WO2015178248A1 - 親水性単層膜 - Google Patents
親水性単層膜 Download PDFInfo
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- WO2015178248A1 WO2015178248A1 PCT/JP2015/063615 JP2015063615W WO2015178248A1 WO 2015178248 A1 WO2015178248 A1 WO 2015178248A1 JP 2015063615 W JP2015063615 W JP 2015063615W WO 2015178248 A1 WO2015178248 A1 WO 2015178248A1
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- AVFZOVWCLRSYKC-UHFFFAOYSA-N CN1CCCC1 Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 description 1
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
- C08F12/30—Sulfur
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
- C08F212/30—Sulfur
Definitions
- the present invention relates to a hydrophilic single layer film.
- the crosslinkable polymerizable monomer composition is applied to the surface of the base material to form an incompletely polymerized crosslinked polymer by controlling the amount of UV irradiation, and then the hydrophilic monomer is applied and irradiated again with UV rays.
- a hydrophilic material that blocks or graft-polymerizes the polymer on the surface of a crosslinked polymer (Patent Documents 1 and 2).
- the above-described method of blocking or graft polymerizing a hydrophilic monomer on the surface of a base material has a problem that durability is low and it cannot withstand long-term use because a hydrophilic group exists only on the surface.
- Patent Document 3 Previously proposed (Patent Document 3 and Patent Document 4).
- the present invention relates to a single layer film excellent in hydrophilicity and transparency made of a crosslinked resin having a hydrophilic group segregated on the surface, and a material having the single layer film excellent in hydrophilicity, antifogging property, antifouling property, etc.
- the issue is to provide.
- the present inventors have determined that the compound (I) having an anionic hydrophilic group and a functional group having a polymerizable carbon-carbon double bond, and three or more hydroxyl groups By polymerizing a composition containing the compound (II) having two or more, preferably three or more, functional groups having a polymerizable carbon-carbon double bond, hydrophilic groups are segregated on the surface.
- the inventors have found that a hydrophilic single layer film having high transparency can be obtained, and have completed the present invention.
- the present invention relates to a compound (I) having an anionic hydrophilic group and at least one functional group having a polymerizable carbon-carbon double bond, three or more hydroxyl groups, and a polymerizable carbon-carbon double Compound (II) having two or more, preferably three or more functional groups having a bond (however, it does not have an anionic hydrophilic group)
- a monolayer film made of a cross-linked resin obtained by polymerizing a composition comprising: the surface concentration (Sa) of the anionic hydrophilic group of the monolayer film and the hydrophilicity at a half point of the monolayer film thickness It is a single layer film in which the gradient (Sa / Da) of the base depth concentration (Da) is 1.1 or more.
- the compound (I) is preferably a compound represented by the general formula (100) described later.
- a in the general formula (100) is preferably a functional group having at least one polymerizable carbon-carbon double bond selected from general formulas (121) to (125) described later.
- the laminate of the present invention is characterized by having at least one single-layer film.
- a single layer film made of a crosslinked resin having a hydrophilic group segregated on the surface is obtained.
- the single layer film is excellent in hydrophilicity and transparency, and is antifogging and antifouling. It can be used as an excellent material.
- FIG. 1 is a schematic diagram showing a sample preparation method for measuring the gradient of anion concentration (Sa / Da) in Examples.
- the composition used for the production of the monolayer film of the present invention is characterized by containing the following compound (I) and compound (II).
- Compound (I) The compound (I) has an anionic hydrophilic group and a functional group having a polymerizable carbon-carbon double bond. By polymerizing a composition containing such a compound having an anionic hydrophilic group and a functional group having a carbon-carbon double bond, hydrophilicity can be imparted to the resulting monolayer film made of a crosslinkable resin. .
- anionic hydrophilic group examples include a sulfonic acid group, a carboxyl group, a phosphoric acid group, an O-sulfuric acid group (—O—SO 3 ⁇ ), and an N-sulfuric acid group (—NH—SO 3 ⁇ ). It is done.
- anionic hydrophilic groups a sulfonic acid group, a carboxyl group, and a phosphoric acid group are preferable, and a sulfonic acid group is more preferable.
- Compound (I) has at least one anionic hydrophilic group.
- the anionic hydrophilic group may be in the form of an acid in which a hydrogen ion is bonded to the anion, or may be in the form of a salt in which a counter cation other than a hydrogen ion is bonded to the anion.
- the sulfonic acid group is represented by the following formula ( ⁇ )
- the carboxyl group is represented by the following formula ( ⁇ )
- the phosphoric acid group is represented by the following formula ( ⁇ 1) or ( ⁇ 2)
- the O-sulfuric acid group is represented by the following formula ( ⁇ ) and N-sulfate groups may be contained in the compound (I) in the form of the following formula ( ⁇ ).
- Z is at least one monovalent cation selected from a hydrogen ion, an ammonium ion, an alkali metal ion, and a 1/2 atom alkaline earth metal.
- the ammonium ion in the present invention is a cation formed by bonding a hydrogen ion to ammonia, a primary amine, a secondary amine, or a tertiary amine.
- the ammonium ion is preferably a cation in which hydrogen ions are bonded to ammonia and an amine having a small number of carbon atoms, more preferably an ammonium ion formed by bonding hydrogen ions to ammonia, or methylammonium.
- alkali metal examples include lithium, sodium, potassium, rubidium, and the like.
- alkaline earth metal examples include beryllium, magnesium, calcium, strontium, and barium.
- the salt form (form in which a counter cation other than hydrogen ions is bonded) tends to be more hydrophilic and tends to be more preferable.
- Z is preferably an ammonium ion, an alkali metal ion, or a 1/2 atom alkaline earth metal ion. Metal ions are more preferable, and sodium ions, potassium ions, and rubidium ions are more preferable.
- Compound (I) further has at least one functional group having a polymerizable carbon-carbon double bond.
- the functional group having a polymerizable carbon-carbon double bond is not particularly limited as long as the functional group can be radically polymerized or ionically polymerized.
- acryloyl group methacryloyl group, allyl group, methallyl group, vinyl Group, isopropenyl group, maleyl group (—CO—CH ⁇ CH—CO—), itaconyl group (—CO—CH ⁇ CH—CO—), styryl group, ⁇ -methyl-styryl group and groups containing these groups Is mentioned.
- Examples of the acryloyl group include acryloyloxy group, acryloylthio group, and acrylamide group.
- Examples of the methacryloyl group include a methacryloyloxy group, a methacryloylthio group, and a methacrylamide group.
- acryloyl and methacryloyl are collectively referred to as (meth) acryloyl
- acryloyloxy and methacryloyloxy are collectively referred to as (meth) acryloyloxy
- acryloylthio and methacryloylthio are collectively referred to as (meth) acryloylthio
- acrylamide and methacryl Amides are sometimes collectively referred to as (meth) acrylamide
- allyl groups and methallyl groups are sometimes collectively referred to as (meth) allyl groups.
- the compound represented by the following general formula (100) is preferable.
- A represents an organic group having 2 to 100 carbon atoms having 1 to 5 functional groups having a polymerizable carbon-carbon double bond
- CD represents the following general formulas (101) to (106 ) Represents a group containing at least one hydrophilic group selected from the group represented by: n 12 represents the number of A bonded to CD, represents 1 or 2, and n 15 represents the number of CD bonded to A. Yes, represents an integer of 1 to 5.
- the functional group having a polymerizable carbon-carbon double bond means the group described above.
- M represents a hydrogen atom, an alkali metal, a 1/2 atom alkaline earth metal, or an ammonium ion
- # 1 is a bond bonded to the carbon atom contained in A of the formula (100). Represents.
- M represents a hydrogen atom, an alkali metal, a 1/2 atom alkaline earth metal, or an ammonium ion
- # 1 is a bond bonded to the carbon atom contained in A of the formula (100). Represents.
- M represents a hydrogen atom, an alkali metal, a 1/2 atom alkaline earth metal, or an ammonium ion
- # 1 is a bond bonded to the carbon atom contained in A of the formula (100). Represents.
- M represents a hydrogen atom, an alkali metal, a 1/2 atom alkaline earth metal, an ammonium ion, and an amine ion, and # 1 is bonded to the carbon atom contained in A of the formula (100). Represents a joint hand.
- r 5 and r 6 independently represent a hydrogen atom, a methyl group, an ethyl group, or a hydroxyl group
- n 05 represents an integer of 0 to 5
- X represents —O—
- M represents a hydrogen atom, an alkali metal, a 1/2 atom alkaline earth metal, or an ammonium ion
- # 1 is included in A of formula (100) Represents a bond bonded to a carbon atom.
- X represents —O—, —S—, —NH—, or —NCH 3 —
- M represents a hydrogen atom, an alkali metal, a 1/2 atom alkaline earth metal, or ammonium.
- # 1 represents a bond bonded to the carbon atom contained in A of Formula (100).
- groups represented by the general formulas (101) to (106) are preferable, and groups represented by the general formula (101) are more preferable.
- a in the general formula (100) is preferably a functional group having at least one polymerizable carbon-carbon double bond selected from the following general formulas (121) to (125).
- r represents a hydrogen atom or a methyl group
- r 1 and r 2 independently represent a hydrogen atom, a methyl group, an ethyl group, or a hydroxyl group
- n 010 is an integer of 0 to 10
- # 2 represents a bond bonded to # 1 contained in at least one group selected from the groups represented by the general formulas (101) to (106).
- r represents a hydrogen atom or a methyl group
- r 1 and r 2 independently represent a hydrogen atom, a methyl group, an ethyl group, or a hydroxyl group
- n 010 is an integer of 0 to 10
- N 05 represents an integer of 0 to 5
- n 15 represents an integer of 1 to 5
- # 2 represents at least one group selected from the groups represented by the above general formulas (101) to (106) Represents a bond to be bonded to # 1 included in.
- r 1 and r 2 independently represent a hydrogen atom, a methyl group, an ethyl group, or a hydroxyl group
- # 2 represents a group represented by the above general formulas (101) to (106) Represents a bond bonded to # 1 contained in at least one group selected from
- r 1 represents a hydrogen atom, a methyl group, an ethyl group, or a hydroxyl group
- # 2 is at least one group selected from the groups represented by the above general formulas (101) to (106) Represents a bond to be bonded to # 1 included in.
- X represents —O—, —S—, —NH—, or —NCH 3 —
- r and r0 independently represent a hydrogen atom or a methyl group
- r 5 and r 6 independently represents a hydrogen atom, a methyl group, an ethyl group, or a hydroxyl group
- R 10 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or a phenyl group.
- n 01 represents 0 or 1
- n 010 represents an integer of 1 to 10.
- # 2 represents a bond bonded to # 1 contained in at least one group selected from the groups represented by the above general formulas (101) to (106).
- compound (I) having an anionic hydrophilic group compounds represented by the following general formulas (Ia) to (Ib) and (Ih) to (Ij) are more preferable.
- r represents a hydrogen atom or a methyl group
- r 1 and r 2 independently represent a hydrogen atom, a methyl group, an ethyl group, or a hydroxyl group
- m1 represents an integer of 0 to 10
- N1 represents an integer of 1 to 10.
- M represents a hydrogen ion, an ammonium ion, an alkali metal ion, or a 1 ⁇ 2 atom alkaline earth metal ion.
- an ammonium ion, an alkali metal ion, or 1 ⁇ 2 Atomic alkaline earth metal ions are preferred, and alkali metal ions are more preferred.
- Examples of the compound represented by the general formula (Ia) include vinyl sulfonic acid, lithium vinyl sulfonate, sodium vinyl sulfonate, potassium vinyl sulfonate, rubidium vinyl sulfonate, ammonium vinyl sulfonate, magnesium vinyl sulfonate, Calcium vinyl sulfonate, isopropenyl sulfonate, lithium isopropenyl sulfonate, sodium isopropenyl sulfonate, potassium isopropenyl sulfonate, rubidium isopropenyl sulfonate, ammonium isopropenyl sulfonate, magnesium isopropenyl sulfonate, isopropenyl sulfonate Calcium, (meth) allyl sulfonic acid, lithium (meth) allyl sulfonate, sodium (meth) allyl sulfonate, (meth) ally
- r represents a hydrogen atom or a methyl group
- r 1 and r 2 independently represent a hydrogen atom, a methyl group, an ethyl group, or a hydroxyl group
- m1 represents an integer of 0 to 10
- m2 represents an integer of 0 to 5
- n0 represents an integer of 1 to 5
- n1 represents an integer of 1 to 10.
- M represents a hydrogen ion, an ammonium ion, an alkali metal ion, or a 1/2 atom alkaline earth metal ion.
- an ammonium ion, an alkali metal ion, or 1/2 Atomic alkaline earth metal ions are preferred, and alkali metal ions are more preferred.
- Examples of the compound represented by the general formula (Ib) include styrene sulfonic acid, lithium styrene sulfonate, sodium styrene sulfonate, potassium styrene sulfonate, rubidium styrene sulfonate, ammonium styrene sulfonate, magnesium styrene sulfonate, Calcium styrenesulfonate, ⁇ -methyl-styrenesulfonate, lithium ⁇ -methyl-styrenesulfonate, sodium ⁇ -methyl-styrenesulfonate, ⁇ -methyl-potassium styrenesulfonate, rubidium ⁇ -methyl-styrenesulfonate, ⁇ -Ammonium methyl styrene sulfonate, magnesium ⁇ -methyl styrene sulfonate, calcium ⁇
- M 1 and M 2 independently represent a hydrogen ion, an ammonium ion, an alkali metal ion, or a 1 ⁇ 2 atom alkaline earth metal ion.
