JP2001201500A - Photosetting resin and solid channel member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a highly reliable compact and multi water quality meter by providing a light mold member with resistance to heat and moisture and mechanical strength (tensile modulus of elasticity) and using a photosetting resin which can be used for a solid channel member. SOLUTION: In the channel member, in which a solid channel is formed through the use of a photosetting resin, the photosetting resin containing (A) an urethane-based compound expressed by general formula and (B) an imide- based compound with a photopolymerizing functional group or polyimide precursor is used for the solid channel member and water quality meter. The general formula is A-CONH-R-NHCO-Y-CONH-R-NHCO-A, where A is a (meta)acroyl residue, R is an isocyanate component residue, and Y is a diol component residue.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to heat resistance, moisture resistance,
The present invention relates to a three-dimensional flow path member using a photocurable resin having excellent mechanical strength, and a water quality meter using the three-dimensional flow path member.

[0002]

2. Description of the Related Art Conventionally, in stereolithography, a resin containing a photopolymerization compound is irradiated with an ultraviolet laser to cure an irradiated portion and to cure the resin.
The layer is completed, an uncured resin is introduced into the upper layer, and the curing operation is repeated to form a second layer, a third layer,.
A three-dimensional member is manufactured by forming a layer.

[0003] For the production of a resin mold as described above, a method of optically three-dimensionally molding a photocurable resin based on data input to a three-dimensional CAD is disclosed.

As a photocurable resin, JP-A-6-1999
No. 62, JP-A-7-26060, JP-A-7-260
Various types are proposed in JP-A-26062. However, these photocurable resins have a heat deformation temperature of about 70 ° C. or less and a tensile modulus of about 8 in a resin mold obtained by optical three-dimensional molding.
At GPa or less, heat resistance and mechanical strength are insufficient, and deformation and breakage of the resin mold are remarkable and hinder commercialization.

[0005]

SUMMARY OF THE INVENTION An optical three-dimensional molded member (hereinafter, referred to as an optical molded member) made using a photocurable resin is used to confirm the shape and dimensions of a machined product or a molded product or to develop a product. It is used for applications such as temporary assembly.
The optical shaping member is required to be able to accurately reproduce the shape and have excellent mechanical strength. However, since the photocurable resin is cured by ultraviolet light, the mechanical strength of the molded optical molding member is inferior to that of general plastics such as acrylic resin and hard vinyl chloride resin.

Further, when an optical three-dimensional molding member using a photocurable resin is used as a flow path member for a long period of time, there is a problem in application to a water quality meter or the like due to deterioration of physical properties due to water absorption of the resin.

Further, the on-line water quality meter used in the conventional water flow path system requires a large, expensive, and wide installation space, such as an analyzer used in a water purification plant, and requires sufficient measurement. It was difficult to obtain items and measurement points. Therefore, it is necessary to reduce the size of the analysis unit and make it a multi-purpose water quality meter. For this purpose, there is an increasing need for a three-dimensional flow path member having a plurality of flow paths formed in a small volume.

In order to realize this, it is necessary to develop a water quality meter by an optical shaping method using a photocurable resin which can easily form a complicated three-dimensional member. That is, in order to realize a water quality meter using a three-dimensional flow channel member, a photocurable resin having excellent heat resistance, moisture resistance (water) resistance, and mechanical strength is required.

Further, in order to reduce the diameter and cross-sectional area of the flow path of the flow path member, the photocurable resin is easy to remove the uncured portion after the optical molding, and the viscosity at the time of uncured is appropriately low. It is important that the handleability is good.

According to the present invention, in order to apply the three-dimensional channel member to a water quality meter, the stereolithographic member has heat resistance, moisture (water) resistance, and mechanical strength (tensile modulus), and can be used as a channel member. Provide a photocurable resin. By using the photocurable resin, the problem of the three-dimensional flow channel member is solved, and a miniaturized and multi-purpose water quality meter is provided.

[0011]

SUMMARY OF THE INVENTION The present invention has been made in view of the above situation. That is, as a result of examining a photocurable resin having excellent heat resistance, moisture resistance, and mechanical strength that can be cured by ultraviolet light, a resin based on a urethane-based compound (resin) and an imide-based compound (resin) was obtained. It has been found that a resin system obtained by adding an epoxy-based compound (resin) to the above is promising.

The gist is as follows.

[1] In a flow path member in which a three-dimensional flow path is formed using a photocurable resin, the photocurable resin is represented by the following general formula (A):

[0014]

Embedded image

Wherein A is a (meth) acryloyl residue, R
Is an isocyanate component residue, and Y is a diol component residue. And (B) a photocurable resin containing an imide compound having a photopolymerizable functional group or a polyimide precursor.

The photocurable resin according to item [1], further comprising (C) an epoxy compound having a photopolymerizable functional group.

In the above, it is preferable that the urethane compound represented by the general formula [1] is contained in an amount of 10 to 80% by weight. The photocurable resin can be cured by using ultraviolet rays to obtain a cured resin having excellent heat resistance (thermal deformation temperature), moisture resistance (water absorption), and mechanical strength (tensile modulus).

Further, the three-dimensional flow channel member is characterized in that a hard coat treatment is performed on the inner surface of the flow channel of the flow channel member, and a coating process is performed on the inner surface of the flow channel with a fluororesin or vinylidene fluoride. Furthermore, a three-dimensional flow channel member having one or more branches or a plurality of flow channels and a container portion, wherein the diameter of the flow channel is less than 2 mm or the cross-sectional area of the flow channel is less than 4 mm ^2. .

[2] In a water quality meter which can be attached to a drainage path of a drainage system, the water quality meter includes a water introduction section and an analysis section for analyzing the introduced water, a flow path formed of a photocurable resin. Wherein the photocurable resin of the flow member is a resin system containing the urethane compound of the above item [1] and an imide compound or a polyimide precursor, or a resin system containing an epoxy resin further. It is a water quality meter characterized by being.

The photocurable resin of the present invention improves the moisture resistance (water) resistance by reducing or substantially removing hydrophilic groups or polar groups of the resin component used for stereolithography, and improves urethane compounds, imide compounds and epoxy resins. Heat resistance and mechanical strength are improved by adding a system compound in a well-balanced manner.

Further, an additive is added to improve the strength at the time of curing the resin and to suppress the progress of the reaction of the uncured portion by appropriately setting the reaction rate at the time of curing the resin. The uncured resin can be easily removed from the inside of the member, and the diameter and cross-sectional area of the flow passage member can be reduced. Thus, a three-dimensional flow path member satisfying moisture resistance (water absorption rate) and mechanical strength (tensile modulus) can be obtained.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the urethane compound represented by the general formula [1] as the component (A) includes, for example, an unsaturated urethane and a vinyl monomer. The vinyl monomer = 80/20 to 40/60
(Weight ratio).

As the unsaturated urethane, for example, the molecule has three or more methacryloyl groups and acryloyl groups as radical polymerizable groups in a molecule, and the molecular weight per radical polymerizable group is 150 to 150 on average. 250 is an unsaturated urethane.

Specifically, (1) a polyol (meth) acrylic acid moiety having one hydroxyl group in a molecule obtained by esterifying 1 mol of an n-valent polyisocyanate with a polyol and (meth) acrylic acid; Ester nmol (hereinafter referred to as (meth) acrylic ester monol)
Unsaturated urethane obtained from (2) 1 mol of n-valent polyol, n mol of diisocyanate, and n mol of (meth) acrylic ester monol, and (3) n-valent polyol 1 mole of an unsaturated urethane obtained from 1 mole of an isocyanatoalkyl (meth) acrylate, (4) 1 mole of a polyol (meth) acrylate having n free hydroxyl groups in a molecule, and 1 mole of an isocyanatoalkyl (meth) acrylate And unsaturated urethane obtained from n moles of acrylate, a mixture of the above unsaturated urethanes, and the like.

The present invention has a methacryloyl group and an acryloyl group as radical polymerizable groups in the molecule in a total of three or more of them, and as an index of the content of such radical polymerizable groups per radical polymerizable group. The unsaturated urethane having a molecular weight of 150 to 250 on average is used, and the unsaturated urethane having such a concentration of the radical polymerizable group can be obtained by appropriately selecting a raw material to be used for the synthesis of the unsaturated urethane. Can be.

For example, in the case of a polyisocyanate, its molecular weight and the number of isocyanate functional groups, in the case of a polyol, its molecular weight and the number of hydroxy functional groups,
In the case of a (meth) acrylate partial ester, it can be obtained by appropriately selecting and combining the number of (meth) acryloyl functional groups and the like.

In the present invention, the unsaturated urethane has three or more methacryloyl groups and acryloyl groups as radical polymerizable groups in the molecule as described above, and the radical polymerizable group is contained in the molecule. As a methacryloyl group / acryloyl group = 1/3 to 3/1 (molar ratio), and the radical-compatible group is 3 to
Those having eight are preferred.

