JP2015074715A - Radiation shielding ink - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a radiation shielding ink capable of forming a radiation shielding coating layer having transparency while having a radiation shielding function. A radiation shielding ink comprises (B) a (meth) acrylic group comprising (A) a hydrolyzate of an organosilicon compound having a (meth) acrylic group and a hydrolyzate of a specific metal alkoxide. And (C) a photopolymerization initiator. Furthermore, the hydrolyzate of (A) may contain a hydrolyzate of an organosilicon compound. [Selection figure] None

Description

  The present invention relates to a radiation shielding ink. Specifically, the present invention relates to an ink capable of forming a radiation shielding coat layer having transparency while having a radiation shielding function.

  In order to protect engineers who perform inspection and analysis using X-rays in the medical and scientific fields, and workers at nuclear power plants in the nuclear industry, from radiation such as X-rays and low-energy γ-rays and β-rays, A radiation shielding material is used.

  In general, heavy metals such as lead and tungsten are used as the radiation shielding material. For example, Patent Document 1 discloses a radiation shielding material in which a heavy metal composed of lead, a lead compound, tungsten, or tin is mixed with a resin to form a sheet. A radiation protective garment comprising a sheet is disclosed.

  However, a material having both a radiation shielding function and transparency has not been developed.

Utility model registration No. 3098317

  An object of the present invention is to provide a radiation shielding ink capable of forming a radiation shielding coating layer having transparency while having a radiation shielding function.

  The inventor has made various studies in order to achieve both a radiation shielding function and transparency. As a result, by adding a hydrolyzate containing a hydrolyzate of an organosilicon compound having a (meth) acryl group and a hydrolyzate of a specific metal alkoxide, an ink and a coating layer having excellent metal dispersibility can be obtained. As a result, it was found that the radiation shielding function and transparency are compatible, and the present invention has been completed.

That is, the present invention
(A) The following formula (1)

(Where
R ¹ is a hydrogen atom or a methyl group,
R ² is an alkylene group having 1 to 20 carbon atoms or a cycloalkylene group having 3 to 10 carbon atoms,
R ³ is an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 4 carbon atoms, or an aryl group having 6 to 12 carbon atoms,
R ⁴ is an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 3 to 4 carbon atoms,
l is an integer of 1 to 3, m is an integer of 0 to 2, k is an integer of 1 to 3,
l + m + k is 4,
R ^{1, R} 2, ^{R 3} and ^{R 4} respectively, when there are a plurality, the plurality of ^{R 1,} R 2, ^{R 3} and ^{R 4,} respectively, may be the same or different groups) A hydrolyzate of an organosilicon compound having the (meth) acrylic group shown,
And the following formula (2)

(Where
M is tungsten, zirconium, titanium, molybdenum, indium, or hafnium;
R ⁵ is an alkyl group having 1 to 10 carbon atoms, and may be the same group or different groups,
When M is tungsten, p is 6 or 5;
When M is molybdenum, p is 5,
When M is zirconium, titanium or hafnium, p is 4,
When M is indium, p is 3. )
A hydrolysis mixture comprising a hydrolyzate of a metal alkoxide represented by
(B) A radiation shielding ink containing a polymerizable monomer having a (meth) acryl group and (C) a photopolymerization initiator.

  Since the radiation shielding ink of the present invention is excellent in metal dispersibility, it can form a radiation shielding coating layer having transparency in addition to the radiation shielding function, so that radiation resistant paint, radiation shielding spray agent, wall, glass, In addition to being able to be used as a coating agent for various members such as eyeglass lenses, wallpaper, mirrors, fibers, etc., a radiation shielding coating layer is formed on a film or sheet and attached to the above various members, for medical use, crime prevention, It can be used as a radiation shielding film or sheet for disaster prevention.

The present invention relates to a radiation shielding ink,
(A) The following formula (1)

(Where
R ¹ is a hydrogen atom or a methyl group,
R ² is an alkylene group having 1 to 20 carbon atoms or a cycloalkylene group having 3 to 10 carbon atoms,
R ³ is an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 4 carbon atoms, or an aryl group having 6 to 12 carbon atoms,
R ⁴ is an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 3 to 4 carbon atoms,
l is an integer of 1 to 3, m is an integer of 0 to 2, k is an integer of 1 to 3,
l + m + k is 4,
R ^{1, R} 2, ^{R 3} and ^{R 4} respectively, when there are a plurality, the plurality of ^{R 1,} R 2, ^{R 3} and ^{R 4,} respectively, may be the same or different groups) A hydrolyzate of an organosilicon compound having the (meth) acrylic group shown,
And the following formula (2)

(Where
M is tungsten, zirconium, titanium, molybdenum, indium, or hafnium;
R ⁵ is an alkyl group having 1 to 10 carbon atoms, and may be the same group or different groups,
When M is tungsten, p is 6 or 5;
When M is molybdenum, p is 5,
When M is zirconium, titanium or hafnium, p is 4,
When M is indium, p is 3. )
A hydrolysis mixture comprising a hydrolyzate of a metal alkoxide represented by
(B) A polymerizable monomer having a (meth) acryl group and (C) a photopolymerization initiator are included.

  In the following, description will be given in order.

  First, the hydrolysis mixture (A) will be described.

(Hydrolysis mixture (A))
In the present invention, the hydrolysis mixture (A) comprises a hydrolyzate of an organosilicon compound having a (meth) acryl group represented by the formula (1) and a hydrolyzate of a metal alkoxide represented by the formula (2). Hydrolysis mixture containing. The degree of hydrolysis of the hydrolyzate of the organosilicon compound having a (meth) acryl group represented by the formula (1) and the hydrolyzate of the metal alkoxide represented by the formula (2) All may be hydrolyzed, and a part of the alkoxy group may be hydrolyzed.

(Organic silicon compound having (meth) acrylic group)
In the present invention, the following formula (1)
(A) The following formula (1)

(Where
R ¹ is a hydrogen atom or a methyl group,
R ² is an alkylene group having 1 to 20 carbon atoms or a cycloalkylene group having 3 to 10 carbon atoms,
R ³ is an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 4 carbon atoms, or an aryl group having 6 to 12 carbon atoms,
R ⁴ is an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 3 to 4 carbon atoms,
l is an integer of 1 to 3, m is an integer of 0 to 2, k is an integer of 1 to 3,
l + m + k is 4,
R ^{1, R} 2, ^{R 3} and ^{R 4} respectively, when there are a plurality, the plurality of ^{R 1,} R 2, ^{R 3} and ^{R 4} may each be the same or different groups)
A hydrolyzate of an organosilicon compound having a (meth) acryl group represented by the following (hereinafter also simply referred to as “organosilicon compound having a (meth) acryl group”) is used.

  By using a hydrolyzate of an organosilicon compound having this (meth) acrylic group, a radiation shielding ink with good dispersibility is obtained, and adhesion to various members is also improved. Moreover, in the fine structure of the cured film obtained by photocuring, the inorganic component and the organic component are dispersed in a relatively homogeneous state (the dispersed state is not such that the inorganic component is extremely aggregated). As a result, the metal component derived from the metal alkoxide is uniformly dispersed to have a radiation shielding function, and a transparent coat layer can be formed.

In the formula (1), R ¹ is a hydrogen atom or a methyl group. Among these, hydrogen atoms are preferable because they have a high photocuring speed when curing the radiation shielding ink.

  R2 is a C1-C20 alkylene group or a C3-C10 cycloalkylene group. Specifically, methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, sec-butylene group, tert-butylene group, 2,2-dimethylpropylene group, 2-methylbutylene group, 2- Methyl-2-butylene group, 3-methylbutylene group, 3-methyl-2-butylene group, pentylene group, 2-pentylene group, 3-pentylene group, 3-dimethyl-2-butylene group, 3,3-dimethylbutylene Group, 3,3-dimethyl-2-butylene group, 2-ethylbutylene group, hexylene group, 2-hexylene group, 3-hexylene group, 2-methylpentylene group, 2-methyl-2-pentylene group, 2- Methyl-3-pentylene group, 3-methylpentylene group, 3-methyl-2-pentylene group, 3-methyl-3-pentylene group, 4-methylpentylene Group, 4-methyl-2-pentylene group, 2,2-dimethyl-3-pentylene group, 2,3-dimethyl-3-pentylene group, 2,4-dimethyl-3-pentylene group, 4,4-dimethyl 2-pentylene group, 3-ethyl-3-pentylene group, heptylene group, 2-heptylene group, 3-heptylene group, 2-methyl-2-hexylene group, 2-methyl-3-hexylene group, 5-methylhexene Xylene group, 5-methyl-2-hexylene group, 2-ethylhexylene group, 6-methyl-2-heptylene group, 4-methyl-3-heptylene group, octylene group, 2-octylene group, 3-octylene group, Alkylene groups such as 2-propylpentylene group, 2,4,4-trimethylpentylene group, decaoctylene group; cyclopropylene group, cyclobutylene group, cyclopropylmethylene , Cyclopentyl alkylene group, cyclohexylene group, and a cycloalkylene group such as a cyclooctylene group.

  Among these, C1-C4 alkylene groups, such as a methylene group, ethylene group, propylene group, isopropylene group, butylene group, and C3-C4 cycloalkylene groups, such as a cyclopropylene group and a cyclobutylene group, are preferable. .

  R3 is an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 4 carbon atoms, or an aryl group having 6 to 12 carbon atoms. Specifically, alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group; cyclopropyl group, cyclobutyl group, cyclopropylmethyl group, etc. Cycloalkyl group; aryl groups such as phenyl group, benzyl group, 1-naphthyl group, 2-naphthyl group and o-methylnaphthyl group can be exemplified. Of these, a methyl group and an ethyl group are preferable.

  R4 is a C1-C4 alkyl group or a C3-C4 cycloalkyl group. Specifically, alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group; cyclopropyl group, cyclobutyl group, cyclopropylmethyl group, etc. A cycloalkyl group is mentioned.

The alkoxy group represented by -OR ⁴ generates an alcohol derived from R ⁴ upon hydrolysis, but the radiation shielding ink of the present invention may contain this alcohol. Therefore, considering that it becomes an alcohol that can be easily mixed with other components, and that it becomes an alcohol that can be easily removed after forming a coating film on the substrate, specifically, R ⁴ represents a methyl group, an ethyl group, It is preferably an alkyl group having 1 to 4 carbon atoms such as a group, a propyl group, an isopropyl group, and a butyl group.

  L is preferably 1, m is preferably 0 to 2, and k is preferably 1 to 3. However, the sum of l, m, and k, that is, l + m + k is 4.

  Specific examples of such (meth) acrylic group-containing silicon compounds include trimethoxysilylmethylene (meth) acrylate, trimethoxysilyldimethylene (meth) acrylate, trimethoxysilyltrimethylene (meth) acrylate, triethoxy Silylmethylene (meth) acrylate, triethoxysilyldimethylene (meth) acrylate, triethoxysilyltrimethylene (meth) acrylate, tripropoxysilylmethylene (meth) acrylate, tripropoxysilylethylene (meth) acrylate, tripropoxysilyl trimethylene (Meth) acrylate, Tributoxysilylmethylene (meth) acrylate, Tributoxysilyldimethylene (meth) acrylate, Tributoxysilyltrimethylene (meth) acrylate Triisopropoxysilylmethylene (meth) acrylate, triisopropoxysilyldimethylene (meth) acrylate, triisopropoxysilyltrimethylene (meth) acrylate, dimethoxymethylsilylmethylene (meth) acrylate, dimethoxymethylsilyldimethylene (meth) acrylate , Dimethoxymethylsilyltrimethylene (meth) acrylate, diethoxymethylsilylmethylene (meth) acrylate, diethoxymethylsilyldimethylene (meth) acrylate, diethoxymethylsilyltrimethylene (meth) acrylate, dimethoxyethylsilylmethylene (meth) Acrylate, dimethoxyethylsilyldimethylene (meth) acrylate, dimethoxyethylsilyltrimethylene (meth) acrylate, diethoxy Tylsilylmethylene (meth) acrylate, diethoxyethylsilyldimethylene (meth) acrylate, diethoxyethylsilyltrimethylene (meth) acrylate, methoxydimethylsilylmethylene (meth) acrylate, methoxydimethylsilyldimethylene (meth) acrylate, methoxy Dimethylsilyltrimethylene (meth) acrylate, ethoxydimethylsilylmethylene (meth) acrylate, ethoxydimethylsilyldimethylene (meth) acrylate, ethoxydimethylsilyltrimethylene (meth) acrylate, methoxydiethylsilylmethylene (meth) acrylate, methoxydiethylsilyl Dimethylene (meth) acrylate, methoxydiethylsilyltrimethylene (meth) acrylate, ethoxydiethylsilylmethylene (Meth) acrylate, ethoxydiethylsilyldimethylene (meth) acrylate, ethoxydiethylsilyltrimethylene (meth) acrylate and the like can be mentioned. Of these, trimethoxysilyltrimethylene (meth) acrylate and triethoxysilyltrimethylene (meth) acrylate are preferable.

