resin composition (e1)
A substrate (1) on which a cured coating film was formed was prepared.

The active energy ray-curable resin composition (e1) was applied to the substrate (1) using a 50 μm bar coater. Exposure was performed by irradiating a UV light of 50 mW / cm ² for 1 second in a nitrogen atmosphere through a photomask for a resolution test using a light source unit for a Multilight 200 type exposure apparatus manufactured by Ushio Inc. The coating film of the curable resin composition (e1) was cured.

The active energy ray-curable resin composition (e
2-butanone, which is a solvent for dissolving 1), was blown out of the washing bottle to wash and remove the uncured active energy ray-curable resin composition (e1) in the non-exposed portions to form grooves. Thereafter, the same ultraviolet light used for the above exposure was irradiated for 30 seconds to completely cure the coating film.

[Observation of Resolution] Scanning electron microscope (SE
Observation of the groove-like pattern formed on the coating film using M) revealed that all grooves were clearly formed. However,
In a fine pattern portion, the groove becomes shallow, and in a portion having a groove width of 20 μm and an interval of 4 μm, the aspect ratio is about 3 (groove depth of about 1).
2 μm), and the aspect ratio was about 1 (the groove depth was about 4 μm) in a portion where both the groove width and the interval were 4 μm. When the groove width and the groove interval are 100 μm, the groove depth is about 36 μm.
Met.

[Hydrophilicity test] The contact angle with water was added to the portion of the cured coating film where no grooves were formed. As a result, the contact angle with water of this cured coating film was 20 degrees.

[Hot Water Test] As a result of a boiling test at 100 ° C. for 30 minutes, no cloudiness of the cured coating film or peeling from the substrate was observed.

[Water Resistance Test] The active energy ray-curable resin composition (e1) was applied to a glass plate using a 127 μm bar coater, and irradiated with the same ultraviolet rays as above for 30 seconds to form a cured coating film. This was peeled off from the glass plate to obtain a sample. As a result of a immersion test in water at 25 ° C. for 24 hours,
The weight gain of the cured coating was 0.5%.

Example 2 A cured coating film was formed in the same manner as in Example 1 except that the active energy ray-curable resin composition (e2) was used instead of the active energy ray-curable resin composition (e1). Then, the same test as in Example 1 was performed.
As a result, when the groove width or the distance between the grooves was 6 μm or less, the pattern was crushed. The contact angle with water is 21
Degree. The water resistance and hot water resistance were the same as in Example 1.

[Example 3] A cured coating film was formed in the same manner as in Example 1 except that the active energy ray-curable resin composition (e3) was used instead of the active energy ray-curable resin composition (e1). Then, the same test as in Example 1 was performed.
As a result, the pattern resolution, water resistance, and hot water resistance were the same as in Example 1. The contact angle with water was 12 degrees.

Example 4 A cured coating film was formed in the same manner as in Example 1 except that the active energy ray-curable resin composition (e4) was used instead of the active energy ray-curable resin composition (e1). Then, the same test as in Example 1 was performed.
As a result, when the groove width or the distance between the grooves was 10 μm or less, the pattern was crushed. The contact angle with water was 12 degrees. The water resistance and hot water resistance were the same as in Example 1.

Example 5 A cured coating film was formed in the same manner as in Example 1 except that the active energy ray-curable resin composition (e5) was used instead of the active energy ray-curable resin composition (e1). Then, the same test as in Example 1 was performed.
As a result, when the groove width or the distance between the grooves was 10 μm or less, the pattern was crushed. The contact angle with water is 2
5 degrees. The water resistance and hot water resistance were the same as in Example 1 except that the degree of swelling was about 0.3%.

Example 6 A cured coating film was produced in the same manner as in Example 1 except that a bar coater of 127 μm was used instead of the bar coater of 50 μm, and the same test as in Example 1 was conducted. As a result, everything was substantially the same as Example 1 except that the depth of the groove in the pattern portion having a width of 100 μm was about 110 μm.

[Comparative Examples 1, 2, 3, and 4] The active energy ray-curable resin compositions (e1), (e2), (e3), and (e) were respectively added except that no polymerization retarder was added.
4) and (e5), active energy ray-curable resin compositions (c1), (c2), (c3), (c4),
(C5) was prepared. Resin compositions (c1), (c2),
Table 1 shows the gelation points of (c3), (c4), and (c5).

The active energy ray-curable resin composition (e
Instead of 1), (e2), (e3), (e4), and (e5), active energy ray-curable resin compositions (c1, Comparative Example 1), (c2, Comparative Example 2), (c3) , Comparative Example 3), (c4, Comparative Example 4), (c5, Comparative Example 5) except that a cured coating film was prepared in the same manner as in Examples 1 to 5, and the same as in Examples 1 to 5. Was tested.

As a result, when the groove width or the distance between the grooves was smaller than the value shown in Table 1, the pattern was shallow and crushed. Comparing Comparative Examples 1 to 5 with Examples 1 to 5, it can be seen that a fine pattern cannot be formed without adding a polymerization retarder. In addition, the contact angles with water were almost the same, though slightly higher than those of Examples 1 to 5, respectively. The water resistance and hot water resistance were the same as in Examples 1 to 5, respectively. Note that the resolution in the table refers to the width at which the pattern becomes shallower and collapses in the illuminated portion or the non-illuminated portion having a width one step smaller than the value displayed in the table.