Examples of such unsaturated urethanes include (1) a reaction product of diisocyanate / triol monomethacrylate / monoacrylate = 1/2 (molar ratio), diisocyanate / triol monomethacrylate / monoacrylate / diol monomethacrylate = 1. / 1 /
1 (molar ratio), diisocyanate / triol monomethacrylate / monoacrylate / diol monoacrylate = 1/1/1 (molar ratio), (2)
Diisocyanate / triol monomethacrylate / monoacrylate / triol dimethacrylate = 1/1
/ 1 (molar ratio), diisocyanate / triol monomethacrylate / monoacrylate / triol diacrylate = 1/1/1 (molar ratio),
(3) Reaction product of triol / diisocyanate / triol monomethacrylate / monoacrylate = 1/3/3 (molar ratio), triol / diisocyanate / triol monomethacrylate / monoacrylate / diol monomethacrylate = 1/3/2/1 ( Molar ratio) or 1
/ 3/1/2 (molar ratio), triol / diisocyanate / triol monomethacrylate / monoacrylate / diol monoacrylate = 1/3/2/1
Or a reactant of 1/3/1/2 (molar ratio), (4) a reactant of tetraol / diisocyanate / triol monomethacrylate / monoacrylate = 1/4/4 (molar ratio), tetraol / diisocyanate / triol Monomethacrylate / monoacrylate / diol monomethacrylate = 1/4/3/1 (molar ratio) and 1/4/2
/ 2 (molar ratio), tetraol / diisocyanate / triol monomethacrylate / monoacrylate / diol monoacrylate = 1/4/3/1 (molar ratio) and 1/4/2/2 (molar ratio) Reactant, (5) tetraol / diisocyanate / triol monomethacrylate / diol monoacrylate = 1/4/2/2
(Molar ratio) and 1/4/3/1 (molar ratio).

According to the present invention, among the above-mentioned unsaturated urethanes, the unsaturated urethanes in the above (1), (3) and (4) using an aromatic diisocyanate, wherein the radically polymerizable group The average molecular weight per piece is 150
To 215 are particularly preferred.

The raw materials used for the synthesis of the unsaturated urethane include (1) dihydric alcohols such as ethylene glycol, propylene glycol, 1,4-butanediol, and 1,6-hexanediol;
Acrylates, (2) trihydric alcohols such as glycerin and trimethylolpropane, triols such as polyether triols such as ethylene oxide and propylene oxide adducts, and monomethacrylates and the like
Monoacrylates, (3) pentaerythritol, and polyethertetraols such as ethylene oxide and propylene oxide adducts of pentaerythritol can be advantageously used. As the aromatic diisocyanate, known ones can be applied, but tolylene diisocyanate, metalene-bis- (4-phenyl isocyanate) and the like can be advantageously used.

In the present invention, when an unsaturated urethane having a molecular weight of less than 150 per radically polymerizable group contained in the unsaturated urethane is used, the resin mold obtained will be deformed due to internal strain stress, fine cracks, etc. And the molecular weight per radical polymerizable group is 2
If it exceeds 50, the thermal and mechanical properties of the resin mold deteriorate.

The imide compound having a photopolymerizable functional group or the polyimide precursor which is a component (B) of the present invention is, for example, an olefin obtained by reacting an aromatic tetracarboxylic dianhydride with an olefin unsaturated alcohol. An aromatic tetracarboxylic acid diester is synthesized, the compound and a diamine are polymerized by a dehydration condensation reaction using, for example, carbodiimide, and a photosensitive group is introduced by a covalent bond,
Those obtained by reacting an aromatic tetracarboxylic dianhydride with an aromatic diamine compound to introduce a photosensitive group by ionic bonding are exemplified.

These are applied to a substrate in the form of a varnish dissolved in an appropriate organic solvent, dried to form a film, and then irradiated with ultraviolet rays through an appropriate photomask to cure the exposed portions. By performing development and rinsing, a relief pattern having a relatively thick film thickness can be obtained.

As the component (B), a polyimide precursor having a photopolymerizable carbon-carbon double bond and a hexaarylbiimidazole compound, a titanocene compound or an arylglycine compound as a photoinitiator system are contained. Can be used as a photosensitive polyimide precursor composition.

The photoinitiator is preferably contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the component (B). The photoinitiator is a hexaarylbiimidazole compound containing a fluorine atom, a titanocene compound or an arylglycine-based compound, so that the polymerization proceeds even after irradiation with ultraviolet rays as compared with other photoinitiators and finally cures. The ratio is improved, and the adhesion between the layers is improved.

As the titanocene compound, bis (y5
-Cyclopentadienyl) bis [2,6-difluoro-
3- (1H-pyro-1-yl) phenyl] -titanium, bis (y5-methylcyclopentadienyl) bis [2,6-difluorophenyl] -titanium, bis (y5-methylcyclopentadienyl) bis [ 2,3
4,5,6-Pentafluorophenyl] -titanium and the like are preferable.

The content of the hexaarylbiimidazole compound and the titanocene compound is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the polyimide precursor.

Further, in the present invention, by adding a hydrogen donor such as an aromatic mercapto compound, a mercaptobenzoxazole, a mercaptobenzothiazole, a mercaptobenzimidazole, an amine or an arylglycine compound to the above-mentioned initiator system, the ultraviolet sensitivity can be improved. Can be increased.

Examples of the hydrogen donor include N-phenylglycine (NPG), N- (p-chlorophenyl) glycine,
N- (p-bromophenyl) glycine, N- (p-cyanophenyl) glycine, N- (p-methylphenyl) glycine, N-methyl-N-phenylglycine, N- (p
-Bromophenyl) -N-methylglycine, N- (p-
Aryl glycine compounds such as (chlorophenyl) -N-ethylglycine. The content of the hydrogen donor is based on 100 parts by weight of the polyimide precursor (A).
It is preferably 0.1 to 15 parts by weight.

Examples of the polyimide precursor having a photopolymerizable carbon-carbon double bond include a photopolymerizable carbon-carbon double bond.
Polyamic acid unsaturated ester having a structure in which a compound having a carbon double bond is covalently bonded to a side chain of polyamic acid,
Examples thereof include unsaturated amides of polyamic acid and those obtained by mixing a polyamic acid with an amine having a carbon-carbon double bond to introduce a carbon-carbon double bond by an ionic bond between a carboxyl group and an amino group. More preferably, the carbon-carbon unsaturated double bond is included in the form of an acryloyl group or a methacryloyl group.

Of these, polyamic acid esters are preferred because they have excellent solubility in a basic aqueous solution and can be used in combination with the component (C) of the present invention to achieve excellent sensitivity and shorten development time.

For example, a methacryloyloxyalkyl group and an acryloyloxyalkyl group are suitable for the present invention because they not only realize high ultraviolet sensitivity but also are easy to synthesize.

The polyimide precursor of the present invention can be variously adjusted by the types and amounts of the tetracarboxylic dianhydride, diamine and the compound containing a carbon-carbon double bond.

The polyamic acid ester is mixed with a tetracarboxylic dianhydride and a hydroxy group-containing compound having an unsaturated group and reacted to produce a half ester of tetracarboxylic acid, which is then acid chlorided with thionyl chloride. Then, it can be synthesized by a method of reacting with a diamine or a method of reacting the tetracarboxylic acid half ester with a diamine using a carbodiimide as a condensing agent.

The tetracarboxylic dianhydride includes:
For example, oxydiphthalic acid, pyromellitic acid, 3,
3 ', 4,4'-benzophenonetetracarboxylic acid,
3,3 ', 4,4'-biphenyltetracarboxylic acid,
1,2,5,6-naphthalenetetracarboxylic acid, 2,
3,6,7-naphthalenetetracarboxylic acid, 1,4
5,8-naphthalenetetracarboxylic acid, 2,3,5,6
-Pyridinetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, sulfonyldiphthalic acid, m-terphenyl-3,3 ', 4,4'-tetracarboxylic acid,
p-terphenyl-3,3 ', 4,4'-tetracarboxylic acid, 1,1,1,3,3,3-hexafluoro-2,
2-bis (2,3- or 3,4-dicarboxyphenyl) propane, 2,2-bis (2,3- or 3,4-dicarboxyphenyl) propane, 2,2-bis {4'-
(2,3- or 3,4-dicarboxyphenoxy) phenyl} propane, 1,1,1,3,3,3-hexafluoro-2,2-bis {4 ′-(2,3- or 3, Examples thereof include dianhydrides of aromatic tetracarboxylic acids such as 4-dicarboxyphenoxy) phenyl} propane, and these are used alone or in combination of two or more.

Examples of the diamine include 3,5-diaminobenzoic acid, 4,4'-dihydroxy-3,3'-diaminobiphenyl, 3,4-diaminobenzoic acid, and 3,3 '
-Dihydroxy-4,4'-diaminobiphenyl, 2,
3-diamino-4-hydroxypyridine, 2,2-bis (4-hydroxy-3-aminophenyl) hexafluoropropane, 2,4-diaminophenol, 2,4-diaminobenzoic acid, 3-carboxy-4,4 '-Diaminodiphenyl ether, 3,3'-dicarboxy-4,
4'-diaminodiphenyl ether, 3-carboxy-
4,4'-diaminodiphenylmethane, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane, 3,
3′-dicarboxy-4,4′-diaminobiphenyl,
3,3 ′, 5,5′-tetracarboxy-4,4′-diaminobiphenyl, 3-carboxy-4,4′-diaminodiphenylsulfone, 3,3′-dicarboxy-4,
4'-diaminodiphenyl sulfone, 1,1,1,3
3,3-hexafluoro-2,2-bis (3-carboxy-4-aminophenyl) propane, 4,4 '-(or 3,4'-, 3,3'-, 2,4'-, , 2 '-) diaminodiphenyl ether, 4,4'-(or 3,4 '
-, 3,3 '-, 2,4'-, 2,2 '-) diaminodiphenylmethane, 4,4'- (or 3,4'-, 3,
3'-, 2,4'-, 2,2'-) diaminodiphenylsulfone, 4,4'- (or 3,4'-, 3,3'-,
2,4 '-, 2,2'-) diaminodiphenyl sulfide, paraphenylenediamine, metaphenylenediamine, p-xylylenediamine, m-xylylenediamine, o-tolidine, o-tolidine sulfone, 4,4'-
Methylene-bis- (2,6-diethylaniline), 4,
4'-methylene-bis- (2,6-diisopropylaniline), 2,4-diaminomesitylene, 1,5-diaminonaphthalene, 4,4'-benzophenonediamine, bis- {4- (4'-aminophenoxy) Phenyl disulfone, 1,1,1,3,3,3-hexafluoro-2,
2-bis (4-aminophenyl) propane, 2,2-bis {4- (4'-aminophenoxy) phenyl} propane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetramethyl-4,
4'-diaminodiphenylmethane, bis {4- (3'-
Aminophenoxy) phenyl} sulfone; 2,2-bis (4-aminophenyl) propane; and the like, and these are used alone or in combination of two or more.