(Metal alkoxide)
In the present invention, the following formula (2)

(Where
M is tungsten, zirconium, titanium, molybdenum, indium, or hafnium;
R ⁵ is an alkyl group having 1 to 10 carbon atoms, and may be the same group or different groups,
When M is tungsten, p is 6 or 5;
When M is molybdenum, p is 5,
When M is zirconium, titanium or hafnium, p is 4,
When M is indium, p is 3. )
A hydrolyzate of a metal alkoxide represented by the following (hereinafter also simply referred to as “metal alkoxide”) is used. The metal alkoxide may be used alone or a mixture of the metal alkoxides.

  The radiation shielding function can be adjusted by using the metal alkoxide hydrolyzate and the amount of the metal alkoxide hydrolyzate used.

  In the formula (2), M is preferably tungsten, zirconium, or hafnium in order to further enhance the radiation shielding function.

  Further, tungsten oxide alkoxides such as tungsten oxide alkoxide (IV) may be included within a range not impairing the effects of the present invention.

In the formula (2), R ⁵ is preferably an alkyl group having 1 to 4 carbon atoms from the viewpoint of an appropriate hydrolysis rate. The alkoxy group represented by -OR ⁵ also produces an alcohol derived from R ⁵ upon hydrolysis, similar to the above-described organosilicon compound having a (meth) acryl group, but the radiation shielding ink of the present invention uses this alcohol. May be included. Therefore, considering that —OR ⁵ becomes an alcohol that can be easily mixed with other components and that it becomes an alcohol that can be easily removed after forming a coating film on the substrate, specifically, R ⁵ is: An alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group is preferable.

  Examples of suitable metal alkoxides include hexamethyl tungsten alkoxide, hexaethyl tungsten alkoxide, hexaisopropyl tungsten alkoxide, hexapropyl tungsten alkoxide, hexaisobutyl tungsten alkoxide, hexabutyl tungsten alkoxide, hexa t-butyl tungsten alkoxide, hexapentyl tungsten alkoxide. , Hexahexyl tungsten alkoxide, hexaheptyl tungsten alkoxide, hexaoctyl tungsten alkoxide, hexanonyl tungsten alkoxide, hexadecyl tungsten alkoxide, pentamethyl tungsten alkoxide, pentaethyl tungsten alkoxide, pentaisopropyl tungsten alkoxide Sid, pentapropyl tungsten alkoxide, pentaisobutyl tungsten alkoxide, pentabutyl tungsten alkoxide, pentapentyl tungsten alkoxide, pentahexyl tungsten alkoxide, pentaheptyl tungsten alkoxide, pentaoctyl tungsten alkoxide, pentanonyl tungsten alkoxide, pentadecyl tungsten alkoxide; tetramethyl zirconium Alkoxide, tetraethylzirconium alkoxide, tetraisopropylzirconium alkoxide, tetrapropylzirconium alkoxide, tetraisobutylzirconium alkoxide, tetrabutylzirconium alkoxide, tetrat-butylzirconium alkoxide, tetrapentylzirco Aluminum alkoxide, tetrahexyl zirconium alkoxide, tetraheptyl zirconium alkoxide, tetraoctyl zirconium alkoxide, tetranonyl zirconium alkoxide, tetradecyl zirconium alkoxide; tetramethyl titanium alkoxide, tetraethyl titanium alkoxide, tetraisopropyl titanium alkoxide, tetrapropyl titanium alkoxide, tetraisobutyl titanium Alkoxide, tetrabutyl titanium alkoxide, tetrapentyl zirconium alkoxide, tetraheptyl titanium alkoxide, tetrahexyl titanium alkoxide, tetraheptyl titanium alkoxide, tetraoctyl titanium alkoxide, tetranonyl titanium alkoxide Tetradecyl titanium alkoxide; pentamethyl molybdenum alkoxide, pentaethyl molybdenum alkoxide, pentaisopropyl molybdenum alkoxide, pentapropyl molybdenum alkoxide, pentaisobutyl molybdenum alkoxide, pentabutyl molybdenum alkoxide, penta t-butyl molybdenum alkoxide, pentapentyl molybdenum alkoxide, penta Hexyl molybdenum alkoxide, pentaheptyl molybdenum alkoxide, pentaoctyl molybdenum alkoxide, pentanonyl molybdenum alkoxide, pentadecyl molybdenum alkoxide; tetramethyl hafnium alkoxide, tetraethyl hafnium alkoxide, tetraisopropyl hafnium alkoxide, tetrapropyl hafnium Alkoxide, tetraisobutyl hafnium alkoxide, tetrabutyl hafnium alkoxide, tetra t-butyl hafnium alkoxide, tetrapentyl hafnium alkoxide, tetraheptyl hafnium alkoxide, tetrahexyl hafnium alkoxide, tetraheptyl hafnium alkoxide, tetraoctyl hafnium alkoxide, tetranonyl hafnium alkoxide , Tetradecyl hafnium alkoxide; trimethylindium alkoxide, triethylindium alkoxide, triisopropylindium alkoxide, tripropylindium alkoxide, triisobutylindium alkoxide, tributylindium alkoxide, trit-butylindium alkoxide, tripentylindiu Alkoxides, trihexyl indium alkoxides, triheptyl indium alkoxides, trioctyl indium alkoxide, trinonylamine indium alkoxides include tridecyl indium alkoxide. Among them, pentaethyl tungsten alkoxide, pentaisopropyl tungsten alkoxide, pentapropyl tungsten alkoxide, pentaisobutyl tungsten alkoxide, pentabutyl tungsten alkoxide, penta t-butyl tungsten alkoxide, tetraethyl zirconium alkoxide, tetraisopropyl zirconium alkoxide, tetrapropyl zirconium alkoxide, tetra Isobutyl zirconium alkoxide, tetrabutyl zirconium alkoxide, tetra t-butyl zirconium alkoxide, tetraethyl hafnium alkoxide, tetraisopropyl hafnium alkoxide, tetrapropyl hafnium alkoxide, tetraisobutyl hafnium alkoxide, tetrabuty Hafnium alkoxides, tetra t- butyl hafnium alkoxides, tetra-octyl hafnium alkoxide is preferred.

(Organic silicon compound)
The hydrolysis mixture (A) is further represented by the following formula (3):

(Where
R ⁶ and R ⁷ are the same or different alkyl group having 1 to 4 carbon atoms or hydrogen,
R ⁸ and R ⁹ are an aryl group or an alkoxy group having 1 to 4 carbon atoms, and n is an integer of 1 to 10. )
And a hydrolyzate of an organosilicon compound (hereinafter also simply referred to as “organosilicon compound”). By using this organosilicon compound, it is possible to form a denser coating layer with good dispersibility, and can be preferably used for enhancing the radiation shielding function.

In the formula (3), R ⁶ and R ⁷ are hydrogen, methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, isobutyl group, and tert-butyl group. Group, ethyl group, propyl group, isopropyl group and butyl group are preferred. -OR ^6, alkoxy group represented by -OR ⁷ is ^-OR 6 upon hydrolysis, but produces an alcohol derived from -OR ^7, radiation shielding ink of the present invention may contain the alcohol. Therefore, considering that the alcohol can be easily mixed with other components and that the alcohol can be easily removed after forming a coating film on the substrate, specifically, R ⁶ and R ⁷ are methyl. An alkyl group having 1 to 4 carbon atoms such as a group, an ethyl group, a propyl group, an isopropyl group and a butyl group is preferable.

In R ⁸ and R ⁹ , the aryl group is preferably an aryl group having 6 to 20 carbon atoms, and examples thereof include a phenyl group, a biphenyl group, and a naphthyl group, and among them, a phenyl group is preferable.

R ⁸ and R ⁹ are alkoxy groups such as methyl alkoxy group, ethyl alkoxy group, propyl alkoxy group, isopropyl alkoxy group, butyl alkoxy group, sec-butyl alkoxy group, isobutyl alkoxy group, tert-butyl alkoxy group, etc. Can be mentioned. As the alkoxy group, a methyl alkoxy group, an ethyl alkoxy group, a propyl alkoxy group, an isopropyl alkoxy group, and a butyl alkoxy group are particularly preferable. Alkoxy group represented by the R ^8, R ^9, which generates an alcohol derived from R ^8, R ⁹ upon hydrolysis, radiation shielding ink of the present invention may contain the alcohol. Therefore, considering that it becomes an alcohol that can be easily mixed with other components, and that it becomes an alcohol that can be easily removed after forming a coating film on the substrate, specifically, a methyl alkoxy group, an ethyl alkoxy group, An alkoxy group having 1 to 4 carbon atoms such as propylalkoxy group, isopropylalkoxy group, butylalkoxy group, sec-butylalkoxy group, isobutylalkoxy group, tert-butylalkoxy group and the like is preferable. The aryl group and alkoxy group may have a substituent such as an alkyl group, an ether group, a glycol ether group, a hydroxyl group, or a halogen.

Especially, R < ⁸ >, R < ⁹ > is preferable from a viewpoint of the storage stability of the radiation shielding ink from which it is obtained that it is a C6-C20 aryl group.

  The organosilicon compound may be a single compound or a plurality of organosilicons having different values of n as long as n satisfies the integer of 1 to 10 in the formula (3). It may be a mixture of compounds.

  Specific examples of these organosilicon compounds are tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, ethyltriethoxysilane, propyltripropoxysilane, butyltributoxysilane, phenyltrioxysilane. Examples include methoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenyltributoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldipropoxysilane, diphenyldibutoxysilane, and polycondensates thereof. Among them, the alcohol produced during hydrolysis is an alcohol that can be easily removed after forming a coating film, and for reasons such as reactivity, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyldioxydioxide. Ethoxysilanes and their polycondensates are preferred.

(Production method of hydrolysis mixture (A))
In this invention, it is preferable that the organosilicon compound and metal alkoxide which have a (meth) acryl group which comprise a hydrolysis mixture (A) shall be the following compounding quantities. That is, the hydrolysis mixture (A) is composed of 3 to 300 parts by mass of an organosilicon compound having a (meth) acryl group, and 100 parts by mass of a polymerizable monomer (B) described in detail below, and a metal alkoxide. It is preferable that it is a hydrolysis mixture obtained by hydrolyzing the mixture containing 0.1-150 mass parts. All the alkoxy groups may be hydrolyzed by hydrolysis, or a part of the alkoxy group may be partially hydrolyzed. The amount of water used for the hydrolysis is not particularly limited, but considering the wettability and dispersibility of the coating film, the amount is 0.1 times mol or more and 2.0 times the number of moles of all alkoxy groups in the mixture. It can be preferably selected from a molar ratio of 2 or less.

  When the blending amount of the organosilicon compound having a (meth) acryl group and the metal alkoxide satisfies the above range, a radiation shielding ink having good dispersibility and transparency of the hydrolysis mixture is obtained. Considering the dispersibility of the hydrolysis mixture, the amount of the organosilicon compound having a (meth) acrylic group is preferably 5 to 250 parts by mass with respect to 100 parts by mass of the polymerizable monomer (B). Preferably, the metal alkoxide is used in an amount of 0.5 to 100 parts by mass. Furthermore, it is preferable that the usage-amount of the organosilicon compound which has a (meth) acryl group is 10-200 mass parts, and it is preferable that the usage-amount of a metal alkoxide is 1-80 mass parts. The amount of the organosilicon compound having a (meth) acryl group is particularly preferably 15 to 180 parts by mass, and the amount of the metal alkoxide is particularly preferably 3 to 50 parts by mass.

  Moreover, it is preferable that a metal alkoxide is 0.2-50 mass parts with respect to 100 mass parts of organosilicon compounds which have a (meth) acryl group. By making the usage-amount of a metal alkoxide into the said range, the improvement of a radiation shielding function is improved especially. Therefore, the usage-amount of a metal alkoxide becomes like this. More preferably, it is 1-40 mass parts, More preferably, it is 2-30 mass parts.