- an ammonium ion, Alkali metal ions or 1 ⁇ 2 atom alkaline earth metal ions are preferred, and alkali metal ions are more preferred.
- Examples of the compound represented by the general formula (Ih) include maleic acid, lithium maleate, dilithium maleate, sodium maleate, disodium maleate, potassium maleate, dipotassium maleate, ammonium maleate, and maleic acid. Examples thereof include diammonium, macnesium maleate, and calcium maleate.
- M 1 and M 2 independently represent a hydrogen ion, an ammonium ion, an alkali metal ion, or a 1 ⁇ 2 atom alkaline earth metal ion.
- an ammonium ion, Alkali metal ions or 1 ⁇ 2 atom alkaline earth metal ions are preferred, and alkali metal ions are more preferred.
- Examples of the compound represented by the general formula (Ii) include itaconic acid, lithium itaconate, dilithium itaconate, sodium itaconate, disodium itaconate, potassium itaconate, dipotassium itaconate, ammonium itaconate, and itaconic acid. Examples thereof include diammonium, macnesium itaconate, and calcium itaconate.
- r independently represents a hydrogen atom or a methyl group
- R 10 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or a phenyl group. , Benzyl group, hydroxyl group, hydroxymethyl or hydroxyethyl.
- M represents a hydrogen ion, an ammonium ion, an alkali metal ion, or a 1 ⁇ 2 atom alkaline earth metal ion.
- an ammonium ion, an alkali metal ion, or 1 ⁇ 2 Atomic alkaline earth metal ions are preferred, and alkali metal ions are more preferred.
- Examples of the compound represented by the general formula (Ij) include 2,2-bis ⁇ (meth) acryloyloxyethyl ⁇ acetic acid, 2,2-bis ⁇ (meth) acryloyloxyethyl ⁇ acetic acid sodium salt, 2, 2-bis ⁇ (meth) acryloyloxyethyl ⁇ acetic acid potassium salt, 2,2-bis ⁇ (meth) acryloyloxyethyl ⁇ acetic acid rubidium salt, 2,2-bis ⁇ (meth) acryloyloxyethyl ⁇ acetic acid ammonium salt, 2 , 2-bis ⁇ (meth) acryloyloxyethyl ⁇ acetic acid calcium salt, 2,2-bis ⁇ (meth) acryloyloxyethyl ⁇ acetic acid magnesium salt, 2,2-bis ⁇ (meth) acryloyloxyethyl ⁇ propionic acid, 2,2-bis ⁇ (meth) acryloyloxyethyl ⁇ propi
- the molecular weight of the compound (I) is usually 72 to 18,000, preferably 72 to 3,000, more preferably 72 to 1,000.
- the said compound (I) may be used individually by 1 type, and may be used in mixture of 2 or more types.
- the said compound (I) is contained in the composition used in order to manufacture a single layer film
- the term “oligomer” as used herein means one containing usually 2 to 20 repeating units formed from the compound (I).
- the above-mentioned compound (I) can be produced by a known method or a method according to a known method. Moreover, the said compound (I) can also be obtained as a commercial item.
- the compound (II) has three or more hydroxyl groups and two or more functional groups having a polymerizable carbon-carbon double bond, preferably three or more. However, compound (II) does not have an anionic hydrophilic group and is different from compound (I). By polymerizing a composition containing such a compound, a single layer film made of a sufficiently crosslinked crosslinked resin can be obtained.
- the functional group having a polymerizable carbon-carbon double bond include the groups exemplified as the functional group having a polymerizable carbon-carbon double bond contained in the compound (I).
- the functional group having a polymerizable carbon-carbon double bond is preferably a (meth) acryloyl group, a vinyl group, a (meth) allyl group, a styryl group or an isopropenyl group, and a (meth) acryloyl group or a (meth) allyl group. More preferred is a styryl group, and more preferred is a (meth) acryloyl group.
- Examples of the (meth) acryloyl group include a (meth) acryloyloxy group, a (meth) acryloylthio group, and a (meth) acrylamide group as described in the section of the compound (I). Among these, (Meth) acryloyloxy groups and (meth) acryloylthio groups are preferred.
- the compound (II) is preferably a compound represented by the following general formula (200).
- Mc represents at least one group selected from the groups represented by the following general formulas (201) to (209), and the main skeleton of the compound (II) represented by the formula (200) It is a part.
- X represents —O—, —S—, —NH—, or —NCH 3 —
- r represents a hydrogen atom or a methyl group
- r 1 to r 4 are each independently A hydrogen atom, a methyl group, an ethyl group, or a hydroxyl group
- m 010 represents an integer of 0 to 10
- n 030 represents an integer of 0 to 30, and
- n 220 represents an integer of 2 to 20, preferably 3 to 20 Represents an integer.
- m 110 represents an integer of 1 to 10
- N 110 represents an integer of 1 to 10
- # 3 represents a hydrogen atom or a carbon atom contained in the group represented by formula (200).
- R 5 and R 6 independently represent a hydrogen atom, a hydroxyl group, —O— # 3, —CH 2 OH, —CH 2 O— # 3, or alkyl having 1 to 4 carbon atoms.
- R 5 and R 6 may be the same or different.
- # 3 may be the same or different.
- # 3 which is the same number as n 220 in the formula (200)
- R 5 represents —O— # 3 or —CH 2 O— # 3
- R 6 represents a hydrogen atom, a hydroxyl group, —O— # 3, —CH 2 OH, —CH 2 It preferably represents O- # 3 or an alkyl group having 1 to 4 carbon atoms.
- m 110 represents an integer of 1 to 10
- N 110 represents an integer of 1 to 10
- # 3 represents a hydrogen atom or a carbon atom contained in the group represented by the formula (200).
- R 5 and R 6 independently represent a hydrogen atom, a hydroxyl group, —O— # 3, —CH 2 OH, —CH 2 O— # 3, or alkyl having 1 to 4 carbon atoms.
- R 5 and R 6 may be the same or different.
- # 3 may be the same or different.
- # 3 which is the same number as n 220 in the formula (200)
- R 5 represents —O— # 3 or —CH 2 O— # 3
- R 6 represents a hydrogen atom, a hydroxyl group, —O— # 3, —CH 2 OH, —CH 2 It preferably represents O- # 3 or an alkyl group having 1 to 4 carbon atoms.
- m 110 represents an integer of 1 to 10
- # 3 represents a hydrogen atom or a bond bonded to a carbon atom contained in the group represented by formula (200)
- R 5 and R 5 6 independently represents a hydrogen atom, a hydroxyl group, —O— # 3, —CH 2 OH, —CH 2 O— # 3, or an alkyl group having 1 to 4 carbon atoms
- m 110 is 2 or more.
- R 5 and R 6 may be the same or different, and when m 110 is 2 or more, # 3 may be the same or different.
- # 3, which is the same number as n 220 in the formula (200) is a bond bonded to the carbon atom contained in the group represented by the formula (200).
- R 5 represents —O— # 3 or —CH 2 O— # 3
- R 6 represents a hydrogen atom, a hydroxyl group, —O— # 3, —CH 2 OH, —CH 2 It preferably represents O- # 3 or an alkyl group having 1 to 4 carbon atoms.
- n 03 represents an integer of 0 to 3
- n 05 represents an integer of 0 to 5
- # 3 represents a hydrogen atom or a carbon atom contained in the group represented by formula (200).
- X 3 and X 4 independently represent —CH 2 —, —CH (OH) —, —CH (—O— # 3) —, or —CO—, and n 03 Is 2 or more, X 3 may be the same or different, and when n 05 is 2 or more, X 4 may be the same or different, and the cycloalkyl ether ring in the above formula (204) Some of the carbon-carbon bonds included may be carbon-carbon double bonds. However, # 3, which is the same number as n 220 in the formula (200), is a bond bonded to the carbon atom contained in the group represented by the formula (200).
- # 3 represents a hydrogen atom or a bond bonded to a carbon atom contained in the group represented by the formula (200).
- # 3 which is the same number as n 220 in the formula (200), is a bond bonded to the carbon atom contained in the group represented by the formula (200).
- # 3 represents a hydrogen atom or a bond bonded to a carbon atom contained in the group represented by the formula (200).
- # 3 which is the same number as n 220 in the formula (200), is a bond bonded to the carbon atom contained in the group represented by the formula (200).
- # 3 represents a hydrogen atom or a bond bonded to a carbon atom contained in the group represented by the formula (200).
- # 3 which is the same number as n 220 in the formula (200), is a bond bonded to the carbon atom contained in the group represented by the formula (200).
- # 3 represents a bond bonded to a hydrogen atom or a carbon atom contained in the group represented by the formula (200).
- # 3 which is the same number as n 220 in the formula (200), is a bond bonded to the carbon atom contained in the group represented by the formula (200).
- R 10 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a benzyl group, a hydroxyl group, a hydroxymethyl group, or a hydroxyethyl group.
- # 3 represents a bond bonded to a hydrogen atom or a carbon atom contained in the group represented by the formula (200).
- # 3 which is the same number as n 220 in the formula (200), is a bond bonded to the carbon atom contained in the group represented by the formula (200).
- R 1 , R 2 , and R 3 independently represent a hydrogen atom or a methyl group.
- m 010 represents an integer of 0 to 10
- n 110 represents an integer of 1 to 10
- m 010 is preferably an integer of 0 to 6, more preferably an integer of 0 to 4.
- n 110 is preferably an integer of 1 to 6, and more preferably an integer of 1 to 4.
- N 12 represents 1 or 2, and N 12 is preferably 1.
- R 1, R 2, and R 3 represents a hydrogen atom or a methyl group independently.
- m 010 represents an integer of 0 to 10
- n 110 represents an integer of 1 to 10
- m 010 is preferably an integer of 0 to 6, more preferably an integer of 0 to 4.
- n 110 is preferably an integer of 1 to 6, and more preferably an integer of 1 to 4.
- N 12 represents 1 or 2, and N 12 is preferably 1.
- Examples of the compound represented by the general formula (IIc) include glyceric acid-di ⁇ 3- (meth) acryloyloxy-2-hydroxypropyl ⁇ ether- ⁇ 3- (meth) acryloyloxy-2-hydroxypropyl ⁇ ester, Threonic acid-di ⁇ 3- (meth) acryloyloxy-2-hydroxypropyl ⁇ ether- ⁇ 3- (meth) acryloyloxy-2-hydroxypropyl ⁇ ester, threonic acid-tri ⁇ 3- (meth) acryloyloxy-2 -Hydroxypropyl ⁇ ether- ⁇ 3- (meth) acryloyloxy-2-hydroxypropyl ⁇ ester, Gluconic acid-di ⁇ 3- (meth) acryloyloxy-2-hydroxypropyl ⁇ ether- ⁇ 3- (meth) acryloyloxy-2-hydroxypropyl ⁇ ester, Gluconic acid-di ⁇ 3- (
- n 010 is preferably an integer of 1 to 6, and more preferably an integer of 1 to 4.
- m 09 is preferably an integer of 0 to 6, more preferably an integer of 0 to 4.
- m 010 is preferably an integer of 0 to 6, more preferably an integer of 0 to 4.
- n 110 is preferably an integer of 1 to 6, and more preferably an integer of 1 to 4.
- N 12 represents 1 or 2, and N 12 is preferably 1.
- R 1 , R 2 , R 3 , and R 4 independently represent a hydrogen atom or a methyl group, but when m 09 is 2 or more, R 4 is the same or different. May be.
- Examples of the compound represented by the general formula (IId) include malic acid-mono ⁇ 3- (meth) acryloyloxy-2-hydroxypropyl ⁇ ether-di ⁇ 3- (meth) acryloyloxy-2-hydroxypropyl ⁇ ester, Tartaric acid-mono ⁇ 3- (meth) acryloyloxy-2-hydroxypropyl ⁇ ether-di ⁇ 3- (meth) acryloyloxy-2-hydroxypropyl ⁇ ester, tartaric acid-di ⁇ 3- (meth) acryloyloxy-2- Hydroxypropyl ⁇ ether-di ⁇ 3- (meth) acryloyloxy-2-hydroxypropyl ⁇ ester, Tetrahydroxyadipic acid-mono ⁇ 3- (meth) acryloyloxy-2-hydroxypropyl ⁇ ether-di ⁇ 3- (meth) acryloyloxy-2-hydroxypropyl ⁇ ester, tetrahydroxyadip
- R 1 represents a hydrogen atom or a methyl group
- # 3 and # 4 represent a bond
- # 3 and # 4 are bonded.
- m 13 represents an integer of 1 to 3
- m 28 represents an integer of 2 to 8, preferably an integer of 3 to 8
- m 06 represents an integer of 0 to 6
- m 28 + m 06 4
- m 13 is preferably an integer of 1 to 2, and more preferably 1.
- Examples of the compound represented by the general formula (IIe) include pentaerythritol-tri ⁇ 3- (meth) acryloyloxy-2-hydroxypropyl ⁇ ether, pentaerythritol-tetra ⁇ 3- (meth) acryloyloxy-2 -Hydroxypropyl ⁇ ether, Dipentaerythritol-tri ⁇ 3- (meth) acryloyloxy-2-hydroxypropyl ⁇ ether, dipentaerythritol-tetra ⁇ 3- (meth) acryloyloxy-2-hydroxypropyl ⁇ ether, dipentaerythritol-penta ⁇ 3- (Meth) acryloyloxy-2-hydroxypropyl ⁇ ether, dipentaerythritol-hexa ⁇ 3- (meth) acryloyloxy-2-hydroxypropyl ⁇ ether, Tripentaerythritol-tri ⁇ 3- (
- R 1 represents a hydrogen atom or a methyl group
- # 3 and # 4 represent a bond
- # 3 and # 4 are bonded.