In addition, as the diamine residue, a diamine such as diaminopolysiloxane can be used to improve the adhesiveness.

As diamines, 4,4'-diaminodiphenylether-3-sulfonamide, 3,4'-diaminodiphenylether-
4-sulfonamide, 3,4'-diaminodiphenylether-3'-sulfonamide, 3,3'-diaminodiphenylether-4-sulfonamide, 4,4'-diaminodiphenylether-3-carboxamide, 3,
Use of a diamine compound having a sulfonamide group or a carboxamide group such as 4'-diaminodiphenyl ether-4-carboxamide, 3,4'-diaminodiphenyl ether-3'-carboxamide, and 3,3'-diaminodiphenyl ether-4-carboxamide. Can also. When these are used, 1 to all amine components
Preferably, it is used in an amount of up to 30 mol%.

These diamines are used alone or in combination of two or more.

In the present invention, the molecular weight of the polyimide precursor is preferably 10,000 to 200,000 in terms of weight average molecular weight from the viewpoint of the properties of the cured film after imidization.

For the photosensitive polyimide precursor of the present invention, it is preferable to use an addition-polymerizable compound having a boiling point of 100 ° C. or more at normal pressure, since a better flow path (pattern) can be formed. Here, when the boiling point is lower than 100 ° C. at normal pressure, when the solvent contained in the system is removed by drying or the like or when irradiating with ultraviolet rays,
The addition polymerizable compound volatilizes, which is not preferable in characteristics.
The addition polymerizable compound is preferably soluble in an organic solvent.

As such an addition polymerizable compound, a compound obtained by condensing a polyhydric alcohol with an α, β-unsaturated carboxylic acid, for example, ethylene glycol di (meth) acrylate (diacrylate or dimethacrylate) Meaning, the same shall apply hereinafter), triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, trimethylolpropane di (meth)
Acrylate, trimethylolpropane tri (meth) acrylate, 1,2-propylene glycol di (meth)
Acrylate, di (1,2-propylene glycol) di (meth) acrylate, tri (1,2-propylene glycol) di (meth) acrylate, tetra (1,2-propylene glycol) di (meth) acrylate, dimethylaminoethyl (Meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate, 1,4-butanediol di (meth)
Acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, etc.), styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, 2-hydroxyethyl (meth) ) Acrylate, 1,
3- (meth) acryloyloxy-2-hydroxypropane, methylenebisacrylamide, N, N-dimethylacrylamide, N-methylolacrylamide, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, dipentaerythritol hexa (Meth) acrylate, tetramethylolpropanetetra (meth) acrylate, and the like.
These are used alone or in combination of two or more.

The addition polymerizable compound having a boiling point of 100 ° C. or more at normal pressure is preferably used in a proportion of 5 to 50 parts by weight based on 100 parts by weight of the component (B).

The photosensitive polyimide precursor composition of the present invention may contain other additives, for example, additives such as a plasticizer and an adhesion promoter.

As the polyimide having a photopolymerizable carbon-carbon double bond as the component (B), at least 1
Compounds having two N-substituted unsaturated imide groups are useful. For example, there are mono-substituted maleimide, bis-substituted maleimide, tri-substituted maleimide, tetra-substituted maleimide and the like. One or more of these can be used in combination. Among these, particularly useful compounds include N, N'-diphenylmethanebismaleimide, N, N'-phenylenebismaleimide, N, N'-diphenyletherbismaleimide, N, N'-diphenylsulfonebismaleimide,
N, N′-dicyclohexylmethanebismaleimide,
N, N′-xylenebismaleimide, N, N′-tolylenebismaleimide, N, N′-xylylenebismaleimide, N, N′-diphenylcyclohexanebismaleimide, N, N′-dichlorodiphenylbismaleimide,
N, N'-diphenylmethanebismethylmaleimide,
N, N′-diphenyl ether bismethylmaleimide,
N, N'-diphenylsulfonebismaleimide, 2,2
-Bis-4 [-4- [maleimidophenoxy] phenyl] propane, 2,2-bis-4 [-4- [maleimidophenoxy] phenyl] hexafluoropropane (including isomers), N, N'-ethylene Bismaleimide, N, N'-hexamethylenebismaleimide, N, N '
N, N'- such as hexamethylenebismethylmaleimide
Bismaleimide compounds, the terminal obtained by adding these N, N'-bismaleimide compounds and diamines are N,
Examples thereof include a prepolymer having an N′-bismaleimide skeleton, a maleimidated aniline, a formalin condensate, and a methylmaleimide.

In the present invention, the imide component is effective for improving the heat resistance and mechanical strength of the cured photoresin.

The present invention provides a photocurable resin obtained by blending the above components (A) and (B) with an epoxy compound having a photopolymerizable functional group as component (C).

As the epoxy compound of the component (C),
For example, an epoxy resin obtained by reacting a novolak resin obtained by a condensation reaction of a phenol and an aldehyde, such as a phenol novolak type epoxy resin and an orthotalkol novolak type epoxy resin, with an acidic catalyst and epichlorohydrin, bisphenol A, Glycidyl ethers such as bisphenol F, bisphenol S and hydrogenated bisphenol A; glycidyl ester type epoxy resins obtained by the reaction of epichlorohydrin with polybasic acids such as phthalic acid and dimer acid; polyamines such as para-phenylenediamine and diaminodiphenylmethane; Glycidylamine type epoxy resin obtained by reaction with epichlorohydrin, linear aliphatic epoxy resin or alicyclic epoxy resin obtained by oxidizing olefin bond with peracid such as peracetic acid There epoxy (meth) acrylate. Of these, epoxy (meth) acrylate is particularly preferred because of its excellent sensitivity to ultraviolet light.

The epoxy (meth) acrylate is obtained by reacting the above epoxy resin with an unsaturated monobasic acid. For example, unsaturated monobasic acids include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, and tricyclo [5.2.1.
0 ^2,6 ] -4-decene-8 or 9 residues and an unsaturated dibasic acid residue as a component.

Examples of partially esterified carboxylic acids include:
8 or 9-hydroxytricyclodecene-4- [5.
2.1.0 ^2,6 ] 1.00 to 1.20 mol and 1 mol of unsaturated dibasic acid such as maleic anhydride, itaconic acid, citraconic acid and the like are heated at 70 to 150 ° C. under a stream of inert gas. The unsaturated dibasic acid monoester, tricyclodecadiene-4,8- [5.2.1.0 ^2,6 ] obtained by the above method is treated with an unsaturated dibasic acid such as maleic acid, fumaric acid, itaconic acid and the like. And unsaturated dibasic acid monoesters obtained by addition in the presence of a catalyst such as a Lewis acid.

The epoxy resin may be reacted with a polybasic acid, if necessary, in view of the toughness and durability of the coating film. Polybasic acids include maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, adipic acid, azelaic acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, trimellitic anhydride, etc. Is mentioned. It is preferable to further use a dibasic acid having 12 or more carbon atoms as the polybasic acid used as necessary. Specific examples of this dibasic acid include:
Todecanedioic acid, a mixture of isomers of unsaturated dibasic acids having 16 carbon atoms, a mixture mainly composed of saturated dibasic acids having 20 carbon atoms, dimerized fatty acids derived from tall oil fatty acids (dimer acids having 36 carbon atoms), etc. Is mentioned.

The component (C) is preferably a vinyl ester resin. Particularly, the compounding ratio of the epoxide resin to the unsaturated monobasic acid or polybasic acid is such that the carboxyl group of these acid components and the epoxy group of the epoxide resin are equivalent. 1.0: 0.9 to 1.0: 1 in a ratio (carboxyl group: epoxy group).
A range of 3 is preferred. In this esterification reaction, quaternary ammonium salts such as trimethylbenzylammonium chloride and pyridinium chloride, tertiary amines such as triethylamine and dimethylaniline, ferric chloride, lithium hydroxide, lithium chloride, stannic chloride and the like The reaction time can be shortened by using an esterification catalyst.

The vinyl ester resin as the component (C) includes, as polymerizable monomers, for example, styrene, chlorostyrene, divinylbenzene, tertiary butyl styrene, styrene bromide, diallyl phthalate, methyl methacrylate, methacrylic acid. Ethyl acrylate, ethyl acrylate, butyl acrylate, β-hydroxyethyl methacrylate, β
-Ethyl hydroxyacrylate, acrylamide, phenylmaleimide and the like are used. Further, polyfunctional (meth) acrylates such as ethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, and trimethylolpropane trimethacrylate can also be used. These can be used alone or in combination with other polymerizable monomers. The compounding amount is 10 to 2 with respect to 100 parts by weight of the vinyl ester resin.
00 parts by weight is preferable, and 30 to 150 parts by weight is more preferable.