  In the present invention, the hydrolysis mixture (A) can further contain a hydrolyzate of an organosilicon compound. By including the hydrolyzate of the organosilicon compound, it is possible to form a denser coating layer with good dispersibility.

  The organosilicon compound is preferably used in the following amount. That is, the mixture may be further made into a mixture containing 10 to 400 parts by mass of an organosilicon compound with respect to 100 parts by mass of the polymerizable monomer (B) described in detail below, and the mixture may be hydrolyzed.

  Considering the dispersibility of the hydrolysis mixture (A) and the densification of the coat layer, the amount of the organosilicon compound used may be 30 to 300 parts by mass with respect to 100 parts by mass of the polymerizable monomer (B). preferable. Furthermore, it is more preferable that it is 50-250 mass parts, and it is especially preferable that it is 80-200 mass parts.

  Further, when the metal alkoxide contains a hydrolyzate of an organosilicon compound, the metal alkoxide is 0.2 to 50 with respect to 100 parts by mass in total of the organosilicon compound and the organosilicon compound having a (meth) acryl group. It is preferable that it is a mass part. By making the usage-amount of a metal alkoxide into the said range, the improvement of a radiation shielding function is improved especially. Therefore, the usage-amount of a metal alkoxide becomes like this. More preferably, it is 1-40 mass parts, More preferably, it is 2-30 mass parts.

(Production method of hydrolysis mixture (A): water used for hydrolysis and its amount)
In the present invention, the amount of water used to obtain the hydrolysis mixture (A) is not particularly limited, but is an amount of 0.1 to 2.0 times the mole of the total number of alkoxide groups. It is preferable from the viewpoint of wettability and dispersibility of the coating film.

  The number of moles of all alkoxy groups is the product of the number of moles of the organosilicon compound having a (meth) acryl group and the number of alkoxy groups present in one molecule of the organosilicon compound having the (meth) acryl group. And the number of moles of metal alkoxide used and the number of alkoxy groups present in one molecule of the metal alkoxide, and when an organosilicon compound is used, the mole number of organosilicon compound used and the organosilicon compound 1 It is the product of the number of alkoxy groups present in the molecule.

  When the amount of water is less than 0.1-fold mol, the wettability to various members may be lowered although it is at a practical level when a coating film is formed. On the other hand, when it becomes 2.0 times mol or more, it may become a factor which dispersibility falls. Considering the degree of condensation, the amount of water is preferably 0.2 to 1.5 times mol, more preferably 0.5 to 0.1 times mol, based on the number of moles of all alkoxide groups in the mixture. It is preferable that it is less than double mole.

  Since the water used for obtaining the hydrolysis mixture (A) in the present invention delays the hydrolysis reaction rate of the hydrolysis mixture in the resulting radiation shielding ink, the hydrolysis mixture (A) and the radiation shielding of the present invention are used. In any step for obtaining ink, water may be removed by vacuum drying, distillation, heating, or the like. At that time, in the case where the solvent is also removed at the same time, a necessary amount of the solvent may be appropriately added after removing water.

  In the present invention, the water may contain an acid. Acids used include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, organic phosphoric acid, formic acid, acetic acid, acetic anhydride, chloroacetic acid, propionic acid, butyric acid, valeric acid, citric acid, gluconic acid, Examples thereof include organic acids such as succinic acid, tartaric acid, lactic acid, fumaric acid, malic acid, itaconic acid, oxalic acid, mucinic acid, uric acid, barbituric acid, and p-toluenesulfonic acid, and acidic cation exchange resins. When an acid is used, it is not particularly limited, but the amount used is an amount such that the amount of hydrogen ions is 0.0001 times to 0.01 times mol relative to the number of moles of all alkoxy groups. It is preferable that The acid can be used as it is, but it is preferable to use an acid aqueous solution or a solution dispersed in water. In this case, it is preferable to use one having a concentration of 0.1 to 6N. In this case, the used water is included in the amount of water used.

  In the present invention, the hydrolysis mixture (A) contains the components to be hydrolyzed (an organosilicon compound having a (meth) acryl group and a metal alkoxide (including an organosilicon compound when an organosilicon compound is used)) in the above amount. Mix with water. The method of mixing with water is not particularly limited, but in order to produce a uniform radiation shielding ink, it is preferable to mix water with the mixture of the components to be hydrolyzed. That is, it is preferable that the components to be hydrolyzed are first mixed to form a mixture, and then water is added to the mixture to perform hydrolysis.

  Moreover, what is necessary is just to implement mixing of the component to hydrolyze and water at the temperature of 5 to 60 degreeC. At this time, a diluting solvent may be used to facilitate the hydrolysis. As a dilution solvent, a C1-C4 alcohol is preferable and it is preferable to use ethanol especially. Although the usage-amount of a dilution solvent should just be suitably determined with the kind of component to hydrolyze, it is preferable that it is 50-400 mass parts with respect to 100 mass parts of mixtures of the component to hydrolyze.

(Production method of hydrolysis mixture (A): hydrolysis conditions)
In the present invention, the reaction temperature in the hydrolysis is not particularly limited, but is usually selected from the range of 5 ° C to 60 ° C. The reaction time may be appropriately selected in consideration of the reaction temperature, and is usually selected from the range of 10 minutes to 12 hours.

(Use method and physical properties of hydrolysis mixture (A))
According to said method, a hydrolysis mixture (A) can be prepared. An alcohol derived from an alkoxy group is produced during hydrolysis. The radiation shielding ink of the present invention may contain, in addition to the hydrolysis mixture (A), alcohol produced as a by-product during hydrolysis and water used for hydrolysis. Furthermore, the diluent solvent used in order to advance a hydrolysis easily can also be included.

  The hydrolysis mixture (A) preferably has a viscosity of 0.1 to 100 mPa · sec at 25 ° C. in consideration of ease of mixing with other components, productivity of radiation shielding ink, and the like. This viscosity value is a value measured with a tuning fork viscometer: AND VIBRO VISCOMETER SV-1A. When used in a condition containing by-produced alcohol, water used, and dilution solvent used for dilution. Is a value obtained by measuring those including these.

  Moreover, it is preferable that a hydrolysis mixture (A) is mixed with another component immediately after manufacture, and it is set as a radiation shielding ink. However, if this is not possible, it is preferably stored at a temperature of −30 ° C. to 15 ° C. or lower in order not to change with time after production. Also in this case, it is preferable that the viscosity of the hydrolysis mixture (A) satisfies the above range.

Next, the polymerizable monomer (B) having a (meth) acryl group used in combination with the hydrolysis mixture (A) obtained by the above method will be described.
(Polymerizable monomer having (meth) acrylic group (B))
In the present invention, the polymerizable monomer (B) having a (meth) acryl group (hereinafter, also simply referred to as “polymerizable monomer (B)”) is not particularly limited, and is used for photopolymerization. A known polymerizable monomer having a (meth) acryl group can be used. In addition to the polymerizable monomer (B) having a (meth) acryl group, the radiation shielding ink of the present invention includes a polymerizable functional group other than the (meth) acryl group as long as the effects of the present invention are not impaired. A polymerizable monomer having a group may be included.

  The polymerizable monomer (B) does not include the (meth) acryl group-containing silicon compound represented by the formula (1). A preferable compound includes a polymerizable monomer having a (meth) acryl group and containing no silicon atom in the molecule. These polymerizable monomers (B) may be monofunctional polymerizable monomers having one (meth) acrylic group in one molecule, or two or more (meth) acrylic in one molecule. It may be a polyfunctional polymerizable monomer having a group. Furthermore, these monofunctional polymerizable monomers and polyfunctional polymerizable monomers can also be used in combination.

  If the example of a polymerizable monomer (B) is specifically illustrated, as a monofunctional polymerizable monomer which has one (meth) acryl group in 1 molecule, for example, methyl (meth) acrylate, ethyl (Meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, isoamyl (meth) ) Acrylate, isomyristyl (meth) acrylate, n-lauryl (meth) acrylate, n-stearyl (meth) acrylate, isostearyl (meth) acrylate, long chain alkyl (meth) acrylate, n-butoxyethyl (meth) acrylate, Butoxydiethylene glycol (meth) Chrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, 2-ethylhexyl-diglycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) Acrylate, dicyclopentanyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, hydroxyethyl (meth) acrylamide, 2- (2- Vinyloxyethoxy) ethyl (meth) acrylate, glycidyl (meth) acrylate, methoxyethylene glycol modified (meth) acrylate, ethoxyethylene glycol modified (meth) acrylate Relate, propoxyethylene glycol modified (meth) acrylate, methoxypropylene glycol modified (meth) acrylate, ethoxypropylene glycol modified (meth) acrylate, propoxypropylene glycol modified (meth) acrylate, isobornyl (meth) acrylate, adamantane (meth) acrylate derivative Aliphatic acrylates such as acryloylmorpholine; benzyl (meth) acrylate, phenoxymethyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyethylene glycol modified (meth) acrylate, phenoxypropylene glycol modified (meth) acrylate, hydroxyphenoxyethyl (Meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate Hydro phenolate Kishikishi ethylene glycol-modified (meth) acrylate, hydroxyphenoxy propylene glycol-modified (meth) acrylate, alkyl phenol ethylene glycol-modified (meth) acrylate, alkyl phenol propylene glycol-modified (meth) acrylate, the following formula (4)

(Where
R ¹⁰ is a hydrogen atom or a methyl group,
R ¹¹ is an alkylene group having 1 to 10 carbon atoms or a hydroxyalkylene group having 1 to 10 carbon atoms, and q is an integer of 1 to 6. And (meth) acrylate having an aromatic ring such as a monomer having an o-phenylphenol group in the molecule.

  As a polyfunctional polymerizable monomer (bifunctional polymerizable monomer) having two (meth) acryl groups in one molecule, for example, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, Polyolefin glycol di (meth) acrylate, ethoxylated polypropylene glycol di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, 2-hydroxy-1,3-dimethacryloxypropane, dioxane glycol di (meth) acrylate , Tricyclodecane dimethanol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, glycerin di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (Meth) acrylate, 1,10-decanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, butyl Aliphatic di (meth) acrylates such as ethylpropanediol di (meth) acrylate and 3-methyl-1,5-pentanediol di (meth) acrylate; ethoxylated bisphenol A di (meth) acrylate, propoxylated ethoxylated bisphenol A Di (meth) acrylate, ethoxylated bisphenol F di (meth) acrylate, formula (5)

(Where
R ¹² and R ¹³ are each independently a hydrogen atom or a methyl group,
R ¹⁴ and R ¹⁵ are an alkylene group having 1 to 10 carbon atoms, a hydroxyalkylene group having 1 to 10 carbon atoms, or a group represented by the following formula (6). Also good. )

(In the formula, R ¹⁶ and R ¹⁷ are an ethylene group or a propylene group, and n is an integer of 1 to 3.)
And di (meth) acrylate having an aromatic ring such as di (meth) acrylate having a fluorene structure represented by

  Furthermore, in this polyfunctional polymerizable monomer, as the polymerizable monomer having three or more (meth) acrylate groups in one molecule, ethoxylated glycerin tri (meth) acrylate, trimethylolpropane tri (meta) ) Acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, Examples include ethoxylated pentaerythritol tetra (meth) acrylate and dipentaerythritol polyacrylate.

  Moreover, you may use the said polymerizable monomer (B) combining multiple types of things.

  The (meth) acrylate having an o-phenylphenol group in the molecule represented by the formula (4) will be described.