- m 13 represents an integer of 1 ⁇ 3
- m 25 is 2 to 5, preferably an integer of 3 to 5
- m 03 represents an integer of 0 ⁇ 3
- m 13 is preferably an integer of 1 to 2, and more preferably 1.
- Examples of the compound represented by the general formula (IIf) include trimethylolpropane-tri ⁇ 3- (meth) acryloyloxy-2-hydroxypropyl ⁇ ether, Ditrimethylolpropane-tri ⁇ 3- (meth) acryloyloxy-2-hydroxypropyl ⁇ ether, ditrimethylolpropane-tetra ⁇ 3- (meth) acryloyloxy-2-hydroxypropyl ⁇ ether, Tritrimethylolpropane-tri ⁇ 3- (meth) acryloyloxy-2-hydroxypropyl ⁇ ether, tritrimethylolpropane-tetra ⁇ 3- (meth) acryloyloxy-2-hydroxypropyl ⁇ ether, tritrimethylolpropane-penta ⁇ 3- And (meth) acryloyloxy-2-hydroxypropyl ⁇ ether.
- R 1 represents a hydrogen atom or a methyl group
- # 3 and # 4 represent a bond
- # 3 and # 4 are bonded.
- X 3 and X 4 independently represent —CH 2 —, —CH (OH) —, —CH (—O-3 #) —, or —CO—, and n 13 When X is 2 or more, X 4 may be the same or different.
- m 26 represents an integer of 2 to 6, preferably an integer of 3 to 6
- m 04 represents an integer of 0 to 4
- n 01 represents an integer of 0 or 1
- a part of the carbon-carbon bond contained in the cycloalkyl ether ring in the above formula (IIg) may be a carbon-carbon double bond.
- Examples of the compound represented by the general formula (IIg) include ribose-tri ⁇ 3- (meth) acryloyloxy-2-hydroxypropyl ⁇ ether, ribose-tetra ⁇ 3- (meth) acryloyloxy-2-hydroxy Propyl ⁇ ether, Ascorbic acid-tri ⁇ 3- (meth) acryloyloxy-2-hydroxypropyl ⁇ ether, ascorbic acid-tetra ⁇ 3- (meth) acryloyloxy-2-hydroxypropyl ⁇ ether, Xylose-tri ⁇ 3- (meth) acryloyloxy-2-hydroxypropyl ⁇ ether, xylose-tetra ⁇ 3- (meth) acryloyloxy-2-hydroxypropyl ⁇ ether, Sorbitan-tri ⁇ 3
- R 1 represents a hydrogen atom or a methyl group
- # 3 and # 4 represent a bond
- # 3 and # 4 are bonded.
- m 28 represents an integer of 2 to 8, preferably an integer of 3 to 8
- Examples of the compound represented by the general formula (IIh) include sucrose (also known as sucrose) -tri ⁇ 3- (meth) acryloyloxy-2-hydroxypropyl ⁇ ether, sucrose-tetra ⁇ 3- (meta ) Acryloyloxy-2-hydroxypropyl ⁇ ether, sucrose-penta ⁇ 3- (meth) acryloyloxy-2-hydroxypropyl ⁇ ether, sucrose-hexa ⁇ 3- (meth) acryloyloxy-2-hydroxypropyl ⁇ ether Sucrose-hepta ⁇ 3- (meth) acryloyloxy-2-hydroxypropyl ⁇ ether, sucrose-octa ⁇ 3- (meth) acryloyloxy-2-hydroxypropyl ⁇ ether, and the like.
- R 1 represents a hydrogen atom or a methyl group
- # 3 and # 4 represent a bond
- # 3 and # 4 are bonded.
- m 28 represents an integer of 2 to 8, preferably an integer of 3 to 8
- Examples of the compound represented by the general formula (IIi) include palatinose-tri ⁇ 3- (meth) acryloyloxy-2-hydroxypropyl ⁇ ether, palatinose-tetra ⁇ 3- (meth) acryloyloxy-2-hydroxy Propyl ⁇ ether, palatinose-penta ⁇ 3- (meth) acryloyloxy-2-hydroxypropyl ⁇ ether, palatinose-hexa ⁇ 3- (meth) acryloyloxy-2-hydroxypropyl ⁇ ether, palatinose-hepta ⁇ 3- (meta ) Acryloyloxy-2-hydroxypropyl ⁇ ether, palatinose-octa ⁇ 3- (meth) acryloyloxy-2-hydroxypropyl ⁇ ether, and the like.
- R 1 represents a hydrogen atom or a methyl group
- # 3 and # 4 represent a bond
- # 3 and # 4 are bonded.
- m 28 represents an integer of 2 to 8, preferably an integer of 3 to 8
- Examples of the compound represented by the general formula (IIj) include lactose-tri ⁇ 3- (meth) acryloyloxy-2-hydroxypropyl ⁇ ether, lactose-tetra ⁇ 3- (meth) acryloyloxy-2-hydroxy Propyl ⁇ ether, lactose-penta ⁇ 3- (meth) acryloyloxy-2-hydroxypropyl ⁇ ether, lactose-hexa ⁇ 3- (meth) acryloyloxy-2-hydroxypropyl ⁇ ether, lactose-hepta ⁇ 3- (meta ) Acryloyloxy-2-hydroxypropyl ⁇ ether, lactose-octa ⁇ 3- (meth) acryloyloxy-2-hydroxypropyl ⁇ ether, Maltose-tri ⁇ 3- (meth) acryloyloxy-2-hydroxypropyl ⁇ ether, maltose-tetra ⁇ 3- (meth)
- R 1 represents a hydrogen atom or a methyl group
- # 3 and # 4 represent a bond
- # 3 and # 4 are bonded.
- m 24 represents an integer of 2 to 4, preferably an integer of 3 to 4
- m 02 represents an integer of 0 to 2, preferably 0 or 1
- m 24 + m 02 4 Satisfied.
- Examples of the compound represented by the general formula (IIk) include citric acid-tri ⁇ 3- (meth) acryloyloxy-2-hydroxypropyl ⁇ ester, citric acid-mono ⁇ 3- (meth) acryloyloxy-2 -Hydroxypropyl ⁇ ether-tri ⁇ 3- (meth) acryloyloxy-2-hydroxypropyl ⁇ ester and the like.
- R 10 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a benzyl group, a hydroxyl group, hydroxymethyl, or hydroxyethyl
- R 1 represents a hydrogen atom or a methyl group
- # 3 and # 4 represent a bond
- # 3 and # 4 are bonded.
- m 23 represents an integer of 2 to 3
- m 01 represents an integer of 0 or 1
- m 23 + m 01 3 is satisfied.
- m 23 and m 01 it is preferable that m 23 represents 3 and m 01 represents 0.
- Examples of the compound represented by the general formula (IIl) include dimethylolacetic acid-di ⁇ 3- (meth) acryloyloxy-2-hydroxypropyl ⁇ ether-mono ⁇ 3- (meth) acryloyloxy-2-hydroxypropyl ⁇ ester, Dimethylolpropionic acid-di ⁇ 3- (meth) acryloyloxy-2-hydroxypropyl ⁇ ether-mono ⁇ 3- (meth) acryloyloxy-2-hydroxypropyl ⁇ ester, And dimethylolbutyric acid-di ⁇ 3- (meth) acryloyloxy-2-hydroxypropyl ⁇ ether-mono ⁇ 3- (meth) acryloyloxy-2-hydroxypropyl ⁇ ester.
- the molecular weight of the compound (II) is usually 100 to 30,000, preferably 200 to 10,000, more preferably 300 to 5,000.
- the said compound (II) may be used individually by 1 type, and may be used in mixture of 2 or more types.
- the said compound (II) is contained in the composition used in order to manufacture a single layer film
- the term “oligomer” as used herein generally includes 2 to 20 repeating units formed from the compound (II).
- the compound (II) can be produced by a known method or a method according to a known method. Moreover, the said compound (II) can also be obtained as a commercial item.
- a conventional crosslinkable compound for example, a crosslinkable compound described in WO2007 / 064003 and WO2012 / 014829
- a highly polar cross-linked polymerizable compound (II) having a specific structure capable of enhancing solubility without inhibiting (gradientation). It has become possible to dramatically improve the transparency of the single-layer film made of the crosslinked resin while maintaining the hydrophilicity.
- the hydrophilic compound (I) in which it has been very difficult to achieve both hydrophilicity and high transparency with conventional techniques: compounds represented by the general formula (101) and the general formula (121), the general formula ( 101) and a compound represented by general formula (122), a compound represented by general formula (102) and general formula (121), a compound represented by general formula (102) and general formula (122), a general formula
- a high effect can be obtained.
- the compounds represented by the general formula (101) and the general formula (121) and the compounds represented by the general formula (101) and the general formula (122) a more remarkable effect is obtained. It came to be able to.
- composition used for producing the monolayer film in the present invention may contain other components other than the compound (I) and the compound (II) as necessary.
- silica particles (V) examples include silica particles (V).
- leveling properties can be improved and a matting effect (gloss control) can be imparted.
- the silica particles (V) are usually contained in the range of 0.00001 to 50% by weight, preferably in the range of 0.0001 to 30% by weight, more preferably in the range of 0.001 to 20% by weight. It is.
- other components include, for example, a polymerization initiator, a polymerization accelerator, an ultraviolet absorber, a hindered amine light stabilizer (HALS), a solvent, a catalyst, an infrared ray.
- Additives such as an absorbent, a radical scavenger, an internal mold release agent, an antioxidant, a polymerization inhibitor, a dye, a binder, a surfactant, a dispersant, and a leveling agent may be contained.
- the composition is polymerized.
- a photopolymerization initiator is added to the mixture.
- a thermal polymerization initiator is added.
- Examples of the photopolymerization initiator include a photoradical polymerization initiator, a photocationic polymerization initiator, and a photoanionic polymerization initiator. Among these photopolymerization initiators, a photoradical polymerization initiator is preferable.
- photo radical polymerization initiator examples include Irgacure 127 (manufactured by Ciba Specialty Chemicals), Irgacure 651 (manufactured by Ciba Specialty Chemicals), and Irgacure 184 (Ciba Specialty Chemicals).
- Darocur 1173 (manufactured by Ciba Specialty Chemicals), benzophenone, 4-phenylbenzophenone, Irgacure 500 (manufactured by Ciba Specialty Chemicals), Irgacure 2959 (manufactured by Ciba Specialty Chemicals) Irgacure 907 (Ciba Specialty Chemicals), Irgacure 369 (Ciba Specialty Chemicals), Irgacure 1300 (Ciba Specialty Chemicals) Irgacure 819 (manufactured by Ciba Specialty Chemicals), Irgacure 1800 (manufactured by Ciba Specialty Chemicals), Darocur TPO (manufactured by Ciba Specialty Chemicals), Darocur 4265 (Ciba Specialty Chemicals) Irgacure OXE01 (Ciba Specialty Chemicals), Irgacure OXE02
- Irgacure 127 (manufactured by Ciba Specialty Chemicals), Irgacure 184 (manufactured by Ciba Specialty Chemicals), Darocur 1173 (manufactured by Ciba Specialty Chemicals), Irga Cure 500 (manufactured by Ciba Specialty Chemicals), Irgacure 819 (manufactured by Ciba Specialty Chemicals), Darocur TPO (manufactured by Ciba Specialty Chemicals), Esacure ONE (manufactured by Lamberty), Esacure KIP100F (Lamberti), Esacure KT37 (Lamberti) and Esacure KTO46 (Lamberti) are preferred.
- photocationic polymerization initiator examples include Irgacure 250 (manufactured by Ciba Specialty Chemicals), Irgacure 784 (manufactured by Ciba Specialty Chemicals), Esacure 1064 (manufactured by Lamberti), CYRAURE® UVI6900. (Union Carbide Japan), Adeka optomer SP-172 (Asahi Denka), Adeka optomer SP-170 (Asahi Denka), Adeka optomer SP-152 (Asahi Denka), Adekaopt Mar SP-150 (manufactured by Asahi Denka Co., Ltd.).
- thermal polymerization initiator examples include ketone peroxides such as methyl isobutyl ketone peroxide and cyclohexanone peroxide; Diacyl peroxides such as isobutyryl peroxide, o-chlorobenzoyl peroxide, benzoyl peroxide; Dialkyl peroxides such as tris (t-butylperoxy) triazine, t-nutylcumyl peroxide; Peroxyketals such as 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane and 2,2-di (t-butylperoxy) butane; ⁇ -cumylperoxyneodecanoate, t-butylperoxypivalate, 2,4,4-trimethylpentylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, alkyl peresters such as t-
- the amount of the photopolymerization initiator and the thermal polymerization initiator used is preferably in the range of 0.1 to 20% by weight, more preferably 0.5 to 10% by weight with respect to the total of the compounds (I) and (II). %, More preferably in the range of 1 to 5% by weight.
- a photopolymerization accelerator When using the photopolymerization initiator, a photopolymerization accelerator may be used in combination.
- the photopolymerization accelerator include 2,2-bis (2-chlorophenyl) -4,5′-tetraphenyl-2′H- ⁇ 1,2 ′> biimidazolol, tris (4-dimethylaminophenyl) methane, Examples include 4,4′-bis (dimethylamino) benzophenone, 2-ethylanthraquinone, camphorquinone, and the like.
- the composition used for producing the monolayer film in the present invention It is desirable to make the composition of the weather-resistant formulation which added the ultraviolet absorber and the hindered amine light stabilizer to the thing further.
- the ultraviolet absorber is not particularly limited.