The epoxy compound as the component (C) of the present invention can be further cured by adding a curing agent and irradiating ultraviolet rays. The curing agent is not particularly limited as long as it shows a curing reaction with the epoxy resin, and a known curing agent can be used. For example, phthalic anhydride, methyltetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, trimellitic anhydride, maleic anhydride, pyromellitic anhydride and the like Acid anhydride, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazo -L, 1-cyanoethyl-2-undecylimidazole, 1
-Cyanoethyl-2-undecylimidazolium trimellitate, 2,4-diamino-6- [2-ethyl-4-methylimidazolyl- (1)]-ethyl-S-triazine, 2-phenyl-4,5-
Dihydroxymethylimidazole, 1-dodecyl-2-methyl
Imidazoles such as -3-benzylimidazolium chloride, diaminodiphenylmethane, diaminodiphenylsulfone, dicyandiamide, diamines such as the diamine compound represented by the general formula (2), triphenylphosphine tetraphenylborate, triethylamine tetraphenylborate , Carbohydrate salts such as N-methylmorpholine tetraphenyl borate, pyridine tetraphenyl borate, phenol novolak resins, cresol novolak resins, phenols such as polyvinyl phenol, boron trifluoride-amine complex, organic acid hydrazide, aromatic diazonium salt, etc. But are not limited to these. These can be used alone or
Two or more types are used. The amount of the curing agent is not particularly limited, but is preferably 0.1 to 1.0 equivalent to 1 equivalent of the epoxy group in order to obtain a good cured product.

Further, to the epoxy compound of the present invention, for example, amines, imidazoles, caribol salts, aromatic diazonium salts and the like can be added as a curing accelerator. Specific examples of the compound include tertiary amines such as 1,8-diazabicyclo (5,4,0) undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine and tris (dimethylaminomethyl) phenol. Imidazoles such as 2,2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, organic phosphines such as tributylphosphine, triphenylphosphine, diphenylphosphine, tetra Examples thereof include tetraphenylboron salts (caribole salts) such as phenylphosphonium tetraphenylborate, triphenylphosphine tetraphenylborate, and 2-ethyl-4-methylimidazole tetraphenylborate. The compounding amount is appropriately determined according to the use conditions and applications.
It may be used in an amount of 0.05 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 00 parts by weight.

As long as the effects of the present invention are not impaired, diluents such as phenylglycidyl ether, diglycidyl ether and diglycidylaniline, polyglycidyl ethers, polyols, carboxyl compounds, urethane prepolymers, silicone compounds, fluorine compounds, etc. And a water repellent material.

Further, the photocurable resin of the present invention contains (meth)
Acrylic acid morpholide alone or a mixture of (meth) acrylic acid morpholide and diol di (meth) acrylate can be used.

The photocurable resin for a resin mold of the present invention may contain a filler in an amount of 50 to 400 parts by weight per 100 parts by weight of the photocurable resin. In this case, the filler is preferably a mixture of inorganic solid fine particles and inorganic fiber whiskers having an average fiber length of 1 to 70 μm and surface-treated with (meth) acryloyl-modified silane or vinyl-modified silane (hereinafter, these are referred to as silane coupling agents). .

Examples of the inorganic solid fine particles include silica, alumina, clay, calcium carbonate, glass beads and the like having an average particle diameter of 0.1 to 50 μm. Among them, glass beads are preferable, and the surface is treated with a silane coupling agent. Glass beads having an average particle diameter of 3 to 30 μm are particularly preferred.

Examples of the inorganic fiber whiskers include potassium titanate fibers, alumina fibers, magnesium sulfate fibers, magnesium borate fibers, and aluminum borate fibers having an average fiber length of 1 to 70 μm and surface-treated with a silane coupling agent. Among them, aluminum borate fibers having a fiber diameter of 0.3 to 1 μm and an average fiber length of 10 to 20 μm are preferred.

Examples of silane coupling agents used for surface treatment of inorganic fiber whiskers and glass beads include 1) (meth) acryloyloxypropyltrimethoxysilane,
(Meth) acryloyl-modified alkoxysilanes such as di (meth) acryloyloxypropyldimethoxysilane,
2) Vinyl-modified alkoxysilanes such as vinyltrimethoxysilane, divinyldimethoxysilane, vinyloxypropyltrimethoxysilane and divinyloxypropyldimethoxysilane. The surface treatment of inorganic fiber whiskers or glass beads using such a silane coupling agent does not limit the treatment method or the amount of surface treatment, but the surface treatment amount is usually 0.1 to 20 with respect to the object to be treated. % By weight, preferably 1 to 10% by weight.

When the photocurable resin for a resin mold of the present invention is subjected to optical three-dimensional modeling, a photopolymerization initiator is previously contained therein. In the present invention, the kind of the photopolymerization initiator to be used is not particularly limited. Examples of the photopolymerization photoopening agent include (1) carbonyl compounds such as benzoin, α-metal benzoin, anthraquinone, chloranthraquinone, and acetophenone; (2) sulfur compounds such as diphenylsulfide, diphenyldisulfide, and dithiocarbamate; 3) Polycyclic aromatic compounds such as α-chloromethylnaphthalene and anthracene. The content of these photopolymerization initiators in the photocurable resin for a resin mold is 0.1 to 10 parts by weight, preferably 2 to 5 parts by weight, per 100 parts by weight of the photocurable resin. N-butylamine, triethanolamine, N, N
-Dimethylaminobenzenesulfonic acid diallylamide,
A photosensitizer such as N, N-dimethylaminoethyl methacrylate can be used.

The photocurable resin of the present invention includes antimony oxide, zinc oxide, basic lead carbonate, basic lead sulfate, barium carbonate, calcium carbonate, aluminum silica, magnesium carbonate, magnesium silica, clay, talc and the like. Moisture resistant pigments, strontium chromate, lead chromate,
Basic Lead Chromate, Lead Tan, Lead Silicate, Basic Lead Silicate,
Anticorrosive pigments such as lead phosphate, basic lead phosphate, lead tripolyphosphate, lead silicate, lead, cyanamide lead, calcium lead oxide, lead suboxide and lead sulfate can also be used. Usually, the mixing ratio of the pigment and the epoxy resin is preferably in the range of 2/1 to 7/1 by weight ratio of solid content.

In the present invention, an optical three-dimensional molding method for producing a resin mold is not particularly limited, and a known method can be applied. For example, an operation of first forming a cured layer of the photocurable composition, then supplying a new photocurable composition on the cured layer to form the cured layer is repeatedly performed, and a desired layer is formed. There is a method of forming a resin mold.
The formed resin mold can be further post-cured if necessary. Examples of the energy beam used for curing include visible light, ultraviolet light, and electron beam, and ultraviolet light is preferable.

The photocurable resin for a resin mold of the present invention can be optically three-dimensionally molded on the basis of data input to three-dimensional CAD. Thus, the resin mold of the present invention directly obtained can be manufactured in a much shorter time and easily than a general conventional means that requires the manufacture of a master model. In addition, it has higher heat resistance, moisture resistance, and mechanical strength than a resin mold obtained by a conventional means of optical three-dimensional molding using a known photocurable resin, and is excellent in durability as a mold.

In performing optical three-dimensional modeling using the optical three-dimensional modeling resin of the present invention, any of conventionally known optical three-dimensional modeling methods and apparatuses can be used. In the present invention, the light energy for photocuring the resin is A
An active energy beam generated from an r laser, a He-Cd laser, a xenon lamp, a metal halide lamp, a mercury lamp, a fluorescent lamp, or the like can be used, and a laser beam is particularly preferable. When a laser beam is used, the molding time can be shortened, and a three-dimensional object with high modeling accuracy can be obtained by utilizing the good light-condensing property of the laser beam.

In order to prepare the three-dimensional flow channel member of the present invention using the photocurable resin, a conventionally known method and a conventionally known stereolithography system device can be adopted, and there is no particular limitation.

As a typical example of the optical three-dimensional molding method used in the present invention, an active energy ray is selected so as to obtain a cured layer having a desired pattern in a liquid photocurable resin containing a light energy absorber. Irradiation to form a cured layer, and then supply the uncured liquid composition to the cured layer, and similarly irradiate with an active energy ray to newly form a cured layer continuous with the cured layer. There is a method of finally obtaining a target three-dimensional channel member by repeating the operation. The three-dimensional flow channel member obtained as described above may be used as it is, or may be used after further post-curing by light irradiation or heat to enhance its mechanical properties and shape stability.

In the present invention, the structure, shape, size, and the like of the three-dimensional flow path member are not particularly limited, and can be appropriately adjusted according to each use.

Hereinafter, the most preferable method for producing the three-dimensional flow channel member of the present invention will be described.

FIG. 1 is a schematic view showing an example of an optical shaping apparatus according to the present invention.

In FIG. 1, reference numeral 1 denotes a molding container 2 having a predetermined capacity.
Is an apparatus main body (support) that detachably supports the apparatus and is equipped with a control unit and the like to be described later.
It is a fluid material containing a predetermined photocurable resin (e.g., a UV curable resin) stored in the inside. A horizontal free liquid surface L of the fluid material 10 is formed on the upper part of the modeling container 2. The uncured flowable material may be, for example, a photocurable resin of the present invention having a substantially non-shrinkage average particle size of 3 within a predetermined temperature range.
A paste (for example, having a viscosity of 5,000 cps to 100,000 cps) in which fine particles (for example, glass beads or resin beads) having a viscosity of about 5 to 70% by volume, preferably 10 to 55% by volume are blended. The fine particles are treated with a known silane coupling agent so as to increase the mechanical strength after curing. Alternatively, the uncured fluid material has a diameter of 0.3 to 1 μm and a length of 10 to 70 μm instead of the fine particles.
A whisker having an aspect ratio in the range of 10 to 100 may be used (in this case, the whisker is mixed with the liquid photocurable resin in an amount of 5 to 30% by volume).