  Following formula (4)

(Where
R ¹⁰ is a hydrogen atom or a methyl group,
R ¹¹ is an alkylene group having 1 to 10 carbon atoms or a hydroxyalkylene group having 1 to 10 carbon atoms, and q is an integer of 1 to 6. )
In the formula, R ¹⁰ is a hydrogen atom or a methyl group. Among these, hydrogen atoms are preferable because they have a high photocuring speed when curing the radiation shielding ink.
R ¹¹ is an alkylene group having 1 to 10 carbon atoms or a hydroxyalkylene group having 1 to 10 carbon atoms. Specifically, methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, sec-butylene group, tert-butylene group, 2,2-dimethylpropylene group, 2-methylbutylene group, 2- Methyl-2-butylene group, 3-methylbutylene group, 3-methyl-2-butylene group, pentylene group, 2-pentylene group, 3-pentylene group, 3-dimethyl-2-butylene group, 3,3-dimethylbutylene Group, 3,3-dimethyl-2-butylene group, 2-ethylbutylene group, hexylene group, 2-hexylene group, 3-hexylene group, 2-methylpentylene group, 2-methyl-2-pentylene group, 2- Methyl-3-pentylene group, 3-methylpentylene group, 3-methyl-2-pentylene group, 3-methyl-3-pentylene group, 4-methylpentylene Group, 4-methyl-2-pentylene group, 2,2-dimethyl-3-pentylene group, 2,3-dimethyl-3-pentylene group, 2,4-dimethyl-3-pentylene group, 4,4-dimethyl 2-pentylene group, 3-ethyl-3-pentylene group, heptylene group, 2-heptylene group, 3-heptylene group, 2-methyl-2-hexylene group, 2-methyl-3-hexylene group, 5-methylhexene Xylene group, 5-methyl-2-hexylene group, 2-ethylhexylene group, 6-methyl-2-heptylene group, 4-methyl-3-heptylene group, octylene group, 2-octylene group, 3-octylene group, Alkylene groups such as 2-propylpentylene group and 2,4,4-trimethylpentylene group; 1-hydroxyethylene group, 2-hydroxyethylene group, 1-hydroxypropylene group 2-hydroxypropylene group, 3-hydroxypropylene group, 1-hydroxyisopropylene group, 2-hydroxyisopropylene group, 3-hydroxyisopropylene group, 1-hydroxybutylene group, 2-hydroxybutylene group, 3-hydroxybutylene group 4-hydroxybutylene group, 1-hydroxyisobutylene group, 2-hydroxyisobutylene group, 3-hydroxyisobutylene group, 1-hydroxysec-butylene group, 2-hydroxysec-butylene group, 3-hydroxysec-butylene group, 4 -Hydroxy sec-butylene group, 1-hydroxy-2,2-dimethylpropylene group, 3-hydroxy-2,2-dimethylpropylene group, 1-hydroxy-2-methylbutylene group, 2-hydroxy-2-methylbutylene group , 3-hydroxy- 2-methylbutylene group, 4-hydroxy-2-methylbutylene group, 1-hydroxy-2-methyl-2-butylene group, 3-hydroxy-2-methyl-2-butylene group, 4-hydroxy-2-methyl-2-butylene Group, 1-hydroxy-3-methylbutylene group, 2-hydroxy-3-methylbutylene group, 3-hydroxy-3-methylbutylene group, 4-hydroxy-3-methylbutylene group, 1-hydroxy-3-methyl- 2-butylene group, 2-hydroxy-3-methyl-2-butylene group, 3-hydroxy-3-methyl-2-butylene group, 4-hydroxy-3-methyl-2-butylene group, 1-hydroxypentylene group 2-hydroxypentylene group, 3-hydroxypentylene group, 4-hydroxypentylene group, 5-hydroxypentylene group, 1-hydroxy 2-pentylene group, 2-hydroxy-2-pentylene group, 3-hydroxy-2-pentylene group, 4-hydroxy-2-pentylene group, 5-hydroxy-2-pentylene group, 1-hydroxy-3-pentylene group 2-hydroxy-3-pentylene group, 3-hydroxy-3-pentylene group, 4-hydroxy-3-pentylene group, 5-hydroxy-3-pentylene group, 1-hydroxy-3-dimethyl-2-butylene group, 2-hydroxy-3-dimethyl-2-butylene group, 3-hydroxy-3-dimethyl-2-butylene group, 4-hydroxy-3-dimethyl-2-butylene group, 1-hydroxy-3,3-dimethylbutylene group 2-hydroxy-3,3-dimethylbutylene group, 4-hydroxy-3,3-dimethylbutylene group, 1-hydroxy-3,3 Dimethyl-2-butylene group, 2-hydroxy-3,3-dimethyl-2-butylene group, 4-hydroxy-3,3-dimethyl-2-butylene group, 1-hydroxy-2-ethylbutylene group, 2-hydroxy 2-ethylbutylene group, 3-hydroxy-2-ethylbutylene group, 4-hydroxy-2-ethylbutylene group, 1-hydroxy-hexylene group, 2-hydroxy-hexylene group, 3-hydroxy-hexylene group, 4- Hydroxy-hexylene group, 5-hydroxy-hexylene group, 6-hydroxy-hexylene group, 1-hydroxy-2-hexylene group, 2-hydroxy-2-hexylene group, 3-hydroxy-2-hexylene group, 4-hydroxy- 2-hexylene group, 5-hydroxy-2-hexylene group, 6-hydroxy-2-hexylene group, 1- Hydroxy-3-hexylene group, 2-hydroxy-3-hexylene group, 3-hydroxy-3-hexylene group, 4-hydroxy-3-hexylene group, 5-hydroxy-3-hexylene group, 6-hydroxy-3-hexylene Group, 1-hydroxy-2-methylpentylene group, 2-hydroxy-2-methylpentylene group, 3-hydroxy-2-methylpentylene group, 4-hydroxy-2-methylpentylene group, 5-hydroxy- 2-methylpentylene group, 1-hydroxy-2-methyl-2-pentylene group, 2-hydroxy-2-methyl-2-pentylene group, 3-hydroxy-2-methyl-2-pentylene group, 4-hydroxy- 2-methyl-2-pentylene group, 5-hydroxy-2-methyl-2-pentylene group, 1-hydroxy-2-methyl-3-pen Len group, 2-hydroxy-2-methyl-3-pentylene group, 3-hydroxy-2-methyl-3-pentylene group, 4-hydroxy-2-methyl-3-pentylene group, 5-hydroxy-2-methyl- 3-pentylene group, 1-hydroxy-3-methylpentylene group, 2-hydroxy-3-methylpentylene group, 3-hydroxy-3-methylpentylene group, 4-hydroxy-3-methylpentylene group, 5 -Hydroxy-3-methylpentylene group, 1-hydroxy-3-methyl-2-pentylene group, 2-hydroxy-3-methyl-2-pentylene group, 3-hydroxy-3-methyl-2-pentylene group, 4 -Hydroxy-3-methyl-2-pentylene group, 5-hydroxy-3-methyl-2-pentylene group, 1-hydroxy-3-methyl-3-pentylene 2-hydroxy-3-methyl-3-pentylene group, 3-hydroxy-3-methyl-3-pentylene group, 4-hydroxy-3-methyl-3-pentylene group, 5-hydroxy-3-methyl-3- Pentylene group, 1-hydroxy-4-methylpentylene group, 2-hydroxy-4-methylpentylene group, 3-hydroxy-4-methylpentylene group, 4-hydroxy-4-methylpentylene group, 5-hydroxy -4-methylpentylene group, 1-hydroxy-4-methyl-2-pentylene group, 2-hydroxy-4-methyl-2-pentylene group, 3-hydroxy-4-methyl-2-pentylene group, 4-hydroxy -4-methyl-2-pentylene group, 5-hydroxy-4-methyl-2-pentylene group, 1-hydroxy-2,2-dimethyl-3-pentylene group 3-hydroxy-2,2-dimethyl-3-pentylene group, 4-hydroxy-2,2-dimethyl-3-pentylene group, 5-hydroxy-2,2-dimethyl-3-pentylene group, 1-hydroxy- 2,3-dimethyl-3-pentylene group, 2-hydroxy-2,3-dimethyl-3-pentylene group, 4-hydroxy-2,3-dimethyl-3-pentylene group, 5-hydroxy-2,3-dimethyl -3-pentylene group, 1-hydroxy-2,4-dimethyl-3-pentylene group, 2-hydroxy-2,4-dimethyl-3-pentylene group, 3-hydroxy-2,4-dimethyl-3-pentylene group 4-hydroxy-2,4-dimethyl-3-pentylene group, 5-hydroxy-2,4-dimethyl-3-pentylene group, 1-hydroxy-4,4-dimethyl-2-pe Tylene group, 2-hydroxy-4,4-dimethyl-2-pentylene group, 3-hydroxy-4,4-dimethyl-2-pentylene group, 5-hydroxy-4,4-dimethyl-2-pentylene group, 1- Hydroxy-3-ethyl-3-pentylene group, 2-hydroxy-3-ethyl-3-pentylene group, 4-hydroxy-3-ethyl-3-pentylene group, 5-hydroxy-3-ethyl-3-pentylene group, 1-hydroxyheptylene group, 2-hydroxyheptylene group, 3-hydroxyheptylene group, 4-hydroxyheptylene group, 5-hydroxyheptylene group, 6-hydroxyheptylene group, 7- Hydroxyheptylene group, 1-hydroxy-2-heptylene group, 2-hydroxy-2-heptylene group, 3-hydroxy-2-heptylene group, 4-hydroxy- -Heptylene group, 5-hydroxy-2-heptylene group, 6-hydroxy-2-heptylene group, 7-hydroxy-2-heptylene group, 1-hydroxy-3-heptylene group, 2-hydroxy-3-heptylene group, 3 -Hydroxy-3-heptylene group, 4-hydroxy-3-heptylene group, 5-hydroxy-3-heptylene group, 6-hydroxy-3-heptylene group, 7-hydroxy-3-heptylene group, 1-hydroxy-2- Methyl-2-hexylene group, 3-hydroxy-2-methyl-2-hexylene group, 4-hydroxy-2-methyl-2-hexylene group, 5-hydroxy-2-methyl-2-hexylene group, 6-hydroxy- 2-methyl-2-hexylene group, 1-hydroxy-2-methyl-3-hexylene group, 2-hydroxy-2-methyl-3-he Xylene group, 3-hydroxy-2-methyl-3-hexylene group, 4-hydroxy-2-methyl-3-hexylene group, 5-hydroxy-2-methyl-3-hexylene group, 6-hydroxy-2-methyl- 3-hexylene group, 1-hydroxy-5-methylhexylene group, 2-hydroxy-5-methylhexylene group, 3-hydroxy-5-methylhexylene group, 4-hydroxy-5-methylhexylene group, 5 -Hydroxy-5-methylhexylene group, 6-hydroxy-5-methylhexylene group, 1-hydroxy-5-methyl-2-hexylene group, 2-hydroxy-5-methyl-2-hexylene group, 3-hydroxy -5-methyl-2-hexylene group, 4-hydroxy-5-methyl-2-hexylene group, 5-hydroxy-5-methyl-2-hexylene group, -Hydroxy-5-methyl-2-hexylene group, 1-hydroxy-2-ethylhexylene group, 2-hydroxy-2-ethylhexylene group, 3-hydroxy-2-ethylhexylene group, 4-hydroxy-2 -Ethylhexylene group, 5-hydroxy-2-ethylhexylene group, 6-hydroxy-2-ethylhexylene group, 1-hydroxy-6-methyl-2-heptylene group, 2-hydroxy-6-methyl-2 -Heptylene group, 3-hydroxy-6-methyl-2-heptylene group, 4-hydroxy-6-methyl-2-heptylene group, 5-hydroxy-6-methyl-2-heptylene group, 6-hydroxy-6-methyl 2-heptylene group, 7-hydroxy-6-methyl-2-heptylene group, 1-hydroxy-4-methyl-3-heptylene group, 2-hydroxyl -4-methyl-3-heptylene group, 3-hydroxy-4-methyl-3-heptylene group, 4-hydroxy-4-methyl-3-heptylene group, 5-hydroxy-4-methyl-3-heptylene group, 6 -Hydroxy-4-methyl-3-heptylene group, 1-hydroxyoctylene group, 2-hydroxyoctylene group, 3-hydroxyoctylene group, 4-hydroxyoctylene group, 5-hydroxyoctylene group, 6-hydroxy Octylene group, 7-hydroxyoctylene group, 8-hydroxyoctylene group, 1-hydroxy-2-octylene group, 2-hydroxy-2-octylene group, 3-hydroxy-2-octylene group, 4-hydroxy-2 -Octylene group, 5-hydroxy-2-octylene group, 6-hydroxy-2-octylene group, 7-hydroxy-2-o Cutylene group, 8-hydroxy-2-octylene group, 1-hydroxy-3-octylene group, 2-hydroxy-3-octylene group, 3-hydroxy-3-octylene group, 4-hydroxy-3-octylene group, 5- Hydroxy-3-octylene group, 6-hydroxy-3-octylene group, 7-hydroxy-3-octylene group, 8-hydroxy-3-octylene group, 1-hydroxy-2-propylpentylene group, 2-hydroxy-2 -Propylpentylene group, 3-hydroxy-2-propylpentylene group, 4-hydroxy-2-propylpentylene group, 5-hydroxy-2-propylpentylene group, 1-hydroxy-2,4,4-trimethyl Pentylene group, 2-hydroxy-2,4,4-trimethylpentylene group, 3-hydroxy-2,4,4-trime Rupenchiren groups include hydroxy alkylene groups such as 5-hydroxy-2,4,4-trimethyl pentylene group.