- a benzotriazole ultraviolet absorber a triazine ultraviolet absorber, a benzophenone ultraviolet absorber, a benzoate ultraviolet absorber, a propanedioic acid ester ultraviolet absorber, or an oxanilide type.
- Various ultraviolet absorbers such as an ultraviolet absorber can be used.
- Examples of the ultraviolet absorber include 2- (2H-benzotriazol-2-yl) -p-cresol, 2- (2H-benzotriazol-2-yl) -4-tert-butylphenol, 2- (2H- Benzotriazol-2-yl) -4,6-di-tert-butylphenol, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) -6- (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-2 -Yl) -4- (3-one-4-oxa-dodecyl) -6-tert-butyl-phenol, 2- ⁇ 5-chloro (2H) -benzotriazol-2-yl -4- (3-one-4-oxa-dodecyl
- HALS hindered amine light stabilizer
- HALS Hindered Amin Light Stabilizers
- the hindered amine light stabilizer for example, the trade name Tinuvin 111FDL (manufactured by Ciba Specialty Chemicals Co., Ltd.), bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate (product) Name Tinuvin 123 (manufactured by Ciba Specialty Chemicals Co., Ltd.), brand name Tinuvin 144 (manufactured by Chiba Specialty Chemicals Co., Ltd.), brand name Tinuvin 292 (manufactured by Ciba Specialty Chemicals Co., Ltd.), trade name Tinuvin 765 (manufactured by Ciba Specialty Chemicals Co., Ltd.), trade name Tinuvin 770 (manufactured by Ciba Specialty Chemicals Co., Ltd.), N, N′-bis (3-aminopropyl) ethylenediamine-2,4-bis [ N-butyl-N- (1,2,2,6,
- the addition amount of the ultraviolet absorber and the hindered amine light stabilizer is not particularly limited, but the ultraviolet absorber is usually 0.1 to 20% by weight, preferably with respect to the total of the compounds (I) and (II).
- the hindered amine light stabilizer is usually in the range of 0.1 to 10% by weight, preferably 0.5 to 5% by weight, more preferably 1 to 3% by weight.
- the addition amount of the ultraviolet absorber and the hindered amine light stabilizer is within the above range, the effect of improving the weather resistance of the monolayer film obtained from the composition used for producing the monolayer film in the present invention is increased. .
- the addition amount of the ultraviolet absorber or the hindered amine light stabilizer is less than the above range, the effect of improving the weather resistance of the obtained hydrophilic crosslinked resin, for example, a monolayer film tends to be small.
- the addition amount of the ultraviolet absorber or the hindered amine light stabilizer exceeds the above range, the polymerization of the composition may be insufficient.
- the composition used for producing the monolayer film of the present invention containing the compound (I) and the compound (II) may contain a solvent in consideration of workability at the time of producing the monolayer film.
- the solvent is not particularly limited as long as a crosslinked resin having a hydrophilic surface can be obtained, but reacts with or forms a salt with the component contained in the monomer composition used in the present invention.
- Solvents that are too strong to interact such as, or solvents that have a boiling point that is too high, for example, solvents that have a boiling point greater than 200 ° C. are not preferred.
- ethanolamine diethanolamine, triethanolamine, N-ethyl-ethanolamine, N- (2-ethylhexyl) ethanolamine, N-butyl-diethanolamine, N-hexyl-diethanolamine, N-lauryl-diethanolamine, N-cetyl- Ethanolamine compounds having a hydroxyethylamino structure such as diethanolamine [NRaRb (CH 2 CH 2 OH): Ra and Rb are independently hydrogen, an alkyl group having 1 to 15 carbon atoms, or a CH 2 CH 2 OH group. is there.
- a hydrophilic group contained in compound (I) for example, an anionic hydrophilic group typified by a sulfonic acid group, easily forms a salt or a form close to a salt, and is difficult to evaporate. Even if the solvent is removed from the liquid, it tends to remain inside because it is difficult to move to the surface in contact with the outside air. Therefore, the hydrophilic group contained in the compound (I) tends not to be inclined (concentrated) to the surface of the coated material in contact with the outside air. Therefore, the ethanolamine compound is not desirable as a solvent.
- an appropriate solvent can be used in consideration of the solubility of the compound (I) and the compound (II) except for the solvent as described above.
- the solvent more types of solvents can be used as compared with the solvent used in the conventional composition.
- a conventional composition WO2007 / 064003, WO2012 / 014829, etc.
- a low-polarity solvent when only a large amount is used, the hydrophilic compound (corresponding to the present compound (I)) or the cross-linkable polymerizable compound (corresponding to the present compound (II)) may be separated and a uniform solution (composition) may not be prepared.
- a non-uniform solution is applied to the substrate as it is, only a non-uniformly applied product (for example, a coating film) can be obtained.
- a non-uniformly applied product for example, a coating film
- the composition contains a specific compound (II) having three or more hydroxyl groups and two or more functional groups having a polymerizable carbon-carbon double bond.
- the solubility of the compound (I) in the medium was improved, and even a solvent having a relatively low polarity can be used, and the amount of the solvent used can be reduced.
- the solubility parameter (SP value) ⁇ (cal / cm 3 ) 1/2 of the solvent is preferably 8.4 (cal / cm 3 ) 1/2 or more, and 9.0 (cal / cm 3 ) 1/2.
- the above is more preferable, 9.3 (cal / cm 3 ) 1/2 or more is more preferable, and 9.5 (cal / cm 3 ) 1/2 or more is more preferable.
- Suitable solvents include, for example, methanol, ethanol, 1-propanol, isopropanol (IPA), 1-butanol, isobutanol, 1-pentanol (1-amyl alcohol), isopentanol, 2-pentanol, 3- Pentanol, cyclohexanol, 1-methoxy-2-propanol (methoxypropanol), 2-methoxy-1-propanol, 2-methoxy-1-ethanol (methoxyethanol), 2-isopropoxy-1-ethanol, acetonitrile, and Water etc. are mentioned.
- primary alcohols having an SP value of 9.0 (cal / cm 3 ) 1/2 or more such as methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol (1-amyl alcohol), etc.
- 1-methoxy-2-propanol methoxypropanol
- 2-methoxy-1-ethanol methoxyethanol
- Two or more alkoxy alcohols are more preferred.
- solubility parameter (SP value) here can be easily calculated by the following simple calculation method.
- Formula 1 for dissolving parameter ⁇ 1) latent heat of vaporization per mol Hb 21 ⁇ (273 + Tb) (unit: cal / mol), Tb: boiling point (° C.) 2) Evaporation latent heat per mol at 25 ° C.
- H25 Hb ⁇ ⁇ 1 + 0.175 ⁇ (Tb ⁇ 25) / 100 ⁇ (unit: cal / mol), Tb: boiling point (° C.) 3)
- Intermolecular bond energy E H25-596 (unit: cal / mol) 4)
- the amount of the solvent contained in the composition of the present invention can be appropriately determined in consideration of the physical properties, economy, etc. of the hydrophilic cross-linked resin obtained by the present invention, for example, a single layer film.
- the amount of the solvent used is the concentration (solid content) of the solid content (compound (I), compound (II), and optionally contained silica (IV) and the above additive) contained in the composition). / (Solid content + solvent) ⁇ 100), usually in the range of 1 wt% or more, preferably 10 to 90 wt%, more preferably 20 to 80 wt%, and still more preferably 30 to 70 wt%.
- additives other than the above additives may be added as necessary.
- a hydrophilic crosslinked resin in which hydrophilic groups are unevenly distributed (graded) on the surface can be obtained. Therefore, a single layer having high hydrophilicity and transparency made of these crosslinked resins.
- a highly hydrophilic laminate in which a membrane and its single-layer membrane are laminated can be obtained from a wide range of materials more easily than in the past.
- titanium oxide, other metals and metals in the composition of the present invention for the purpose of improving the mechanical strength and thermal strength of the obtained hydrophilic crosslinked resin or imparting photoresponsiveness and bactericidal properties.
- a compound having a sulfur atom can be added for the purpose of imparting bactericidal and antibacterial properties, etc.
- Metal salts such as silver and lithium, iodine and iodonium salts, and the like can be added to the composition.
- the addition amount of these additives can be appropriately set according to the purpose, but is usually in the range of 0.01 to 200% by weight, preferably 0.1 to 200% by weight with respect to the total of compound (I) and compound (II). It is in the range of 100% by weight.
- the composition of the present invention contains the above-mentioned solvent, it is preferable to sufficiently remove the solvent by heating or the like after the composition is applied to a substrate or the like and before polymerization described later.
- a hydrophilic group derived from the compound (I) at least one hydrophilic group selected from an anionic hydrophilic group, a cationic hydrophilic group, and a hydroxyl group
- the hydrophilicity and the like of the resulting hydrophilic crosslinked resin tend to be smaller.
- the hydrophilic group moves to the surface in contact with the outside air of the coating, if the solvent remains in the composition, the repulsive interaction with the atmosphere (hydrophobic) existing on the surface in contact with the outside air And the hydrophilic group tends to move more easily into the coated product. Therefore, the resulting hydrophilic cross-linked resin, for example, the inclination of the hydrophilic group of the monolayer film to the surface in contact with the outside air may be insufficient, the hydrophilicity may be reduced, and the adhesion to the substrate may further decrease Tend to decrease. Therefore, the residual solvent immediately before the polymerization in the composition tends to be preferable, and is usually 10% by weight or less, preferably 5% by weight or less, more preferably 3% by weight or less, and further preferably 1% by weight or less. It is.
- the temperature at which the solvent is removed is determined as appropriate, but is usually in the range of room temperature to 200 ° C, preferably in the range of 30 to 150 ° C, more preferably in the range of 40 to 120 ° C.
- the time for removing the solvent from the composition may be determined in a timely manner, but in consideration of productivity, a shorter time tends to be preferable.
- the solvent may be removed usually in 30 minutes or less, preferably 10 minutes or less, preferably 5 minutes or less, more preferably 3 minutes or less, and even more preferably 2 minutes or less.
- the atmosphere for removing the solvent may be air or an inert gas such as nitrogen, but the appearance of the hydrophilic cross-linked resin (for example, a single layer film) obtained when the humidity of the atmosphere is lower is deteriorated (Yuzu skin, reduced transparency) Etc.), etc.
- the humidity of the atmosphere is preferably 80% or less, more preferably 65% or less, and further preferably 55% or less.
- the wind speed is preferably 30 m / sec or less, more preferably in the range of 0.1 to 30 m / sec, still more preferably in the range of 0.2 to 20 m / sec, particularly preferably 0.
- the range is 3 to 10 m / sec.
- the pressure at the time of solvent removal is not particularly limited, and normal pressure or reduced pressure is relatively preferable, but may be slightly pressurized.
- the hydrophilic cross-linked resin of the present invention for example, a single layer film, is obtained by applying the above composition of the present invention to a substrate or the like and polymerizing it.
- the above polymerization can be carried out in the air, but it is preferable in that the polymerization time can be shortened when carried out in an inert gas atmosphere such as nitrogen.
- a heat radical generator such as an organic peroxide is usually added to the above composition and heated in the range of room temperature to 300 ° C.
- energy rays having a wavelength range of 0.0001 to 800 nm can be used as the radiation.
- the radiation is classified into ⁇ -rays, ⁇ -rays, ⁇ -rays, X-rays, electron beams, ultraviolet rays, visible light, and the like, and can be appropriately selected and used according to the composition of the mixture.
- ultraviolet rays are preferable, and the output peak of ultraviolet rays is preferably in the range of 200 to 450 nm, more preferably in the range of 230 to 445 nm, still more preferably in the range of 240 to 430 nm, and particularly preferably in the range of 250 to 400 nm.
- ultraviolet rays in the above output peak range are used, there are few problems such as yellowing and thermal deformation during polymerization, and the polymerization can be completed in a relatively short time even when an ultraviolet absorber is added.
- ultraviolet absorber or a hindered amine stabilizer when added to the composition, it is preferable to use ultraviolet rays having an output peak in the range of 250 to 280 nm or 370 to 430 nm.
- the composition When the composition is polymerized by radiation, the composition is applied to a substrate or the like for the purpose of avoiding inhibition of polymerization by oxygen, and dried as necessary, and then the coating layer is coated. It may be coated with a material (film or the like) and polymerized by irradiation with radiation. When the coating layer is coated with a coating material, it is desirable that the coating layer and the coating material are in close contact so as not to include air (oxygen). By blocking oxygen, for example, the amount of (photo) polymerization initiator and the amount of radiation irradiation may be reduced.
- the covering material may be any material and form as long as it is a material capable of blocking oxygen, but is preferably a film from the viewpoint of operability, and among these films, a transparent film that is easily radiation-polymerized is preferable.
- the thickness of the film is usually in the range of 3 to 200 ⁇ m, among which 5 to 100 ⁇ m is preferable, and 10 to 50 ⁇ m is more preferable.
- Examples of the material of the film preferably used as the coating material include, for example, polyvinyl alcohol (PVA), vinyl alcohol polymers such as ethylene / vinyl alcohol copolymer, polyacrylamide, polyisopropylacrylamide, polyacrylonitrile, and polycarbonate (PC). , Polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), polystyrene (PS), and biaxially oriented polypropylene (OPP).
- PVA polyvinyl alcohol
- vinyl alcohol polymers such as ethylene / vinyl alcohol copolymer
- polyacrylamide polyacrylamide
- polyisopropylacrylamide polyacrylonitrile
- PC polycarbonate
- PMMA Polymethyl methacrylate
- PET polyethylene terephthalate
- PS polystyrene
- OPP biaxially oriented polypropylene
- the apparatus is expensive, it is preferable to use an electron beam in the range of 0.01 to 0.002 nm as radiation because the polymerization can be completed in a short time.