The height of the free liquid level L of the uncured material 10 is maintained at a constant level from the bottom surface of the molding container 2 by a known liquid level adjusting means (not shown).
A movable platform 11 having an upper surface 11a substantially parallel to the free liquid level L is provided therein. The platform 11 is guided and supported by a known lifting mechanism 15 (guide supporting means) so as to be able to move up and down in a vertical direction substantially perpendicular to the free liquid surface. The guide supporting mechanism 15 is controlled by the control unit 30. Thus, the platform 11 is lowered stepwise in units of a predetermined lowering pitch amount (predetermined moving amount) corresponding to the layer thickness of the hardened layer described later, and rises to near the initial position when the modeling is completed. .

A laser beam scanning device 20 (exposure means) is provided above the platform 11. The scanning device 20 focuses, for example, a laser beam emitted from a laser light source on a surface portion of an uncured material layer on the platform 11 while deflecting the laser beam through a reflection optical system (not shown), and Scanning is performed in both the main and sub scanning directions (horizontal direction) within the area.

The drawing pattern by the light from the optical scanning device 20 corresponds to the shape of each layer when the three-dimensional object to be formed is a laminate of the hardened layers 13, and the scanning is stored in the device main body 1. Is controlled by the control unit 30. Then, when a part of the fluid material 10 is cured from the free liquid level to a predetermined depth by being exposed to light (selective exposure) scanned by the optical scanning device 20, the material is cured to a predetermined layer thickness. At the same time that the layer 13 is formed, it is laminated on the lower cured layer.

The control unit 30 is connected to, for example, a three-dimensional CAD (computer aided design) system 35, and based on modeling data from the three-dimensional CAD system 35, a lifting mechanism 15 for moving the movable platform 11. The shaping control for controlling the operation of the motor for moving the material supply dipper and scraper and the operation of the laser beam scanning device 20 can be executed.

The control unit 30 executes a stirring control for operating the lifting mechanism 15 in a state where the operation of the optical scanning device 20 is stopped. The movable platform 11 can be reciprocated below the free liquid level with a large stroke, and the uncured fluid material 10 in the modeling container 2 can be stirred by the movable platform 11. The speed of the movable platform 11 at the time of reciprocating movement is preferably sufficiently higher than at the time of molding, but a sufficient reciprocating stroke is set.

Next, another method of manufacturing the three-dimensional channel member of the present invention will be described.

First, a photocurable resin comprising the above-mentioned components (A) and (B) of the present invention or a photocurable resin obtained by further adding the component (C) to the surface of a supporting substrate is used. A coating may be formed. In the method for producing a three-dimensional flow channel member of the present invention, the surface of the support substrate may be previously treated with an adhesion aid in order to improve the adhesion between the film or the heat-cured resin film and the support substrate. .

The film made of the photo-curable resin is formed, for example, by forming a varnish film of the photo-curable resin and then drying it. The formation of the varnish film is performed by spin coating using a spinner, dipping,
It can be carried out by means appropriately selected from means such as spray printing and screen printing. The thickness of the coating is
It can be adjusted by the application conditions, the solid content concentration of the present composition and the like. In addition, a film made of a photocurable resin is formed by peeling the film formed on the support in advance from the support, and the sheet is attached to the surface of the support substrate to form the film. You may.

Next, after irradiating the film with light (such as ultraviolet rays) through a photomask having a predetermined pattern, the unexposed portion is dissolved and removed with an organic solvent or a basic aqueous solution to form a desired relief pattern. obtain. By stacking the layers of the relief pattern, the three-dimensional channel member of the present invention can be prepared.

The above-mentioned basic aqueous solution is usually a solution in which a basic compound is dissolved in water. The concentration of the basic compound is
The content is usually 0.1 to 50% by weight, preferably from the influence on the supporting substrate and the like, and more preferably 0.1 to 30% by weight. Further, in order to improve the solubility of the polyimide precursor, methanol, ethanol, propanol, isopropyl alcohol, N-methyl-2-pyrrolidone,
A water-soluble organic solvent such as N, N-dimethylformamide and N, N-dimethylacetamide may be further contained.

Examples of the basic compound include hydroxides or carbonates of alkali metals, alkaline earth metals or ammonium ions, amine compounds and the like. Specific examples include 2-dimethylaminoethanol, 3
-Dimethylamino-1-propanol, 4-dimethylamino-1-butanol, 5-dimethylamino-1-pentanol, 6-dimethylamino-1-hexanol, 2
-Dimethylamino-2-methyl-1-propanol, 3
-Dimethylamino-2,2-dimethyl-1-propano-
2-diethylaminoethanol, 3-diethylamino-1-propanol, 2-diisopropylaminoethanol, 2-di-n-butylaminoethanol, N, N
-Dibenzyl-2-aminoethanol, 2- (2-dimethylaminoethoxy) ethanol, 2- (2-diethylaminoethoxy) ethanol, 1-dimethylamino-2
-Propanol, 1-diethylamino-2-propano-
, N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N
-T-butyldiethanolamine, N-lauryldiethanolamine, 3-diethylamino-1,2-propanediol, triethanolamine, triisopropanolamine, N-methylethanolamine, N-ethylethanolamine, Nn-butylethanolamine, N
-T-butylethanolamine, diethanolamine,
Diisopropanolamine, 2-aminoethanol, 3
-Amino-1-propanol, 4-amino-1-butanol, 6-amino-1-hexanol, 1-amino-2
-Propanol, 2-amino-2,2-dimethyl-1-
Propanol, 1-aminobutanol, 2-amino-1
-Butanol, N- (2-aminoethyl) ethanolamine, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, 3-amino-1, 2-propanediol, 2-amino-2-hydroxymethyl-1,3-propanediol, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate , Ammonium hydrogen carbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetraisopropylammonium hydroxide, aminomethanol, 2-
Aminoethanol, 3-aminopropanol, 2-aminopropanol, methylamine, ethylamine, propylamine, isopropylamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, trimethylamine, triethylamine, tripropylamine, triisopropylamine It is preferable to use other compounds as long as they are soluble in water and the aqueous solution exhibits basicity.

The resulting relief pattern can be formed into a pattern made of polyimide by performing a heat treatment at a temperature preferably selected from the range of 150 ° C. to 350 ° C. This pattern is high resolution,
High heat resistance and excellent mechanical properties.

Hereinafter, the present invention will be described specifically with reference to examples.

Preparation of urethane acrylate-based photocurable resin composition as urethane compound (A) (1) Four-necked flask with inner volume of 20 liters equipped with stirrer, temperature controller, thermometer and condenser , 4600 parts of a 4-mol adduct of bisphenol A with propylene glycol and 4420 parts of isophorone diisocyanate were added, and di-n-butyltin radiurate was added at 40 to 50 ° C.
6 parts were added and reacted at the same temperature for 30 minutes. Then
After raising the reaction temperature to 80-90 ° C and reacting for 2 hours,
2320 parts of 2-hydroxyethyl acrylate and 5.5 parts of hydroquinone monomethyl ether were added and reacted at the same temperature for another 2 hours to produce a urethane acrylate oligomer having a bisphenol A diol skeleton.

(2) 1320 parts of the urethane acrylate oligomer obtained in the above (1), 1080 parts of polyethylene glycol 200 diacrylate (“NK ester A-200” manufactured by Shin-Nakamura Chemical Co., Ltd.) and ethylene oxide-modified trimethylolpropane triacrylate 480 parts ("A-TMPT-3EO" manufactured by Shin-Nakamura Chemical Co., Ltd.) were charged into a 5-liter container, and the contents were stirred under reduced pressure and degassed nitrogen for about 1 hour at a temperature of 50 ° C.

(3) The mixture 28 obtained in the above (2)
To 80 parts, 120 parts of 2,2-dimethoxy-2-phenylacetophenone (“Irgacure 651” manufactured by Ciba-Geigy; photoradical polymerization initiator) is added in an environment where ultraviolet rays are blocked, until completely dissolved. Temperature 25 ° C
(Mixing and stirring time: about 6 hours) to prepare a urethane acrylate-based liquid photocurable resin composition, which was stored at 25 ° C. while blocking ultraviolet rays.

Synthesis of polyimide precursor (PI-1) as imide compound of component (B) (1) Synthesis of acid chloride 3,3 ', 4,4'-biphenyltetrahydrochloride was placed in a 200 ml four-necked flask. Carboxylic anhydride (BPDA) 9.
42 g (0.032 mol), 2-hydroxyethyl methacrylate (HEMA) 8.32 g (0.064 mol), pyridine 5.06 g (0.064 mol), t-butylcatechol 0.03 g, N-methyl-2-pyrrolidone ( NMP) was added and stirred at 60 ° C. to form a clear solution in 2 hours. After stirring the solution at room temperature for 7 hours, the flask was cooled with ice and 9.88 g (0.083 mol) of thionyl chloride was added dropwise over 10 minutes. Thereafter, the mixture was stirred at room temperature for 1 hour to obtain a solution containing acid chloride.

(2) Synthesis of polyimide precursor (polyamic acid ester) In another 200 ml four-necked flask, 4.72 g (0.031 mol) of 3,5-diaminobenzoic acid and pyridine 5.
06 g (0.064 mol), t-butyl catechol 0.
03 g, N-methyl-2-pyrrolidone (NMP) 50 m
The acid chloride solution obtained above was slowly added dropwise over 1 hour while cooling the 1-liter flask with ice and stirring (keeping the temperature at 10 ° C. or lower). Thereafter, the mixture was stirred at room temperature for 1 hour, poured into 1 liter of water, and the precipitated polymer was collected by filtration.
After repeated washing and vacuum drying, 22 g of a polyamic acid ester was obtained. When the weight average molecular weight of this polyamic acid ester was measured by GPC (gel permeation chromatography), it was 44,0 in terms of polystyrene.
00.