  Among these, an alkylene group having 1 to 4 carbon atoms such as a methylene group, an ethylene group, a propylene group, an isopropylene group, and a butylene group, or a 1-hydroxymethylene group, a 2-hydroxymethylene group, a 1-hydroxypropylene group, 2- Hydroxypropylene group, 3-hydroxypropylene group, 1-hydroxyisopropylene group, 2-hydroxyisopropylene group, 3-hydroxyisopropylene group, 1-hydroxybutylene group, 2-hydroxybutylene group, 3-hydroxybutylene group, 4 A hydroxyalkylene group having 1 to 4 carbon atoms such as a hydroxybutylene group is preferred.

  Examples of the (meth) acrylate having a ο-phenylphenol group in the molecule represented by the formula (4) include, for example, 3-ο-phenylphenolmethyl (meth) acrylate, 3-ο-phenylphenolethyl (meth) acrylate, 3 -Ο-phenylphenol propyl (meth) acrylate, 3-ο-phenylphenol butyl (meth) acrylate, 3-ο-phenylphenol diethoxy (meth) acrylate, 3-ο-phenylphenol triethoxy (meth) acrylate, 3 -Ο-phenylphenol tetraethoxy (meth) acrylate, 2-hydroxy-3-ο-phenylphenolpropyl (meth) acrylate, 2-hydroxy-3-ο-phenylphenolbutyl (meth) acrylate, 3-hydroxy-3- ο-Phenylpheno And rupropyl (meth) acrylate.

  The di (meth) acrylate having a fluorene structure in the molecule represented by the formula (5) will be described.

  Following formula (5)

(Where
R ¹² and R ¹³ are each independently a hydrogen atom or a methyl group,
R ¹⁴ and R ¹⁵ are an alkylene group having 1 to 10 carbon atoms, a hydroxyalkylene group having 1 to 10 carbon atoms, or a group represented by the following formula (6). Also good. )

(In the formula, R ¹⁶ and R ¹⁷ are an ethylene group or a propylene group, and n is an integer of 1 to 3.)
In these, R ¹² and R ¹³ are each independently a hydrogen atom or a methyl group. Among these, hydrogen atoms are preferable because they have a high photocuring speed when curing the radiation shielding ink.

R ¹⁴ and R ¹⁵ are an alkylene group having 1 to 10 carbon atoms, a hydroxyalkylene group having 1 to 10 carbon atoms, or a group represented by the formula (6). Specifically, methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, sec-butylene group, tert-butylene group, 2,2-dimethylpropylene group, 2-methylbutylene group, 2- Methyl-2-butylene group, 3-methylbutylene group, 3-methyl-2-butylene group, pentylene group, 2-pentylene group, 3-pentylene group, 3-dimethyl-2-butylene group, 3,3-dimethylbutylene Group, 3,3-dimethyl-2-butylene group, 2-ethylbutylene group, hexylene group, 2-hexylene group, 3-hexylene group, 2-methylpentylene group, 2-methyl-2-pentylene group, 2- Methyl-3-pentylene group, 3-methylpentylene group, 3-methyl-2-pentylene group, 3-methyl-3-pentylene group, 4-methylpentylene Group, 4-methyl-2-pentylene group, 2,2-dimethyl-3-pentylene group, 2,3-dimethyl-3-pentylene group, 2,4-dimethyl-3-pentylene group, 4,4-dimethyl 2-pentylene group, 3-ethyl-3-pentylene group, heptylene group, 2-heptylene group, 3-heptylene group, 2-methyl-2-hexylene group, 2-methyl-3-hexylene group, 5-methylhexene Xylene group, 5-methyl-2-hexylene group, 2-ethylhexylene group, 6-methyl-2-heptylene group, 4-methyl-3-heptylene group, octylene group, 2-octylene group, 3-octylene group, Alkylene groups such as 2-propylpentylene, 2,4,4-trimethylpentylene; trimethylene, tetramethylene, pentamethylene, hexamethylene, heptam Polymethylene groups such as len group, octamethylene group, nonamethylene group, decamethylene group, 1-hydroxyethylene group, 2-hydroxyethylene group, 1-hydroxypropylene group, 2-hydroxypropylene group, 3-hydroxypropylene group, 1-hydroxy Isopropylene group, 2-hydroxyisopropylene group, 3-hydroxyisopropylene group, 1-hydroxybutylene group, 2-hydroxybutylene group, 3-hydroxybutylene group, 4-hydroxybutylene group, 1-hydroxyisobutylene group, 2- Hydroxyisobutylene group, 3-hydroxyisobutylene group, 1-hydroxysec-butylene group, 2-hydroxysec-butylene group, 3-hydroxysec-butylene group, 4-hydroxysec-butylene group, 1-hydroxy-2,2- Jime Tylpropylene group, 3-hydroxy-2,2-dimethylpropylene group, 1-hydroxy-2-methylbutylene group, 2-hydroxy-2-methylbutylene group, 3-hydroxy-2-methylbutylene group, 4-hydroxy- 2-methylbutylene group, 1-hydroxy 2-methyl-2-butylene group, 3-hydroxy 2-methyl-2-butylene group, 4-hydroxy 2-methyl-2-butylene group, 1-hydroxy-3-methylbutylene Group, 2-hydroxy-3-methylbutylene group, 3-hydroxy-3-methylbutylene group, 4-hydroxy-3-methylbutylene group, 1-hydroxy-3-methyl-2-butylene group, 2-hydroxy-3 -Methyl-2-butylene group, 3-hydroxy-3-methyl-2-butylene group, 4-hydroxy-3-methyl-2-butylene 1-hydroxypentylene group, 2-hydroxypentylene group, 3-hydroxypentylene group, 4-hydroxypentylene group, 5-hydroxypentylene group, 1-hydroxy-2-pentylene group, 2-hydroxy-2 -Pentylene group, 3-hydroxy-2-pentylene group, 4-hydroxy-2-pentylene group, 5-hydroxy-2-pentylene group, 1-hydroxy-3-pentylene group, 2-hydroxy-3-pentylene group, 3 -Hydroxy-3-pentylene group, 4-hydroxy-3-pentylene group, 5-hydroxy-3-pentylene group, 1-hydroxy-3-dimethyl-2-butylene group, 2-hydroxy-3-dimethyl-2-butylene Group, 3-hydroxy-3-dimethyl-2-butylene group, 4-hydroxy-3-dimethyl-2-butylene group 1-hydroxy-3,3-dimethylbutylene group, 2-hydroxy-3,3-dimethylbutylene group, 4-hydroxy-3,3-dimethylbutylene group, 1-hydroxy-3,3-dimethyl-2-butylene group 2-hydroxy-3,3-dimethyl-2-butylene group, 4-hydroxy-3,3-dimethyl-2-butylene group, 1-hydroxy-2-ethylbutylene group, 2-hydroxy-2-ethylbutylene group 3-hydroxy-2-ethylbutylene group, 4-hydroxy-2-ethylbutylene group, 1-hydroxy-hexylene group, 2-hydroxy-hexylene group, 3-hydroxy-hexylene group, 4-hydroxy-hexylene group, 5 -Hydroxy-hexylene group, 6-hydroxy-hexylene group, 1-hydroxy-2-hexylene group, 2-hydroxy-2 -Hexylene group, 3-hydroxy-2-hexylene group, 4-hydroxy-2-hexylene group, 5-hydroxy-2-hexylene group, 6-hydroxy-2-hexylene group, 1-hydroxy-3-hexylene group, 2 -Hydroxy-3-hexylene group, 3-hydroxy-3-hexylene group, 4-hydroxy-3-hexylene group, 5-hydroxy-3-hexylene group, 6-hydroxy-3-hexylene group, 1-hydroxy-2- Methylpentylene group, 2-hydroxy-2-methylpentylene group, 3-hydroxy-2-methylpentylene group, 4-hydroxy-2-methylpentylene group, 5-hydroxy-2-methylpentylene group, 1 -Hydroxy-2-methyl-2-pentylene group, 2-hydroxy-2-methyl-2-pentylene group, 3-hydroxy-2 Methyl-2-pentylene group, 4-hydroxy-2-methyl-2-pentylene group, 5-hydroxy-2-methyl-2-pentylene group, 1-hydroxy-2-methyl-3-pentylene group, 2-hydroxy- 2-methyl-3-pentylene group, 3-hydroxy-2-methyl-3-pentylene group, 4-hydroxy-2-methyl-3-pentylene group, 5-hydroxy-2-methyl-3-pentylene group, 1- Hydroxy-3-methylpentylene group, 2-hydroxy-3-methylpentylene group, 3-hydroxy-3-methylpentylene group, 4-hydroxy-3-methylpentylene group, 5-hydroxy-3-methylpentylene Len group, 1-hydroxy-3-methyl-2-pentylene group, 2-hydroxy-3-methyl-2-pentylene group, 3-hydroxy-3-methyl 2-pentylene group, 4-hydroxy-3-methyl-2-pentylene group, 5-hydroxy-3-methyl-2-pentylene group, 1-hydroxy-3-methyl-3-pentylene group, 2-hydroxy-3 -Methyl-3-pentylene group, 3-hydroxy-3-methyl-3-pentylene group, 4-hydroxy-3-methyl-3-pentylene group, 5-hydroxy-3-methyl-3-pentylene group, 1-hydroxy -4-methylpentylene group, 2-hydroxy-4-methylpentylene group, 3-hydroxy-4-methylpentylene group, 4-hydroxy-4-methylpentylene group, 5-hydroxy-4-methylpentylene Group, 1-hydroxy-4-methyl-2-pentylene group, 2-hydroxy-4-methyl-2-pentylene group, 3-hydroxy-4-methyl-2- Pentylene group, 4-hydroxy-4-methyl-2-pentylene group, 5-hydroxy-4-methyl-2-pentylene group, 1-hydroxy-2,2-dimethyl-3-pentylene group, 3-hydroxy-2, 2-dimethyl-3-pentylene group, 4-hydroxy-2,2-dimethyl-3-pentylene group, 5-hydroxy-2,2-dimethyl-3-pentylene group, 1-hydroxy-2,3-dimethyl-3 -Pentylene group, 2-hydroxy-2,3-dimethyl-3-pentylene group, 4-hydroxy-2,3-dimethyl-3-pentylene group, 5-hydroxy-2,3-dimethyl-3-pentylene group, 1 -Hydroxy-2,4-dimethyl-3-pentylene group, 2-hydroxy-2,4-dimethyl-3-pentylene group, 3-hydroxy-2,4-dimethyl-3-pe Tylene group, 4-hydroxy-2,4-dimethyl-3-pentylene group, 5-hydroxy-2,4-dimethyl-3-pentylene group, 1-hydroxy-4,4-dimethyl-2-pentylene group, 2- Hydroxy-4,4-dimethyl-2-pentylene group, 3-hydroxy-4,4-dimethyl-2-pentylene group, 5-hydroxy-4,4-dimethyl-2-pentylene group, 1-hydroxy-3-ethyl -3-pentylene group, 2-hydroxy-3-ethyl-3-pentylene group, 4-hydroxy-3-ethyl-3-pentylene group, 5-hydroxy-3-ethyl-3-pentylene group, 1-hydroxyheptyl Len group, 2-hydroxyheptylene group, 3-hydroxyheptylene group, 4-hydroxyheptylene group, 5-hydroxyheptylene group, 6-hydroxyheptene group Len group, 7-hydroxyheptylene group, 1-hydroxy-2-heptylene group, 2-hydroxy-2-heptylene group, 3-hydroxy-2-heptylene group, 4-hydroxy-2-heptylene group, 5-hydroxy 2-heptylene group, 6-hydroxy-2-heptylene group, 7-hydroxy-2-heptylene group, 1-hydroxy-3-heptylene group, 2-hydroxy-3-heptylene group, 3-hydroxy-3-heptylene group 4-hydroxy-3-heptylene group, 5-hydroxy-3-heptylene group, 6-hydroxy-3-heptylene group, 7-hydroxy-3-heptylene group, 1-hydroxy-2-methyl-2-hexylene group, 3-hydroxy-2-methyl-2-hexylene group, 4-hydroxy-2-methyl-2-hexylene group, 5-hydroxy- 2-methyl-2-hexylene group, 6-hydroxy-2-methyl-2-hexylene group, 1-hydroxy-2-methyl-3-hexylene group, 2-hydroxy-2-methyl-3-hexylene group, 3- Hydroxy-2-methyl-3-hexylene group, 4-hydroxy-2-methyl-3-hexylene group, 5-hydroxy-2-methyl-3-hexylene group, 6-hydroxy-2-methyl-3-hexylene group, 1-hydroxy-5-methylhexylene group, 2-hydroxy-5-methylhexylene group, 3-hydroxy-5-methylhexylene group, 4-hydroxy-5-methylhexylene group, 5-hydroxy-5- Methylhexylene group, 6-hydroxy-5-methylhexylene group, 1-hydroxy-5-methyl-2-hexylene group, 2-hydroxy-5-methyl- -Hexylene group, 3-hydroxy-5-methyl-2-hexylene group, 4-hydroxy-5-methyl-2-hexylene group, 5-hydroxy-5-methyl-2-hexylene group, 6-hydroxy-5-methyl 2-hexylene group, 1-hydroxy-2-ethylhexylene group, 2-hydroxy-2-ethylhexylene group, 3-hydroxy-2-ethylhexylene group, 4-hydroxy-2-ethylhexylene group, 5-hydroxy-2-ethylhexylene group, 6-hydroxy-2-ethylhexylene group, 1-hydroxy-6-methyl-2-heptylene group, 2-hydroxy-6-methyl-2-heptylene group, 3- Hydroxy-6-methyl-2-heptylene group, 4-hydroxy-6-methyl-2-heptylene group, 5-hydroxy-6-methyl-2-heptylene group Group, 6-hydroxy-6-methyl-2-heptylene group, 7-hydroxy-6-methyl-2-heptylene group, 1-hydroxy-4-methyl-3-heptylene group, 2-hydroxy-4-methyl-3 -Heptylene group, 3-hydroxy-4-methyl-3-heptylene group, 4-hydroxy-4-methyl-3-heptylene group, 5-hydroxy-4-methyl-3-heptylene group, 6-hydroxy-4-methyl -3-heptylene group, 1-hydroxyoctylene group, 2-hydroxyoctylene group, 3-hydroxyoctylene group, 4-hydroxyoctylene group, 5-hydroxyoctylene group, 6-hydroxyoctylene group, 7- Hydroxyoctylene group, 8-hydroxyoctylene group, 1-hydroxy-2-octylene group, 2-hydroxy-2-octylene group, 3 -Hydroxy-2-octylene group, 4-hydroxy-2-octylene group, 5-hydroxy-2-octylene group, 6-hydroxy-2-octylene group, 7-hydroxy-2-octylene group, 8-hydroxy-2- Octylene group, 1-hydroxy-3-octylene group, 2-hydroxy-3-octylene group, 3-hydroxy-3-octylene group, 4-hydroxy-3-octylene group, 5-hydroxy-3-octylene group, 6- Hydroxy-3-octylene group, 7-hydroxy-3-octylene group, 8-hydroxy-3-octylene group, 1-hydroxy-2-propylpentylene group, 2-hydroxy-2-propylpentylene group, 3-hydroxy 2-propylpentylene group, 4-hydroxy-2-propylpentylene group, 5-hydroxy-2-pro Rupentylene group, 1-hydroxy-2,4,4-trimethylpentylene group, 2-hydroxy-2,4,4-trimethylpentylene group, 3-hydroxy-2,4,4-trimethylpentylene group, 5- Examples include hydroxyalkylene groups such as hydroxy-2,4,4-trimethylpentylene group.