- the surface concentration (Sa) of the anionic hydrophilic group and the deep portion concentration at the 1/2 point of the thickness of the monolayer film of these hydrophilic groups The degree of inclination (anion concentration ratio) (Sa / Da) of (Da) is usually 1.1 or more, preferably 1.2 or more, more preferably 1.3 or more, and further preferably 1.5 or more. is there.
- the single-layer film of the present invention is usually provided as a film having the hydrophilic group provided on at least one surface of a substrate.
- the hydrophilic group is distributed from the deep part of the film on the substrate side to the surface, and in particular, the concentration difference (gradient (hydrophilic group concentration) is distributed over the outermost surface in contact with the outside air. Ratio) (Sa / Da)).
- composition is applied to a substrate or the like and polymerized by heat, radiation or the like, at least one hydrophilic group selected from an anionic hydrophilic group, a cationic hydrophilic group, and a hydroxyl group is brought into contact with the outside air. This is probably because a single-layer film made of a crosslinked resin is formed after self-assembly.
- the single layer film made of the crosslinked resin of the present invention has the above hydrophilic group at a high concentration on the surface thereof, so that the antifogging property, antifouling property or self-cleaning property, antistatic property or dust adhesion preventing property is present.
- the gradient (hydrophilic group concentration ratio) is determined by anionicity between the surface of a single layer film cut obliquely and in contact with the outside air of the single layer film, and the film thickness 1/2 point of the single layer film.
- concentration of hydrophilic groups for example, sulfonic acid group, carboxyl group, phosphoric acid group, etc.
- TOF-SIMS time-of-flight secondary ion mass spectrometer
- the water contact angle of the monolayer film made of the crosslinked resin of the present invention is usually 50 ° or less, preferably 30 ° or less, more preferably 20 ° or less, and further preferably 10 ° or less.
- a monolayer film having a water contact angle of not more than the above numerical value has high hydrophilicity and is easy to blend (wet) with water and is excellent as a hydrophilic material. Therefore, it is useful for antifogging materials, antifogging coatings (hereinafter also referred to as antifogging coatings), antifouling materials, antifouling coatings or self-cleaning coatings, and antistatic materials, antistatic coatings or dust adhesion prevention coatings, etc. is there.
- the hydrophilic monolayer film has a larger evaporation area due to the spread of water, improves the evaporation rate, and accelerates drying.
- the monolayer film of the present invention since the monolayer film of the present invention has hydrophilic groups segregated (concentrated) on the surface at a high concentration, it has superior antistatic properties compared to conventional hydrophilic coatings that are not segregated, and an antistatic material. It is also useful as an antistatic coating, a dust adhesion prevention coating, and the like.
- the monolayer film made of the crosslinked resin of the present invention has an antifogging material, an antifouling material, a quick-drying material, It is particularly preferably used as an antistatic material.
- the water contact angle is usually 0 ° or more.
- the thickness of the hydrophilic cross-linked resin of the present invention can be appropriately determined depending on the use, but is usually 0.0001 to 500 ⁇ m, preferably 0.05 to 500 ⁇ m, more preferably. Is in the range of 0.1 to 300 ⁇ m, more preferably 0.5 to 100 ⁇ m, even more preferably 1 to 50 ⁇ m, particularly preferably 2 to 30 ⁇ m.
- the method for forming the hydrophilic cross-linked resin of the present invention for example, a monolayer film is not particularly limited.
- the composition is formed by applying the above composition to the substrate surface, drying it as necessary, and polymerizing it. can do.
- the base material examples include base materials made of non-base materials such as glass, silica, metal, metal oxide, polymethyl methacrylate (PMMA), polycarbonate, polyethylene terephthalate, polyacetyl cellulose (TAC), acrylonitrile butadiene, Styrene copolymer (ABS), polyethylene, polypropylene, polystyrene, polyurethane resin, epoxy resin, vinyl chloride resin, silicone resin, base materials made of organic materials such as paper, pulp, fillers such as unsaturated polyester resin and calcium carbonate
- An organic / inorganic base material such as SMC and BMC, which is a composite of glass fiber and the like, and a hardened paint layer coated with the surface of the base material made of these inorganic material, organic material, and organic / inorganic composite material The base material which has is mentioned.
- these substrate surfaces are activated, as necessary, by corona treatment, ozone treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, chemicals, etc.
- a physical or chemical treatment such as an oxidation treatment or a flame treatment can be performed.
- primer treatment, undercoat treatment, and anchor coat treatment may be performed.
- Examples of the coating agent used in the primer treatment, undercoat treatment, and anchor coat treatment include, for example, polyester resins, polyamide resins, polyurethane resins, epoxy resins, phenol resins, (meth) acrylic resins, and polyvinyl acetate resins.
- a coating agent containing a resin, a polyolefin resin such as polyethylene and polypropylene, or a copolymer or modified resin thereof, a resin such as a cellulose resin as a main component of the vehicle can be used.
- the coating agent may be either a solvent type coating agent or an aqueous type coating agent.
- modified polyolefin coating agents ethyl vinyl alcohol coating agents, polyethyleneimine coating agents, polybutadiene coating agents, polyurethane coating agents; Polyester polyurethane emulsion coating agent, polyvinyl chloride emulsion coating agent, retane acrylic emulsion coating agent, silicone acrylic emulsion coating agent, vinyl acetate acrylic emulsion coating agent, acrylic emulsion coating agent; Styrene-butadiene copolymer latex coating agent, acrylonitrile-butadiene copolymer latex coating agent, methyl methacrylate-butadiene copolymer latex coating agent, chloroprene latex coating agent, rubber-based latex coating agent of polybutadiene latex, polyacrylic acid ester A latex coating agent, a polyvinylidene chloride latex coating agent, a polybutadiene latex coating agent, or a coating agent comprising a carboxylic acid-modified latex or
- These coating agents can be applied by, for example, a gravure coating method, a reverse roll coating method, a knife coating method, a kiss coating method, etc., and the amount applied to the substrate is usually 0.05 g / m 2 to 50% in a dry state. 10 g / m 2 .
- polyurethane-based coating agents are more preferable.
- the polyurethane-based coating agent has a urethane bond in the main chain or side chain of the resin contained in the coating agent.
- a polyurethane-type coating agent is a coating agent containing the polyurethane obtained by making polyol and isocyanate compounds, such as polyester polyol, polyether polyol, or acrylic polyol, react, for example.
- polyurethane coating agents obtained by mixing polyester polyols such as condensation polyester polyols and lactone polyester polyols with isocyanate compounds such as tolylene diisocyanate, hexamethylene diisocyanate, and xylene diisocyanate are closely attached. It is preferable because of its excellent properties.
- the method of mixing the polyol compound and the isocyanate compound is not particularly limited.
- the mixing ratio is not particularly limited, but if the isocyanate compound is too small, it may cause curing failure, so that the OH group of the polyol compound and the NCO group of the isocyanate compound are in the range of 2/1 to 1/40 in terms of equivalents. Is preferred.
- the base material in this invention you may include the base material surface by which the said surface activation process was carried out.
- the single layer film which consists of the crosslinked resin of this invention in the base-material surface can be used as a laminated body containing a base material and a single layer film.
- the single-layer film is an antifogging film, an antifouling film, a quick-drying film, or an antistatic film
- the substrate is coated with the antifogging film, the antifouling film, the quick-drying film, or the antistatic film.
- a laminated body is obtained.
- the substrate is a film
- an adhesive layer described later can be provided on the surface on which the monolayer film of the present invention is not formed, and a release film can be further provided on the surface of the adhesive layer.
- the adhesive layer is laminated on the other side of the base film
- the laminated film having the single-layer film of the present invention is used as an antifogging film and an antifouling film, such as glass, bathroom mirrors, displays, television displays, etc. It can be easily attached to material surfaces, signboards, advertisements, information boards such as information boards, signs for railways, roads, etc., outer walls of buildings, window glass, etc.
- a well-known adhesive can be used.
- the adhesive include acrylic adhesives, rubber adhesives, vinyl ether polymer adhesives, and silicone adhesives.
- the thickness of the adhesive layer is usually in the range of 2 to 50 ⁇ m, preferably in the range of 5 to 30 ⁇ m.
- the surface of the single layer film in contact with the outside air may be covered with a coating material.
- the single layer film can be prevented from being damaged or soiled during transportation, storage, display, or the like.
- the coating material As the coating material, the above-mentioned coating material that has been in close contact with the coating film when polymerized by radiation to form the single layer film of the present invention on a substrate or the like can be used as it is as the coating material.
- Examples of the material of the film preferably used as the covering material include, for example, polyvinyl alcohol (PVA), polyacetyl cellulose (TAC), vinyl alcohol polymers such as ethylene / vinyl alcohol copolymer, polyacrylamide, polyisopropyl acrylamide, Examples include polyacrylonitrile, polycarbonate (PC), polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), polyacrylonitrile / butadiene / styrene copolymer (ABS), polystyrene (PS), and biaxially oriented polypropylene (OPP).
- PVA polyvinyl alcohol
- TAC polyacetyl cellulose
- vinyl alcohol polymers such as ethylene / vinyl alcohol copolymer
- polyacrylamide polyisopropyl acrylamide
- Examples include polyacrylonitrile, polycarbonate (PC), polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), polyacrylonitrile / butad
- composition containing the compound (I) and the compound (II) is polymerized in a mold having various shapes to obtain a crosslinked resin having various shapes, for example, a monolayer film or a molded body. .
- the hydrophilic cross-linked resin obtained in the present invention for example, a single layer film and a laminate including the single layer film can be suitably used as an antifogging material, an antifouling material, a quick drying material, an antistatic material and the like.
- the cross-linked resin, for example, a single layer film and a laminate includes, for example, a vehicle and a vehicle material, a ship and a ship material, an aircraft and an aviation base material, a building and a building material, a window of a vehicle, a ship, an aircraft and a building, and a mirror.
- the sample is cut obliquely as shown in the sample preparation shown in FIG. 1, and using a time-of-flight secondary ion mass spectrometer (TOF-SIMS), a hydrophilic group such as a sulfonic acid group, a carboxyl group, a phosphoric acid group, a quaternary group.
- TOF-SIMS time-of-flight secondary ion mass spectrometer
- the fragment ion concentration (Sa) of the outer surface derived from the hydrophilic compound and the fragment ion concentration (Da) at the intermediate point are measured, and the value
- the ratio of the concentration of hydrophilic groups derived from the hydrophilic compound at the midpoint between the outer surface of the membrane in contact with the outside air and the inner surface and outer surface of the membrane, that is, the gradient of the hydrophilic group concentration (Sa / Da) was determined.
- sample preparation etc. As shown in FIG. 1, a sample provided with a coating layer 20 on the surface of a base material 10 is cut in a precise oblique direction toward a cutting direction 30, and then cut into a size of about 10 ⁇ 10 mm 2 to measure the surface. Apply the mesh to the sample holder, fix it on the sample holder, and fly on the coat layer surface 40 in contact with the outside air and the coat layer inside 50 (the point at which the film thickness is 1/2, the inner surface of the coat layer in contact with the substrate 10) which is the inside of the film.
- the hydrophilic group concentration was measured using a time-type secondary ion mass spectrometer (TOF-SIMS).
- Example 1 Preparation Example 1: Preparation of 10 wt% Compound (I)) 10 g of sodium styrenesulfonate (hereinafter abbreviated as STS-Na), 30 g of water, and 60 g of 1-methoxy-2-propanol (hereinafter abbreviated as PGM) were mixed with a homomixer (Primics Co., Ltd., Robomix (registered trademark) S-model). ) was stirred at 15000 rpm for 3 minutes to prepare an STS-Na mixed solution having a solid content of 10 wt%.
- STS-Na sodium styrenesulfonate
- PGM 1-methoxy-2-propanol
- coating composition 1 (Preparation of coating composition 1) According to the following Table 1, coating composition 1 having a solid content of 39 wt% was prepared.
- the coating composition 1 is applied to a polycarbonate plate (size: 100 mm ⁇ 100 mm, manufactured by Takiron Co., Ltd., hereinafter abbreviated as PC plate) with a bar coater # 07 and dried for 3 minutes with a 55 ° C. hot air dryer.
- a polycarbonate plate size: 100 mm ⁇ 100 mm, manufactured by Takiron Co., Ltd., hereinafter abbreviated as PC plate
- UV irradiation electrodeless discharge lamp, H bulb 240 W / cm, irradiation distance 70 mm, conveyor speed 10 m / min (illuminance 170 mW / cm 2 , integrated light quantity 130 mJ / cm 2 , measured with Ushio UIT-150)
- a single layer film made of a crosslinked resin having a hydrophilic surface of 3 ⁇ m was formed on a PC plate. Thereafter, the membrane surface was washed with running water and dried with an air gun to obtain a sample for evaluation. Samples were evaluated according to the methods described in the above physical property evaluation. The resulting monolayer membrane had a sulfonic acid group gradient (Sa / Da) of 2.3. Other evaluation results are listed in Table 2.
- Example 2 Preparation of a coating composition, coating on a substrate, UV coating, as in Example 1, except that the amount of STS-Na added and the type of compound (II) were changed as shown in Table 2 below. Formation of a single layer film on a PC plate by irradiation, washing of the film surface with running water and drying were performed to obtain a sample for evaluation. Samples were evaluated according to the methods described in the above physical property evaluation. The evaluation results are listed in Table 2.