Preparation of Epoxy Photocurable Resin Composition as Epoxy Compound of Component (C) (1) A 20-liter four-necked flask equipped with a stirrer, a temperature controller, a thermometer, and a condenser is provided. 4,000 parts of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1,000 parts of 1,4-butanediol diglycidyl ether, 2,2
-Bis [4- (acryloxydiethoxy) phenylpropane ("NK ester A-BPE" manufactured by Shin-Nakamura Chemical Co., Ltd.)
-4 ") 2,500 parts and ethylene oxide-modified trimethylolpropane triacrylate (" A-TMPT-3EO "manufactured by Shin-Nakamura Chemical Co., Ltd.) 2,500 parts, and the mixture is stirred at a temperature of 20 to 25C for about 1 hour. Mixed.

(2) The mixture 30 obtained in the above (1)
00 parts, 60 parts of 2,2-dimethoxy-2-phenylacetophenone (“IRGACURE 651” manufactured by Ciba-Geigy; photoradical polymerization initiator) and bis [4- (diphenyl) Sulfonio)
Phenyl] sulfide bishexafluoroantimonate (photocationic polymerization initiator) (45 parts) was added, and mixed and stirred at a temperature of 25 ° C. until mixing was completely completed (mixing and stirring time: about 6 hours). The composition was prepared and stored at 25 ° C. with the exclusion of ultraviolet light.

<< Preparation of Photocurable Resin and Photocurable Resin Composition >> The components (A), (B) and (c) obtained above were obtained.
The following eight types of photocurable resins and photocurable resin compositions were prepared using the components.

[0104]

Example 1 Unsaturated urethane obtained by reacting tolylene diisocyanate / glycerine monomethacrylate / monoacrylate at a ratio of 1/2 (molar ratio) (a-
1: The molecular weight per radical polymerizable group (151) is 60
Parts by weight and the imide precursor (PI
-1) was mixed with 40 parts by weight of a photocurable resin,
00 parts by weight, average particle size 17 surface-treated with methacryloyloxypropyltrimethoxysilane as a filler
200 parts by weight of glass beads having a diameter of 200 μm, 50 parts by weight of aluminum borate fibers having a fiber diameter of 0.8 μm and an average fiber length of 20 μm, surface-treated with methacryloyloxypropyltrimethoxysilane, and 50 parts by weight. A photocurable resin composition [X-1] comprising 2.5 parts by weight of a morpholine salt of a polyoxypropylene diol phosphate ester salt.

[0105]

Example 2 Unsaturated urethane (a-2: one radical polymerizable group) obtained by reacting tolylene diisocyanate / glycerin monomethacrylate / monoacrylate / hydroxyethyl acrylate at a 1/1/1 (molar ratio) ratio Per 100 parts by weight of a photocurable resin obtained by mixing 40 parts by weight of the imide precursor (PI-1) with 200 parts by weight of the inorganic solid fine particles. A photocurable resin composition [X-2] comprising 50 parts by weight of the inorganic fiber whiskers and 2.5 parts by weight of the above phosphate ester salt.

[0106]

Example 3 50 parts by weight of unsaturated urethane (a-2), 33 parts by weight of the imide precursor (PI-1) and 17 parts by weight of dicyclopentyl dimethylene diacrylate were mixed. 100 parts by weight of the photocurable resin, 200 parts by weight of the inorganic solid fine particles, and 50 parts by weight of aluminum borate fiber having a fiber diameter of 1.0 μm and an average fiber length of 40 μm surface-treated with vinyltrimethoxysilane, A photocurable composition [X-3] comprising 2.5 parts by weight of a phosphate salt.

[0107]

Example 4 50 parts by weight of unsaturated urethane (a-2), 33 parts by weight of the imide precursor (PI-1),
Bisphenol A methacrylate (reacted product of epicoat 828 and metal acrylic acid) as an epoxy compound
100 parts by weight of the photocurable resin mixed at a ratio of 7 parts by weight, 200 parts by weight of the inorganic solid fine particles, 50 parts by weight of the inorganic fiber whisker, and 2.5 parts by weight of the phosphate ester salt. Photocurable resin composition [X-4].

[0108]

EXAMPLE 5 50 parts by weight of unsaturated urethane (a-3: molecular weight 163 per radical polymerization group) obtained by reacting isophorone diisocyanate / glycerin monomethacrylate / monoacrylate = 1/2 (molar ratio) And as an imide compound

[0109]

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(A) and (b) were each 20 parts by weight, a total of 40 parts by weight, and 100 parts by weight of a photocurable resin obtained by mixing neopentyl glycol hydroxypivalate diacrylate in a ratio of 10 parts by weight. A photocurable resin composition [X-5] comprising 200 parts by weight of the inorganic solid fine particles, 50 parts by weight of the inorganic fiber whiskers, and 2.5 parts by weight of the phosphate ester F-1.

[0111]

EXAMPLE 6 Unsaturated urethane obtained by reacting isophorone diisocyanate / glycerin monomethacrylate / monoacrylate / hydroxyethyl acrylate at a ratio of 1/1/1 (molar ratio) (a-4: per radical polymer group) Of 184) and 60 parts by weight of the imide precursor (PI-1) as an imide compound.
Parts by weight,

[0112]

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100 parts by weight of a photocurable resin obtained by mixing 20 parts by weight of the above, 200 parts by weight of the inorganic solid fine particles, 50 parts by weight of the inorganic fiber whiskers, and 2.0 parts by weight of the phosphate ester salt. A photocurable resin composition [X-6] consisting of 5 parts by weight.

[0114]

Example 7 Unsaturated urethane (a-) obtained by reacting polypropoxylated glycerin (average molecular weight: 270) / tolylene diisocyanate / glycerin monomethacrylate / monoacrylate = 1/3/3 (molar ratio)
5: 50 (molecular weight 240 per radical polymerizable group)
Parts by weight, 33 parts by weight of the imide precursor (PI-1) as an imide compound, and 1 part of methyl methacrylate.
100 parts by weight of the photocurable liquid mixed at a ratio of 7 parts by weight, 200 parts by weight of the inorganic solid fine particles, 50 parts by weight of the inorganic fiber whisker, and 2.5 parts by weight of the phosphate ester salt A photocurable resin composition [X-7].

[0115]

Example 8 Glycerin / tolylene diisocyanate /
Glycerin monomethacrylate / monoacrylate = 1
/ 3/3 (molar ratio), 60 parts by weight of unsaturated urethane (a-6: molecular weight per one radical polymerizable group: 209) obtained by reacting with imide precursor (PI- 1) with 10 parts by weight as an epoxy compound

[0116]

Embedded image

[Wherein, n, m and y are integers of 1 or more. 100 parts by weight of a photocurable liquid obtained by mixing 20 parts by weight of the vinyl monomer and 10 parts by weight of the vinyl monomer, 200 parts by weight of the inorganic solid fine particles and 50 parts by weight of the inorganic fiber whisker, A photocurable resin composition [X-8] comprising 2.5 parts by weight of the above phosphate ester salt.

The photocurable resin compositions [X-1] to [X]
-8] Add 0.01 part of 2-hydroxy-4-n-octoxybenzophenone (light energy absorber) to 100 parts of each, and add about 1 part at 25 ° C. until a uniform liquid is obtained. The mixture was sufficiently stirred for a time to prepare an optical three-dimensional modeling resin composition.

Next, a water-cooled Ar laser beam (output: 400 mW; wavelength: 354, 36, using an ultra-high-speed optical shaping system (“SOLIFORM 300” manufactured by Teijin Seiki Co., Ltd.)
5 nm; beam diameter: 0.2 mm; liquid level output: 175 mW), and at an irradiation energy of 50 mJ / cm ² , a slice pitch (lamination thickness) of 0.2 mm, and an optical molding at an average molding time of 2 minutes per layer of 2 minutes. Was done.

Further, the above-mentioned photocurable resin composition [X-1]
To [X-8], using the same ultra-high-speed stereolithography system as described above, irradiating a water-cooled Ar laser beam (output: 400 mW; wavelength: 354.365 nm), and an irradiation energy of 5
Three-dimensional modeling corresponding to a dumbbell specimen [maximum size of X axis × Y axis × Z axis (thickness) = 20.0 mm × 175.0 mm × 3.0 mm] in accordance with JIS K7113 under the condition of 0 mJ / cm ^2. A product (cured product) was prepared.

Using the molded product (cured product), heat resistance (H
DT), moisture resistance (immersion in water at room temperature, PCT standing), hardness (Shore D), and tensile modulus (kg / mm ² ). Table 1 shows the measurement results.

[0122]

[Table 1]

<< Evaluation of Characteristics of Photocurable Resin >> (a) Mechanical Strength A dumbbell shape having a thickness of 3.0 mm specified in JIS-K7113 is optically three-dimensionally formed, and the formed product is washed with isopropyl alcohol, and then subjected to a 98-degree cleaning. The specimen was heated at 2 ° C. for 2 hours and post-cured to prepare a test piece. The same three test pieces were prepared, and the tensile strength and the tensile modulus were measured at a tensile speed of 5 mm / sec according to JIS-K7113.
The strength was an average value of three test pieces.

(B) Heat Resistance (Heat Deformation Temperature) According to JIS-K7207, a 10 × 4 × 127 mm prismatic test piece was prepared. Using this test piece, the heat distortion temperature (HDT) at a bending stress of 181.4 MPa was determined.