[0128]

[Table 1]

[Comparative Examples 6, 7 and 8] In Example 1, instead of the amphiphilic polymerizable compound (b), the compound had a hydrophilic group and a hydrophobic group, but was not amphiphilic and was insoluble in water. AMP-10G (HLB value: 4.58) (Comparative Example 3), M-113 (HLB value: 7.82) (Comparative Example 4) or a polymerizable compound soluble in a mixed solvent of cyclohexane / toluene. -102 (HLB value: 10.86) (Comparative Example 5), except that it was used in the ratio shown in Table 1.
A molded product was prepared in the same manner as in Example 1, and the same measurement as in Example 1 was performed.

Table 2 summarizes the results. A and b in the table represent the following meanings. a: Active energy ray polymerizable compound (a), V-426
3: HDDA = 1: 1 b: Polymerizable compound having a hydrophilic group

[0131]

[Table 2]

From the results shown in Table 2, it can be seen that, instead of the amphiphilic polymerizable compound (b), the polymer has a hydrophilic group and a hydrophobic group but is not amphiphilic, is insoluble in water, and can be used in a mixed solvent of cyclohexane / toluene. It can be seen that when a soluble polymerizable compound is used, the contact angle of the obtained molded product with water does not decrease regardless of the mixing ratio.

[Comparative Example 9] In Example 1, AM-90G (a polymerizable compound soluble in water and insoluble in a mixed solvent of cyclohexane / toluene) was used in place of the amphiphilic polymerizable compound (b). A molded article was produced in the same manner as in Example 1 except that the HLB value was 16.43) and the proportions shown in Table 2 were used, and the same measurement as in Example 1 was performed.

Table 3 summarizes the results. A and b in the table represent the following meanings. a: Active energy ray polymerizable compound (a), V-426
3: HDDA = 1: 1 b: Hydrophilic polymerizable compound, AM-90G * 1: The coating film swells and deforms during the measurement * 2: The sample self-destructs during measurement

[0135]

[Table 3]

From the results shown in Table 3, a hydrophilic compound which is not amphiphilic is used in place of the amphiphilic polymerizable compound (b).
That is, when a polymerizable compound that is soluble in water and insoluble in a mixed solvent of cyclohexane / toluene is used, the contact angle of the obtained molded product with water does not decrease when the composition ratio of the compound is low. Conversely, when the composition ratio of the compound is increased, before the contact angle with water of the obtained molded product does not decrease so much,
It turns out that it becomes swellable in water.

[0137]

Industrial Applicability The present invention provides an active energy which exhibits high surface hydrophilicity while being non-swelling in water, and which can easily form a cured product having an extremely fine structure by active energy ray pattern exposure. A line-curable resin composition can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G01N 37/00 102 G03F 7/004 502 G03F 7/004 502 7/027 7/027 502 502 7/26 501 7/26 501 G01N 33/53 M // G01N 33/53 33/566 33/566 27/26 331G F term (reference) 2H025 AB20 AC01 AC05 AC06 AC08 AD01 BC23 BC34 BC43 BC49 BC83 CC01 FA03 2H096 AA00 AA30 BA05 BA06 BA20 EA02 EA04 EA06 EA07 LA16 4J011 AA05 CA08 CC10 DA02 FA05 FA07 FB01 NA00 NB06 QA12 QA13 QA22 QA26 QB04 QB16 QB19 QB24 QB29 UA01 VA01 WA01 WA09 WA10 4J027 AC02 AG01 AJ08 BA19 CC23 BA25 CB10

Claims (9)

[Claims] An active energy ray-polymerizable compound (a), wherein the homopolymer has a contact angle of 50 ° or more with water;
Active energy ray containing an amphiphilic polymerizable compound (b) and a polymerization retarder and / or a polymerization inhibitor, capable of forming a copolymer with the active energy ray polymerizable compound (a) upon irradiation with the active energy ray. Curable resin composition. 2. The addition amount of a polymerization retarder and / or a polymerization inhibitor contained in an active energy ray-curable resin composition is as follows:
The dose of active energy rays required to cause the active energy ray-curable resin composition to lose fluidity by irradiation with active energy rays becomes 1.5 to 50 times that of the system without the polymerization retarder and / or the polymerization inhibitor. The active energy ray-curable resin composition according to claim 1, which is in an amount. 3. An active energy ray polymerizable compound (a)
Is a compound having two or more polymerizable carbon-carbon unsaturated bonds in one molecule, and the amphiphilic polymerizable compound (b) is one or more polymerizable carbon-carbon in one molecule. The active energy ray-curable resin composition according to claim 1, which is a compound having an unsaturated bond. 4. An amphiphilic polymerizable compound (b) comprising 25
4. The composition according to claim 1, which is soluble in a mixed solvent of cyclohexane: toluene = 5: 1 (weight ratio) at 25.degree. C. in an amount of 25% by weight or more and 0.5% by weight or more in water at 0.degree. The active energy ray-curable resin composition according to the above. 5. The active energy ray-curable resin composition according to claim 1, wherein the glycine of the amphiphilic polymerizable compound (b) has an HLB value of 10 to 16. 6. The active energy ray-curable resin according to claim 1, wherein the amphiphilic polymerizable compound (b) is a compound having a polyethylene glycol chain having 6 to 20 repetitions. Composition. 7. The active energy ray according to claim 1, wherein the amphiphilic polymerizable compound (b) is a compound having an alkyl group or an alkylene group having 6 to 20 carbon atoms. Curable resin composition. 8. The active energy according to claim 1, wherein the amphiphilic polymerizable compound (b) is an alkylphenyl group-containing compound having an alkyl group having 6 to 20 carbon atoms. A line-curable resin composition. 9. The amount of the amphiphilic polymerizable compound (b) contained in the active energy ray-curable resin composition is 0.1 to 1 part by weight of the active energy ray-polymerizable compound (a).
The active energy ray-curable resin composition according to any one of claims 1 to 8, wherein the amount is from 5 to 5 parts by weight.