- Example 6 Reference Example 2
- the amount of STS-Na added was changed as shown in Table 3 below, and the type of compounds (II) (Examples 6 to 8) was changed as shown in Table 3 below or Compound (II) was changed Except for changing to a crosslinking monomer other than Compound (II) (Reference Example 2), preparation of a coating composition, coating on a substrate, and formation of a monolayer film on a PC plate by UV irradiation, as in Example 1. Formation, washing of the membrane surface with running water and drying were performed to obtain samples for evaluation. Samples were evaluated according to the methods described in the above physical property evaluation. The evaluation results are listed in Table 3.
- Examples 9 to 13, Reference Example 3, Comparative Examples 6 to 12 As shown in Table 4 below, the type of compound (I) was changed from STS-Na to sodium allyl sulfonate (hereinafter abbreviated as AS-Na), and the amount added was also changed. Except for changing the type as described in Table 4 below, preparation of a coating composition, coating on a substrate, formation of a monolayer film on a PC plate by UV irradiation, and film as in Example 1 The surface was washed with running water and dried to obtain a sample for evaluation. Samples were evaluated according to the methods described in the above physical property evaluation. The evaluation results are listed in Table 4.
- a coating solution obtained by mixing 2 g of Irgacure 184 (Ciba Japan Co., Ltd.) as a polymerization initiator into the comparative composition 30 was used as a polymethyl methacrylate plate (size: 100 mm ⁇ 100 mm, manufactured by Nitto Resin Industry, (Hereinafter abbreviated as PMMA plate) with bar coater # 06, dried at 100 ° C.
- the membrane after the water washing was immersed in a 10 wt% sodium hydroxide solution for 5 minutes, the membrane surface was washed with running water, dried with a hot air dryer at 50 ° C., and subjected to the same evaluation as an alkali immersion membrane.
- the evaluation results are listed in Table 6 below.
- the obtained single layer film had low hydrophilicity and low transparency both in the film after washing with water and the alkali soaked film.
- Comparative Composition 31 (Preparation of Comparative Composition 31) According to the blending ratio shown in Table 7 below, an attempt was made to prepare a uniform comparative composition 31 having a solid content of 50 wt% by vigorously stirring and mixing, but acrylamide-2-methylpropanesulfonic acid (ATBS) did not dissolve and became cloudy. It was.
- ATBS acrylamide-2-methylpropanesulfonic acid
- the above-described coating solution that remains clouded is forcibly applied to the PMMA plate with a bar coater # 06, dried at 100 ° C. for 5 minutes, and further heated at 60 ° C. for 8 hours and at 100 ° C. for 5 hours. Then, a single layer film having a thickness of 4 ⁇ m was formed on the PMMA plate.
- the obtained monolayer film is, as expected, the ATBS-derived component remaining separated and cloudy, has a low hydrophilicity, and is a soft film that can be easily scratched with a nail and used as a monolayer film. It was something that could not stand.
- the film after water washing and the alkali soaked film were evaluated in the same manner as in Comparative Example 13. The evaluation results are listed in Table 8.
- the carboxyl group strength and sulfonic acid group strength were analyzed by the following methods. Analysis method: The sample was precisely obliquely cut in the film thickness direction, and the cut surface was analyzed by TOF-SIMS. Analytical instrument: TOF-SIMS manufactured by ION-TOF Primary ion: Bi 3 2+ Accelerating voltage: 25kV
- the above-mentioned comparative coating composition 32 was applied to a PMMA plate with a bar coater # 8 and allowed to stand at room temperature for 10 minutes, followed by UV irradiation (Fusion UV Systems Japan, electrodeless discharge lamp / D bulb, conveyor speed 5 m / (Measured with an illuminance of 670 mW / cm 2 , an integrated light quantity of 450 mJ / cm 2 , and Ushio UIT-150), a single layer film having a thickness of 3.5 ⁇ m was formed on the PMMA plate.
- UV irradiation Fusion UV Systems Japan, electrodeless discharge lamp / D bulb, conveyor speed 5 m / (Measured with an illuminance of 670 mW / cm 2 , an integrated light quantity of 450 mJ / cm 2 , and Ushio UIT-150)
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Abstract
Description
曇りの問題を解決する方法として、反応性界面活性剤、アクリル系オリゴマーを含む防曇塗料により、親水性、吸水性を向上する方法が提案されている(例えば、非特許文献1参照。)。また、汚れの問題を解決する手段として、材料表面の親水性を向上させることによって、外壁等に付着した外気疎水性物質などの汚れを散水又は降雨により浮き上がらせて除去する方法が提案されている(例えば、非特許文献2及び3参照。)。
3つ以上の水酸基と2つ以上、好ましくは3つ以上の重合性炭素-炭素二重結合を有する官能基とを有する化合物(II)を含む組成物を重合することにより、親水基が表面に偏析し、且つ従来よりも高い透明性を有する親水性の単層膜が得られることを見い出し、本発明を完成するに至った。
水酸基を3つ以上と、重合性炭素-炭素二重結合を有する官能基を2つ以上、好ましくは3つ以上とを有する化合物(II)(ただし、アニオン性親水基は有さない。)
を含む組成物を重合することにより得られる架橋樹脂からなる単層膜であり、該単層膜のアニオン性親水基の表面濃度(Sa)と該単層膜膜厚1/2地点における該親水基の深部濃度(Da)の傾斜度(Sa/Da)が1.1以上である単層膜であることを特徴とする。
本発明の積層体は、上記単層膜を少なくとも1層有することを特徴とする。
[化合物(I)]
上記化合物(I)は、アニオン性親水基と、重合性炭素-炭素二重結合を有する官能基とを有する。このようなアニオン性親水基と炭素-炭素二重結合を有する官能基とを有する化合物が含まれる組成物を重合することにより、得られる架橋性樹脂からなる単層膜に親水性が付与され得る。
-SO3Z (α) -COOZ(β) -OP=O(OZ)2(γ1) (-O)2P=O(OZ)1(γ2)
-O-SO3Z(δ) -NH-SO3Z(ε)
上記アルカリ土類金属としては、例えば、ベリリウム、マグネシウム、カルシウム、ストロンチウム、バリウムなどが挙げられる。
アニオン性親水基が上記式(α)~(ε)で表される場合には、Zとしては、アンモニウムイオン、アルカリ金属イオン、1/2原子のアルカリ土類金属イオンであることが好ましく、アルカリ金属イオンがより好ましく、ナトリウムイオン、カリウムイオン、及びルビジウムイオンがさらに好ましい。
化合物(I)は、さらに重合性炭素-炭素二重結合を有する官能基を少なくとも1つ有する。その重合性炭素-炭素二重結合を有する官能基としては、その官能基がラジカル重合またはイオン重合可能であれば特に制限はないが、例えば、アクリロイル基、メタクリロイル基、アリル基、メタリル基、ビニル基、イソプロペニル基、マレイル基(-CO-CH=CH-CO-)、イタコニル基(-CO-CH=CH-CO-)、スチリル基、およびα-メチル-スチリル基及びこれら基を含む基が挙げられる。
上記化合物(I)としては、下記一般式(100)で表される化合物が好ましい。
上記一般式(100)中のAとしては、下記一般式(121)~(125)から選ばれる少なくとも1つの重合性炭素-炭素二重結合を有する官能基が好ましい。
2,2-ビス{(メタ)アクリロイルオキシエチル}プロピオン酸、2,2-ビス{(メタ)アクリロイルオキシエチル}プロピオン酸ナトリウム塩、2,2-ビス{(メタ)アクリロイルオキシエチル}プロピオン酸カリウム塩、2,2-ビス{(メタ)アクリロイルオキシエチル}プロピオン酸ルビジウム塩、2,2-ビス{(メタ)アクリロイルオキシエチル}プロピオン酸アンモニウム塩、2,2-ビス{(メタ)アクリロイルオキシエチル}プロピオン酸カルシウム塩、2,2-ビス{(メタ)アクリロイルオキシエチル}プロピオン酸マグネシウム塩、
2,2-ビス{(メタ)アクリロイルオキシエチル}酪酸、2,2-ビス{(メタ)アクリロイルオキシエチル}酪酸ナトリウム塩、2,2-ビス{(メタ)アクリロイルオキシエチル}酪酸カリウム塩、2,2-ビス{(メタ)アクリロイルオキシエチル}酪酸ルビジウム塩、2,2-ビス{(メタ)アクリロイルオキシエチル}酪酸アンモニウム塩、2,2-ビス{(メタ)アクリロイルオキシエチル}酪酸カルシウム塩、2,2-ビス{(メタ)アクリロイルオキシエチル}酪酸マグネシウム塩、
2,2-ビス{(メタ)アクリロイルオキシエチル}吉草酸、2,2-ビス{(メタ)アクリロイルオキシエチル}吉草酸ナトリウム塩、2,2-ビス{(メタ)アクリロイルオキシエチル}吉草酸カリウム塩、2,2-ビス{(メタ)アクリロイルオキシエチル}吉草酸ルビジウム塩、2,2-ビス{(メタ)アクリロイルオキシエチル}吉草酸アンモニウム塩、2,2-ビス{(メタ)アクリロイルオキシエチル}吉草酸カルシウム塩、2,2-ビス{(メタ)アクリロイルオキシエチル}吉草酸マグネシウム塩などが挙げられる。
なお、本発明で単層膜を製造するために用いる組成物には上記化合物(I)が含まれるが、上記化合物(I)の少なくとも一部が反応してオリゴマーの形になって上記組成物に含まれていてもよい。なお、ここでいうオリゴマーとは上記化合物(I)から形成される繰り返し単位を通常2~20含むものである。
上記化合物(I)は公知の方法又は公知に準ずる方法により製造できる。また、上記化合物(I)は市販品としても入手できる。
上記化合物(II)は、水酸基を3つ以上と、重合性炭素-炭素二重結合を有する官能基を2つ以上、好ましくは3つ以上とを有する。ただし、化合物(II)はアニオン性親水基を有さず、化合物(I)とは異なる。このような化合物が含まれた組成物を重合することにより、十分に架橋した架橋樹脂からなる単層膜が得られ得る。重合性炭素-炭素二重結合を有する官能基としては、化合物(I)に含まれる重合性炭素-炭素二重結合を有する官能基として例示した基が挙げられる。重合性炭素-炭素二重結合を有する官能基としては、(メタ)アクリロイル基、ビニル基、(メタ)アリル基、スチリル基、イソプロペニル基が好ましく、(メタ)アクリロイル基、 (メタ)アリル基、スチリル基がより好ましく、(メタ)アクリロイル基がさらに好ましい。
上記式(IIb)中、m010は0~10の整数を表し、n110は1~10の整数を表し、m010+n110=1~10を満足する。m010としては、0~6の整数が好ましく、0~4の整数がより好ましい。n110としては、1~6の整数が好ましく、1~4の整数がより好ましい。
上記式(IIb)中、N12は1または2を表すが、N12としては、1が好ましい。
エリスリトール-トリ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、エリスリトール-テトラ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、
キシリトール-トリ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、キシリトール-テトラ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、キシリトール-ペンタ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、
アラビトール-トリ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、アラビトール-テトラ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、アラビトール-ペンタ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、
リビトール-トリ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、リビトール-テトラ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、リビトール-ペンタ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、
ガラクチトール-トリ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、ガラクチトール-テトラ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、ガラクチトール-ペンタ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、ガラクチトール-ヘキサ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、
マニトール-トリ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、マニトール-テトラ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、マニトール-ペンタ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、マニトール-ヘキサ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、
ソルビトール-トリ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、ソルビトール-テトラ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、ソルビトール-ペンタ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、ソルビトール-ヘキサ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル等が挙げられる。
上記式(IIc)中、m010は0~10の整数を表し、n110は1~10の整数を表し、m010+n110=1~10を満足する。m010としては、0~6の整数が好ましく、0~4の整数がより好ましい。n110としては、1~6の整数が好ましく、1~4の整数がより好ましい。
上記式(IIc)中、N12は1または2を表すが、N12としては、1が好ましい。
トレオン酸-ジ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル-{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エステル、トレオン酸-トリ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル-{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エステル、