Among these, an alkylene group having 1 to 4 carbon atoms such as methylene group, ethylene group, propylene group, isopropylene group, butylene group, 1-hydroxyethylene group, 2-hydroxyethylene group, 1-hydroxypropylene group, 2 -Hydroxypropylene group, 3-hydroxypropylene group, 1-hydroxyisopropylene group, 2-hydroxyisopropylene group, 3-hydroxyisopropylene group, 1-hydroxybutylene group, 2-hydroxybutylene group, 3-hydroxybutylene group, A hydroxyalkylene group having 1 to 4 carbon atoms such as 4-hydroxybutylene group and 1-hydroxyisobutylene group, or a group of formula (6), wherein R ¹⁶ and R ¹⁷ are ethylene groups, and n is 1 to 2 or R ¹⁶ and R ¹⁷ are propylene groups, and n is preferably 1 or 2 groups. Good.

  Examples of the di (meth) acrylate having a fluorene structure in the molecule represented by the formula (5) include 9,9-bis [4- (2- (meth) acryloyloxymethoxy) phenyl] fluorene, 9,9-bis. [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, 9,9-bis [4- (2- (meth) acryloyloxypropyloxy) phenyl] fluorene, 9,9-bis [4- (2 -(Meth) acryloyloxyisopropyloxy) phenyl] fluorene, 9,9-bis [4- (2- (meth) acryloyloxybutyloxy) phenyl] fluorene, 9,9-bis [4- (2- (meth)) Acryloyloxyhydroxyethylethoxy) phenyl] fluorene, 9,9-bis [4- (2- (meth) acryloyloxy) Roxypropyloxy) phenyl] fluorene, 9,9-bis [4- (2- (meth) acryloyloxyhydroxyisopropyloxy) phenyl] fluorene, 9,9-bis [4- (2- (meth) acryloyloxyhydroxybutyl) Oxy) phenyl] fluorene, 9,9-bis [4- (2- (meth) acryloyloxyethyleneglycoxy) phenyl] fluorene, 9,9-bis [4- (2- (meth) acryloyloxypropyleneglycoxy) Phenyl] fluorene and the like.

  Next, the photopolymerization initiator (C) will be described.

(Photopolymerization initiator (C))
In the present invention, the photopolymerization initiator (C) is not particularly limited, and any photopolymerization initiator can be used as long as it can photopolymerize the polymerizable monomer (B).

  Specific examples of the photopolymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1- ON, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy- 2-methylpropionyl) -benzyl] -phenyl} -2-methyl-propan-1-one, phenylglyoxylic acid methyl ester, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane -1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-dimethylamino-2- (4-methylben) Acetophenone derivatives such as (zyl) -1- (4-morpholin-4-yl-phenyl) butan-1-one; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2, 6-dichlorobenzoyldiphenylphosphine oxide, 2,6-trimethylbenzoylphenylphosphinic acid methyl ester, 2-methylbenzoyldiphenylphosphine oxide, pivaloylphenylphosphinic acid isopropyl ester, bis- (2,6-dichlorobenzoyl) phenylphosphine oxide Bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide Bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis- (2,5,6-trimethylbenzoyl)- Acylphosphine oxide derivatives such as 2,4,4-trimethylpentylphosphine oxide; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9 -Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, O-acyloxime derivatives such as 1- (O-acetyloxime); diacetyl, acetylbenzoyl, benzyl, 2,3-pentadione, 2,3-octadione, 4,4′-dimethoxybenzyl, 4,4′-oxybenzyl Α-diketones such as camphorquinone, 9,10-phenanthrenequinone, and acenaphthenequinone; benzoin alkyl ethers such as benzoin methyl ether, benzoin ethyl ether, and benzoin propyl ether; 2,4-diethoxythioxanthone, 2 -Thioxanthone derivatives such as chlorothioxanthone and methylthioxanthone; benzophenone derivatives such as benzophenone, p, p'-dimethylaminobenzophenone and p, p'-methoxybenzophenone; bis (η5-2,4-cyclopentadiene-1- Il) -bis (2,6 A titanocene derivative such as -difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium is preferably used.

  These photopolymerization initiators are used alone or in combination of two or more.

  When α-diketone is used, it is preferably used in combination with a tertiary amine compound. Tertiary amine compounds that can be used in combination with α-diketone include N, N-dimethylaniline, N, N-diethylaniline, N, N-di-n-butylaniline, N, N-dibenzylaniline. N, N-dimethyl-p-toluidine, N, N-diethyl-p-toluidine, N, N-dimethyl-m-toluidine, p-bromo-N, N-dimethylaniline, m-chloro-N, N- Dimethylaniline, p-dimethylaminobenzaldehyde, p-dimethylaminoacetophenone, p-dimethylaminobenzoic acid, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid amyl ester, N, N-dimethylanthranic acid methyl Ester, N, N-dihydroxyethylaniline, N, N-dihydroxyethyl-p-toluidine, p Dimethylaminophenethyl alcohol, p-dimethylaminostilbene, N, N-dimethyl-3,5-xylidine, 4-dimethylaminopyridine, N, N-dimethyl-α-naphthylamine, N, N-dimethyl-β-naphthylamine, tri Butylamine, tripropylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, N, N-dimethylhexylamine, N, N-dimethyldodecylamine, N, N-dimethylstearylamine, N, N-dimethylaminoethyl methacrylate N, N-diethylaminoethyl methacrylate, 2,2 ′-(n-butylimino) diethanol, and the like.

  In the present invention, it is preferable to use an acetophenone derivative, an acylphosphine oxide derivative, an O-acyloxime derivative, or an α-diketone.

  In this invention, it is preferable that the usage-amount of the said photoinitiator is 0.1-10 mass parts with respect to 100 mass parts of said polymerizable monomers (B), and 0.1-5 mass parts It is more preferable from the viewpoint of the radiation shielding function.

(Other additive components in radiation shielding ink)
The radiation shielding ink of the present invention can be blended with other components as long as the effects of the present invention are not impaired.

  In using the radiation shielding ink of the present invention, the radiation shielding ink is applied or sprayed onto various members. In this case, the radiation shielding ink may be diluted with a solvent. Further, for the purpose of stabilizing the radiation shielding ink of the present invention, or for other purposes, a solvent, a stabilizer and other known additives may be blended. As a solvent to be used, any solvent can be used as long as it can dissolve the radiation shielding ink of the present invention. For example, acetonitrile, tetrahydrofuran, toluene, chloroform, acetic acid ethyl ester, methyl ethyl ketone, dimethylformamide, cyclohexanone, ethylene glycol can be used. , Ethylene glycol isopropyl ether, propylene glycol, propylene glycol methyl ether, propylene glycol monomethyl ether acetate, methyl-3-methoxypropionate, ethylene glycol monoethyl ether acetate, ethyl lactate, ethyl-3-ethoxypropionate, butyl acetate , 2-heptanone, methyl isobutyl ketone, acetylacetone, diacetone alcohol, t-butyl alcohol It may be mentioned polyethylene glycol, water, and other alcohols. In addition, water and alcohol can also be mix | blended newly, The water used when manufacturing the hydrolysis mixture (A) and the alcohol byproduced may be sufficient. Moreover, the solvent used as a dilution solvent when manufacturing a hydrolysis mixture (A) may be contained in the said solvent.

  When using a solvent, the amount used is not particularly limited and is appropriately selected according to the thickness of the target coating film. In particular, when the total amount of the solvent and the radiation shielding ink is 100% by mass, the concentration of the solvent is preferably in a range of 10 to 99% by mass.

  Any stabilizer can be used without limitation as long as it is generally known as a stabilizer for sol-gel components. For example, α-hydroxycarboxylic acid alkyl ethers such as methoxyacetic acid; glycolic acid Α-hydroxycarboxylic acids such as lactic acid, oxalic acid, mandelic acid and 2-hydroxyisobutyric acid; ethanolamines such as diethanolamine; diketones such as diacetyl, 2,5-hexanedione, acetylacetone, methylpropyl diketone and dimedone Can be mentioned. When a stabilizer is used, the amount used is not particularly limited, but it is preferable to adjust the amount used according to the amount of the sol-gel component.

  In the present invention, when tungsten alkoxide is used as the metal alkoxide, β-hydroxyketones having a β-hydroxyketone skeleton (O═C—C—C—OH) can be preferably used as a stabilizer. 4-hydroxy-2-butanone, 4-hydroxy-5,5-dimethyl-2-hexanone, 3-methyl-4-hydroxy-2-butanone, 3,3′-dimethyl-4-hydroxy-2-butanone, 4 -Hydroxy-4-methyl-2-pentanone, 4-hydroxy-4-methyl-5-phenyl-2-pentanone, 3-hydroxy-1,3-diphenyl-1-propanone, 3-hydroxy-1-phenyl-3 -(4-Methoxyphenyl) -1-propanone, 3-hydroxy-1- (3,4,5-trimethoxyphenyl) -3 -Phenyl-1-propanone, 3-hydroxy-1- (3,4-methylenedioxyphenyl) -3-phenyl-1-propanone, 3-hydroxy-1- (4-methylphenyl) -3-phenyl-1 -Propanone, 3-hydroxy-1- (3-methoxyphenyl) -3-phenyl-1-propanone, 4- (2-methylphenyl) -4-hydroxy-2-butanone, 4-phenyl-4-hydroxy-3 -Methyl-2-butanone, 4- (4-fluorophenyl) -4-hydroxy-3-methyl-2-butanone and the like.