(C) Hardness The three-dimensional molded product (cured product) obtained above is taken out of the above-mentioned stereolithography system, and the three-dimensional molded product after washing and removing the uncured material attached thereto with isopropyl alcohol is 3K.
The photocurable resin of the present invention, which was post-cured for 10 minutes using a W ultraviolet lamp and the Shore D hardness was measured according to JIS K7113, had an HDT of 100 ° C. or more,
Shore hardness is 89 or more, tensile modulus is 200kg
/ Mm ² or more.

(D) Moisture resistance (i) Measurement of water absorption Five test pieces each of 50 mm × 50 mm × 3 mm were prepared. The weight when the test piece was left in a vacuum state until there was no change in weight was defined as the initial weight. Next, each test piece was immersed in a tap water tank at room temperature, the test piece was taken out of the water tank every predetermined number of days, the weight of the test piece was measured, and the water absorption (g / c) was measured.
m ² ) was determined.

(Ii) Measurement of Water Absorption (by PCT) Two test pieces of 50 mm × 50 mm × 3 mm were prepared. The weight when the test piece was left in a vacuum state until there was no change in weight was defined as the initial weight. Next, the test piece was left in a pressure cooker (121 ° C., 2 atmospheres supersaturated steam) for a predetermined time, then taken out, the weight of the test piece was measured, and the rate of change in weight relative to the initial weight was taken as the water absorption. .

FIG. 8 shows the photocurable resin composition (X-
The change with time in the amount of water absorption when the resin cured (molded) product cured by irradiation with ultraviolet light in 1) is immersed in a tap water tank at room temperature for a predetermined time is shown. The photocurable resin of the present invention has a smaller water absorption than a conventional photocurable resin (PMMA type).

FIG. 9 shows the photocurable resin composition (X-
The resin molded product cured by irradiating the ultraviolet ray to 1) is 121
The change with time in the amount of water absorption when immersed in a PCT kettle in the supersaturated water vapor state at 2 ° C. for 2 hours. The photocurable resin of the present invention has a smaller water absorption than a conventional photocurable resin (PMMA type).

<< Preparation of Three-Dimensional Channel Member >> Three-dimensional channel member FIG.
Was prepared by using the apparatus shown in FIG. The operating procedure is as described above.

A three-dimensional NC table equipped with a container and a helium / cadmium laser beam (output 25 mW, wavelength 32
50 °) An optical three-dimensional printing apparatus mainly including a control system was used. The above-mentioned container is filled with a mixture obtained by mixing and dissolving the photocurable composition prepared in Test Category 2 and the photopolymerization initiator (hereinafter, referred to as a mixture), and a horizontal surface (X-
The mixed solution is supplied to the Y-axis plane) at a thickness of 0.1 mm, and a helium-cadmium laser beam focused from the direction perpendicular to the surface (XY-axis plane) (Z-axis direction) is supplied to the three-dimensional C plane.
Scanning was performed based on the data input to the AD, and a predetermined portion was cured. A new mixture is added to the cured product at 0.
It was supplied in a thickness of 1 mm and was similarly cured. Hereinafter, similarly, a total of 550 layers were laminated, and the three-dimensional channel member of the present invention was optically three-dimensionally molded. Next, the optical three-dimensional model was washed with isopropyl alcohol, irradiated with a 3 Kw ultraviolet lamp for 30 minutes, further heated at 100 ° C. for 2 hours, and post-cured to prepare an optical three-dimensional model.

An example in which the three-dimensional channel member of the present invention is applied to a water quality meter will be described below.

FIG. 2 is a configuration diagram in which functional components of a three-dimensional flow path member (hereinafter, referred to as a motherboard 101) formed by an optical molding method are mounted.

The analysis units 76, 77, 78 modularized on the motherboard 101 and the sequence control of the water supply of the sample water 52, the reagent 82, the washing water 86, and the zero water 89 to the analysis units 76, 77, 78. Pumps and solenoid valves are pump units 153 and 154, solenoid valve units 151 and 1
As for 52, each unit is a screw 156, 157, 1
At 58 and 159, the structure is directly assembled. Analysis units 76, 77, 78, pump units 153, 154,
The motherboard 101 on which the solenoid valve units 151 and 152 are mounted is used for positioning and preventing tightening on a mounting board 160 which also serves as a supply / drainage of the sample water 52, the reagent 82, the washing water 86, and the zero water 89 to the analysis units 76, 77 and 78. Mounting pin 1
It is attached according to the guidance of 61 and is attached with the screw 155. The mounting pins 161 are attached to the motherboard 10.
1, the motherboard 101 will not be damaged even if the screw 155 is tightened too much. Also, it can be easily fixed with the minimum number of parts. At this time, the flow path connecting section 168 for supplying and draining water to the analysis sections 76, 77, 78 at the same time also has a sealing material 169 on the flow path connecting section 173 of the mounting board 160 according to the plan of each flow path and the mounting pin 161.
Connected via

FIG. 3 is an external view of the motherboard.

In the motherboard 101, all the flow paths (flow paths 65, 68, 70, 72, 92.
94 etc.) are three-dimensionally formed inside the three-dimensional motherboard 101. Appearance is formed as a rectangular parallelepiped, and its outer peripheral surface is provided with a plurality of flow path openings so that a plurality of valves, pumps, analyzers, etc. can be held directly without using piping or through a sealing material. 102 and a screw hole 103 for mounting each unit.

FIG. 4 is a specific configuration diagram.

[0138] Water distribution pipe 51 on the water utility or customer side
Drinking water (sample water) 52 flowing through the inside is sampled via a pipe 53, and a manual valve 54, a pipe 55, a pressure reducing valve 56
Through the pipe 57, the manual valve 58, and the drain pipe 59 to the drain 60.

From the pipe 57, a part of the sample water 52 maintained at a constant pressure is branched by a pipe 61, passes through a manual valve 62, passes through a filter 63 for removing large foreign matter in the sample water, and passes through a main body 64 of the analyzer. Is led to the defoaming tank 66 through the flow path 65. Bubbles 67 contained in the sample water 52 in the defoaming tank 66 accumulate in the upper part of the defoaming tank 66 and drain from the analyzer main body 64 via a flow path 68, a solenoid valve 69, and a flow path 70 as needed. Discarded in the groove 60.

On the other hand, the sample water 71 from which the bubbles in the defoaming tank 66 have been removed is guided to a metering pump 74 via a flow path 72 and an electromagnetic valve 73. Further, the sample water 71 has a plurality of solenoid valves 75.
a, 75b, and 75c are selectively sent to a plurality of analysis units 76, 77, and 78 that analyze independent items. The analysis unit has a common mounting shape and pipe connection, and is detachably held on the analyzer main body 64 so as to be completely the same or compatible with other analysis units. A plurality of cartridges 79, 80, and 81 containing a liquid are detachably held outside the analyzer main body, and the liquid inside the cartridge is supplied to the analyzer main body 64. Liquid 82 from cartridge 79
Is led to a solenoid valve 83 metering pump 84, and the analysis unit 76, via a plurality of solenoid valves 85a, 85b, 85c.
77 and 78. Similarly, the liquid 86 in the cartridge 80 passes through the pump 87 and then to the analysis section via a plurality of solenoid valves 88a, 88b, 88, and the liquid 89 in the cartridge 81 passes through the pump 90 to the solenoid valves 91a, 91a. The analysis units 76 and 7 are connected via 91b and 91c.
7, 78 selectively.

A complicated flow path satisfying the above functions is formed inside the motherboard 101.

FIG. 5 is a diagram showing the internal structure of the motherboard 101.
The flow path is arranged in a three-dimensional manner, and a three-dimensional pipe is formed between each valve, pump, and flow path opening of the analysis unit.

In this embodiment, an ultraviolet curable plastic is used, and an optical laser forming method is employed in which a liquid resin is selectively irradiated with an ultraviolet laser beam, and only a portion irradiated with the ultraviolet light is cured to form a shape. ing. In this stereolithography method, the part that hits the flow path is not exposed to light and remains uncured liquid,
After the molding, the uncured resin is washed away, whereby an arbitrary three-dimensional channel can be formed. The resin used was an ultraviolet-curing transparent resin, so that the state inside the flow path could be observed from the outside. In addition, the stereolithography method has an advantage that it can be realized inexpensively and quickly with only CAD (computer aided design) three-dimensional design data without requiring a special molding die, and the reliability of the piping connection can be improved.

In general, the resin used in the optical shaping method is a liquid when uncured, and the physical properties of the cured product vary depending on the application. Usually, hardening by shaping is used for checking the shape and dimensions of a machined product or a molded product, temporarily incorporating the product into a developed product, and the like. For this reason, at present, several types of resins are prepared for each application in view of desired strength, heat resistance, and transparency for making the cured product visible.

In the present invention, a urethane-based compound mainly composed of a usual photo-curable resin is removed by removing a hydrophilic group (polar group) which is likely to be compatible with water as a fluid component which is a composition contained in the resin. The main composition is an imide compound and an epoxy compound. For this reason, the motherboard 1 is made of an ultraviolet curable resin that has improved resistance to water and has a high heat resistant temperature.
01 is modeled.

Further, by adding a light absorbing agent to make the photopolymerization reaction appropriate, the reaction rate of the resin is increased, the mechanical properties of the cured product are improved, and the curing of the uncured portion is prevented. The operation of removing the uncured resin portion inside the cured product is facilitated.

As described above, the cured product of the mother board 101 has the same water absorption and strength as the general plastic material. In particular, a water absorption of 2% or less, which is lower than that of an acrylic material, is obtained.