グルコン酸-ジ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル-{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エステル、グルコン酸-トリ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル-{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エステル、グルコン酸-テトラ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル-{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エステル、グルコン酸-ペンタ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル-{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エステル、
グルコヘプタン酸-ジ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル-{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エステル、グルコヘプタン酸-トリ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル-{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エステル、グルコヘプタン酸-テトラ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル-{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エステル、グルコヘプタン酸-ペンタ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル-{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エステル、グルコヘプタン酸-ヘキサ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル-{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エステル等が挙げられる。
上記式(IId)中、R1、R2、R3、およびR4は、独立して水素原子またはメチル基を表すが、m09が2以上の場合にはR4同士は同一でも異なっていてもよい。
酒石酸-モノ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル-ジ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エステル、酒石酸-ジ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル-ジ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エステル、
テトラヒドロキシアジピン酸-モノ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル-ジ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エステル、テトラヒドロキシアジピン酸-ジ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル-ジ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エステル、テトラヒドロキシアジピン酸-トリ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル-ジ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エステル、テトラヒドロキシアジピン酸-テトラ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル-ジ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エステル等が挙げられる。
上記式(IIe)中、m13は1~3の整数を表し、m28は2~8の整数、好ましくは3~8の整数を表し、m06は0~6の整数を表すが、m13が1の場合はm28+m06=4であり、m13が2の場合はm28+m06=6であり、m13が3の場合はm28+m06=8である。m13としては、1~2の整数が好ましく、1がより好ましい。
ジペンタエリスリトール-トリ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、ジペンタエリスリトール-テトラ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、ジペンタエリスリトール-ペンタ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、ジペンタエリスリトール-ヘキサ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、
トリペンタエリスリトール-トリ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、トリペンタエリスリトール-テトラ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、トリペンタエリスリトール-ペンタ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、トリペンタエリスリトール-ヘキサ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、トリペンタエリスリトール-ヘプタ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、トリペンタエリスリトール-オクタ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル等が挙げられる。
上記式(IIf)中、m13は1~3の整数を表し、m25は2~5、好ましくは3~5の整数を表し、m03は0~3の整数を表すが、m13が1の場合はm28+m03=3であり、m13が2の場合はm28+m03=4であり、m13が3の場合はm28+m03=5である。m13としては、1~2の整数が好ましく、1がより好ましい。
ジトリメチロールプロパン-トリ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、ジトリメチロールプロパン-テトラ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、
トリトリメチロールプロパン-トリ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、トリトリメチロールプロパン-テトラ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、トリトリメチロールプロパン-ペンタ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル等が挙げられる。
上記式(IIg)中、X3およびX4は、独立して、-CH2-、-CH(OH)-、-CH(-O-3#)-、または-CO-を表し、n13が2以上の場合、X4同士は同一でも異なっていてもよい。
上記一般式(IIg)で表される化合物としては、例えば、リボース-トリ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、リボース-テトラ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、
アスコルビン酸-トリ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、アスコルビン酸-テトラ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、
キシロース-トリ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、キシロース-テトラ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、
ソルビタン-トリ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、ソルビタン-テトラ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、
グルコース-トリ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、グルコース-テトラ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、グルコース-ペンタ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、
ガラクトース-トリ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、ガラクトース-テトラ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、ガラクトース-ペンタ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、
マンノース-トリ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、マンノース-テトラ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、マンノース-ペンタ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、
(グルコノ-1,5-ラクトン)-トリ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、(グルコノ-1,5-ラクトン)-テトラ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、(グルコノ-1,5-ラクトン)-ペンタ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル等が挙げられる。
上記式(IIe)中、m28は2~8の整数、好ましくは3~8の整数を表し、m06は0~6の整数を表し、m28+m06=8を満足する。
上記一般式(IIh)で表される化合物としては、例えば、ショ糖(別名:スクロース)-トリ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、ショ糖-テトラ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、ショ糖-ペンタ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、ショ糖-ヘキサ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、ショ糖-ヘプタ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、ショ糖-オクタ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル等が挙げられる。
上記式(IIi)中、m28は2~8の整数、好ましくは3~8の整数を表し、m06は0~6の整数を表し、m28+m06=8を満足する。
上記一般式(IIi)で表される化合物としては、例えば、パラチノース-トリ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、パラチノース-テトラ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、パラチノース-ペンタ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、パラチノース-ヘキサ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、パラチノース-ヘプタ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、パラチノース-オクタ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル等が挙げられる。
上記式(IIj)中、m28は2~8の整数、好ましくは3~8の整数を表し、m06は0~6の整数を表し、m28+m06=8を満足する。
上記一般式(IIj)で表される化合物としては、例えば、ラクトース-トリ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、ラクトース-テトラ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、ラクトース-ペンタ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、ラクトース-ヘキサ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、ラクトース-ヘプタ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、ラクトース-オクタ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、
マルトース-トリ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、マルトース-テトラ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、マルトース-ペンタ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、マルトース-ヘキサ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、マルトース-ヘプタ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、マルトース-オクタ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、
トレハロース-トリ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、トレハロース-テトラ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、トレハロース-ペンタ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、トレハロース-ヘキサ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、トレハロース-ヘプタ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル、トレハロース-オクタ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル等が挙げられる。
上記式(IIk)中、m24は2~4の整数、好ましくは3~4の整数を表し、m02は0~2の整数、好ましくは0または1を表し、m24+m02=4を満足する。
上記一般式(IIk)で表される化合物としては、例えば、クエン酸-トリ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エステル、クエン酸-モノ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル-トリ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エステル等が挙げられる。
上記一般式(IIl)で表される化合物としては、例えば、ジメチロール酢酸-ジ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル-モノ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エステル、
ジメチロールプロピオン酸-ジ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル-モノ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エステル、
ジメチロール酪酸-ジ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エーテル-モノ{3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル}エステル等が挙げられる。
上記化合物(II)は1種単独で用いてもよいし、2種以上混合して用いてもよい。
本発明に於いて、従来の架橋重合性化合物(例えば、WO2007/064003号公報,WO2012/014829号公報などに記載の架橋重合性化合物)に対して、親水性化合物(I)の表面へ偏析(傾斜化)を阻害せず溶解性を高められる特定構造の高極性の架橋重合性化合物(II)を見出すことにより、化合物(I)と化合物(II)とを含む組成物を重合して得られた架橋樹脂からなる単層膜について、親水性を維持しつつ透明性を飛躍的に向上させることが可能となった。
本発明で単層膜を製造するために用いる組成物には、必要に応じて、上記化合物(I)および化合物(II)以外のその他の成分が含まれていてもよい。
イソブチリルパーオキサイド、o-クロロベンゾイルパーオキサイド、ベンゾイルパーオキサイド等のジアシルパーオキサイド類;
トリス(t-ブチルパーオキシ)トリアジン、t-ヌチルクミルパーオキサイド等のジアルキルパーオキサイド類;
2,2-ビス(4,4-ジ-t-ブチルパーオキシシクロヘキシル)プロパン、2,2-ジ(t-ブチルパーオキシ)ブタン等のパーオキシケタール類;
α-クミルパーオキシネオデカノエート、t-ブチルパーオキシピバレート、2,4,4-トリメチルペンニルパーオキシ-2-エチルヘキサノエート、t-ブチルパーオキシ-2-エチルヘキサノエート、t-ブチルパーオキシ-3,5,5-トリメチルヘキサノエート等のアルキルパーエステル類;
ジ-3-メトキシブチルパーオキシジカーボネート、ビス(4-t-ブチルシクロヘキシル)パーオキシジカーボネート、t-ブチルパーオキシイソプロピルカーボネート、ジエチレングリコールビス(t-ブチルパーオキシカーボネート)等のパーカボネート類等が挙げられる。
上記溶剤としては、表面が親水性の架橋樹脂が得られる限り特に制限はないが、本発明で用いる単量体組成物に含まれる構成成分に対して反応したり、該構成成分と塩を形成したりするなど相互作用の強すぎる溶剤、および沸点が高すぎる溶剤、例えば沸点が200℃を超える溶剤は好ましくない。例えば、エタノールアミン、ジエタノールアミン、トリエタノールアミン、N-エチル-エタノールアミン、N-(2-エチルヘキシル)エタノールアミン、N-ブチル-ジエタノールアミン、N-ヘキシル-ジエタノールアミン、N-ラウリル-ジエタノールアミン、N-セチル-ジエタノールアミンなどのヒドロキシエチルアミノ構造を有するエタノールアミン系化合物〔NRaRb(CH2CH2OH): RaおよびRbは独立して、水素、炭素数1~15のアルキル基、またはCH2CH2OH基である。〕は、化合物(I)に含まれる親水基と相互作用、例えばスルホン酸基に代表されるアニオン性親水基とは塩または塩に近い形を形成しやすく、また蒸発しにくいため、塗布した混合物から溶剤を除去しようとしても、外気に接する表面へ移動しにくく内部に残留する傾向にある。したがって、化合物(I)に含まれる親水基が、塗布物の外気に接する表面への傾斜(集中化)起こりにくい傾向にある。そのため、上記エタノールアミン系化合物は溶剤としては望ましくない。
溶解パラメーターσの計算式
1)1mol当たりの蒸発潜熱
Hb=21×(273+Tb) (単位:cal/mol),Tb:沸点(℃)
2)25℃での1mol当たりの蒸発潜熱
H25=Hb×{1+0.175×(Tb-25)/100} (単位:cal/mol),Tb:沸点(℃)
3)分子間結合エネルギー E=H25-596 (単位:cal/mol)
4)溶剤1ml(cm3)当たりの分子間結合エネルギー
E1=E×D/Mw (単位:cal/cm3),D:密度(g/cm3),MW:分子量
5)溶解パラメーター(SP値) σ=(E1)1/2 (単位:(cal/cm3)1/2)
本発明の組成物に含まれる溶剤の量は、本発明により得られる親水性架橋樹脂、例えば単層膜の物性、経済性等を考慮して適宜決定できる。
上記組成物からの溶剤除去のための時間は適時決定すればよいが、生産性を考慮した場合、短時間の方が好ましい傾向にある。例えば、通常30分以下、好ましくは10分以下、好ましくは5分以下、より好ましくは3分以下、さらに好ましくは2分以下の時間で溶剤除去すればよい。溶剤除去の際の雰囲気は大気でも窒素等の不活性ガスでも構わないが、雰囲気の湿度が低い方が得られる親水性架橋樹脂(例えば単層膜)の外観が悪化(ゆず肌、透明性低下など)しないなど好ましい傾向にある。具体的には、雰囲気の湿度は80%以下が好ましく、65%以下がより好ましく、55%以下がさらに好ましい。