  The radiation shielding ink of the present invention can contain other known additives. Specifically, a surfactant, a polymerization inhibitor, a reactive diluent and the like can be blended. From the viewpoint of the uniformity of the coating film, the surfactant is added to stabilize the polymerization inhibitor so that it does not polymerize during storage.

  When the surfactant is blended, it is blended at a ratio of 0.0001 to 1 part by mass, preferably 0.001 to 0.1 part by mass with respect to 100 parts by mass of the polymerizable monomer (B). can do.

  As the surfactant, a fluorine-containing surfactant, a silicone-containing surfactant, and an aliphatic surfactant can be used. In particular, when a radiation shielding ink is applied or sprayed onto a member such as glass, eyeglass lens, wallpaper, fiber, etc., an aliphatic surfactant is used because it is easy to apply the composition uniformly without causing repelling. More preferably.

  Examples of surfactants include metal salts of higher alcohol sulfates such as sodium decyl sulfate and sodium lauryl sulfate, aliphatic carboxylic acid metal salts such as sodium laurate, sodium stearate and sodium oleate, lauryl alcohol and ethylene oxide. Anionic activity such as metal salts of higher alkyl ether sulfates such as sodium lauryl ether sulfate esterified with adducts with sodium, sulfosuccinic diesters such as sodium sulfosuccinate, phosphate esters of higher alcohol ethylene oxide adducts, etc. Agents; Cationic surfactants such as alkylamine salts such as dodecylammonium chloride and quaternary ammonium salts such as trimethyldodecylammonium bromide; such as dodecyldimethylamine oxide Zwitterionic surfactants such as alkyl dimethyl betaines such as alkyl dimethyl amine oxides, alkyl carboxy betaines such as dodecyl carboxy betaine, alkyl sulfo betaines such as dodecyl sulfo betaine, and amide amino acid salts such as lauramido propyl amine oxide; Polyoxyethylene alkyl ethers, polyoxyalkylene alkyl ethers, polyoxyethylene distyrenated phenyl ethers, polyoxyethylene alkyl phenyl ethers such as polyoxyethylene lauryl phenyl ether, polyoxyethylene tribenzylphenyl ethers, Fatty acid polyoxyethylene esters such as fatty acid polyoxyethylene lauryl ester, polio such as polyoxyethylene sorbitan lauryl ester It can be mentioned non-ionic surfactants such as polyoxyethylene sorbitan esters. Surfactants can be used not only independently but also in combination of a plurality of types as required.

  When blending a polymerization inhibitor, it is 0.01 to 1.0 part by weight, preferably 0.1 to 0.5 part by weight with respect to 100 parts by weight of the polymerizable monomer (B). Can be blended.

  Examples of the polymerization inhibitor include known ones. For example, the most typical ones include hydroquinone monomethyl ether, hydroquinone, butylhydroxytoluene and the like.

  Examples of the reactive diluent include known ones such as N-vinylpyrrolidone.

  The addition amount of the reactive diluent is not particularly limited and is appropriately selected within a range not affecting the formation of the pattern from the mold, and is usually 1 to 100 parts by mass of the polymerizable monomer (B). It is suitably selected from the range of 100 parts by mass. Among them, the amount is preferably 5 to 50 parts by mass considering the viscosity reduction of the radioactive shielding ink, the mechanical strength of the pattern, and the like.

  The radiation shielding ink of the present invention is prepared by mixing the hydrolysis mixture (A), the polymerizable monomer (B), the photopolymerization initiator (C), and other additive components blended as necessary. The The order of addition of these components is not particularly limited.

  Next, a method for forming a coating layer on various members using this radiation shielding ink will be described.

(Method of forming a coating layer using radiation shielding ink)
A method for forming a coat layer using the radiation shielding ink of the present invention will be described.

  First, a coating film is formed by applying and spraying the radiation shielding ink prepared according to the above method on various members according to a known method.

  The member is not particularly limited, and papers, plates, substrates, fibers, nonwoven fabrics, sheets, and films can be used. Specifically, paper such as paper and wallpaper; plates such as building materials and decorative boards; glass, mirrors, eyeglass lenses, silicon wafers, quartz, sapphire, various metal materials, alumina, aluminum nitride, silicon carbide, silicon nitride -Substrates made of ceramics such as zirconia; feathers, wool, silk, cashmere, tenji thread, mohair, cotton, hemp, jute, aramid fiber, glass fiber, cellulose fiber, nylon fiber, vinylon fiber, polyester fiber, polyolefin fiber, rayon Non-woven fabric made of various fibers; ethylene homopolymer, ethylene and propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, or one or more α- Random or block copolymer with olefin, ethylene and vinyl acetate, acrylic acid, methacrylic acid, acrylic acid , One or more random or block copolymers with methyl methacrylate, propylene homopolymer, 1-butene other than propylene and propylene, 1-pentene, 1-hexene, 4-methyl-1-pentene Such as random or block copolymers with one or more α-olefins, 1-butene homopolymers, ionomer resins, and mixtures of these polymers; petroleum resins, terpene resins, etc. Hydrocarbon resins: Polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate; polyamides such as nylon 6, nylon 66, nylon 11, nylon 12, nylon 610, nylon 6/66, nylon 66/610, nylon MXD Resin: Polymethylmethacrylate Acrylic resin such as polystyrene; styrene, acrylonitrile resin such as polystyrene, styrene-acrylonitrile copolymer, styrene-acrylonitrile-butadiene copolymer, polyacrylonitrile; polyvinyl alcohol such as polyvinyl alcohol and ethylene-vinyl alcohol copolymer Polycarbonate resin; Polyketone resin; Polymethylene oxide resin; Polysulfone resin; Polyimide resin; Polyamideimide resin: Known sheets and films can be used. In addition, these base materials can also be surface-treated in order to improve adhesiveness with the cured film which consists of radiation shielding ink of this invention more.

  The surface treatment is not particularly limited, and for example, known flame treatment, corona discharge treatment in the atmosphere or nitrogen gas, atmospheric pressure plasma treatment, blast treatment, honing treatment, UV ozone treatment, VUV treatment, etc. This method can be adopted.

  In order to enhance the adhesion, an anchor coat layer may be provided between the member and the coat layer made of the radiation shielding ink of the present invention. As the anchor coat agent used for forming the anchor coat layer, known ones can be used without any particular limitation. Examples thereof include anchor coating agents such as isocyanate, polyurethane, polyester, polyether, polyethyleneimine, polybutadiene, polyolefin, and alkyl titanate.

  On these various members, spin coating method, dipping method, dispensing method, ink jet method, roll coating method, reverse roll coating method, gravure coating method, spray coating method, kiss coating method, die coating method, rod coating method, bar coating method, What is necessary is just to form a coating film by apply | coating the radiation shielding ink of this invention and drying by well-known methods, such as the gravure coat method combined with a chamber doctor, a curtain coat method, and a roll to roll method. The thickness of the coating film is not particularly limited, and may be appropriately determined depending on the intended use, but is usually 0.1 to 100 μm.

  The drying temperature is not particularly limited as long as the coating film is dried. Usually, the drying temperature can be selected from a range of 40 ° C to 150 ° C.

  It is also possible to apply the radiation shielding ink of the present invention after diluting with an organic solvent. In that case, the drying temperature may be appropriately determined according to the boiling point and volatility of the organic solvent to be used.

  Thereafter, the coating film is irradiated with light to cure the coating film to form a coat layer. The light to be irradiated has a wavelength of 500 nm or less, and the light irradiation time is selected from the range of 0.1 to 300 seconds. Although it depends on the thickness of the coating film, etc., it is usually 1 to 60 seconds.

  The atmosphere during photopolymerization can be polymerized even in the air, but in order to promote the photopolymerization reaction, photopolymerization in an atmosphere with little oxygen inhibition is preferred. For example, a nitrogen gas atmosphere, an inert gas atmosphere, a fluorine gas atmosphere, a vacuum atmosphere, or the like is preferable.

  In the optional step of obtaining the radiation shielding ink of the present invention, when water and solvent are removed by vacuum drying, distillation, heating, etc., and the required amount of solvent is not added, after applying on various members, the drying step is performed. Omitting, it is possible to cure the coating film by irradiating the coating film with light.

  The thicker the coating layer, the higher the radiation shielding effect. However, a film or sheet formed with a radiation shielding coating layer made of a cured product of the radiation shielding ink of the present invention may be used in an overlapping manner. In that case, they may be simply overlapped, or an adhesive layer may be provided to form a laminate.

  Hereinafter, the present invention will be described with reference to examples and comparative examples, but the present invention is not limited to these examples.

(1) Evaluation of substrate adhesion of cured film The obtained radiation shielding ink was appropriately diluted with 1-methoxy-2-propanol, and a baker-type applicator on a polyethylene terephthalate film (corona-treated surface, thickness 188 μm). And then dried at 110 ° C. for 2 minutes, and then UV-irradiated with LED 365 nm light in a nitrogen stream to prepare a cured film with a radiation shielding ink having a thickness of about 2 μm, and a 15 mm wide cellophane tape manufactured by Nichiban Co., Ltd. 405 (length 5cm), peeled after 3 reciprocal contact with finger pressure,
The cured film was not removed at all: 5
The peeled area is less than 10%: 4
Exfoliation area of 10% or more and less than 50%: 3
Exfoliation area 50% or more and less than 100%: 2
With peeling area of 100% (full peeling): 1
As evaluated.

(2) Evaluation of transparency The radiation shielding ink obtained was appropriately diluted with 1-methoxy-2-propanol and coated on a polyethylene terephthalate film (corona-treated surface, thickness 188 μm) using a Baker type applicator. After drying at 110 ° C. for 2 minutes, UV irradiation was performed with LED 365 nm light in a nitrogen stream to prepare a cured film with a radiation shielding ink having a thickness of about 2 μm, and the haze was measured according to JIS K 6714 and transparent. Evaluation of sex.

Example 1
(Production of hydrolysis mixture (A))
6.9 g of ethanol, 7.5 g of trimethoxysilyl trimethylene acrylate (KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.) as an organosilicon compound having a (meth) acrylic group, tungsten (V) ethoxide as a metal alkoxide (manufactured by Alfa Aesar) And 0.8 g of ethanol, and 0.02 g of 2N-HCl / ethanol mixed aqueous solution of 0.07 g of ethanol was gradually added dropwise at room temperature while stirring and mixing the mixture. Further, an ethanol aqueous solution of 0.5 g of ethanol / 0.5 g of water is gradually added dropwise and stirred at room temperature for 1 hour, and contains a hydrolyzate of an organosilicon compound having a (meth) acryl group and a hydrolyzate of a metal alkoxide. A hydrolysis mixture (A) was obtained.

(Manufacture of radiation shielding ink)
As a polymerizable monomer (B) having a (meth) acryl group, hydroxyethylated o-phenylphenol acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A-LEN-10) 5.0 g, 9,9 5.0 g of -bis [4- (2-acryloyloxyethoxy) phenyl] fluorene (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A-BPEF) was used.

  As a photopolymerization initiator (C), 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one (BASF Japan Ltd.) Manufactured by IRGACURE (registered trademark) 379 EG) 0.1 g.

  As the polymerization inhibitor, 0.015 g of hydroquinone monomethyl ether and 0.002 g of butylhydroxytoluene were used.

  The polymerizable monomer (B) having the (meth) acryl group, the photopolymerization initiator (C), and the polymerization inhibitor were uniformly mixed, and 2.0 g of the mixture was collected. 8.6 g of the hydrolysis mixture (A) was added to 2.0 g of the mixture, and the mixture was stirred at room temperature for 15 minutes to obtain a radiation shielding ink. The obtained radiation shielding ink was filtered through a syringe filter having a 0.2 μmφ hole diameter. The blending ratio of this radiation shielding ink is shown in Table 1.

  The obtained radiation shielding ink was used to evaluate the substrate adhesion and transparency of the cured film. The results are shown in Table 2.

  The obtained radiation shielding ink was coated on a polyethylene terephthalate film (corona-treated surface, thickness 188 μm) using a baker type applicator, dried at 110 ° C. for 2 minutes, and then irradiated with UV light at 365 nm under nitrogen flow. Thus, a film on which a radiation shielding coating layer made of radiation shielding ink having a thickness of about 5 μm was formed was obtained.