Also, the surface hardness HS80 can be obtained by appropriate curing.
Since a hard surface is obtained as described above, elution of impurities from the inner surface of the flow channel into the fluid or gas flowing through the flow channel or adsorption to the inner surface of the flow channel is suppressed to a low level.

Further, in order to easily remove the uncured resin from the inside of the cured product, the viscosity at the time of uncuring is adjusted so as to be relatively easy to flow. Therefore, when the flow path is formed in the cured product, the flow path diameter is 2 mm or less (the cross-sectional area is 4 mm ²
The following small flow path can be easily formed.

Therefore, it is possible to provide a plurality of flow paths having complicated branches in a small space.

Further, the cured product formed by laminating resin films by light irradiation has excellent adhesiveness and adhesion between the respective layers. Even after being left in a high-temperature and high-humidity state (for example, in a PCT state) for a long period of time, A highly reliable motherboard without delamination and a water quality meter using the same can be provided.

FIG. 6 is a cross-sectional view in which the inner surface of the flow channel is coated.

On the cross section of the motherboard 101 in which the inner surface of the flow path is coated with the surface coating agent 301, the inner surface of the flow path is formed with a surface of the surface coating agent 301 with a thickness of several to several tens of μm. In addition, water resistance, elution and adsorption are suppressed, and the life of the three-dimensional channel member is improved. Further, the use of the fluid can be expanded.

Examples of the surface coating agent 301 include a hard coating agent having good fluidity, a fluororesin, and molybdenum chloride. In the motherboard 101 used for the water quality meter, an effect of suppressing elution and adsorption is obtained.

Another feature of the present invention is that the heat resistant temperature of the motherboard 101 serving as the base material for the surface coating is higher than the temperature at which the surface coating agent 301 can be heat-treated.

As an application to a flow path member having a simple shape as shown in FIG. 7, a mold, a core, and the like are manufactured from a master member, and a photocurable resin is injected into the mold and irradiated with ultraviolet rays. It is possible to obtain a flow path member.

If the three-dimensional flow channel member according to the present invention is applied, it can be applied to products handling fluids and gases, and the product can be reduced in size and cost can be reduced.

[0158]

According to the present invention, it is possible to easily and rapidly form a three-dimensional flow path member having excellent water resistance as a flow path member and having a plurality of flow paths in a small volume by a stereolithography method. This allows the shaped member to be used as a product-based flow channel member. Furthermore, the surface treatment of the inner surface of the flow passage reduces the deterioration of the flow passage member and the influence on the fluid, thereby improving the product performance and the life.

[Brief description of the drawings]

FIG. 1 is a schematic view showing an example of an optical shaping apparatus according to the present invention.

FIG. 2 is an example of a member configuration using a three-dimensional flow channel member of the present invention.

FIG. 3 shows an appearance of a three-dimensional flow channel member of the present invention.

FIG. 4 is a configuration diagram of a water quality meter system of the present invention.

FIG. 5 is an internal structural view of a motherboard in which flow paths are arranged in a three-dimensional configuration.

FIG. 6 is a sectional view of a flow channel coated on the inner surface of the flow channel.

FIG. 7 is an example of application to a flow path member having a simple shape.

FIG. 8 shows a change over time in water absorption when the photocurable resin of the present invention is immersed in a water bath at room temperature.

FIG. 9 shows a change over time in water absorption when the photocurable resin of the present invention is immersed in a PCT kettle.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Device main body, 2 ... Modeling container, 10 ... Fluid material, 11
.. Movable platform, 15 lifting mechanism, 20 optical scanning device, 30 control unit (control means, lifting control means), 35 three-dimensional CAD system, 41 stirring member, L free liquid surface (free surface), 55 ... pipe, 56 ... pressure reducing valve, 51 ... water pipe, 52 ... drinking water, 53 ... pipe, 54
... Manual valve, 55 ... Piping, 56 ... Reducing valve, 57 ... Piping, 5
Reference numeral 8: manual valve, 59: drain pipe, 60: drain groove, 61: piping, 62: manual valve, 63: filter, 64: analyzer body, 65: flow path, 66: defoaming tank, 67: air bubble, 68 ... flow path, 69 ... solenoid valve, 70 ... flow path, 71 ... sample water, 72 ...
Flow path, 73: solenoid valve, 74: metering pump, 75: solenoid valve (a, b, c), 76, 77, 78: analysis unit, 79: cartridge, 80: cartridge, 81: cartridge, 82: liquid, 83 ... solenoid valve, 84 ... metering pump, 8
5 ... solenoid valves (a, b, c), 86 ... liquid, 87 ... pump, 88 ... solenoid valves (a, b, c), 89 ... liquid, 90 ...
Pump, 91: solenoid valve (a, b, c), 92: waste, 9
3 ... solenoid valve, 94 ... flow path, 95 ... collection container, 101 ... 3
Dimensional mother board, 102: flow path opening, 103: screw hole, 152: valve unit, 152a: valve holder, 153: pump unit, 153a: pump holder, 154: pump unit, 154a: pump holder, 155: screwdriver, 156: hand screw, 157
... Screwdriver screw, 160 ... Mounting board, 161 ... Mounting pin, 162 ... Flow path connector, 163 ... Flow path connector, 1
64 ... flow path connector, 165 ... cell holder, 166 ... fixing bracket, 167 ... guide, 168 ... flow path connection part, 169
... Seal material, 170 ... Mounting hole, 171 ... Seal material, 17
2: mounting hole, 173: flow path connection part, 301: surface coating agent, 302: flow path, 303: flow path member

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] February 21, 2000 (200.2.2
1)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Name of invention

[Correction method] Change

[Correction contents]

Patent application title: Photocurable resin and three-dimensional channel member

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B29C 67/00 B29C 67/00 B29K 105: 24 B29K 105: 24 (72) Inventor Koji Tamaki Hitachinaka, Ibaraki 882, Omo, Oaza, Japan In the measuring instrument group of Hitachi, Ltd. (72) Inventor Ryosaku Chikaoka, 882, Oga, Oaza, Oita, Hitachinaka, Ibaraki Pref. 882 Hitachi, Ltd.Measuring Instruments Group (72) Inventor Masayuki Muranaka 4-6 Kanda Surugadai, Chiyoda-ku, Tokyo Hitachi, Ltd.Production and Environment Management Department (72) Inventor Norio Goto Totsuka, Yokohama, Kanagawa Prefecture 292 Yoshida-cho, Ward Inside Digital Media Development Division, Hitachi, Ltd. (72) Akiya Junichi Tamura 3-2-1 Sakado, Takatsu-ku, Kawasaki City, Kanagawa Prefecture KSP, D Building 8F Teijin Seiki Co., Ltd. F-term (reference) 4F006 AA58 AB19 BA02 CA00 DA00 4F203 AA40 AA42 AH43 AR20 4F213 AA40 AA42 AH43 AR20 WA14 WA41 WA86 WA87 WB01 4J002 CD012 CD022 CD052 CD062 CD132 CD202 CM041 ET006 FD010 FD090 FD140 FD150 4J027 AD04 AE02 AE03 AE04 AE05 AE07 AG04 AG13 AG14 AG15 AG23 AG27 AG33 AH02 AJ01 AJ08 AJ19 BA18 BA18 BA18 BA18

Claims (12)

[Claims] In a flow path member having a three-dimensional flow path formed therein using a photocurable resin, the photocurable resin is represented by the following general formula (A): [Wherein, A is a (meth) acryloyl residue, R is an isocyanate component residue, and Y is a diol component residue. ], And a (B) imide compound having a photopolymerizable functional group or a polyimide precursor. 2. A flow path member in which a three-dimensional flow path is formed using a photo-curable resin, wherein the photo-curable resin is represented by the following general formula (A): [Wherein, A is a (meth) acryloyl residue, R is an isocyanate component residue, and Y is a diol component residue. A urethane compound represented by the formula: (B) an imide compound or a polyimide precursor having a photopolymerizable functional group, and (C)
A three-dimensional flow path member comprising an epoxy compound having a photopolymerizable functional group. 3. The three-dimensional flow path member according to claim 1, wherein the photocurable resin is a cured resin obtained by curing using ultraviolet rays. 4. The method according to claim 3, wherein the cured resin has a water absorption of 2 wt.
% Or less. 5. The three-dimensional flow path member according to claim 3, wherein the cured resin has a heat resistance temperature (heat deformation temperature) of 100 ° C. or higher. 6. The three-dimensional flow path member according to claim 3, wherein the surface hardness of the cured resin is 80 or more in Shore hardness. 7. The three-dimensional channel member according to claim 1, wherein a hard coat treatment is applied to an inner surface of the channel. 8. A three-dimensional flow channel member according to claim 1, wherein the inner surface of the flow channel is coated with a fluororesin or vinylidene fluoride. 9. A three-dimensional flow path member according to claim 1, comprising one or more branches or a plurality of flow paths and a container portion. 10. The method according to claim 1, wherein the diameter of the flow path is 2 m.
A three-dimensional flow path member, wherein the cross-sectional area of the flow path is less than 4 m ^{2 or} less than 4 m ² . 11. A water quality meter which can be attached to a drainage path of a drainage system, wherein the water quality meter has a water introduction part and an analysis part for analyzing the introduced water, a flow path formed of a photocurable resin. The photocurable resin of the flow member is communicated by a flow path member, and (A) a general formula [1] [Wherein, A is a (meth) acryloyl residue, R is an isocyanate component residue, and Y is a diol component residue. ] And a (B) imide compound having a photopolymerizable functional group or a polyimide precursor. 12. A water quality meter according to claim 11, wherein said photocurable resin is a cured resin obtained by curing using ultraviolet rays.