本発明の上記組成物を基材等に塗布して重合することにより、本発明の親水性架橋樹脂、例えば単層膜が得られる。上記重合方法には特に制限はなく、例えば、熱または放射線を用いて、あるいは両者を併用して重合することができる。
熱を用いて重合する場合、通常、上記組成物に有機過酸化物等の熱ラジカル発生剤を加え室温から300℃以下の範囲で加熱する。
このようにして得られた本発明の親水性架橋樹脂からなる単層膜では、アニオン性親水基の表面濃度(Sa)と、これら親水基の単層膜の膜厚1/2地点における深部濃度(Da)の傾斜度(アニオン濃度比)(Sa/Da)が通常1.1以上であり、好ましくは1.2以上、より好ましくは1.3以上であり、さらに好ましくは1.5以上である。
水接触角が上記数値以下の単層膜は、親水性が高く、水となじみ(濡れ)やすく親水性材料として優れる。そのため、例えば、防曇材料、防曇被膜(以下、防曇コートとも言う)、防汚材料、防汚被膜またはセルフクリーニングコート、並びに帯電防止材、帯電防止被膜またはほこり付着防止コート等に有用である。たとえば、防曇コートとして用いた場合には、膜表面に水滴が広がり水膜を形成させることができるため防曇効果に優れ、またセルフクリーニングコートとして用いると水が汚れとコーティング面の間に入り込み汚れを浮かせて除去することができるため防汚効果に優れている。さらに親水性の単層膜は、水が広がることにより蒸発面積が拡大し、蒸発速度が向上して乾燥が早くなる。
ポリエステル系ポリウレタンエマルジョンコート剤、ポリ塩化ビニルエマルジョンコート剤、レタンアクリルエマルジョンコート剤、シリコンアクリルエマルジョンコート剤、酢酸ビニルアクリルエマルジョンコート剤、アクリルエマルジョンコート剤;
スチレン-ブタジエン共重合体ラテックスコート剤、アクリルニトリル-ブタジエン共重合体ラテックスコート剤、メチルメタクリレート-ブタジエン共重合体ラテックスコート剤、クロロプレンラテックスコート剤、ポリブタジエンラテックスのゴム系ラテックスコート剤、ポリアクリル酸エステルラテックスコート剤、ポリ塩化ビニリデンラテックスコート剤、ポリブタジエンラテックスコート剤、あるいはこれらラテックスコート剤に含まれる樹脂のカルボン酸変性物ラテックスもしくはディスパージョンからなるコート剤が好ましい。
このようにして基材表面を本発明の架橋樹脂からなる単層膜を形成したものは、基材と単層膜とを含む積層体として用いることができる。例えば、上記単層膜が防曇被膜、防汚被膜、速乾性被膜、または帯電防止被膜である場合には、防曇被膜、防汚被膜、速乾性被膜または帯電防止被膜で基材が被覆された積層体が得られる。
上記架橋樹脂、例えば単層膜および積層体は、例えば、車両及び車両材料、船舶及び船舶材料、航空機及び航空基材料、建築物及び建築材料、車両、船舶、航空機及び建築物等の窓、鏡、外壁、外装、ボディー、ホイール、内壁、内装、床、家具及び家具材料、配管および配線などの用役類およびその材料、衣服および布などの繊維製品、洗面台、浴室、化粧室、換気扇、およびキッチンなどの住宅設備およびその材料、洗濯機、食器乾燥機、冷蔵庫、電子レンジ、オーブン、およびシェーバーなどの電化製品及びその材料、ディスプレイ及びその材料、光学フィルム、光ディスク、光学レンズ、眼鏡レンズ、コンタクトレンズ、ゴーグル等の光学物品、入れ歯およびデンチャー等の歯科材料、ランプ及びライト等の照明物品及びその材料、冷却フィン等の熱交換機部品およびその材料、フォトレジスト及びインクジェット記録版等の記録印刷材料、化粧品容器及びその材料、反射フィルム、反射板等の反射材料、高速道路等に設置される遮音板、ディスプレイ材料、印刷または印字用プライマー、その他プライマー、フラットパネル、タッチパネル、シート、速乾燥性、フィルム、テープ、透明樹脂、及びガラス等の透明材料に被覆して、親水性、防曇性、および防汚性を付与することができる。さらに結露防止性を付与したり、帯電防止性を付与したりすることもできる。
なお、本発明において被膜の物性評価は、下記のようにして行った。
図1に示す試料調製の通りサンプルを斜めに切断し、飛行時間型2次イオン質量分析装置(TOF-SIMS)を用いて、親水基であるスルホン酸基、カルボキシル基、リン酸基、4級アンモニム基、および水酸基を有する親水性化合物のフラグメントイオンについて、その親水性化合物に由来する外表面のフラグメントイオン濃度(Sa)と上記中間地点とのフラグメントイオン濃度(Da)とを測定し、その値から外気に接する膜の外表面と膜の内表面と外表面との中間地点の親水性化合物に由来する親水基の濃度の比、すなわち親水基濃度の傾斜度(Sa/Da)を求めた。
(分析装置と測定条件)
TOF-SIMS; ION・TOF社製 TOF-SIMS5
1次イオン; Bi3 2+ (加速電圧25kV)
測定面積; 400μm2
測定には帯電補正用中和銃を使用
図1に示す通りに、基材10の表面にコート層20が設けられたサンプルを切削方向30に向かって、精密斜め切削を行った後、10×10mm2程度の大きさに切り出し、測定面にメッシュを当て、サンプルホルダーに固定し、外気と接するコート層表面40および膜の内部であるコート層内部50(膜厚1/2の地点、基材10に接するコート層の内表面)で飛行時間型2次イオン質量分析装置(TOF-SIMS)を用いて親水基濃度を測定した。
評価は以下の計算式で行った。尚、各測定点のイオン濃度は、相対強度(トータル検出イオンに対する)を用いた。
Sa/Da(親水基濃度比,傾斜度)=コート層表面40での親水基濃度/コート層20の膜厚1/2の地点での親水基濃度
協和界面科学社製の水接触角測定装置CA-V型を用いて、1サンプルについて3箇所測定し、これらの値の平均値を水接触角の値とした。
日本電色工業社製のヘーズメーターNDH2000を用いて、1サンプルについて4箇所測定し、これらの値の平均値をヘーズの値とした。
JIS K5400 碁盤目剥離試験 に準じて評価を行った。
ゼブラ(株)製の油性マーカー「マッキー極細」(黒,品番MO-120-MC-BK)でマークし、その上に水滴を垂らして30秒間放置し、テッシュペーパーでふき取る。拭き取る前にマークが水で浮き上がり容易に拭き取れた場合を◎、残らずふき取れた場合を○、一部マークが残った場合を△、ふき取れなかった場合を×とした。
呼気により曇らなかった場合を〇、曇った場合を×とした。
(調製例1:10wt%化合物(I)の調製)
スチレンスルホン酸ナトリウム(以下STS-Naと略す)10g、水30g、および1-メトキシ-2-プロパノール(以下PGMと略す)60gを、ホモミキサー(プライミクス株式会社,ロボミックス(登録商標)S-model)を用いて15000rpmで3分間かき混ぜ、固形分10wt%のSTS-Na混合液を調製した。
下記表1に従い、固形分39wt%のコーティング組成物1を作製した。
ポリカーボネート板(大きさ:100mm×100mm,タキロン株式会社製,以下PC板と略す。)に、上記コーティング用組成物1をバーコーター#07で塗布し、55℃の温風乾燥機で3分間乾燥後、UV照射(無電極放電ランプ,Hバルブ 240W/cm,照射距離70mm,コンベアー速度10m/分(照度170mW/cm2,積算光量130mJ/cm2,ウシオUIT-150にて測定))して、PC板上に3μmの親水性表面を有する架橋樹脂からなる単層膜を形成させた。その後、膜表面を流水洗浄し、エアガンで乾燥して評価用サンプルとした。上述の物性評価に記載される方法にしたがって、サンプルの評価を行った。得られた単層膜のスルホン酸基傾斜度(Sa/Da)は2.3であった。その他の評価結果を表2に掲載する。
STS-Naの添加量と、化合物(II)の種類を下記表2に記載されるとおりに変更する以外は、実施例1と同様に、コーティング用組成物の調製、基材へのコーティング、UV照射によるPC板上への単層膜の形成、膜表面の流水洗浄および乾燥を行い、評価用サンプルを得た。上述の物性評価に記載される方法にしたがって、サンプルの評価を行った。評価結果を表2に掲載する。
STS-Naの添加量を下記表3に記載されるとおりに変更し、下記表3に記載されるとおりに化合物(II)の種類(実施例6~8)を変更または、化合物(II)を化合物(II)以外の架橋モノマーに変更(参考例2)する以外は、実施例1と同様にコーティング用組成物の調製、基材へのコーティング、UV照射によるPC板上への単層膜の形成、膜表面の流水洗浄および乾燥を行い、評価用サンプルを得た。上述の物性評価に記載される方法にしたがって、サンプルの評価を行った。評価結果を表3に掲載する。
下記表4に記載されるとおりに、化合物(I)の種類をSTS-Naからアリルスルホン酸ナトリウム(以下AS-Naと略す。)に変更するとともにその添加量も変更し、化合物(II)の種類を下記表4に記載されるとおりに変更する以外は、実施例1と同様にコーティング用組成物の調製、基材へのコーティング、UV照射によるPC板上への単層膜の形成、膜表面の流水洗浄および乾燥を行い、評価用サンプルを得た。上述の物性評価に記載される方法にしたがって、サンプルの評価を行った。評価結果を表4に掲載する。
先行技術(特開2005-187576 実施例2)追試
(比較組成物30の調製)
下記表5の配合比に従い、固形分50wt%の均一な比較組成物30を調製した。
上記比較組成物30に、重合開始剤としてイルガキュアー184(チバ・ジャパン株式会社) 2gを混合して得たコーティング溶液を、ポリメタクリル酸メチル板(大きさ:100mm×100mm,日東樹脂工業製,以下PMMA板と略す。)にバーコーター#06で塗布し、100℃で5分間乾燥させた後、UV照射(フュージョンUVシステムズ,無電極Hバルブ240W/cm,照度650mW/cm2,積算光量130mJ/cm2,ウシオ UIT-150 測定値)することにより、PMMA板上に膜厚4μmの単層膜を形成させた。次いで、膜表面を流水洗浄し、50℃温風乾燥機で乾燥して、まず水洗後の膜として、上述の物性評価に記載される方法にしたがってサンプルの評価を行った。さらにその水洗後の膜を10wt%水酸化ナトリウム溶液に5分間浸漬し、膜表面を流水洗浄し、50℃温風乾燥機で乾燥してアルカリ浸漬膜として、同様の評価を行った。評価結果を下記表6に掲載する。得られた単層膜は、水洗後の膜およびアルカリ浸漬膜のいずれも親水性は低く、透明性も低かった。
**C2H4PO4 -(m/z=123)の相対強度(対トータルイオン)
尚、カルボキシル基強度およびリン酸基強度の分析は以下の方法により行なった。
分析方法: サンプルを膜厚方向に精密斜め切削し、切削面をTOF-SIMSにて分析した。
分析機器: ION・TOF社製 TOF-SIMS
一次イオン: Bi3 2+
加速電圧: 25kV
先行技術(特開2005-187576 実施例5)追試
下記表7の配合比に従い、激しく攪拌混合して固形分50wt%の均一な比較組成物31を調製しようとしたが、アクリルアミド-2-メチルプロパンスルホン酸(ATBS)が溶解せず分離白濁していた。
上記の白濁した比較組成物31に、熱重合開始剤としてパーブチルオキシピバレート(パーブチルPV、日本油脂製) 3gを添加して再度激しく混合攪拌したが、不均一なままのコーティング液であった。
念のため、比較例13と同様にして、水洗後の膜およびアルカリ浸漬膜の評価を行った。評価結果を表8に掲載する。
分析方法: サンプルを膜厚方向に精密斜め切削し、切削面をTOF-SIMSにて分析した。
分析機器: ION・TOF社製 TOF-SIMS
一次イオン: Bi3 2+
加速電圧: 25kV
先行技術(特開昭55-90516 実施例1)追試
下記表9の配合比に従い、激しく攪拌混合して固形分36wt%の均一な比較コーティング用組成物32を調製した。
PMMA板に、上記比較コーティング用組成物32をバーコーター#8で塗布した後、室温で10分間放置後、UV照射(フュージョンUVシステムズ・ジャパン製,無電極放電ランプ・Dバルブ,コンベアー速度5m/分,照度670mW/cm2,積算光量450mJ/cm2,ウシオ UIT-150 にて測定)することにより、PMMA板上に膜厚3.5μmの単層膜を形成させた。
Claims (5)
- アニオン性親水基と、重合性炭素-炭素二重結合を有する官能基とを有する化合物(I)、および
水酸基を3つ以上と、重合性炭素-炭素二重結合を有する官能基を3つ以上とを有する化合物(II)
を含む組成物を重合することにより得られる架橋樹脂からなる単層膜であり、
該単層膜のアニオン性親水基の表面濃度(Sa)と該単層膜の膜厚1/2地点における該親水基の深部濃度(Da)の傾斜度(Sa/Da)が1.1以上である単層膜。 - 上記化合物(I)が下記一般式(100)で表される化合物である請求項1に記載の単層膜。
- 上記一般式(100)中のAが、下記一般式(121)~(125)から選ばれる少なくとも1つの重合性炭素-炭素二重結合を有する官能基である請求項2に記載の単層膜。
- 上記化合物(II)が下記一般式(200)で表される化合物である請求項1に記載の単層膜。
- 請求項1~4のいずれかに記載の単層膜を少なくとも1層有する積層体。
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CN201580022466.4A CN106459653B (zh) | 2014-05-19 | 2015-05-12 | 亲水性单层膜 |
KR1020167029698A KR101870554B1 (ko) | 2014-05-19 | 2015-05-12 | 친수성 단층막 |
JP2015549699A JP5959764B2 (ja) | 2014-05-19 | 2015-05-12 | 親水性単層膜 |
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US (1) | US9976049B2 (ja) |
EP (1) | EP3147336A4 (ja) |
JP (1) | JP5959764B2 (ja) |
KR (1) | KR101870554B1 (ja) |
CN (1) | CN106459653B (ja) |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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KR20190038868A (ko) | 2016-08-26 | 2019-04-09 | 미쯔이가가꾸가부시끼가이샤 | 방담성 적층체 |
KR20190038867A (ko) | 2016-08-26 | 2019-04-09 | 미쯔이가가꾸가부시끼가이샤 | 반사 방지성 적층체 |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
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US20210165134A1 (en) * | 2019-12-02 | 2021-06-03 | Ripclear Llc | Anti-fog lens covering systems |
US20230272143A1 (en) * | 2020-08-27 | 2023-08-31 | Tokyo Ohka Kogyo Co., Ltd. | Surface treatment liquid and hydrophilizing treatment method |
JP2022156125A (ja) * | 2021-03-31 | 2022-10-14 | 東京応化工業株式会社 | 硬化性組成物、防曇コーティング剤、及び硬化膜 |
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JP2001098007A (ja) | 1999-09-29 | 2001-04-10 | Kawamura Inst Of Chem Res | 親水性成形物およびその製造法 |
JP2011229734A (ja) | 2010-04-28 | 2011-11-17 | Sekisui Home Techno Kk | 浴槽及び浴槽の製造方法 |
EP2738188B1 (en) | 2011-07-25 | 2019-05-22 | Mitsui Chemicals, Inc. | Monolayer film and hydrophilic material comprising same |
US20180163056A1 (en) * | 2013-12-11 | 2018-06-14 | Mitsui Chemicals, Inc. | Hydrophilic curable compositions |
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2015
- 2015-05-12 KR KR1020167029698A patent/KR101870554B1/ko active IP Right Grant
- 2015-05-12 CN CN201580022466.4A patent/CN106459653B/zh active Active
- 2015-05-12 EP EP15796384.4A patent/EP3147336A4/en not_active Withdrawn
- 2015-05-12 JP JP2015549699A patent/JP5959764B2/ja active Active
- 2015-05-12 WO PCT/JP2015/063615 patent/WO2015178248A1/ja active Application Filing
- 2015-05-12 US US15/307,045 patent/US9976049B2/en active Active
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JPS5590516A (en) * | 1978-12-28 | 1980-07-09 | Mitsubishi Rayon Co Ltd | Coating composition with excellent functionality |
JP2005187576A (ja) * | 2003-12-25 | 2005-07-14 | Seed Co Ltd | 親水性ハードコート用組成物、ハードコート用材料及びハードコート膜の形成方法 |
WO2007064003A1 (ja) * | 2005-12-02 | 2007-06-07 | Mitsui Chemicals, Inc. | 単層膜およびこれからなる親水性材料 |
WO2012014829A1 (ja) * | 2010-07-29 | 2012-02-02 | 三井化学株式会社 | 単層膜およびこれからなる親水性材料 |
WO2013187311A1 (ja) * | 2012-06-12 | 2013-12-19 | 三井化学株式会社 | 親水性の変性アクリル樹脂膜 |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20190038868A (ko) | 2016-08-26 | 2019-04-09 | 미쯔이가가꾸가부시끼가이샤 | 방담성 적층체 |
KR20190038867A (ko) | 2016-08-26 | 2019-04-09 | 미쯔이가가꾸가부시끼가이샤 | 반사 방지성 적층체 |
EP3505344A4 (en) * | 2016-08-26 | 2020-04-15 | Mitsui Chemicals, Inc. | FOG PROTECTION LAMINATE |
US11338562B2 (en) | 2016-08-26 | 2022-05-24 | Mitsui Chemicals, Inc. | Antifogging laminate |
Also Published As
Publication number | Publication date |
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US9976049B2 (en) | 2018-05-22 |
CN106459653B (zh) | 2019-03-01 |
JPWO2015178248A1 (ja) | 2017-04-20 |
US20170044393A1 (en) | 2017-02-16 |
CN106459653A (zh) | 2017-02-22 |
KR20160138206A (ko) | 2016-12-02 |
JP5959764B2 (ja) | 2016-08-02 |
EP3147336A4 (en) | 2017-12-20 |
KR101870554B1 (ko) | 2018-06-22 |
EP3147336A1 (en) | 2017-03-29 |
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