  Four films obtained as described above were placed on the radiation source of the spot detector, and the radiation dose was measured from the film side with a GM survey meter manufactured by Hitachi Aloca. The reading of the measured value was held for 1 minute or longer and was read after the measuring needle became difficult to move.

  The measured radiation dose was 1,100 cpm. When the space was measured as it was without placing the film obtained above, it was 1,350 cpm. Further, when the radiation dose of four polyethylene terephthalate films (corona-treated surface, thickness: 188 μm) not coated with radiation shielding ink was measured on the radiation source of the above-mentioned squeak detector, it was 1300 cpm. The four-layer film (about 20 μm in total coating layer thickness) in which the coating layer was formed with the radiation shielding ink obtained above had a radiation shielding effect of about 19%.

Example 2
(Production of hydrolysis mixture (A))
8.4 g of ethanol, 1.5 g of trimethoxysilyl trimethylene acrylate (KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.) as an organosilicon compound having a (meth) acrylic group, tungsten (V) ethoxide as a metal alkoxide (manufactured by Alfa Aesar) ) 0.8 g and 5.8 g of diphenyldimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) as an organic silicon compound, and while stirring and mixing the mixture, ethanol 2.6 g / water 0.5 g / 2N-HCl 0 0.09 g of a 2N HCl / ethanol mixed aqueous solution was gradually added dropwise at room temperature. Further, an ethanol aqueous solution of 0.6 g of ethanol / 0.3 g of water was gradually added dropwise and stirred at room temperature for 1 hour to hydrolyze an organosilicon compound having a (meth) acryl group, a hydrolyzate of a metal alkoxide, and organic A hydrolysis mixture (A) containing a hydrolyzate of a silicon compound was obtained.

(Manufacture of radiation shielding ink)
After mixing the same type, the same amount of the polymerizable monomer (B), the photopolymerization initiator (C), and the polymerization inhibitor as used in Example 1, the same amount of the mixture (2.0 g) After adding 9.8 g of the hydrolysis mixture (A) to the mixture, the mixture was stirred and mixed at room temperature for 15 minutes to obtain a radiation shielding ink. The obtained radiation shielding ink was filtered through a syringe filter having a 0.2 μmφ hole diameter. The blending ratio of this radiation shielding ink is shown in Table 1.
The obtained radiation shielding ink was used to evaluate the substrate adhesion and transparency of the cured film. The results are shown in Table 2.

  The obtained radiation shielding ink was coated on a polyethylene terephthalate film (corona-treated surface, thickness 188 μm) using a baker type applicator, dried at 110 ° C. for 2 minutes, and then irradiated with UV light at 365 nm under nitrogen flow. Thus, a film on which a radiation shielding coating layer made of radiation shielding ink having a thickness of about 5 μm was formed was obtained.

  Four films obtained as described above were placed on an oil lanthanum combustion core as a radiation source, and the radiation dose was measured with a GM survey meter manufactured by Hitachi Aloca from the film side. The reading of the measured value was held for 1 minute or longer and was read after the measuring needle became difficult to move.

  The measured radiation dose was 2,000 cpm. When the space was measured as it was without placing the film obtained above, it was 4,400 cpm. Further, when the radiation dose of four polyethylene terephthalate films (corona-treated surface, thickness 188 μm) not coated with radiation shielding ink was measured on the combustion core of the oil lanthanum, it was 4,000 cpm. The radiation shielding effect of about 55% was obtained by stacking four films (with a total coating layer thickness of about 20 μm) on which a coating layer was formed with the radiation shielding ink obtained above.

Example 3
Example 2 is the same as Example 2 except that the three films obtained above were placed on the combustion core of oil lanthanum as a radiation source and the radiation dose was measured with a GM survey meter manufactured by Hitachi Aloca from the film side. As well as. The reading of the measured value was held for 1 minute or longer and was read after the measuring needle became difficult to move.

  The measured radiation dose was 2,600 cpm. When the space was measured as it was without placing the film obtained above, it was 4,400 cpm. The radiation dose of three polyethylene terephthalate films (corona-treated surface, thickness 188 μm) not coated with radiation shielding ink was measured on the oil lanthanum combustion core and found to be 4,100 cpm. The radiation shielding effect of about 41% was obtained by stacking three films (about 15 μm in total coating layer thickness) in which a coating layer was formed with the radiation shielding ink obtained above.

Comparative Example 1
(Production of hydrolysis mixture)
13.6 g of ethanol, 3.0 g of trimethoxysilyl trimethylene acrylate (KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.) as the organosilicon compound having a (meth) acryl group, and diphenyldimethoxysilane (Tokyo Chemical Industry ( 11.0 g), and the mixture was stirred and mixed while slowly mixing ethanol 4.3 g / water 0.9 g / 2N-HCl 0.16 g 2N-HCl / ethanol mixed aqueous solution at room temperature. It was dripped. Furthermore, an ethanol aqueous solution of 1.0 g of ethanol / 0.5 g of water was gradually added dropwise and stirred at room temperature for 1 hour to obtain a hydrolyzate of an organosilicon compound having a (meth) acryl group and a hydrolyzate of an organosilicon compound. A hydrolysis mixture containing was obtained.

(Manufacture of radiation shielding ink)
After mixing the same type, the same amount of the polymerizable monomer (B), the photopolymerization initiator (C), and the polymerization inhibitor as used in Example 1, the same amount of the mixture (2.0 g) After adding 8.5 g of the hydrolysis mixture, the mixture was stirred and mixed at room temperature for 15 minutes to obtain a radiation shielding ink. The obtained radiation shielding ink was filtered through a syringe filter having a 0.2 μmφ hole diameter. The blending ratio of this radiation shielding ink is shown in Table 1.
The obtained radiation shielding ink was used to evaluate the substrate adhesion and transparency of the cured film. The results are shown in Table 2.

  The obtained radiation shielding ink was coated on a polyethylene terephthalate film (corona-treated surface, thickness 188 μm) using a baker type applicator, dried at 110 ° C. for 2 minutes, and then irradiated with UV light at 365 nm under nitrogen flow. Thus, a film on which a radiation shielding coating layer made of radiation shielding ink having a thickness of about 5 μm was formed was obtained.

  Four films obtained as described above were placed on the radiation source of the spot detector, and the radiation dose was measured from the film side with a GM survey meter manufactured by Hitachi Aloca. The reading of the measured value was held for 1 minute or longer and was read after the measuring needle became difficult to move.

  The measured radiation dose was 1,300 cpm. When the space was measured as it was without placing the film obtained above, it was 1,350 cpm. Further, when the radiation dose of four polyethylene terephthalate films (corona-treated surface, thickness: 188 μm) not coated with radiation shielding ink was measured on the radiation source of the above-mentioned squeak detector, it was 1300 cpm. The polyethylene terephthalate film in which the coating layer was formed with the radiation shielding ink obtained above had the same radiation shielding effect as the polyethylene terephthalate film without the coating layer.

Comparative Example 2
(Production of hydrolysis mixture)
6.9 g of ethanol, 7.5 g of trimethoxysilyl trimethylene acrylate (KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.) as an organosilicon compound having a (meth) acryl group, 0.4 g of tungsten powder having an average particle size of 1.5 μm While mixing this mixture with stirring, a 2.2N ethanol / water 0.8g / 2N-HCl 0.07 g 2N-HCl / ethanol mixed aqueous solution was gradually added dropwise at room temperature. Further, an ethanol aqueous solution of 0.5 g of ethanol / 0.5 g of water was gradually added dropwise and stirred at room temperature for 1 hour, and a hydrolyzate mixture containing a hydrolyzate of an organosilicon compound having a (meth) acryl group and tungsten powder ( A) was obtained.

(Manufacture of radiation shielding ink)
After mixing the same type, the same amount of the polymerizable monomer (B), the photopolymerization initiator (C), and the polymerization inhibitor as used in Example 1, the same amount of the mixture (2.0 g) After adding 8.6 g of the hydrolysis mixture, the mixture was stirred and mixed at room temperature for 15 minutes to obtain a radiation shielding ink. The blending ratio of this radiation shielding ink is shown in Table 1.

The obtained radiation shielding ink was used to evaluate the substrate adhesion and transparency of the cured film. The results are shown in Table 2. The dispersibility of the tungsten powder was poor, and a lot of streaks were generated in the coating layer.
The radiation shielding ink was coated on a polyethylene terephthalate film (corona-treated surface, thickness 188 μm) using a baker type applicator, dried at 110 ° C. for 2 minutes, and then irradiated with UV light at 365 nm under a nitrogen stream. A film having a radiation shielding coating layer made of radiation shielding ink having a thickness of about 5 μm was obtained. The obtained film had poor dispersibility of the tungsten powder, and a uniform coat layer could not be formed.

  Four films obtained as described above were placed on the radiation source of the spot detector, and the radiation dose was measured from the film side with a GM survey meter manufactured by Hitachi Aloca. The reading of the measured value was held for 1 minute or longer and was read after the measuring needle became difficult to move.

  The measured radiation dose was 1,250 cpm. When the space was measured as it was without placing the film obtained above, it was 1,350 cpm. Further, when the radiation dose of four uncoated polyethylene terephthalate films (corona-treated surface, thickness: 188 μm) was measured on the radiation source of the above-mentioned peeling detector, it was 1,300 cpm. A four-layered film (about 20 μm in total coating layer thickness) in which a coating layer was formed with the radiation shielding ink obtained above had a radiation shielding effect of about 7%.

Claims (6)

(A) The following formula (1)

(Where
R ¹ is a hydrogen atom or a methyl group,
R ² is an alkylene group having 1 to 20 carbon atoms or a cycloalkylene group having 3 to 10 carbon atoms,
R ³ is an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 4 carbon atoms, or an aryl group having 6 to 12 carbon atoms,
R ⁴ is an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 3 to 4 carbon atoms,
l is an integer of 1 to 3, m is an integer of 0 to 2, k is an integer of 1 to 3,
l + m + k is 4,
R ^{1, R} 2, ^{R 3} and ^{R 4} respectively, when there are a plurality, the plurality of ^{R 1,} R 2, ^{R 3} and ^{R 4,} respectively, may be the same or different groups) A hydrolyzate of an organosilicon compound having the (meth) acrylic group shown,
And the following formula (2)

(Where
M is tungsten, zirconium, titanium, molybdenum, indium, or hafnium;
R ⁵ is an alkyl group having 1 to 10 carbon atoms, and may be the same group or different groups,
When M is tungsten, p is 6 or 5;
When M is molybdenum, p is 5,
When M is zirconium, titanium or hafnium, p is 4,
When M is indium, p is 3. )
A hydrolysis mixture comprising a hydrolyzate of a metal alkoxide represented by
(B) A radiation shielding ink containing a polymerizable monomer having a (meth) acryl group and (C) a photopolymerization initiator. For 100 parts by mass of the polymerizable monomer (B),
Hydrolysis mixture (A) obtained by hydrolyzing a mixture containing 3 to 300 parts by mass of the organosilicon compound having the (meth) acrylic group and 0.1 to 150 parts by mass of the metal alkoxide, and the initiation of photopolymerization The radiation shielding ink according to claim 1, comprising 0.1 to 10 parts by mass of the agent (C). The hydrolysis mixture (A) is represented by the following formula (3)

(Where
R ⁶ and R ⁷ are the same or different alkyl group having 1 to 4 carbon atoms or hydrogen,
R ⁸ and R ⁹ are an aryl group or an alkoxy group having 1 to 4 carbon atoms, and n is an integer of 1 to 10. )
The radiation shielding ink according to claim 1, further comprising a hydrolyzate of an organosilicon compound represented by the formula: For 100 parts by mass of the polymerizable monomer (B),
Hydrolysis obtained by hydrolyzing a mixture containing 3 to 300 parts by mass of the organosilicon compound having the (meth) acryl group, 0.1 to 150 parts by mass of the metal alkoxide, and 10 to 400 parts by mass of the organosilicon compound. The radiation shielding ink according to claim 3, comprising 0.1 to 10 parts by mass of the mixture (A) and the photopolymerization initiator (C).   The metal alkoxide is contained in an amount of 0.2 to 50 parts by mass with respect to a total of 100 parts by mass of the organosilicon compound and the organosilicon compound having the (meth) acryl group. Radiation shielding ink.   A film or sheet having a radiation shielding coating layer comprising a cured body of the radiation shielding ink according to claim 1.